Assessment of polyelectrolyte coating stability under dynamic buffer conditions in CE.

PubMed

Swords, Kyleen E; Bartline, Peter B; Roguski, Katherine M; Bashaw, Sarah A; Frederick, Kimberley A

2011-09-01

Dynamic buffer conditions are present in many electrophoretically driven separations. Polyelectrolyte multilayer coatings have been employed in CE because of their chemical and physical stability as well as their ease of application. The goal of this study is to measure the effect of dynamic changes in buffer pH on flow using a real-time method for measuring EOF. Polyelectrolyte multilayers (PEMs) were composed of pairs of strong or completely ionized polyelectrolytes including poly(diallyldimethylammonium) chloride and poly(styrene sulfonate) and weak or ionizable polyelectrolytes including poly(allylamine) and poly(methacrylic acid). Polyelectrolyte multilayers of varying thicknesses (3, 4, 7, 8, 15, or 16 layers) were also studied. While the magnitude of the EOF was monitored every 2 s, the buffer pH was exchanged from a relatively basic pH (7.1) to increasingly acidic pHs (6.6, 6.1, 5.5, and 5.1). Strong polyelectrolytes responded minimally to changes in buffer pH (<1%), whereas substantial (>10%) and sometimes irreversible changes were measured with weak polyelectrolytes. Thicker coatings resulted in a similar magnitude of response but were more likely to degrade in response to buffer pH changes. The most stable coatings were formed from thinner layers of strong polyelectrolytes. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multi-functional polyelectrolyte multilayer films: combining mechanical resistance, biodegradability and bioactivity

PubMed Central

Schneider, Aurore; Vodouhê, Constant; Richert, Ludovic; Francius, Gregory; Le Guen, Erell; Schaaf, Pierre; Voegel, Jean-Claude; Frisch, Benoît; Picart, Catherine

2008-01-01

Cross-linked polyelectrolyte multilayer films (CL PEM) have an increased rigidity and are mechanically more resistant than native (e.g. uncrosslinked) films. However, they are still biodegradable, which make them interesting candidates for biomedical applications. In this study, CL PEM films have been explored for their multifunctional properties as i) mechanically resistant ii) biodegradable and iii) bioactive films. Toward this end, we investigated drug loading into CL chitosan/hyaluronan (CHI/HA) and poly(L-lysine)/hyaluronan (PLL/HA) films by simple diffusion of the drugs. Sodium diclofenac and paclitaxel were chosen as model drugs and were successfully loaded into the films. The effect of varying the number of layers in the (CHI/HA) films as well as the cross-linker concentration on diclofenac loading were studied. Diclofenac was released from the film in about ten hours. Paclitaxel was also found to diffuse within CL films. Its activity was maintained after loading in the CL films and cellular viability could be reduced by about 55% over three days. Such simple approach may be applied to other types of cross-linked films and to other drugs. These results prove that it is possible to design multifunctional multilayer films that combine mechanical resistance, biodegradability and bioactivity properties into a single PEM architecture. PMID:17206799

Properties of POPC/POPE supported lipid bilayers modified with hydrophobic quantum dots on polyelectrolyte cushions.

PubMed

Kolasinska-Sojka, Marta; Wlodek, Magdalena; Szuwarzynski, Michal; Kereiche, Sami; Kovacik, Lubomir; Warszynski, Piotr

2017-10-01

The formation and properties of supported lipid bilayers (SLB) containing hydrophobic nanoparticles (NP) was studied in relation to underlying cushion obtained from selected polyelectrolyte multilayers. Lipid vesicles were formed from zwitterionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and negatively charged 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) in phosphate buffer (PBS). As hydrophobic nanoparticles - quantum dots (QD) with size of 3.8nm (emission wavelength of 420nm) were used. Polyelectrolyte multilayers (PEM) were constructed by the sequential, i.e., layer-by-layer (LbL) adsorption of alternately charged polyelectrolytes from their solutions. Liposomes and Liposome-QDs complexes were studied with Transmission Cryo-Electron Microscopy (Cryo-TEM) to verify the quality of vesicles and the position of QD within lipid bilayer. Deposition of liposomes and liposomes with quantum dots on polyelectrolyte films was studied in situ using quartz crystal microbalance with dissipation (QCM-D) technique. The fluorescence emission spectra were analyzed for both: suspension of liposomes with nanoparticles and for supported lipid bilayers containing QD on PEM. It was demonstrated that quantum dots are located in the hydrophobic part of lipid bilayer. Moreover, we proved that such QD-modified liposomes formed supported lipid bilayers and their final structure depended on the type of underlying cushion. Copyright © 2017 Elsevier B.V. All rights reserved.

Ionic Driven Embedment of Hyaluronic Acid Coated Liposomes in Polyelectrolyte Multilayer Films for Local Therapeutic Delivery

NASA Astrophysics Data System (ADS)

Hayward, Stephen L.; Francis, David M.; Sis, Matthew J.; Kidambi, Srivatsan

2015-10-01

The ability to control the spatial distribution and temporal release of a therapeutic remains a central challenge for biomedical research. Here, we report the development and optimization of a novel substrate mediated therapeutic delivery system comprising of hyaluronic acid covalently functionalized liposomes (HALNPs) embedded into polyelectrolyte multilayer (PEM) platform via ionic stabilization. The PEM platform was constructed from sequential deposition of Poly-L-Lysine (PLL) and Poly(Sodium styrene sulfonate) (SPS) “(PLL/SPS)4.5” followed by adsorption of anionic HALNPs. An adsorption affinity assay and saturation curve illustrated the preferential HALNP deposition density for precise therapeutic loading. (PLL/SPS)2.5 capping layer on top of the deposited HALNP monolayer further facilitated complete nanoparticle immobilization, cell adhesion, and provided nanoparticle confinement for controlled linear release profiles of the nanocarrier and encapsulated cargo. To our knowledge, this is the first study to demonstrate the successful embedment of a translatable lipid based nanocarrier into a substrate that allows for temporal and spatial release of both hydrophobic and hydrophilic drugs. Specifically, we have utilized our platform to deliver chemotherapeutic drug Doxorubicin from PEM confined HALNPs. Overall, we believe the development of our HALNP embedded PEM system is significant and will catalyze the usage of substrate mediated delivery platforms in biomedical applications.

Direct optical imaging of nanoscale internal organization of polymer films

NASA Astrophysics Data System (ADS)

Suran, Swathi; Varma, Manoj

2018-02-01

Owing to its sensitivity and precise control at the nanoscale, polyelectrolytes have been immensely used to modify surfaces. Polyelectrolyte multilayers are generally water made and are easy to fabricate on any surface by the layer-by-layer (LbL) self-assembly process due to electrostatic interactions. Polyelectrolyte multilayers or PEMs can be assembled to form ultrathin membranes which can have potential applications in water filtration and desalination [1-3]. Hydration in PEMs is a consequence of both the bulk and surface phenomenon [4-7]. Bulk behavior of polymer membranes are well understood. Several techniques including reflectivity and contact angle measurements were used to measure the hydration in the bulk of polymer membranes [4, 8]. On the other hand their internal organization at the molecular level which can have a profound contribution in the transport mechanism, are not understood well. Previously, we engineered a technique, which we refer to as Bright-field Nanoscopy, which allows nanoscale optical imaging using local heterogeneities in a water-soluble germanium (Ge) thin film ( 25 nm thick) deposited on gold [8]. We use this technique to study the water transport in PEMs. It is understood that the surface charge and outer layers of the PEMs play a significant role in water transport through polymers [9-11]. This well-known `odd-even' effect arising on having different surface termination of the PEMs was optically observed with a spatial resolution unlike any other reported previously [12]. In this communication, we report that on increasing the etchant's concentration, one can control the lateral etching of the Ge film. This allowed the visualization of the nanoscale internal organization in the PEMs. Knowledge of the internal structure would allow one to engineer polymer membranes specific to applications such as drug delivering capsules, ion transport membranes and barriers etc. We also demonstrate a mathematical model involving a surface permeability term which captures the experimentally observed odd-even effect.

Coulombic interactions on the deposition and rotational mobility distributions of dyes in polyelectrolyte multilayer thin films.

PubMed

Li, Ye; Yip, Wai Tak

2004-12-07

We employed negatively charged fluorescein (FL), positively charged rhodamine 6G (R6G), and neutral Nile Red (NR) as molecular probes to investigate the influence of Coulombic interaction on their deposition into and rotational mobility inside polyelectrolyte multilayer (PEM) films. The entrapment efficiency of the dyes reveals that while Coulombic repulsion has little effect on dye deposition, Coulombic attraction can dramatically enhance the loading efficiency of dyes into a PEM film. By monitoring the emission polarization of single dye molecules in polyethylenimine (PEI) films, the percentages of mobile R6G, NR, and FL were determined to be 87 +/- 4%, 76 +/- 5%, and 68 +/- 3%, respectively. These mobility distributions suggest that cationic R6G enjoys the highest degree of rotational freedom, whereas anionic FL shows the least mobility because of Coulombic attraction toward cationic PEI. Regardless of charges, this high percentage of mobile molecules is in stark contrast to the 5-40% probe mobility reported from spun-cast polymer films, indicating that our PEI films contain more free volume and display richer polymer dynamics. These observations demonstrate the potential of using isolated fluorescent probes to interrogate the internal structure of a PEM film at a microscopic level.

In Situ Synthesis of Silver Nanoparticles on the Polyelectrolyte-Coated Sericin/PVA Film for Enhanced Antibacterial Application

PubMed Central

Cai, Rui; Tao, Gang; Guo, Pengchao; Yang, Meirong; Ding, Chaoxiang; Zuo, Hua; Wang, Lingyan; Zhao, Ping; Wang, Yejing

2017-01-01

To develop silk sericin (SS) as a potential antibacterial biomaterial, a novel composite of polyelectrolyte multilayers (PEMs) coated sericin/poly(vinyl alcohol) (SS/PVA) film modified with silver nanoparticles (AgNPs) has been developed using a layer-by-layer assembly technique and ultraviolet-assisted AgNPs synthesis method. Ag ions were enriched by PEMs via the electrostatic attraction between Ag ions and PEMs, and then reduced to AgNPs in situ with the assistance of ultraviolet irradiation. PEMs facilitated the high-density growth of AgNPs and protected the synthesized AgNPs due to the formation of a 3D matrix, and thus endowed SS/PVA film with highly effective and durable antibacterial activity. Scanning electron microscopy, energy dispersive spectroscopy, X-ray diffractometry, Fourier transfer infrared spectroscopy, water contact angle, mechanical property and thermogravimetric analysis were applied to characterize SS/PVA, PEMs-SS/PVA and AgNPs-PEMs-SS/PVA films, respectively. AgNPs-PEMs-SS/PVA film has exhibited good mechanical performance, hydrophilicity, water absorption capability as well as excellent and durable antibacterial activity against Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa and good stability and degradability. This study has developed a simple method to design and prepare AgNPs-PEMs-SS/PVA film for potential antibacterial application. PMID:28820482

Achiral and Chiral Separations Using Micellar Electrokinetic Chromatography, Polyelectrolyte Multilayer Coatings, and Mixed Mode Separation Techniques with Molecular Micelles

PubMed Central

Luces, Candace A.; Warner, Isiah M.

2014-01-01

Mixed mode separation using a combination of micellar electrokinetic chromatography (MEKC) and polyelectrolyte multilayer (PEM) coatings is herein reported for the separation of achiral and chiral analytes. Many analytes are difficult to separate by MEKC and PEM coatings alone. Therefore, the implementation of a mixed mode separation provides several advantages for overcoming the limitations of these well-established methods. In this study, it was observed that achiral separations using MEKC and PEM coatings individually resulted in partial resolution of 8 very similar aryl ketones when the molecular micelle (sodium poly(N-undecanoyl-l-glycinate) (poly-SUG)) concentration was varied from 0.25% – 1.00% (w/v) and the bilayer number varied from 2 – 4. However, when mixed mode separation was introduced, baseline resolution was achieved for all 8 analytes. In the case of chiral separations, temazepam, aminoglutethimide, benzoin, benzoin methyl ether and coumachlor were separated using the three separation techniques. For chiral separations, the chiral molecular micelle, sodium poly(N-undecanoyl-l-leucylvalinate) (poly-l-SULV), was employed at concentrations of 0.25–1.50% (w/v) for both MEKC and PEM coatings. Overall, the results revealed partial separation with MEKC and PEM coatings individually. However, mixed mode separation enabled baseline separation of each chiral mixture. The separation of achiral and chiral compounds from different compound classes demonstrates the versatility of this mixed mode approach. PMID:20155738

Engineering invitro cellular microenvironment using polyelectrolyte multilayer films to control cell adhesion and for drug delivery applications

NASA Astrophysics Data System (ADS)

Kidambi, Srivatsan

Over the past decades, the development of new methods for fabricating thin films that provide precise control of the three-dimensional topography and cell adhesion has generated lots of interest. These films could lead to significant advances in the fields of tissue engineering, drug delivery and biosensors which have become increasingly germane areas of research in the field of chemical engineering. The ionic layer-by-layer (LbL) assembly technique called "Polyelectrolyte Multilayers (PEMs)", introduced by Decher in 1991, has emerged as a versatile and inexpensive method of constructing polymeric thin films, with nanometer-scale control of ionized species. PEMs have long been utilized in such applications as sensors, eletrochromics, and nanomechanical thin films but recently they have also been shown to be excellent candidates for biomaterial applications. In this thesis, we engineered these highly customizable PEM thin films to engineer in vitro cellular microenvironments to control cell adhesion and for drug delivery applications. PEM films were engineered to control the adhesion of primary hepatocytes and primary neurons without the aid of adhesive proteins/ligands. We capitalized upon the differential cell attachment and spreading of primary hepatocytes and neurons on poly(diallyldimethylammoniumchloride) (PDAC) and sulfonated polystyrene (SPS) surfaces to make patterned co-cultures of primary hepatocytes/fibroblasts and primary neurons/astrocytes on the PEM surfaces. In addition, we developed self-assembled monolayer (SAM) patterns of m-d-poly(ethylene glycol) (m-dPEG) acid molecules onto PEMs. The created m-dPEG acid monolayer patterns on PEMs acted as resistive templates, and thus prevented further deposits of consecutive poly(anion)/poly(cation) pairs of charged particles and resulted in the formation of three-dimensional (3-D) patterned PEM films or selective particle depositions atop the original multilayer thin films. These new patterned and structured surfaces have potential applications in microelectronic devices and electro-optical and biochemical sensors. The PEG patterns developed are tunable at certain salt conditions and be removed from the PEM surface without affecting the PEM layers underneath the patterns. These removable surfaces provide an alternative method to form patterns of multiple particles, proteins and cells. This new approach provides an environmentally friendly and biocompatible route to designing versatile salt tunable surfaces. Finally, we illustrate the use of PEM films to engineer aptamer and siRNA based drug delivery systems.

Gramicidin ion channels in a lipid bilayer supported on polyelectrolyte multilayer films: an electrochemical impedance study.

PubMed

Diamanti, Eleftheria; Gutiérrez-Pineda, Eduart; Politakos, Nikolaos; Andreozzi, Patrizia; Rodriguez-Presa, María José; Knoll, Wolfgang; Azzaroni, Omar; Gervasi, Claudio A; Moya, Sergio E

2017-12-06

Supported membranes on polymer cushions are of fundamental interest as models for cell membranes. The use of polyelectrolyte multilayers (PEMs) assembled by the layer by layer (LbL) technique as supports for a bilayer allows for easy integration of the lipid bilayer on surfaces and devices and for nanoscale tunable spacing of the lipid bilayer. Controlling ionic permeability in lipid bilayers supported on PEMs triggers potential applications in sensing and as models for transport phenomena in cell membranes. Lipid bilayers displaying gramicidin channels are fabricated on top of polyallylamine hydrochloride (PAH) and polystyrene sulfonate (PSS) multilayer films, by the assembly of vesicles of phosphatidylcholine and phosphatidylserine, 50 : 50 M/M, carrying gramicidin (GA). Quartz crystal microbalance with dissipation shows that the vesicles with GA fuse into a bilayer. Atomic force microscopy reveals that the presence of GA alters the bilayer topography resulting in depressions in the bilayer of around 70 nm in diameter. Electrochemical impedance spectroscopy (EIS) studies show that supported bilayers carrying GA have smaller resistances than the bilayers without GA. Lipid layers carrying GA display a higher conductance for K + than for Na + and are blocked in the presence of Ca 2+ .

Enhanced antiadhesive properties of chitosan/hyaluronic acid polyelectrolyte multilayers driven by thermal annealing: Low adherence for mammalian cells and selective decrease in adhesion for Gram-positive bacteria.

PubMed

Muzzio, Nicolás E; Pasquale, Miguel A; Diamanti, Eleftheria; Gregurec, Danijela; Moro, Marta Martinez; Azzaroni, Omar; Moya, Sergio E

2017-11-01

The development of antifouling coatings with restricted cell and bacteria adherence is fundamental for many biomedical applications. A strategy for the fabrication of antifouling coatings based on the layer-by-layer assembly and thermal annealing is presented. Polyelectrolyte multilayers (PEMs) assembled from chitosan and hyaluronic acid were thermally annealed in an oven at 37°C for 72h. The effect of annealing on the PEM properties and topography was studied by atomic force microscopy, ζ-potential, circular dichroism and contact angle measurements. Cell adherence on PEMs before and after annealing was evaluated by measuring the cell spreading area and aspect ratio for the A549 epithelial, BHK kidney fibroblast, C2C12 myoblast and MC-3T3-E1 osteoblast cell lines. Chitosan/hyaluronic acid PEMs show a low cell adherence that decreases with the thermal annealing, as observed from the reduction in the average cell spreading area and more rounded cell morphology. The adhesion of S. aureus (Gram-positive) and E. coli (Gram-negative) bacteria strains was quantified by optical microscopy, counting the number of colony-forming units and measuring the light scattering of bacteria suspension after detachment from the PEM surface. A 20% decrease in bacteria adhesion was selectively observed in the S. aureus strain after annealing. The changes in mammalian cell and bacteria adhesion correlate with the changes in topography of the chitosan/hyaluronic PEMs from a rough fibrillar 3D structure to a smoother and planar surface after thermal annealing. Copyright © 2017. Published by Elsevier B.V.

Tunable swelling of polyelectrolyte multilayers in cell culture media for modulating NIH-3T3 cells adhesion.

PubMed

Qi, Wei; Cai, Peng; Yuan, Wenjing; Wang, Hua

2014-11-01

For polyelectrolyte multilayers (PEMs) assembled by the layer-by-layer (LbL) assembly technique, their nanostructure and properties can be governed by many parameters during the building process. Here, it was demonstrated that the swelling of the PEMs containing poly(diallyldimethylammonium chloride) (PDDA) and poly(sodium 4-styrenesulfonate) (PSS) in cell culture media could be tuned with changing supporting salt solutions during the assembly process. Importantly, the influence of the PEMs assembled in different salt solutions on NIH-3T3 cell adhesion was observable. Specifically, the cells could possess a higher affinity for the films assembled in low salt concentration (i.e. 0.15M NaCl) or no salt, the poorly swelling films in cell culture media, which was manifested by the large cell spreading area and focal adhesions. In contrast, those were assembled in higher salt concentration, highly swelling films in cell culture media, were less attractive for the fibroblasts. As a result, the cell adhesion behaviors may be manipulated by tailoring the physicochemical properties of the films, which could be performed by changing the assembly conditions such as supporting salt concentration. Such a finding might promise a great potential in designing desired biomaterials for tissue engineering and regenerative medicine. © 2014 Wiley Periodicals, Inc.

Tuning compliance of nanoscale polyelectrolyte multilayers to modulate cell adhesion.

PubMed

Thompson, Michael T; Berg, Michael C; Tobias, Irene S; Rubner, Michael F; Van Vliet, Krystyn J

2005-12-01

It is well known that mechanical stimuli induce cellular responses ranging from morphological reorganization to mineral secretion, and that mechanical stimulation through modulation of the mechanical properties of cell substrata affects cell function in vitro and in vivo. However, there are few approaches by which the mechanical compliance of the substrata to which cells adhere and grow can be determined quantitatively and varied independent of substrata chemical composition. General methods by which mechanical state can be quantified and modulated at the cell population level are critical to understanding and engineering materials that promote and maintain cell phenotype for applications such as vascular tissue constructs. Here, we apply contact mechanics of nanoindentation to measure the mechanical compliance of weak polyelectrolyte multilayers (PEMs) of nanoscale thickness, and explore the effects of this tunable compliance for cell substrata applications. We show that the nominal elastic moduli E(s) of these substrata depend directly on the pH at which the PEMs are assembled, and can be varied over several orders of magnitude for given polycation/polyanion pairs. Further, we demonstrate that the attachment and proliferation of human microvascular endothelial cells (MVECs) can be regulated through independent changes in the compliance and terminal polyion layer of these PEM substrata. These data indicate that substrate mechanical compliance is a strong determinant of cell fate, and that PEMs of nanoscale thickness provide a valuable tool to vary the external mechanical environment of cells independently of chemical stimuli.

Layer-by-Layer Assembled Architecture of Polyelectrolyte Multilayers and Graphene Sheets on Hollow Carbon Spheres/Sulfur Composite for High-Performance Lithium-Sulfur Batteries.

PubMed

Wu, Feng; Li, Jian; Su, Yuefeng; Wang, Jing; Yang, Wen; Li, Ning; Chen, Lai; Chen, Shi; Chen, Renjie; Bao, Liying

2016-09-14

In the present work, polyelectrolyte multilayers (PEMs) and graphene sheets are applied to sequentially coat on the surface of hollow carbon spheres/sulfur composite by a flexible layer-by-layer (LBL) self-assembly strategy. Owing to the strong electrostatic interactions between the opposite charged materials, the coating agents are very stable and the coating procedure is highly efficient. The LBL film shows prominent impact on the stability of the cathode by acting as not only a basic physical barrier, and more importantly, an ion-permselective film to block the polysulfides anions by Coulombic repulsion. Furthermore, the graphene sheets can help to stabilize the polyelectrolytes film and greatly reduce the inner resistance of the electrode by changing the transport of the electrons from a "point-to-point" mode to a more effective "plane-to-point'' mode. On the basis of the synergistic effect of the PEMs and graphene sheets, the fabricated composite electrode exhibits very stable cycling stability for over 200 cycles at 1 A g(-1), along with a high average Coulombic efficiency of 99%. With the advantages of rapid and controllable fabrication of the LBL coating film, the multifunctional architecture developed in this study should inspire the design of other lithium-sulfur cathodes with unique physical and chemical properties.

Polyelectrolyte Multilayer-Treated Electrodes for Real-Time Electronic Sensing of Cell Proliferation

PubMed Central

Mijares, Geraldine I.; Reyes, Darwin R.; Geist, Jon; Gaitan, Michael; Polk, Brian J.; DeVoe, Don L.

2010-01-01

We report on the use of polyelectrolyte multilayer (PEM) coatings as a non-biological surface preparation to facilitate uniform cell attachment and growth on patterned thin-film gold (Au) electrodes on glass for impedance-based measurements. Extracellular matrix (ECM) proteins are commonly utilized as cell adhesion promoters for electrodes; however, they exhibit degradation over time, thereby imposing limitations on the duration of conductance-based biosensor experiments. The motivation for the use of PEM coatings arises from their long-term surface stability as promoters for cell attachment, patterning, and culture. In this work, a cell proliferation monitoring device was fabricated. It consisted of thin-film Au electrodes deposited with a titanium-tungsten (TiW) adhesion layer that were patterned on a glass substrate and passivated to create active electrode areas. The electrode surfaces were then treated with a poly(ethyleneimine) (PEI) anchoring layer and subsequent bilayers of sodium poly(styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH). NIH-3T3 mouse embryonic fibroblast cells were cultured on the device, observed by optical microscopy, and showed uniform growth characteristics similar to those observed on a traditional polystyrene cell culture dish. The optical observations were correlated to electrical measurements on the PEM-treated electrodes, which exhibited a rise in impedance with cell proliferation and stabilized to an approximate 15 % increase as the culture approached confluency. In conclusion, cells proliferate uniformly over gold and glass PEM-treated surfaces, making them useful for continuous impedance-based, real-time monitoring of cell proliferation and for the determination of cell growth rate in cellular assays. PMID:27134780

Multiple internalization pathways of polyelectrolyte multilayer capsules into mammalian cells.

PubMed

Kastl, Lena; Sasse, Daniel; Wulf, Verena; Hartmann, Raimo; Mircheski, Josif; Ranke, Christiane; Carregal-Romero, Susana; Martínez-López, José Antonio; Fernández-Chacón, Rafael; Parak, Wolfgang J; Elsasser, Hans-Peter; Rivera Gil, Pilar

2013-08-27

Polyelectrolyte multilayer (PEM) capsules are carrier vehicles with great potential for biomedical applications. With the future aim of designing biocompatible, effective therapeutic delivery systems (e.g., for cancer), the pathway of internalization (uptake and fate) of PEM capsules was investigated. In particular the following experiments were performed: (i) the study of capsule co-localization with established endocytic markers, (ii) switching-off endocytotic pathways with pharmaceutical/chemical inhibitors, and (iii) characterization and quantification of capsule uptake with confocal and electron microscopy. As result, capsules co-localized with lipid rafts and with phagolysosomes, but not with other endocytic vesicles. Chemical interference of endocytosis with chemical blockers indicated that PEM capsules enter the investigated cell lines through a mechanism slightly sensitive to electrostatic interactions, independent of clathrin and caveolae, and strongly dependent on cholesterol-rich domains and organelle acidification. Microscopic characterization of cells during capsule uptake showed the formation of phagocytic cups (vesicles) to engulf the capsules, an increased number of mitochondria, and a final localization in the perinuclear cytoplasma. Combining all these indicators we conclude that PEM capsule internalization in general occurs as a combination of different sequential mechanisms. Initially, an adsorptive mechanism due to strong electrostatic interactions governs the stabilization of the capsules at the cell surface. Membrane ruffling and filopodia extensions are responsible for capsule engulfing through the formation of a phagocytic cup. Co-localization with lipid raft domains activates the cell to initiate a lipid-raft-mediated macropinocytosis. Internalization vesicles are very acidic and co-localize only with phagolysosome markers, excluding caveolin-mediated pathways and indicating that upon phagocytosis the capsules are sorted to heterophagolysosomes.

The stability of BMP loaded polyelectrolyte multilayer coatings on titanium

PubMed Central

Guillot, R.; Gilde, F.; Becquart, P.; Sailhan, F.; Lapeyrere, A.; Logeart-Avramoglou, D.; Picart, C.

2014-01-01

Immobilization of bone morphogenetic proteins (BMP) onto material surfaces is a promising, but still challenging, strategy for achieving dependable and consistent osseointegration of long-term metal implants. In the present study, we have developed an osteoinductive coating of a porous titanium implant using biomimetic polyelectrolyte multilayer (PEM) films loaded with BMP-2. The amount of BMP-2 loaded in these films was tuned -over a large range - depending on the cross-linking extent of the film and of the BMP-2 initial concentration. The air-dried PEM films were stable for at least one year of storage at 4°C. In addition, they resisted exposure to γ-irradiation at clinically approved doses. The preservation of the growth factor bioactivity upon long-term storage and sterilization were evaluated both in vitro (using C2C12 cells) and in vivo (in a rat ectopic model) for the perspective of industrial and clinical development. BMP-2 loaded in dried PEM films exhibited shelf-life stability over one year. However, their bioactivity in vitro decreased from 50 to 80% after irradiation depending on the γ-irradiation dose. Remarkably, the in vivo studies showed that the osteoinductive potential of BMP-2 contained in PEM-coated Ti implants was fully preserved after air-drying of the implants and sterilization at 25 kGy. Film drying or irradiation did not affect the amount of new bone tissue formation. This “off-the-shelf” novel technology of functionalized implants opens promising applications in prosthetic and tissue engineering fields. PMID:23642539

Integration of silver nanoparticle-impregnated polyelectrolyte multilayers into murine splinted cutaneous wound beds

PubMed Central

Guthrie, Kathleen M.; Agarwal, Ankit; Teixeira, Leandro B. C.; Dubielzig, Richard R.; Abbott, Nicholas L.; Murphy, Christopher J.; Singh, Harpreet; McAnulty, Jonathan F.; Schurr, Michael J.

2013-01-01

Silver is a commonly used topical antimicrobial. However, technologies to immobilize silver at the wound surface are lacking, while currently available silver-containing wound dressings release excess silver that can be cytotoxic and impair wound healing. We have shown that precise concentrations of silver at lower levels can be immobilized into a wound bed using a polyelectrolyte multilayer (PEM) attachment technology. These silver nanoparticle-impregnated PEMs are non-cytotoxic yet bactericidal in vitro, but their effect on wound healing in vivo was previously unknown. Objective The purpose of this study was to determine the effect on wound healing of integrating silver nanoparticle/PEMs into the wound bed. Methods A full-thickness, splinted, excisional murine wound healing model was employed in both phenotypically normal mice and spontaneously diabetic mice (healing impaired model). Results Gross image measurements showed an initial small lag in healing in the silver-treated wounds in diabetic mice, but no difference in time to complete wound closure in either normal or diabetic mice. Histological analysis showed modest differences between silver-treated and control groups on day 9, but no difference between groups at the time of wound closure. Conclusions We conclude that silver nanoparticle/PEMs can be safely integrated into the wound beds of both normal and diabetic mice without delaying wound closure, and with transient histological effects. The results of this study suggest the feasibility of this technology for use as a platform to effect nanoscale wound engineering approaches to microbial prophylaxis or to augment wound healing. PMID:23511285

Effects of fluid shear stress on polyelectrolyte multilayers by neutron scattering studies

DOE PAGES

Singh, Saurabh; Junghans, Ann; Watkins, Erik; ...

2015-02-17

The structure of layer-by-layer (LbL) deposited nanofilm coatings consists of alternating polyethylenimine (PEI) and polystyrenesulfonate (PSS) films deposited on a single crystal quartz substrate. LbL-deposited nanofilms were investigated by neutron reflectomery (NR) in contact with water in the static and fluid shear stress conditions. The fluid shear stress was applied through a laminar flow of the liquid parallel to the quartz/polymer interface in a custom-built solid–liquid interface cell. The scattering length density profiles obtained from NR results of these polyelectrolyte multilayers (PEM), measured under different shear conditions, showed proportional decrease of volume fraction of water hydrating the polymers. For themore » highest shear rate applied (ca. 6800 s –1) the water volume fraction decreased by approximately 7%. The decrease of the volume fraction of water was homogeneous through the thickness of the film. Since there were not any significant changes in the total polymer thickness, it resulted in negative osmotic pressures in the film. The PEM films were compared with the behavior of thin films of thermoresponsive poly(N-isopropylacrylamide) (pNIPAM) deposited via spin-coating. The PEM and pNIPAM differ in their interactions with water molecules, and they showed opposite behaviors under the fluid shear stress. In both cases the polymer hydration was reversible upon the restoration of static conditions. Furthermore, a theoretical explanation is given to explain this difference in the effect of shear on hydration of polymeric thin films.« less

Electrically driven ion separations and nanofiltration through membranes coated with polyelectrolyte multilayers

NASA Astrophysics Data System (ADS)

White, Nicholas

Polyelectrolyte multilayer (PEM) films deposited using the layer-by-layer (LBL) method are attractive for their simple deposition, tailorable nature, scalability, and charge or size-based selectivity for solutes. This dissertation explores ion separations in electrodialysis (ED) and solute removal through nanofiltration with PEMs deposited on polymer membranes. ED membranes typically exhibit modest selectivities between monovalent and divalent ions. In contrast, this work shows that K+/Mg 2+ ED selectivities reach values >1000 when using Nafion 115 cation-exchange membranes coated with multilayer poly(4-styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) films. For comparison, the corresponding K+ /Mg2+ selectivity of bare Nafion 115 is <2. However, water-splitting at strongly overlimiting current densities may lead to a local pH increase close to the membrane surface and alter film permeability or allow passage of Mg(OH)x species to decrease selectivity. When the source phase contains high salt concentrations, the K+ transference number approaches unity and the K+/Mg2+ selectivity is >20,000, presumably because the applied current is below the limiting value for K+ and H+ transport is negligible at this high K+ concentration. The high selectivities of these membranes may enable electrodialysis applications such as purification of salts that contain divalent or trivalent ions. The high ED selectivities of (PAH/PSS)5PAH-coated Nafion membranes translate to separations with Li+/Co2+ and K +/La3+. Even with adsorption of only 3 polyelectrolyte layers, Nafion membranes exhibit a Li+/Co2+ selectivity >23. However, the resistance to monovalent-ion passage does not decrease significantly with fewer polyelectrolyte layers. At overlimiting currents, hydroxides from water splitting form insoluble metal hydroxides to foul the membrane. With 0.1 M source-phase salt concentrations, transference numbers for monovalent cations approach unity and selectivities are >5000 because the diffusion-limited K+ or Li+ currents exceed the applied current. However, ED selectivities gradually decline with time. Thus, future research should aim to increase membrane stability and limiting currents to fully exploit the remarkable selectivity of these membranes. PEMs deposited on commercial ultrafiltration (UF) membranes also show high rejections of organic dyes. Coating the surface of polyethersulfone (PES) membranes imparts a selective barrier to dye molecules used in textile production. These films achieve dye rejections >98% and may be useful for wastewater treatment and dye recovery. Other studies in microfluidic channels exploit ion transport phenomena in the vicinity of ion-selective junctions, such as cation-exchange membranes. These studies suggest that ion concentration polarization (ICP) could remove charged species from feed streams.

DNA hydrogel-based supercapacitors operating in physiological fluids

PubMed Central

Hur, Jaehyun; Im, Kyuhyun; Hwang, Sekyu; Choi, ByoungLyong; Kim, Sungjee; Hwang, Sungwoo; Park, Nokyoung; Kim, Kinam

2013-01-01

DNA nanostructures have been attractive due to their structural properties resulting in many important breakthroughs especially in controlled assemblies and many biological applications. Here, we report a unique energy storage device which is a supercapacitor that uses nanostructured DNA hydrogel (Dgel) as a template and layer-by-layer (LBL)-deposited polyelectrolyte multilayers (PEMs) as conductors. Our device, named as PEM-Dgel supercapacitor, showed excellent performance in direct contact with physiological fluids such as artificial urine and phosphate buffered saline without any need of additional electrolytes, and exhibited almost no cytotoxicity during cycling tests in cell culture medium. Moreover, we demonstrated that the PEM-Dgel supercapacitor has greater charge-discharge cycling stability in physiological fluids than highly concentrated acid electrolyte solution which is normally used for supercapacitor operation. These conceptually new supercapacitors have the potential to be a platform technology for the creation of implantable energy storage devices for packageless applications directly utilizing biofluids. PMID:23412432

Toward the Development of an Artificial Brain on a Micropatterned and Material-Regulated Biochip by Guiding and Promoting the Differentiation and Neurite Outgrowth of Neural Stem/Progenitor Cells.

PubMed

Liu, Yung-Chiang; Lee, I-Chi; Lei, Kin Fong

2018-02-14

An in vitro model mimicking the in vivo environment of the brain must be developed to study neural communication and regeneration and to obtain an understanding of cellular and molecular responses. In this work, a multilayered neural network was successfully constructed on a biochip by guiding and promoting neural stem/progenitor cell differentiation and network formation. The biochip consisted of 3 × 3 arrays of cultured wells connected with channels. Neurospheroids were cultured on polyelectrolyte multilayer (PEM) films in the culture wells. Neurite outgrowth and neural differentiation were guided and promoted by the micropatterns and the PEM films. After 5 days in culture, a 3 × 3 neural network was constructed on the biochip. The function and the connections of the network were evaluated by immunocytochemistry and impedance measurements. Neurons were generated and produced functional and recyclable synaptic vesicles. Moreover, the electrical connections of the neural network were confirmed by measuring the impedance across the neurospheroids. The current work facilitates the development of an artificial brain on a chip for investigations of electrical stimulations and recordings of multilayered neural communication and regeneration.

Xanthan/chitosan gold chip for metal enhanced protein biomarker detection.

PubMed

Domnanich, Patrick; Peña, Dacimoneida Brito; Preininger, Claudia

2011-01-15

Protein microarrays for disease diagnostics are required to accurately quantify analytes in the low pg/mL range. This task is hampered by weak signal strengths and too low detector sensitivity. Herein we present reflective gold chips coated with polyelectrolyte multilayers (PEMs) for signal enhancement in immunoassays for melanoma-relevant biomarkers. Among tested (semi)natural polysaccharides (xanthan, chitosan, carboxymethylcellulose, hyaluronic acid) PEMs composed of xanthan and chitosan performed best in terms of detection of low analyte concentrations (ED10), spot morphology, fluorescence background and variability (<10%). Fluorescence signals on gold slides with a 75 nm coating of seven crosslinked polyelectrolyte double layers were up to 50 times higher than on bare glass slides. In comparison to commercial substrates the signal to noise ratio is enhanced by up to factor 11. Furthermore sandwich assays for interleukins 6, 8, 10, tumour necrosis factor alpha (TNFα), vascular endothelial growth factor A (VEGF-A) and S100B show working ranges which cover significantly lower concentrations (up to 38-fold). Not limited to above assays the presented substrates, which combine a biocompatible interface with metal-based signal amplification, are a valuable tool in a variety of biosensor applications. Copyright © 2010 Elsevier B.V. All rights reserved.

Advances in polyelectrolyte multilayer nanofilms as tunable drug delivery systems

PubMed Central

Jiang, Bingbing; Barnett, John B; Li, Bingyun

2009-01-01

There has been considerable interest in polyelectrolyte multilayer nanofilms, which have a variety of applications ranging from optical and electrochemical materials to biomedical devices. Polyelectrolyte multilayer nanofilms are constructed from aqueous solutions using electrostatic layer-by-layer self-assembly of oppositely-charged polyelectrolytes on a solid substrate. Multifunctional polyelectrolyte multilayer nanofilms have been studied using charged dyes, metal and inorganic nanoparticles, DNA, proteins, and viruses. In the past few years, there has been increasing attention to developing polyelectrolyte multilayer nanofilms as drug delivery vehicles. In this mini-review, we present recent developments in polyelectrolyte multilayer nanofilms with tunable drug delivery properties, with particular emphasis on the strategies in tuning the loading and release of drugs in polyelectrolyte multilayer nanofilms as well as their applications. PMID:24198464

Mesenchymal stem cell recruitment by stromal derived factor-1-delivery systems based on chitosan/poly(γ-glutamic acid) polyelectrolyte complexes.

PubMed

Gonçalves, Raquel M; Antunes, Joana C; Barbosa, Mário A

2012-04-10

Human mesenchymal stem cells (hMSCs) have an enormous potential for tissue engineering and cell-based therapies. With a potential of differentiation into multiple lineages and immune-suppression, these cells play a key role in tissue remodelling and regeneration. Here a method of hMSC recruitment is described, based on the incorporation of a chemokine in Chitosan (Ch)/Poly(γ-glutamic acid) (γ-PGA) complexes. Ch is a non-toxic, cationic polysaccharide widely investigated. γ-PGA is a hydrophilic, non-toxic, biodegradable and negatively charged poly-amino acid. Ch and γ-PGA, being oppositely charged, can be combined through electrostatic interactions. These biocompatible structures can be used as carriers for active substances and can be easily modulated in order to control the delivery of drugs, proteins, DNA, etc. Using the layer-by-layer method, Ch and γ-PGA were assembled into polyelectrolyte multilayers films (PEMs) with thickness of 120 nm. The chemokine stromal-derived factor-1 (SDF-1) was incorporated in these complexes and was continuously released during 120 h. The method of SDF-1 incorporation is of crucial importance for polymers assembly into PEMs and for the release kinetics of this chemokine. The Ch/γ-PGA PEMs with SDF-1 were able to recruit hMSCs, increasing the cell migration up to 6 fold to a maximum of 16.2 ± 4.9 cells/mm2. The controlled release of SDF-1 would be of great therapeutic value in the process of hMSC homing to injured tissues. This is the first study suggesting Ch/γ-PGA PEMs as SDF-1 reservoirs to recruit hMSCs, describing an efficient method of chemokine incorporation that allows a sustained released up to 5 days and that can be easily scaled-up.

Yield stress and scaling of polyelectrolyte multilayer modified suspensions: effect of polyelectrolyte conformation during multilayer assembly.

PubMed

Hess, Andreas; Aksel, Nuri

2013-09-10

The yield stress of polyelectrolyte multilayer modified suspensions exhibits a surprising dependence on the polyelectrolyte conformation of multilayer films. The rheological data scale onto a universal master curve for each polyelectrolyte conformation as the particle volume fraction, φ, and the ionic strength of the background fluid, I, are varied. It is shown that rough films with highly coiled, brushy polyelectrolytes significantly enhance the yield stress. Moreover, via the ionic strength I of the background fluid, the dynamic yield stress of brushy polyelectrolyte multilayers can be finely adjusted over 2 decades.

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

PubMed

Hedayati, Mohammadhasan; Kipper, Matt J

2018-06-15

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

Release of DNA from polyelectrolyte multilayers fabricated using 'charge-shifting' cationic polymers: tunable temporal control and sequential, multi-agent release.

PubMed

Sun, Bin; Lynn, David M

2010-11-20

We report an approach to the design of multilayered polyelectrolyte thin films (or 'polyelectrolyte multilayers', PEMs) that can be used to provide tunable control over the release of plasmid DNA (or multiple different DNA constructs) from film-coated surfaces. Our approach is based upon methods for the layer-by-layer assembly of DNA-containing thin films, and exploits the properties of a new class of cationic 'charge-shifting' polymers (amine functionalized polymers that undergo gradual changes in net charge upon side chain ester hydrolysis) to provide control over the rates at which these films erode and release DNA. We synthesized two 'charge-shifting' polymers (polymers 1 and 2) containing different side chain structures by ring-opening reactions of poly(2-alkenyl azlactone)s with two different tertiary amine functionalized alcohols (3-dimethylamino-1-propanol and 2-dimethylaminoethanol, respectively). Subsequent characterization revealed large changes in the rates of side chain ester hydrolysis for these two polymers; whereas the half-life for the hydrolysis of the esters in polymer 1 was ~200 days, the half-life for polymer 2 was ~6 days. We demonstrate that these large differences in side chain hydrolysis make possible the design of PEMs that erode and promote the surface-mediated release of DNA either rapidly (e.g., over ~3 days for films fabricated using polymer 2) or slowly (e.g., over ~1 month for films fabricated using polymer 1). We demonstrate further that it is possible to design films with release profiles that are intermediate to these two extremes by fabricating films using solutions containing different mixtures of these two polymers. This approach can thus expand the usefulness of these two polymers and achieve a broader range of DNA release profiles without the need to synthesize polymers with new structures or properties. Finally, we demonstrate that polymers 1 and 2 can be used to fabricate multilayered films with hierarchical structures that promote the sequential release of two different DNA constructs with separate and distinct release profiles (e.g., the release of a first construct over a period of ~3 days, followed by the sustained release of a second for a period of ~70 days). With further development, this approach could contribute to the design of functional thin films and surface coatings that provide sophisticated control over the timing and the order of the release of two or more DNA constructs (or other agents) of interest in a range of biomedical contexts. Copyright © 2010 Elsevier B.V. All rights reserved.

Interfacial Stacks of Polymeric Nanofilms on Soft Biological Surfaces that Release Multiple Agents.

PubMed

Herron, Maggie; Schurr, Michael J; Murphy, Christopher J; McAnulty, Jonathan F; Czuprynski, Charles J; Abbott, Nicholas L

2016-10-03

We report a general and facile method that permits the transfer (stacking) of multiple independently fabricated and nanoscopically thin polymeric films, each containing a distinct bioactive agent, onto soft biomedically relevant surfaces (e.g., collagen-based wound dressings). By using polyelectrolyte multilayer films (PEMs) formed from poly(allyl amine hydrochloride) and poly(acrylic acid) as representative polymeric nanofilms and micrometer-thick water-soluble poly(vinyl alcohol) sacrificial films to stack the PEMs, we demonstrate that it is possible to create stacked polymeric constructs containing multiple bioactive agents (e.g., antimicrobial and antibiofilm agents) on soft and chemically complex surfaces onto which PEMs cannot be routinely transferred by stamping. We illustrate the characteristics and merits of the approach by fabricating stacks of Ga 3+ (antibiofilm agent)- and Ag + (antimicrobial agent)-loaded PEMs as prototypical examples of agent-containing PEMs and demonstrate that the stacked PEMs incorporate precise loadings of the agents and provide flexibility in terms of tuning release rates. Specifically, we show that simultaneous release of Ga 3+ and Ag + from the stacked PEMs on collagen-based wound dressings can lead to synergistic effects on bacteria, killing and dispersing biofilms formed by Pseudomonas aeruginosa (two strains: ATCC 27853 and MPAO1) at sufficiently low loadings of agents such that cytotoxic effects on mammalian cells are avoided. The approach is general (a wide range of bioactive agents other than Ga 3+ and Ag + can be incorporated into PEMs), and the modular nature of the approach potentially allows end-user functionalization of soft biological surfaces for programmed release of multiple bioactive agents.

Brominated Tyrosine and Polyelectrolyte Multilayer Analysis by Laser Desorption VUV Postionization and Secondary Ion Mass Spectrometry

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

University of Illinois at Chicago; Blaze, Melvin M. T.; Takahashi, Lynelle

2011-03-14

The small molecular analyte 3,5-dibromotyrosine (Br2Y) and chitosan-alginate polyelectrolyte multilayers (PEM) with and without adsorbed Br2Y were analyzed by laser desorption postionization mass spectrometry (LDPI-MS). LDPI-MS using 7.87 eV laser and tunable 8 ? 12.5 eV synchrotron vacuum ultraviolet (VUV) radiation found that desorption of clusters from Br2Y films allowed detection by≤8 eV single photon ionization. Thermal desorption and electronic structure calculations determined the ionization energy of Br2Y to be ~;;8.3?0.1 eV and further indicated that the lower ionization energies of clusters permitted their detection at≤8 eV photon energies. However, single photon ionization could only detect Br2Y adsorbed within PEMsmore » when using either higher photon energies or matrix addition to the sample. All samples were also analyzed by 25 keV Bi3 + secondary ion mass spectrometry (SIMS), with the negative ion spectra showing strong parent ion signal which complemented that observed by LDPI-MS. The negative ion SIMS depended strongly on the high electron affinity of this specific analyte and the analyte?s condensed phase environment.« less

Polyelectrolyte multi-layers assembly of SiCHA nanopowders and collagen type I on aminolysed PLA films to enhance cell-material interactions.

PubMed

Baba Ismail, Yanny Marliana; Ferreira, Ana Marina; Bretcanu, Oana; Dalgarno, Kenneth; El Haj, Alicia J

2017-11-01

This paper presents a new approach in assembling bone extracellular matrix components onto PLA films, and investigates the most favourable environment which can be created using the technique for cell-material interactions. Poly (lactic acid) (PLA) films were chemically modified by covalently binding the poly(ethylene imine) (PEI) as to prepare the substrate for immobilization of polyelectrolyte multilayers (PEMs) coating. Negatively charged polyelectrolyte consists of well-dispersed silicon-carbonated hydroxyapatite (SiCHA) nanopowders in hyaluronic acid (Hya) was deposited onto the modified PLA films followed by SiCHA in collagen type I as the positively charged polyelectrolyte. The outermost layer was finally cross-linked by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrocholoride and N-hydroxysulfosuccinimide sodium salt (EDC/NHS) solutions. The physicochemical features of the coated PLA films were monitored via X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscope (AFM). The amounts of calcium and collagen deposited on the surface were qualitatively and quantitatively determined. The surface characterizations suggested that 5-BL has the optimum surface roughness and highest amounts of calcium and collagen depositions among tested films. In vitro human mesenchymal stem cells (hMSCs) cultured on the coated PLA films confirmed that the coating materials greatly improved cell attachment and survival compared to unmodified PLA films. The cell viability, cell proliferation and Alkaline Phosphatase (ALP) expression on 5-BL were found to be the most favourable of the tested films. Hence, this newly developed coating materials assembly could contribute to the improvement of the bioactivity of polymeric materials and structures aimed to bone tissue engineering applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Resistance of poly(ethylene oxide)-silane monolayers to the growth of polyelectrolyte multilayers.

PubMed

Buron, Cédric C; Callegari, Vincent; Nysten, Bernard; Jonas, Alain M

2007-09-11

The ability of poly(ethylene oxide)-silane (PEO-silane) monolayers grafted onto silicon surfaces to resist the growth of polyelectrolyte multilayers under various pH conditions is assessed for different pairs of polyelectrolytes of varying molar mass. For acidic conditions (pH 3), the PEO-silane monolayers exhibit good polyelectrolyte repellency provided the polyelectrolytes bear no moieties that are able to form hydrogen bonds with the ether groups of the PEO chains. At basic pH, PEO-silane monolayers undergo substantial hydrolysis leading to the formation of negatively charged defects in the monolayers, which then play the role of adsorption sites for the polycation. Once the polycation is adsorbed, multilayer growth ensues. Because this is defect-driven growth, the multilayer is not continuous and is made of blobs or an open network of adsorbed strands. For such conditions, the molar mass of the polyelectrolyte plays a key role, with polyelectrolyte chains of larger molar mass adsorbing on a larger number of defects, resulting in stronger anchoring of the polyelectrolyte complex on the surfaces and faster subsequent growth of the multilayer. For polyelectrolytes of sufficiently low molar mass at pH 9, the growth of the multilayer can nevertheless be prevented for as much as five cycles of deposition.

Highlighting the Importance of Surface Grafting in Combination with a Layer-by-Layer Approach for Fabricating Advanced 3D Poly(l-lactide) Microsphere Scaffolds

PubMed Central

2016-01-01

A combined surface treatment (i.e., surface grafting and a layer-by-layer (LbL) approach) is presented to create advanced biomaterials, i.e., 3D poly(l-lactide) (PLLA) microsphere scaffolds, at room temperature. The grafted surface plays a crucial role in assembling polyelectrolyte multilayers (PEMs) onto the surface of the microspheres, thus improving the physicochemical properties of the 3D microsphere scaffolds. The grafted surface of the PLLA microspheres demonstrates much better PEM adsorption, improved surface coverage at low pH, and smoother surfaces at high pH compared with those of nongrafted surfaces of PLLA microspheres during the assembly of PEMs. They induce more swelling than nongrafted surfaces after the assembly of the PEMs and exhibit blue emission after functionalization of the microsphere surface with a fluorescent dye molecule. The 3D scaffolds functionalized with and without nanosheets not only exhibit good mechanical performance similar to the compressive modulus of cancellous bone but also exhibit the porosity required for cancellous bone regeneration. The magnetic nanoparticle-functionalized 3D scaffolds result in an electrical conductivity in the high range of semiconducting materials (i.e., 1–250 S cm–1). Thus, these 3D microsphere scaffolds fabricated by surface grafting and the LbL approach are promising candidates for bone tissue engineering. PMID:29503506

From the 2-dimensional unstable polyelectrolyte multilayer to the 3-dimensional stable dry polyelectrolyte capsules.

PubMed

Li, Xiaodong; Zhang, Jianxiang; Hu, Qiaoling; Li, Xiaohui

2011-11-01

Polystyrene-poly(acrylic acid)/poly(allylamine hydrochloride) polyelectrolyte multilayer was found to be instable and apt to reconstruct in the pure water. By depositing polystyrene-poly(acrylic acid)/poly(allylamine hydrochloride) multilayer on the polystyrene-poly(acrylic acid) hybrid CaCO(3) templates, novel polyelectrolyte capsules could be prepared after the removal of the templates. The resultant capsules could keep their three-dimensional (3D) spherical shape after being dried at room temperature, dramatically different from the conventional polyelectrolyte capsules based on nonhybrid templates by layer-by-layer procedure. The instable polyelectrolyte multilayer, hybrid templates, and assembly cycles were demonstrated to be three indispensable factors responsible for the formation of this type of 3D stable capsules. The formation mechanism was also discussed in this study. Copyright © 2011 Elsevier Inc. All rights reserved.

Polymeric Multilayers that Localize the Release of Chlorhexidine from Biologic Wound Dressings

PubMed Central

Agarwal, Ankit; Nelson, Tyler B.; Kierski, Patricia R.; Schurr, Michael J.; Murphy, Christopher J.; Czuprynski, Charles J.; McAnulty, Jonathan F.; Abbott, Nicholas L.

2012-01-01

Biologic wound dressings contain animal-derived components and are susceptible to high infection rates. To address this issue, we report an approach that permits incorporation of non-toxic levels of the small-molecule antiseptic ‘chlorhexidine’ into biologic dressings. The approach relies on the fabrication of polyelectrolyte multilayer (PEMs) films containing poly(allylaminehydrochloride) (PAH), poly(acrylicacid) (PAA), and chlorhexidine acetate (CX) on elastomeric poly(dimethylsiloxane) (PDMS) sheets. The PEMs (20-100 nm thick) are subsequently stamped onto the wound-contact surface of a synthetic biologic dressing, Biobrane, which contains collagen peptides. Chlorhexidine loading in the PEMs was tailored by tuning the number of (CX/PAA) bilayers deposited, providing burst release of up to 0.98±0.06 μg/cm2 of CX over 24 h, followed by zero order release of 0.35±0.04 μg/cm2/day for another week. Although the CX concentrations released were below the reported in vitro cytotoxicity limit (5 μg/mL over 24 h) for human dermal fibroblasts, they killed 4 log10 counts of pathogenic bacteria Staphylococcus aureus in solution. The CX/PEMs could be stamped onto Biobrane with high efficiency to provide CX release kinetics and in-vitro antibacterial activity similar to that on PDMS stamps. In a full-thickness ‘splinted’ dermal wound-model in normal wild-type mice, the CX-functionalized Biobrane showed no decrease in either its adherence to the wound-bed or wound-closure rate over 14 days. The murine wounds topically inoculated with ~105 CFU/cm2 of S. aureus and treated with CX-functionalized Biobrane demonstrated a 3 log10 decrease in the wound's bacterial burden within 3 days, compared to persistent bacterial colonization found in wounds treated with unmodified Biobrane (n=10 mice, p<0.005). Overall, this study presents a promising approach to prevent bacterial colonization in wounds under biologic dressings. PMID:22784602

Stability of embossed PEI-(PSS-PDADMAC) 20 multilayer films versus storage time and versus a change in ionic strength

NASA Astrophysics Data System (ADS)

Ladhari, Nadia; Hemmerlé, Joseph; Haikel, Youssef; Voegel, Jean-Claude; Schaaf, Pierre; Ball, Vincent

2008-12-01

The use of microstructured films increased markedly in many areas of science and technology, notably in the design of microfluidic channels and in the design of parallel biosensing arrays. The concept of imprinting polyelectrolyte multilayer films (PEMs) has been introduced recently [C. Gao, B. Wang, J. Feng, J. Shen, Macromolecules 37 (2004) 8836]. These irreversibly imprinted films, obtained by plastic deformation, have to keep their size and shape after contact with fluids having physicochemical properties comparable to those of biological fluids in order to be used as microfluidic channels. We demonstrate herein that PEI-(PSS-PDADMAC) 20 PEMs built-up by the spray deposition from NaCl 1 M solutions and subsequently imprinted with polydimethylsiloxane stamps keep their morphology over time (up to 9 months) when stored in the dry state. In addition the depth of the imprinted channels does not change over this time duration. When the embossed films are immersed in NaCl 0.15 M solutions, mimicking biological fluids, the depth of the imprinted channels also does not significantly change. But, when the imprinted films prepared in the presence of 1 M NaCl are subsequently dipped in a 4 M NaCl solution, partial film loss and subsequent disappearance of the imprinted channels are observed. An explanation for these findings is furnished by means of FTIR spectroscopy in the attenuated total reflection mode (ATR-FTIR). These observations should offer large opportunities for the use of the imprinted multilayer films as microfluidic channels.

From dots to doughnuts: Two-dimensionally confined deposition of polyelectrolytes on block copolymer templates

DOE PAGES

Oded, Meirav; Kelly, Stephen T.; Gilles, Mary K.; ...

2016-07-05

The combination of block copolymer templating with electrostatic self-assembly provides a simple and robust method for creating nano-patterned polyelectrolyte multilayers over large areas. The deposition of the first polyelectrolyte layer provides important insights on the initial stages of multilayer buildup. Here, we focus on two-dimensionally confined “dots” patterns afforded by block copolymer films featuring hexagonally-packed cylinders that are oriented normal to the substrate. Rendering the cylinder caps positively charged enables the selective deposition of negatively charged polyelectrolytes on them under salt-free conditions. The initially formed polyelectrolyte nanostructures adopt a toroidal (“doughnut”) shape, which results from retraction of dangling polyelectrolyte segmentsmore » into the “dots” upon drying. With increasing exposure time to the polyelectrolyte solution, the final shape of the deposited polyelectrolyte transitions from a doughnut to a hemisphere. In conclusion, these insights would enable the creation of patterned polyelectrolyte multilayers with increased control over adsorption selectivity of the additional incoming polyelectrolytes.« less

From dots to doughnuts: Two-dimensionally confined deposition of polyelectrolytes on block copolymer templates

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

Oded, Meirav; Kelly, Stephen T.; Gilles, Mary K.

The combination of block copolymer templating with electrostatic self-assembly provides a simple and robust method for creating nano-patterned polyelectrolyte multilayers over large areas. The deposition of the first polyelectrolyte layer provides important insights on the initial stages of multilayer buildup. Here, we focus on two-dimensionally confined “dots” patterns afforded by block copolymer films featuring hexagonally-packed cylinders that are oriented normal to the substrate. Rendering the cylinder caps positively charged enables the selective deposition of negatively charged polyelectrolytes on them under salt-free conditions. The initially formed polyelectrolyte nanostructures adopt a toroidal (“doughnut”) shape, which results from retraction of dangling polyelectrolyte segmentsmore » into the “dots” upon drying. With increasing exposure time to the polyelectrolyte solution, the final shape of the deposited polyelectrolyte transitions from a doughnut to a hemisphere. In conclusion, these insights would enable the creation of patterned polyelectrolyte multilayers with increased control over adsorption selectivity of the additional incoming polyelectrolytes.« less

Polypeptide multilayer film co-delivers oppositely-charged drug molecules in sustained manners.

PubMed

Jiang, Bingbing; Defusco, Elizabeth; Li, Bingyun

2010-12-13

The current state-of-the-art for drug-carrying biomedical devices is mostly limited to those that release a single drug. Yet there are many situations in which more than one therapeutic agent is needed. Also, most polyelectrolyte multilayer films intended for drug delivery are loaded with active molecules only during multilayer film preparation. In this paper, we present the integration of capsules as vehicles within polypeptide multilayer films for sustained release of multiple oppositely charged drug molecules using layer-by-layer nanoassembly technology. Calcium carbonate (CaCO(3)) particles were impregnated with polyelectrolytes, shelled with polyelectrolyte multilayers, and then assembled onto polypeptide multilayer films using glutaraldehyde. Capsule-integrated polypeptide multilayer films were obtained after decomposition of CaCO(3) templates. Two oppositely charged drugs were loaded into capsules within polypeptide multilayer films postpreparation based on electrostatic interactions between the drugs and the polyelectrolytes impregnated within capsules. We determined that the developed innovative capsule-integrated polypeptide multilayer films could be used to load multiple drugs of very different properties (e.g., opposite charges) any time postpreparation (e.g., minutes before surgical implantation inside an operating room), and such capsule-integrated films allowed simultaneous delivery of two oppositely charged drug molecules and a sustained (up to two weeks or longer) and sequential release was achieved.

Polypeptide Multilayer Film Co-Delivers Oppositely-Charged Drug Molecules in Sustained Manners

PubMed Central

Jiang, Bingbing; DeFusco, Elizabeth; Li, Bingyun

2010-01-01

The current state-of-the-art for drug-carrying biomedical devices is mostly limited to those that release a single drug. Yet there are many situations in which more than one therapeutic agent is needed. Also, most polyelectrolyte multilayer films intending for drug delivery are loaded with active molecules only during multilayer film preparation. In this paper, we present the integration of capsules as vehicles within polypeptide multilayer films for sustained release of multiple oppositely-charged drug molecules using layer-by-layer nanoassembly technology. Calcium carbonate (CaCO3) particles were impregnated with polyelectrolytes, shelled with polyelectrolyte multilayers, and then assembled onto polypeptide multilayer films using glutaraldehyde. Capsule-integrated polypeptide multilayer films were obtained after decomposition of CaCO3 templates. Two oppositely-charged drugs were loaded into capsules within polypeptide multilayer films post-preparation based on electrostatic interactions between the drugs and the polyelectrolytes impregnated within capsules. We determined that the developed innovative capsule-integrated polypeptide multilayer films could be used to load multiple drugs of very different properties (e.g. opposite charges) any time post-preparation (e.g. minutes before surgical implantation inside an operating room), and such capsule-integrated films allowed simultaneous delivery of two oppositely-charged drug molecules and a sustained (up to two weeks or longer) and sequential release was achieved. PMID:21058719

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

PubMed

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

2018-06-01

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

Acquisition of Infrared Variable Angle Spectroscopic Ellipsometer (IR-VASE)

DTIC Science & Technology

2016-04-22

External Advisory Board Meeting in Rio Piedras, PR. March 2016 Quiñonez B.*, Castilla D., Almodóvar J.; “ Polysaccharide -based polyelectrolyte...April 2016 Quiñonez B.*, Castilla D., Almodóvar J.; “ Polysaccharide -based polyelectrolyte multilayers: Physicochemical characterization and in...2016 Quiñonez B.*, Castilla D., Almodóvar J.; “ Polysaccharide -based polyelectrolyte multilayers: Physicochemical characterization and in vitro

Formation and enzymatic degradation of poly-l-arginine/fucoidan multilayer films.

PubMed

Webber, Jessie L; Benbow, Natalie L; Krasowska, Marta; Beattie, David A

2017-11-01

A polyelectrolyte multilayer (PEM) system based on biopolymers has been constructed and studied in its formation and enzymatic breakdown. The multilayer is composed of fucoidan (a proven antimicrobial/anti-inflammatory seaweed-based polysaccharide) and poly-l-arginine (a polypeptide that can be readily degraded with trypsin to yield arginine, a known NO donor), thus making the multilayer a potential dual action surface treatment for wound dressings. Studies on the formation of the multilayer revealed that the film built-up in the expected stepwise manner with consistent reversal of the zeta potential upon the adsorption of each subsequent polyion. The completed film (8 bilayers) was seen to have low hydration (30% water), as determined by H 2 O/D 2 O solvent replacement studies using the quartz crystal microbalance, with an adsorbed mass (without hydration water) of approx. 4.8μgcm -2 , as determined by quantitative attenuated total reflectance Fourier transform infrared (ATR FTIR) spectroscopy. The enzymatic breakdown of the film in response to exposure to trypsin was also investigated, and the film was seen to release both polymers over time, with a projected complete film removal period of approximately 24h. Critically, this information was determined using ATR FTIR spectroscopy experiments, which allowed unambiguous deconvolution of the removal rates of the two polyions, which is information that cannot be obtained from other methodologies used to study enzymatic breakdown of surface films. Copyright © 2017 Elsevier B.V. All rights reserved.

Fabrication and characterization of novel multilayered structures by stereocomplexion of poly(D-lactic acid)/poly(L-lactic acid) and self-assembly of polyelectrolytes.

PubMed

Dellacasa, Elena; Zhao, Li; Yang, Gesheng; Pastorino, Laura; Sukhorukov, Gleb B

2016-01-01

The enantiomers poly(D-lactic acid) (PDLA) and poly(L-lactic acid) (PLLA) were alternately adsorbed directly on calcium carbonate (CaCO3) templates and on poly(styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) multilayer precursors in order to fabricate a novel layer-by-layer (LBL) assembly. A single layer of poly(L-lysine) (PLL) was used as a linker between the (PDLA/PLLA) n stereocomplex and the cores with and without the polymeric (PSS/PAH) n /PLL multilayer precursor (PEM). Nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) were used to characterize the chemical composition and molecular weight of poly(lactic acid) polymers. Both multilayer structures, with and without polymeric precursor, were firstly fabricated and characterized on planar supports. A quartz crystal microbalance (QCM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and ellipsometry were used to evaluate the thickness and mass of the multilayers. Then, hollow, spherical microcapsules were obtained by the removal of the CaCO3 sacrificial template. The chemical composition of the obtained microcapsules was confirmed by differential scanning calorimetry (DSC) and wide X-ray diffraction (WXRD) analyses. The microcapsule morphology was evaluated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements. The experimental results confirm the successful fabrication of this innovative system, and its full biocompatibility makes it worthy of further characterization as a promising drug carrier for sustained release.

Fabrication and characterization of novel multilayered structures by stereocomplexion of poly(D-lactic acid)/poly(L-lactic acid) and self-assembly of polyelectrolytes

PubMed Central

Yang, Gesheng; Pastorino, Laura

2016-01-01

Summary The enantiomers poly(D-lactic acid) (PDLA) and poly(L-lactic acid) (PLLA) were alternately adsorbed directly on calcium carbonate (CaCO3) templates and on poly(styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) multilayer precursors in order to fabricate a novel layer-by-layer (LBL) assembly. A single layer of poly(L-lysine) (PLL) was used as a linker between the (PDLA/PLLA)n stereocomplex and the cores with and without the polymeric (PSS/PAH)n/PLL multilayer precursor (PEM). Nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) were used to characterize the chemical composition and molecular weight of poly(lactic acid) polymers. Both multilayer structures, with and without polymeric precursor, were firstly fabricated and characterized on planar supports. A quartz crystal microbalance (QCM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and ellipsometry were used to evaluate the thickness and mass of the multilayers. Then, hollow, spherical microcapsules were obtained by the removal of the CaCO3 sacrificial template. The chemical composition of the obtained microcapsules was confirmed by differential scanning calorimetry (DSC) and wide X-ray diffraction (WXRD) analyses. The microcapsule morphology was evaluated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements. The experimental results confirm the successful fabrication of this innovative system, and its full biocompatibility makes it worthy of further characterization as a promising drug carrier for sustained release. PMID:26925356

Assembly of purple membranes on polyelectrolyte films.

PubMed

Saab, Marie-belle; Estephan, Elias; Cloitre, Thierry; Legros, René; Cuisinier, Frédéric J G; Zimányi, László; Gergely, Csilla

2009-05-05

The membrane protein bacteriorhodopsin in its native membrane bound form (purple membrane) was adsorbed and incorporated into polyelectrolyte multilayered films, and adsorption was in situ monitored by optical waveguide light-mode spectroscopy. The formation of a single layer or a double layer of purple membranes was observed when adsorbed on negatively or positively charged surfaces, respectively. The purple membrane patches adsorbed on the polyelectrolyte multilayers were also evidenced by atomic force microscopy images. The driving forces of the adsorption process were evaluated by varying the ionic strength of the solution as well as the purple membrane concentration. At high purple membrane concentration, interpenetrating polyelectrolyte loops might provide new binding sites for the adsorption of a second layer of purple membranes, whereas at lower concentrations only a single layer is formed. Negative surfaces do not promote a second protein layer adsorption. Driving forces other than just electrostatic ones, such as hydrophobic forces, should play a role in the polyelectrolyte/purple membrane layering. The subtle interplay of all these factors determines the formation of the polyelectrolyte/purple membrane matrix with a presumably high degree of orientation for the incorporated purple membranes, with their cytoplasmic, or extracellular side toward the bulk on negatively or positively charged polyelectrolyte, respectively. The structural stability of bacteriorhodopsin during adsorption onto the surface and incorporation into the polyelectrolyte multilayers was investigated by Fourier transform infrared spectroscopy in attenuated total reflection mode. Adsorption and incorporation of purple membranes within polyelectrolyte multilayers does not disturb the conformational majority of membrane-embedded alpha-helix structures of the protein, but may slightly alter the structure of the extramembraneous segments or their interaction with the environment. This high stability is different from the lower stability of the predominantly beta-sheet structures of numerous globular proteins when adsorbed onto surfaces.

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

NASA Astrophysics Data System (ADS)

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

2007-09-01

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

Diffusion of Sites versus Polymers in Polyelectrolyte Complexes and Multilayers.

PubMed

Fares, Hadi M; Schlenoff, Joseph B

2017-10-18

It has long been assumed that the spontaneous formation of materials such as complexes and multilayers from charged polymers depends on (inter)diffusion of these polyelectrolytes. Here, we separately examine the mass transport of polymer molecules and extrinsic sites-charged polyelectrolyte repeat units balanced by counterions-within thin films of polyelectrolyte complex, PEC, using sensitive isotopic labeling techniques. The apparent diffusion coefficients of these sites within PEC films of poly(diallyldimethylammonium), PDADMA, and poly(styrenesulfonate), PSS, are at least 2 orders of magnitude faster than the diffusion of polyelectrolytes themselves. This is because site diffusion requires only local rearrangements of polyelectrolyte repeat units, placing far fewer kinetic limitations on the assembly of polyelectrolyte complexes in all of their forms. Site diffusion strongly depends on the salt concentration (ionic strength) of the environment, and diffusion of PDADMA sites is faster than that of PSS sites, accounting for the asymmetric nature of multilayer growth. Site diffusion is responsible for multilayer growth in the linear and into the exponential regimes, which explains how PDADMA can mysteriously "pass through" layers of PSS. Using quantitative relationships between site diffusion coefficient and salt concentration, conditions were identified that allowed the diffusion length to always exceed the film thickness, leading to full exponential growth over 3 orders of magnitude thickness. Both site and polymer diffusion were independent of molecular weight, suggesting that ion pairing density is a limiting factor. Polyelectrolyte complexes are examples of a broader class of dynamic bulk polymeric materials that (self-) assemble via the transport of cross-links or defects rather than actual molecules.

Novel application of polyelectrolyte multilayers as nanoscopic closures with hermetic sealing.

PubMed

Marcott, Stephanie A; Ada, Sena; Gibson, Phillip; Camesano, Terri A; Nagarajan, R

2012-03-01

Closure systems for personnel protection applications, such as protective clothing or respirator face seals, should provide effective permeation barrier to toxic gases. Currently available mechanical closure systems based on the hook and loop types (example, Velcro) do not provide adequate barrier to gas permeation. To achieve hermetic sealing, we propose a nonmechanical, nanoscopic molecular closure system based on complementary polyelectrolyte multilayers, one with a polycation outermost layer and the other with a polyanion outermost layer. The closure surfaces were prepared by depositing polyelectrolyte multilayers under a variety of deposition conditions, on conformable polymer substrates (thin films of polyethylene teraphthalate, PET or polyimide, PI). The hermetic sealing property of the closures was evaluated by measuring the air flow resistance using the dynamic moisture permeation cell (DMPC) at different humidity conditions. The DMPC measurements show that the polyelectrolyte multilayer closures provide significantly large resistance to air flow, approximately 20-800 times larger than that possible with conventional hook and loop type closure systems, at all humidity levels (from 5 to 95% relative humidity). Hence, from the point of view of providing a hermetic seal against toxic gas permeation, the polyelectrolyte multilayer closures are viable candidates for further engineering development. However, the adhesive strength of the multilayer closures measured by atomic force microscopy suggests that the magnitude of adhesion is much smaller than what is possible with mechanical closures. Therefore, we envisage the development of a composite closure system combining the mechanical closure to provide strong adhesion and the multilayer closure to provide hermetic sealing. © 2012 American Chemical Society

3D solid supported inter-polyelectrolyte complexes obtained by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate)

PubMed Central

Maestro, Armando; Llamas, Sara; Álvarez-Rodríguez, Jesús; Ortega, Francisco; Maroto-Valiente, Ángel

2016-01-01

Summary This work addresses the formation and the internal morphology of polyelectrolyte layers obtained by the layer-by-layer method. A multimodal characterization showed the absence of stratification of the films formed by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate). Indeed the final organization might be regarded as three-dimensional solid-supported inter-polyelectrolyte films. The growth mechanism of the multilayers, followed using a quartz crystal microbalance, evidences two different growth trends, which show a dependency on the ionic strength due to its influence onto the polymer conformation. The hydration state does not modify the multilayer growth, but it contributes to the total adsorbed mass of the film. The water associated with the polyelectrolyte films leads to their swelling and plastification. The use of X-ray photoelectron spectroscopy has allowed for deeper insights on the internal structure and composition of the polyelectrolyte multilayers. PMID:26977377

3D solid supported inter-polyelectrolyte complexes obtained by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate).

PubMed

Guzmán, Eduardo; Maestro, Armando; Llamas, Sara; Álvarez-Rodríguez, Jesús; Ortega, Francisco; Maroto-Valiente, Ángel; Rubio, Ramón G

2016-01-01

This work addresses the formation and the internal morphology of polyelectrolyte layers obtained by the layer-by-layer method. A multimodal characterization showed the absence of stratification of the films formed by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate). Indeed the final organization might be regarded as three-dimensional solid-supported inter-polyelectrolyte films. The growth mechanism of the multilayers, followed using a quartz crystal microbalance, evidences two different growth trends, which show a dependency on the ionic strength due to its influence onto the polymer conformation. The hydration state does not modify the multilayer growth, but it contributes to the total adsorbed mass of the film. The water associated with the polyelectrolyte films leads to their swelling and plastification. The use of X-ray photoelectron spectroscopy has allowed for deeper insights on the internal structure and composition of the polyelectrolyte multilayers.

Flow cytometry of HEK 293T cells interacting with polyelectrolyte multilayer capsules containing fluorescein-labeled poly(acrylic acid) as a pH sensor.

PubMed

Reibetanz, Uta; Halozan, David; Brumen, Milan; Donath, Edwin

2007-06-01

Polyelectrolyte multilayer sensor capsules, 5 microm in diameter, which contained fluorescein-labeled poly(acrylic acid) (PAAAF) as pH-sensitive reporter molecules, were fabricated and employed to explore their endocytotic uptake into HEK 293T cells by flow cytometry. The percentage of capsules residing in the endolysosomal compartment was estimated from the fluorescence intensity decrease caused by acidification. Capsules attached to the extracellular surface of the plasma membrane were identified by trypan blue quenching. The number of capsules in the cytoplasm was rather small, being below the detection limit of the method. The advantages of polyelectrolyte multilayer capsules are that the fluorophore is protected from interaction with cellular compartments and that the multilayer can be equipped with additional functions.

Material properties of novel polymeric films

NASA Astrophysics Data System (ADS)

Kim, Gene

This dissertation will study the material properties of two types of novel polymer films (polyelectrolyte multilayer films and photolithographic polymer films). The formation of polylelectrolyte multilayer films onto functionalized aluminum oxide surfaces and functionalized poly(ethylene terephthaltate) (PET) were studied. Functionalization of the aluminum oxide surfaces was achieved via silane coupling. Functionalization of PET surfaces was achieved via hydrolysis and amidation. Surface characterization techniques such as X-ray photoelectron spectroscopy (XPS) and dynamic contact angle measurements were used to monitor the polyelectrolyte multilayer formation. Mechanical properties of the aluminum oxide supported polyelectrolyte multilayer films were tested using a simplified peel test. XPS was used to analyze the surfaces before and after peel. Single lap shear joint specimens were constructed to test the adhesive shear strength of the PET-supported polyelectrolyte multilayer film samples with the aid of a cyanoacrylate adhesive. The adhesive shear strength and its relation with the type of functionalization, number of polyelectrolyte layers, and the effect of polyelectrolyte conformation using added salt were explored. Also, characterization on the single lap joints after adhesive failure was carried out to determine the locus of failure within the multilayers by using XPS and SEM. Two types of photolithographic polymers were formulated and tested. These two polymers (photocrosslinkable polyacrylate (PUA), and a photocrosslinkable polyimide (HRP)) were used to investigate factors that would affect the structural integrity of these particular polymers under environmental variables such as processing (time, UV cure, pressure, and temperature) and ink exposure. Thermomechanical characterization was carried out to see the behavior of these two polymers under these environmental variables. Microscopic techniques were employed to study the morphological behavior of the two polymer systems. Also, unique in-house characterization methods such as the vibrational holographic interferometry to measure residual stress in these polymer coatings upon processing, and the environmental tensile tester (ETT) to measure ink diffusion and swelling stresses were used to further characterize these two polymers.

Motion-based, high-yielding, and fast separation of different charged organics in water.

PubMed

Xuan, Mingjun; Lin, Xiankun; Shao, Jingxin; Dai, Luru; He, Qiang

2015-01-12

We report a self-propelled Janus silica micromotor as a motion-based analytical method for achieving fast target separation of polyelectrolyte microcapsules, enriching different charged organics with low molecular weights in water. The self-propelled Janus silica micromotor catalytically decomposes a hydrogen peroxide fuel and moves along the direction of the catalyst face at a speed of 126.3 μm s(-1) . Biotin-functionalized Janus micromotors can specifically capture and rapidly transport streptavidin-modified polyelectrolyte multilayer capsules, which could effectively enrich and separate different charged organics in water. The interior of the polyelectrolyte multilayer microcapsules were filled with a strong charged polyelectrolyte, and thus a Donnan equilibrium is favorable between the inner solution within the capsules and the bulk solution to entrap oppositely charged organics in water. The integration of these self-propelled Janus silica micromotors and polyelectrolyte multilayer capsules into a lab-on-chip device that enables the separation and analysis of charged organics could be attractive for a diverse range of applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Layer-by-Layer Assembled Nanotubes as Biomimetic Nanoreactors for Calcium Carbonate Deposition.

PubMed

He, Qiang; Möhwald, Helmuth; Li, Junbai

2009-09-17

Enzyme-loaded magnetic polyelectrolyte multilayer nanotubes prepared by layer-by-layer assembly combined with the porous template could be used as biomimetic nanoreactors. It is demonstrated that calcium carbonate can be biomimetically synthesized inside the cavities of the polyelectrolyte nanotubes by the catalysis of urease, and the size of the calcium carbonate precipitates was controlled by the cavity dimensions. The metastable structure of the calcium carbonate precipitates inside the nanotubes was protected by the outer shell of the polyelectrolyte multilayers. These features may allow polyelectrolyte nanotubes to be applied in the fields of nanomaterials synthesis, controlled release, and drug delivery. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic and Inorganic Dyes in Polyelectrolyte Multilayer Films

PubMed Central

Ball, Vincent

2012-01-01

Polyelectrolyte multilayer films are a versatile functionalization method of surfaces and rely on the alternated adsorption of oppositely charged species. Among such species, charged dyes can also be alternated with oppositely charged polymers, which is challenging from a fundamental point of view, because polyelectrolytes require a minimal number of charges, whereas even monovalent dyes can be incorporated during the alternated adsorption process. We will not only focus on organic dyes but also on their inorganic counterparts and on metal complexes. Such films offer plenty of possible applications in dye sensitized solar cells. In addition, dyes are massively used in the textile industry and in histology to stain textile fibers or tissues. However, the excess of non bound dyes poses serious environmental problems. It is hence of the highest interest to design materials able to adsorb such dyes in an almost irreversible manner. Polyelectrolyte multilayer films, owing to their ion exchange behavior can be useful for such a task allowing for impressive overconcentration of dyes with respect to the dye in solution. The actual state of knowledge of the interactions between charged dyes and adsorbed polyelectrolytes is the focus of this review article.

Comparison of multilayer formation between different cellulose nanofibrils and cationic polymers.

PubMed

Eronen, Paula; Laine, Janne; Ruokolainen, Janne; Osterberg, Monika

2012-05-01

The multilayer formation between polyelectrolytes of opposite charge offers possibility for creating new tailored materials. Exchanging one or both components for charged nanofibrillated cellulose (NFC) further increases the variety of achievable properties. We explored this by introducing unmodified, low charged NFC and high charged TEMPO-oxidized NFC. Systematic evaluation of the effect of both NFC charge and properties of cationic polyelectrolytes on the structure of the multilayers was performed. As the cationic component cationic NFC was compared with two different cationic polyelectrolytes, poly(dimethyldiallylammoniumchloride) and cationic starch. Quartz crystal microbalance with dissipation (QCM-D) was used to monitor the multilayer formation and AFM colloidal probe microscopy (CPM) was further applied to probe surface interactions in order to gain information about fundamental interactions and layer properties. Generally, the results verified the characteristic multilayer formation between NFC of different charge and how the properties of formed multilayers can be tuned. However, the strong nonelectrostatic affinity between cellulosic fibrils was observed. CPM measurements revealed monotonically repulsive forces, which were in good correspondence with the QCM-D observations. Significant increase in adhesive forces was detected between the swollen high charged NFC. Copyright © 2011 Elsevier Inc. All rights reserved.

Surface modification of titanium substrates with silver nanoparticles embedded sulfhydrylated chitosan/gelatin polyelectrolyte multilayer films for antibacterial application.

PubMed

Li, Wen; Xu, Dawei; Hu, Yan; Cai, Kaiyong; Lin, Yingcheng

2014-06-01

To develop Ti implants with potent antibacterial activity, a novel "sandwich-type" structure of sulfhydrylated chitosan (Chi-SH)/gelatin (Gel) polyelectrolyte multilayer films embedding silver (Ag) nanoparticles was coated onto titanium substrate using a spin-assisted layer-by-layer assembly technique. Ag ions would be enriched in the polyelectrolyte multilayer films via the specific interactions between Ag ions and -HS groups in Chi-HS, thus leading to the formation of Ag nanoparticles in situ by photo-catalytic reaction (ultraviolet irradiation). Contact angle measurement and field emission scanning electron microscopy equipped with energy dispersive X-ray spectroscopy were employed to monitor the construction of Ag-containing multilayer on titanium surface, respectively. The functional multilayered films on titanium substrate [Ti/PEI/(Gel/Chi-SH/Ag) n /Gel] could efficiently inhibit the growth and activity of Bacillus subtitles and Escherichia coli onto titanium surface. Moreover, studies in vitro confirmed that Ti substrates coating with functional multilayer films remained the biological functions of osteoblasts, which was reflected by cell morphology, cell viability and ALP activity measurements. This study provides a simple, versatile and generalized methodology to design functional titanium implants with good cyto-compatibility and antibacterial activity for potential clinical applications.

Disintegration-controllable stimuli-responsive polyelectrolyte multilayer microcapsules via covalent layer-by-layer assembly.

PubMed

Mu, Bin; Lu, Chunyin; Liu, Peng

2011-02-01

The disintegration-controllable stimuli-responsive polyelectrolyte multilayer microcapsules have been fabricated via the covalent layer-by-layer assembly between the amino groups of chitosan (CS) and the aldehyde groups of the oxidized sodium alginate (OSA) onto the sacrificial templates (polystyrene sulfonate, PSS) which was removed by dialysis subsequently. The covalent crosslinking bonds of the multilayer microcapsules were confirmed by FTIR analysis. The TEM analysis showed that the diameter of the multilayer microcapsules was <200nm. The diameter of the multilayer microcapsules decreased with the increasing of the pH values or the ionic strength. The pH and ionic strength dual-responsive multilayer microcapsules were stable in acidic and neutral media while they could disintegrate only at strong basic media. Copyright © 2010 Elsevier B.V. All rights reserved.

* Calvarial Bone Regeneration Is Enhanced by Sequential Delivery of FGF-2 and BMP-2 from Layer-by-Layer Coatings with a Biomimetic Calcium Phosphate Barrier Layer.

PubMed

Gronowicz, Gloria; Jacobs, Emily; Peng, Tao; Zhu, Li; Hurley, Marja; Kuhn, Liisa T

2017-12-01

A drug delivery coating for synthetic bone grafts has been developed to provide sequential delivery of multiple osteoinductive factors to better mimic aspects of the natural regenerative process. The coating is composed of a biomimetic calcium phosphate (bCaP) layer that is applied to a synthetic bone graft and then covered with a poly-l-Lysine/poly-l-Glutamic acid polyelectrolyte multilayer (PEM) film. Bone morphogenetic protein-2 (BMP-2) was applied before the coating process directly on the synthetic bone graft and then, bCaP-PEM was deposited followed by adsorption of fibroblast growth factor-2 (FGF-2) into the PEM layer. Cells access the FGF-2 immediately, while the bCaP-PEM temporally delays the cell access to BMP-2. In vitro studies with cells derived from mouse calvarial bones demonstrated that Sca-1 and CD-166 positive osteoblast progenitor cells proliferated in response to media dosing with FGF-2. Coated scaffolds with BMP-2 and FGF-2 were implanted in mouse calvarial bone defects and harvested at 1 and 3 weeks. After 1 week in vivo, proliferation of cells, including Sca-1+ progenitors, was observed with low dose FGF-2 and BMP-2 compared to BMP-2 alone, indicating that in vivo delivery of FGF-2 activated a similar population of cells as shown by in vitro testing. At 3 weeks, FGF-2 and BMP-2 delivery increased bone formation more than BMP-2 alone, particularly in the center of the defect, confirming that the proliferation of the Sca-1 positive osteoprogenitors by FGF-2 was associated with increased bone healing. Areas of bone mineralization were positive for double fluorochrome labeling of calcium and alkaline phosphatase staining of osteoblasts, along with increased TRAP+ osteoclasts, demonstrating active bone formation distinct from the bone-like collagen/hydroxyapatite scaffold. In conclusion, the addition of a bCaP layer to PEM delayed access to BMP-2 and allowed the FGF-2 stimulated progenitors to populate the scaffold before differentiating in response to BMP-2, leading to improved bone defect healing.

Electrically Driven Ion Separations in Permeable Membranes

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

Bruening, Merlin

2017-04-21

Membranes are attractive for a wide range of separations due to their low energy costs and continuous operation. To achieve practical fluxes, most membranes consist of a thin, selective skin on a highly permeable substrate that provides mechanical strength. Thus, this project focused on creating new methods for forming highly selective ultrathin skins as well as modeling transport through these coatings to better understand their unprecedented selectivities. The research explored both gas and ion separations, and the latter included transport due to concentration, pressure and electrical potential gradients. This report describes a series of highlights of the research and thenmore » provides a complete list of publications supported by the grant. These publications have been cited more than 4000 times. Perhaps the most stunning finding is the recent discovery of monovalent/divalent cation and anion selectivities around 1000 when modifying cation- and anion-exchange membranes with polyelectrolyte multilayers (PEMs). This discovery builds on many years of exciting research. (Citation numbers refer to the journal articles in the bibliography.)« less

Engineering the extracellular environment: Strategies for building 2D and 3D cellular structures.

PubMed

Guillame-Gentil, Orane; Semenov, Oleg; Roca, Ana Sala; Groth, Thomas; Zahn, Raphael; Vörös, Janos; Zenobi-Wong, Marcy

2010-12-21

Cell fate is regulated by extracellular environmental signals. Receptor specific interaction of the cell with proteins, glycans, soluble factors as well as neighboring cells can steer cells towards proliferation, differentiation, apoptosis or migration. In this review, approaches to build cellular structures by engineering aspects of the extracellular environment are described. These methods include non-specific modifications to control the wettability and stiffness of surfaces using self-assembled monolayers (SAMs) and polyelectrolyte multilayers (PEMs) as well as methods where the temporal activation and spatial distribution of adhesion ligands is controlled. Building on these techniques, construction of two-dimensional cell sheets using temperature sensitive polymers or electrochemical dissolution is described together with current applications of these grafts in the clinical arena. Finally, methods to pattern cells in three-dimensions as well as to functionalize the 3D environment with biologic motifs take us one step closer to being able to engineer multicellular tissues and organs. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of immobilization conditions on the properties of β-galactosidase immobilized in xanthan/chitosan multilayers

NASA Astrophysics Data System (ADS)

Yovcheva, T.; Vasileva, T.; Viraneva, A.; Cholev, D.; Bodurov, I.; Marudova, M.; Bivolarski, V.; Iliev, I.

2017-01-01

The effect of lactose concentration on the activity of the immobilised enzyme β-galactosidase from Aspergillus niger has been evaluated, considering future applications for the production of galactooligosaccahrides with prebiotic potential. The following enzyme was immobilized in xanthan and chitosan polyelectrolyte multilayers (PEMs) deposited by dip coating method on polylactic acid positively corona charged pads. The pads were charged in a corona discharge system, consisting of a corona electrode (needle), a grounded plate, and a metal grid placed between them. Positive 5 kV voltage was applied to the corona electrode. 1 kV voltage of the same polarity as that of the corona electrode was applied to the grid. The chitosan layers were crosslinked with sodium tripolyphosphate (Na-TPP). The enzyme showed a temperature optimum at 50 °C and a pH optimum at 5.0. The immobilization was carried out over the different adsorption time and optimum conditions were determined. These results give insights for further optimization of transgalactosydase reactions in order to produce galactooligosaccharides with specific structure and having pronounced better prebiotic properties. For the determination of the surface morphology of the investigated samples an atomic force microscope was used and root mean square roughness was obtained.

Dynamic contact angle analysis of protein adsorption on polysaccharide multilayer's films for biomaterial reendothelialization.

PubMed

Benni, Safiya; Avramoglou, Thierry; Hlawaty, Hanna; Mora, Laurence

2014-01-01

Atherosclerosis is a major cardiovascular disease. One of the side effects is restenosis. The aim of this work was to study the coating of stents by dextran derivates based polyelectrolyte's multilayer (PEM) films in order to increase endothelialization of injured arterial wall after stent implantation. Films were composed with diethylaminoethyl dextran (DEAE) as polycation and dextran sulphate (DS) as polyanion. One film was composed with 4 bilayers of (DEAE-DS)4 and was labeled D-. The other film was the same as D- but with an added terminal layer of DEAE polycation: (DEAE-DS)4-DEAE (labeled D+). The dynamic adsorption/desorption of proteins on the films were characterized by dynamic contact angle (DCA) and atomic force microscopy (AFM). Human endothelial cell (HUVEC) adhesion and proliferation were quantified and correlated to protein adsorption analyzed by DCA for fibronectin, vitronectin, and bovine serum albumin (BSA). Our results showed that the endothelial cell response was optimal for films composed of DS as external layer. Fibronectin was found to be the only protein to exhibit a reversible change in conformation after desorption test. This behavior was only observed for (DEAE-DS)4 films. (DEAE-DS)4 films could enhance HUVEC proliferation in agreement with fibronectin ability to easily change from conformation.

Dynamic Contact Angle Analysis of Protein Adsorption on Polysaccharide Multilayer's Films for Biomaterial Reendothelialization

PubMed Central

Benni, Safiya; Mora, Laurence

2014-01-01

Atherosclerosis is a major cardiovascular disease. One of the side effects is restenosis. The aim of this work was to study the coating of stents by dextran derivates based polyelectrolyte's multilayer (PEM) films in order to increase endothelialization of injured arterial wall after stent implantation. Films were composed with diethylaminoethyl dextran (DEAE) as polycation and dextran sulphate (DS) as polyanion. One film was composed with 4 bilayers of (DEAE-DS)4 and was labeled D−. The other film was the same as D− but with an added terminal layer of DEAE polycation: (DEAE-DS)4-DEAE (labeled D+). The dynamic adsorption/desorption of proteins on the films were characterized by dynamic contact angle (DCA) and atomic force microscopy (AFM). Human endothelial cell (HUVEC) adhesion and proliferation were quantified and correlated to protein adsorption analyzed by DCA for fibronectin, vitronectin, and bovine serum albumin (BSA). Our results showed that the endothelial cell response was optimal for films composed of DS as external layer. Fibronectin was found to be the only protein to exhibit a reversible change in conformation after desorption test. This behavior was only observed for (DEAE-DS)4 films. (DEAE-DS)4 films could enhance HUVEC proliferation in agreement with fibronectin ability to easily change from conformation. PMID:25276808

Polymer multilayers loaded with antifungal β-peptides kill planktonic Candida albicans and reduce formation of fungal biofilms on the surfaces of flexible catheter tubes.

PubMed

Raman, Namrata; Lee, Myung-Ryul; Palecek, Sean P; Lynn, David M

2014-10-10

Candida albicans is the most common fungal pathogen responsible for hospital-acquired infections. Most C. albicans infections are associated with the implantation of medical devices that act as points of entry for the pathogen and as substrates for the growth of fungal biofilms that are notoriously difficult to eliminate by systemic administration of conventional antifungal agents. In this study, we report a fill-and-purge approach to the layer-by-layer fabrication of biocompatible, nanoscale 'polyelectrolyte multilayers' (PEMs) on the luminal surfaces of flexible catheters, and an investigation of this platform for the localized, intraluminal release of a cationic β-peptide-based antifungal agent. We demonstrate that polyethylene catheter tubes with luminal surfaces coated with multilayers ~700nm thick fabricated from poly-l-glutamic acid (PGA) and poly-l-lysine (PLL) can be loaded, post-fabrication, by infusion with β-peptide, and that this approach promotes extended intraluminal release of this agent (over ~4months) when incubated in physiological media. The β-peptide remained potent against intraluminal inoculation of the catheters with C. albicans and substantially reduced the formation of C. albicans biofilms on the inner surfaces of film-coated catheters. Finally, we report that these β-peptide-loaded coatings exhibit antifungal activity under conditions that simulate intermittent catheter use and microbial challenge for at least three weeks. We conclude that β-peptide-loaded PEMs offer a novel and promising approach to kill C. albicans and prevent fungal biofilm formation on surfaces, with the potential to substantially reduce the incidence of device-associated infections in indwelling catheters. β-Peptides comprise a promising new class of antifungal agents that could help address problems associated with the use of conventional antifungal agents. The versatility of the layer-by-layer approach used here thus suggests additional opportunities to exploit these new agents in other biomedical and personal care applications in which fungal infections are endemic. Copyright © 2014 Elsevier B.V. All rights reserved.

Polyelectrolyte multilayers: preparation and applications

NASA Astrophysics Data System (ADS)

Izumrudov, V. A.; Mussabayeva, B. Kh; Murzagulova, K. B.

2018-02-01

The review concerns the results of studies on the synthesis of polyelectrolyte coatings on charged surfaces. These coatings represent nanostructured systems with clearly defined tendency to self-assembly and self-adjustment, which is of particular interest for materials science, biomedicine and pharmacology. A breakthrough in this area of knowledge is due to the development and introduction of a new technique, so-called layer-by-layer (LbL) deposition of nanofilms. The technique is very simple, viz., multilayers are formed as a result of alternating treatment of a charged substrate of arbitrary shape with water-salt solutions of differently charged polyelectrolytes. Nevertheless, efficient use of the LbL method to fabricate nanofilms requires meeting certain conditions and limitations that were revealed in the course of research on model systems. Prospects for applications of polyelectrolyte layers in various fields are discussed. The bibliography includes 58 references.

Self-assembled graphene/azo polyelectrolyte multilayer film and its application in electrochemical energy storage device.

PubMed

Wang, Dongrui; Wang, Xiaogong

2011-03-01

Graphene/azo polyelectrolyte multilayer films were fabricated through electrostatic layer-by-layer (LbL) self-assembly, and their performance as electrochemical capacitor electrode was investigated. Cationic azo polyelectrolyte (QP4VP-co-PCN) was synthesized through radical polymerization, postpolymerization azo coupling reaction, and quaternization. Negatively charged graphene nanosheets were prepared by a chemically modified method. The LbL films were obtained by alternately dipping a piece of the pretreated substrates in the QP4VP-co-PCN and nanosheet solutions. The processes were repeated until the films with required numbers of bilayers were obtained. The self-assembly and multilayer surface morphology were characterized by UV-vis spectroscopy, AFM, SEM, and TEM. The performance of the LbL films as electrochemical capacitor electrode was estimated using cyclic voltammetry. Results show that the graphene nanosheets are densely packed in the multilayers and form random graphene network. The azo polyelectrolyte cohesively interacts with the nanosheets in the multilayer structure, which prevents agglomeration of graphene nanosheets. The sheet resistance of the LbL films decreases with the increase of the layer numbers and reaches the stationary value of 1.0 × 10(6) Ω/square for the film with 15 bilayers. At a scanning rate of 50 mV/s, the LbL film with 9 bilayers shows a gravimetric specific capacitance of 49 F/g in 1.0 M Na(2)SO(4) solution. The LbL films developed in this work could be a promising type of the electrode materials for electric energy storage devices.

Polymer Multilayers Loaded with Antifungal β-Peptides Kill Planktonic Candida albicans and Reduce Formation of Fungal Biofilms on the Surfaces of Flexible Catheter Tubes

PubMed Central

Raman, Namrata; Lee, Myung-Ryul

2014-01-01

Candida albicans is the most common fungal pathogen responsible for hospital-acquired infections. Most C albicans infections are associated with the implantation of medical devices that act as points of entry for the pathogen and as substrates for the growth of fungal biofilms that are notoriously difficult to eliminate by systemic administration of conventional antifungal agents. In this study, we report a fill-and-purge approach to the layer-by-layer fabrication of biocompatible, nanoscale ‘polyelectrolyte multilayers’ (PEMs) on the luminal surfaces of flexible catheters, and an investigation of this platform for the localized, intraluminal release of a cationic β-peptide-based antifungal agent. We demonstrate that polyethylene catheter tubes with luminal surfaces coated with multilayers ~700 nm thick fabricated from poly-L-glutamic acid (PGA) and poly-L-lysine (PLL) can be loaded, post-fabrication, by infusion with β-peptide, and that this approach promotes extended intraluminal release of this agent (over ~4 months) when incubated in physiological media. The β-peptide remained potent against intraluminal inoculation of the catheters with C albicans and substantially reduced the formation of C albicans biofilms on the inner surfaces of film-coated catheters. Finally, we report that these β-peptide-loaded coatings exhibit antifungal activity under conditions that simulate intermittent catheter use and microbial challenge for at least three weeks. We conclude that β-peptide-loaded PEMs offer a novel and promising approach to kill C albicans and prevent fungal biofilm formation on surfaces, with the potential to substantially reduce the incidence of device-associated infections in indwelling catheters. β-Peptides comprise a promising new class of antifungal agents that could help address problems associated with the use of conventional antifungal agents. The versatility of the layer-by-layer approach used here thus suggests additional opportunities to exploit these new agents in other biomedical and personal care applications in which fungal infections are endemic. PMID:24862322

In situ synthesis of gold nanoparticles in exponentially-growing layer-by-layer films

PubMed Central

Shen, Liyan; Rapenne, Laetitia; Chaudouet, Patrick; Ji, Jian; Picart, Catherine

2014-01-01

In situ synthesis of inorganic nanoparticles (NPs) in polyelectrolytes multilayers (PEMs) has recently gained much attention. Due to the versatility of their composition, PEMs offer a unique opportunity to synthesize a variety of NPs. So far, mostly cationic precursors have been used and only few studies have investigated the possibility of using amine groups to bind anionic precursors. Here, we use exponentially growing poly(L-lysine)/hyaluronan (PLL/HA) films as a nanoreservoir to bind and sequester aurochlorate (AuCl4−) anions thanks to the large number of free amine groups. The polypeptide-polysaccharide reactive template enabled the formation in a spatially-confined environment of gold NP at a very high yield. The synthesized gold NPs were homogenous and well-dispersed in the nanocomposite. Importantly, there was no particular effect of the film-ending layer (either PLL or HA). The largest particles of ~ 9 nm and the largest amount of gold were obtained at acidic pH of 3. When the pH was increased, smaller and more numerous NPs were synthesized but the total amount of gold was lower. Based on UV-visible spectrometry, FTIR and TEM data, we finally propose a scheme for the mechanism of gold NPs formation, in which several groups of PLL and HA contribute to the binding of gold ions, the nucleation and growth of NPs, and their stabilization in the “bulk” of the film. PMID:22981588

Kinetic Modulation of Pulsed Chrono-potentiometric Polymeric Membrane Ion Sensors by Polyelectrolyte Multilayers

PubMed Central

Xu, Yida; Xu, Chao; Shvarev, Alexey; Becker, Thomas; De Marco, Roland

2010-01-01

Polymeric membrane ion selective electrodes are normally interrogated by zero current potentiometry, and their selectivity is understood to be primarily dependent on an extraction/ion-exchange equilibrium between the aqueous sample and polymeric membrane. If concentration gradients in the contacting diffusion layers are insubstantial, the membrane response is thought to be rather independent of kinetic processes such as surface blocking effects. In this work, the surface of calcium-selective polymeric ion-selective electrodes is coated with polyelectrolyte multilayers as evidenced by zeta potential measurements, atomic force microscopy and electrochemical impedance spectroscopy. Indeed, such multilayers have no effect on their potentiometric response if the membranes are formulated in a traditional manner, containing a lipophilic ion-exchanger and a calcium-selective ionophore. However, drastic changes in the potential response are observed if the membranes are operated in a recently introduced kinetic mode using pulsed chronopotentiometry. The results suggest that the assembled nanostructured multilayers drastically alter the kinetics of ion transport to the sensing membrane, making use of the effect that polyelectrolyte multilayers have different permeabilities toward ions with different valences. The results have implications to the design of chemically selective ion sensors since surface localized kinetic limitations can now be used as an additional dimension to tune the operational ion selectivity. PMID:17711298

PEM Anchorage on Titanium Using Catechol Grafting

PubMed Central

Marie, Hélène; Barrere, Amélie; Schoentstein, Frédérique; Chavanne, Marie-Hélène; Grosgogeat, Brigitte; Mora, Laurence

2012-01-01

Background This study deals with the anchorage of polyelectrolyte films onto titanium surfaces via a cathecol-based linker for biomedical applications. Methodology The following study uses a molecule functionalized with a catechol and a carboxylic acid: 3-(3,4-dihydroxyphenyl)propanoic acid. This molecule is anchored to the TiO2 substrate via the catechol while the carboxylic acid reacts with polymers bearing amine groups. By providing a film anchorage of chemisorption type, it makes possible to deposit polyelectrolytes on the surface of titanium. Principal Findings Infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), contact angle and atomic force microscopy (AFM) measurements show that the different steps of grafting have been successfully performed. Conclusions This method based on catechol anchorage of polyelectrolytes open a window towards large possibilities of clinical applications. PMID:23226262

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

PubMed Central

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

2016-01-01

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

Cucurbit[8]uril-Containing Multilayer Films for the Photocontrolled Binding and Release of a Guest Molecule.

PubMed

Nicolas, Henning; Yuan, Bin; Zhang, Xi; Schönhoff, Monika

2016-03-15

The powerful host-guest chemistry of cucurbit[8]uril (CB[8]) was employed to obtain photoresponsive polyelectrolyte multilayer films for the reversible and photocontrolled binding and release of an organic guest molecule. For this purpose, we designed and synthesized a polyelectrolyte with azobenzene side groups. Then, CB[8] was associated with the azo side group to obtain a supramolecular host-guest complex that was further used as building block in order to prepare photoresponsive and CB[8]-containing polyelectrolyte multilayer films. Ultraviolet spectroscopy and a dissipative quartz crystal microbalance are employed to monitor the formation of the host-guest complex and the layer-by-layer self-assembly of the multilayer films, respectively. We demonstrate that the photoresponsive properties of the azo side groups are maintained before and after host-guest complexation with CB[8] in solution and within the multilayer films, respectively. A guest molecule was then specifically included as second binding partner into the CB[8]-containing multilayer films. Subsequently, the release of the guest was performed by UV light irradiation due to the trans-cis isomerization of the adjacent azo side groups. Re-isomerization of the azo side groups was achieved by VIS light irradiation and enabled the rebinding of the guest into CB[8]. Finally, we demonstrate that the photocontrolled binding and release within CB[8]-containing multilayer films can reliably and reversibly be performed over a period of more than 2 weeks with constant binding efficiency. Therefore, we expect such novel type of photosensitive films to have promising future applications in the field of stimuli-responsive nanomaterials.

pH-responsive ion transport in polyelectrolyte multilayers of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(4-styrenesulfonic acid-co-maleic acid) (PSS-MA) bearing strong- and weak anionic groups.

PubMed

Maza, Eliana; Tuninetti, Jimena S; Politakos, Nikolaos; Knoll, Wolfgang; Moya, Sergio; Azzaroni, Omar

2015-11-28

The layer-by-layer construction of interfacial architectures displaying stimuli-responsive control of mass transport is attracting increasing interest in materials science. In this work, we describe the creation of interfacial architectures displaying pH-dependent ionic transport properties which until now have not been observed in polyelectrolyte multilayers. We describe a novel approach to create pH-controlled ion-rectifying systems employing polyelectrolyte multilayers assembled from a copolymer containing both weakly and strongly charged pendant groups, poly(4-styrenesulfonic acid-co-maleic acid) (PSS-MA), alternately deposited with poly(diallyldimethylammonium chloride) (PDADMAC). The conceptual framework is based on the very contrasting and differential interactions of PSS and MA units with PDADMAC. In our setting, sulfonate groups play a structural role by conferring stability to the multilayer due to the strong electrostatic interactions with the polycations, while the weakly interacting MA groups remain "silent" within the film and then act as on-demand pH-responsive units. When these multilayers are combined with a strong cationic capping layer that repels the passage of cationic probes, a pH-gateable rectified transport of anions is observed. Concomitantly, we also observed that these functional properties are significantly affected when multilayers are subjected to extensive pH cycling as a consequence of irreversible morphological changes taking place in the film. We envision that the synergy derived from combining weak and strong interactions within the same multilayer will play a key role in the construction of new interfacial architectures displaying tailorable ion transport properties.

Nanoengineered capsules for selective SERS analysis of biological samples

NASA Astrophysics Data System (ADS)

You, Yil-Hwan; Schechinger, Monika; Locke, Andrea; Coté, Gerard; McShane, Mike

2018-02-01

Metal nanoparticles conjugated with DNA oligomers have been intensively studied for a variety of applications, including optical diagnostics. Assays based on aggregation of DNA-coated particles in proportion to the concentration of target analyte have not been widely adopted for clinical analysis, however, largely due to the nonspecific responses observed in complex biofluids. While sample pre-preparation such as dialysis is helpful to enable selective sensing, here we sought to prove that assay encapsulation in hollow microcapsules could remove this requirement and thereby facilitate more rapid analysis on complex samples. Gold nanoparticle-based assays were incorporated into capsules comprising polyelectrolyte multilayer (PEMs), and the response to small molecule targets and larger proteins were compared. Gold nanoparticles were able to selectively sense small Raman dyes (Rhodamine 6G) in the presence of large protein molecules (BSA) when encapsulated. A ratiometric based microRNA-17 sensing assay exhibited drastic reduction in response after encapsulation, with statistically-significant relative Raman intensity changes only at a microRNA-17 concentration of 10 nM compared to a range of 0-500 nM for the corresponding solution-phase response.

Layer-by-layer buildup of polysaccharide-containing films: Physico-chemical properties and mesenchymal stem cells adhesion.

PubMed

Kulikouskaya, Viktoryia I; Pinchuk, Sergei V; Hileuskaya, Kseniya S; Kraskouski, Aliaksandr N; Vasilevich, Irina B; Matievski, Kirill A; Agabekov, Vladimir E; Volotovski, Igor D

2018-03-22

Layer-by-Layer assembled polyelectrolyte films offer the opportunity to control cell attachment and behavior on solid surfaces. In the present study, multilayer films based on negatively charged biopolymers (pectin, dextran sulfate, carboxymethylcellulose) and positively charged polysaccharide chitosan or synthetic polyelectrolyte polyethyleneimine has been prepared and evaluated. Physico-chemical properties of the formed multilayer films, including their growth, morphology, wettability, stability, and mechanical properties, have been studied. We demonstrated that chitosan-containing films are characterized by the linear growth, the defect-free surface, and predominantly viscoelastic properties. When chitosan is substituted for the polyethyleneimine in the multilayer system, the properties of the formed films are significantly altered: the rigidity and surface roughness increases, the film growth acquires the exponential character. The multilayer films were subsequently used for culturing mesenchymal stem cells. It has been determined that stem cells effectively adhered to chitosan-containing films and formed on them the monolayer culture of fibroblast-like cells with high viability. Our results show that cell attachment is a complex process which is not only governed by the surface functionality because one of the key parameter effects on cell adhesion is the stiffness of polyelectrolyte multilayer films. We therefore propose our Layer-by-Layer films for applications in tissue engineering. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2018. © 2018 Wiley Periodicals, Inc.

Formation, Structure and Electrochemical Impedance Analysis of Microporous Polyelectrolyte Multilayers

NASA Astrophysics Data System (ADS)

Lutkenhaus, Jodie; McEnnis, Kathleen; Hammond, Paula

2007-03-01

Microporous networks are of interest as electrolyte materials, gas separation membranes and catalytic nanoparticle templates. Here, we create microporous polyelectrolyte networks of tunable pore size and connectivity using the layer-by-layer (LBL) technique. In this method, a film is formed from the alternate adsorption of oppositely charged polyelectrolytes from aqueous solution to create a cohesive thin film. Using poly(ethylene imine) (PEI) and poly(acrylic acid) (PAA), LBL thin films of variable composition and charge density were assembled; then, the films were treated in an acidic bath, which ionizes PEI and de-ionizes PAA. This shift in charge density induces morphological rearrangement realized by a microporous network. Depending on the assembly pH and acidic bath pH, we are able to precisely tune the morphology, which is characterized by atomic force microscopy and scanning electron microscopy. To demonstrate the porous nature of the polyelectrolyte multilayer, the pores were filled with non-aqueous electrolyte (i.e. ethylene carbonate, dimethyl carbonate and lithium hexafluorophosphate) and probed with electrochemical impedance spectroscopy. These microporous networks exhibited two time constants, indicative of ions traveling through the liquid-filled pores and ions traveling through the polyelectrolyte matrix.

Colloidal micro- and nano-particles as templates for polyelectrolyte multilayer capsules.

PubMed

Parakhonskiy, Bogdan V; Yashchenok, Alexey M; Konrad, Manfred; Skirtach, Andre G

2014-05-01

Colloidal particles play an important role in various areas of material and pharmaceutical sciences, biotechnology, and biomedicine. In this overview we describe micro- and nano-particles used for the preparation of polyelectrolyte multilayer capsules and as drug delivery vehicles. An essential feature of polyelectrolyte multilayer capsule preparations is the ability to adsorb polymeric layers onto colloidal particles or templates followed by dissolution of these templates. The choice of the template is determined by various physico-chemical conditions: solvent needed for dissolution, porosity, aggregation tendency, as well as release of materials from capsules. Historically, the first templates were based on melamine formaldehyde, later evolving towards more elaborate materials such as silica and calcium carbonate. Their advantages and disadvantages are discussed here in comparison to non-particulate templates such as red blood cells. Further steps in this area include development of anisotropic particles, which themselves can serve as delivery carriers. We provide insights into application of particles as drug delivery carriers in comparison to microcapsules templated on them. Copyright © 2014 Elsevier B.V. All rights reserved.

Architecture, Assembly, and Emerging Applications of Branched Functional Polyelectrolytes and Poly(ionic liquid)s.

PubMed

Xu, Weinan; Ledin, Petr A; Shevchenko, Valery V; Tsukruk, Vladimir V

2015-06-17

Branched polyelectrolytes with cylindrical brush, dendritic, hyperbranched, grafted, and star architectures bearing ionizable functional groups possess complex and unique assembly behavior in solution at surfaces and interfaces as compared to their linear counterparts. This review summarizes the recent developments in the introduction of various architectures and understanding of the assembly behavior of branched polyelectrolytes with a focus on functional polyelectrolytes and poly(ionic liquid)s with responsive properties. The branched polyelectrolytes and poly(ionic liquid)s interact electrostatically with small molecules, linear polyelectrolytes, or other branched polyelectrolytes to form assemblies of hybrid nanoparticles, multilayer thin films, responsive microcapsules, and ion-conductive membranes. The branched structures lead to unconventional assemblies and complex hierarchical structures with responsive properties as summarized in this review. Finally, we discuss prospectives for emerging applications of branched polyelectrolytes and poly(ionic liquid)s for energy harvesting and storage, controlled delivery, chemical microreactors, adaptive surfaces, and ion-exchange membranes.

Tuning cell adhesion and growth on biomimetic polyelectrolyte multilayers by variation of pH during layer-by-layer assembly.

PubMed

Aggarwal, Neha; Altgärde, Noomi; Svedhem, Sofia; Michanetzis, Georgios; Missirlis, Yannis; Groth, Thomas

2013-10-01

Polyelectrolyte multilayers of chitosan and heparin are assembled on glass where heparin is applied at pH = 4, 9 and 4 during the formation of the first layers followed by pH = 9 at the last steps (denoted pH 4 + 9). Measurements of wetting properties, layer mass, and topography show that multilayers formed at pH = 4 are thicker, contain more water and have a smoother surface compared to those prepared at pH = 9 while the pH = 4 + 9 multilayers expressed intermediate properties. pH = 9 multilayers are more cell adhesive and support growth of C2C12 cells better than pH = 4 ones. However, pH 4 + 9 conditions improve the bioactivity to a similar level of pH = 9 layers. Multilayers prepared using pH 4 + 9 conditions form thick enough layers that may allow efficient loading of bioactive molecules. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Deposition of zeolite nanoparticles onto porous silica monolith

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

Gackowski, Mariusz; Bielanska, Elzbieta; Szczepanowicz, Krzysztof

2016-06-01

A facile and effective method of deposition of MFl zeolite nanoparticles (nanocrystals) onto macro-/mesoporous silica monolith was proposed. The electrostatic interaction between those two materials was induces by adsorption of cationic polyelectrolytes. That can be realized either by adsorption of polyelectrolyte onto silica monolith or on zeolite nanocrystals. The effect of time, concentration of zeolite nanocrystals, type of polyelectrolyte, and ultrasound treatment is scrutinized. Adsorption of polyelectrolyte onto silica monolith with subsequent deposition of nanocrystals resulted in a monolayer coverage assessed with SEM images. Infrared spectroscopy was applied as a useful method to determine the deposition effectiveness of zeolite nanocrystalsmore » onto silica. Modification of nanocrystals with polyelectrolyte resulted in a multilayer coverage due to agglomeration of particles. On the other hand, the excess of polyelectrolyte in the system resulted in a low coverage due to competition between polyelectrolyte and modified nanocrystals.« less

Ionic content and permeability of polyelectrolyte multilayers and complexes

NASA Astrophysics Data System (ADS)

Ghostine, Ramy A.

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

Pheromone synthesis in a biomicroreactor coated with anti-adsorption polyelectrolyte multilayer

PubMed Central

Dimov, Nikolay; Muñoz, Lourdes; Carot-Sans, Gerard; Verhoeven, Michel L. P. M.; Bula, Wojciech P.; Kocer, Gülistan; Guerrero, Angel; Gardeniers, Han J. G. E.

2011-01-01

To prepare a biosynthetic module in an infochemical communication project, we designed a silicon/glass microreactor with anti-adsorption polyelectrolyte multilayer coating and immobilized alcohol acetyl transferase (atf), one of the key biosynthetic enzymes of the pheromone of Spodoptera littoralis, on agarose beads inside. The system reproduces the last step of the biosynthesis in which the precursor diene alcohol (Z,E)-9,11-tetradecadienol is transformed into the major component (Z,E)-9,11-tetradecadienyl acetate. The scope of this study was to analyze and implement a multilayer, anti-adsorption coating based on layer-by-layer deposition of polyethylenimine/dextransulfate sodium salt (PEI/DSS). The multilayers were composed of two PEI with molecular weights 750 and 1.2 kDa at pH 9.2 or 6.0. Growth, morphology, and stability of the layers were analyzed by ellipsometry and atomic force microscopy (AFM). The anti-adsorption functionality of the multilayer inside the microreactor was validated. The activity of His6-(atf) was measured by gas chromatography coupled to mass spectrometer (GC-MS). PMID:22662033

Fast Self-Healing of Polyelectrolyte Multilayer Nanocoating and Restoration of Super Oxygen Barrier.

PubMed

Song, Yixuan; Meyers, Kevin P; Gerringer, Joseph; Ramakrishnan, Ramesh K; Humood, Mohammad; Qin, Shuang; Polycarpou, Andreas A; Nazarenko, Sergei; Grunlan, Jaime C

2017-05-01

A self-healable gas barrier nanocoating, which is fabricated by alternate deposition of polyethyleneimine (PEI) and polyacrylic acid (PAA) polyelectrolytes, is demonstrated in this study. This multilayer film, with high elastic modulus, high glass transition temperature, and small free volume, has been shown to be a super oxygen gas barrier. An 8-bilayer PEI/PAA multilayer assembly (≈700 nm thick) exhibits an oxygen transmission rate (OTR) undetectable to commercial instrumentation (<0.005 cc (m -2 d -1 atm -1 )). The barrier property of PEI/PAA nanocoating is lost after a moderate amount of stretching due to its rigidity, which is then completely restored after high humidity exposure, therefore achieving a healing efficiency of 100%. The OTR of the multilayer nanocoating remains below the detection limit after ten stretching-healing cycles, which proves this healing process to be highly robust. The high oxygen barrier and self-healing behavior of this polymer multilayer nanocoating makes it ideal for packaging (food, electronics, and pharmaceutical) and gas separation applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computer Laboratory for Multi-scale Simulations of Novel Nanomaterials

DTIC Science & Technology

2014-09-15

schemes for multiscale modeling of polymers. Permselective ion-exchange membranes for protective clothing, fuel cells , and batteries are of special...polyelectrolyte membranes ( PEM ) with chemical warfare agents (CWA) and their simulants and (2) development of new simulation methods and computational...chemical potential using gauge cell method and calculation of density profiles. However, the code does not run in parallel environments. For mesoscale

Preparation and analysis of multilayer composites based on polyelectrolyte complexes

NASA Astrophysics Data System (ADS)

Petrova, V. A.; Orekhov, A. S.; Chernyakov, D. D.; Baklagina, Yu. G.; Romanov, D. P.; Kononova, S. V.; Volod'ko, A. V.; Ermak, I. M.; Klechkovskaya, V. V.; Skorik, Yu. A.

2016-11-01

A method for preparing multilayer film composites based on chitosan has been developed by the example of polymer pairs: chitosan-hyaluronic acid, chitosan-alginic acid, and chitosan-carrageenan. The structure of the composite films is characterized by X-ray diffractometry and scanning electron microscopy. It is shown that the deposition of a solution of hyaluronic acid, alginic acid, or carrageenan on a chitosan gel film leads to the formation of a polyelectrolyte complex layer at the interface, which is accompanied by the ordering of chitosan chains in the surface region; the microstructure of this layer depends on the nature of contacting polymer pairs.

Doxorubicin-loaded poly (lactic-co-glycolic acid) nanoparticles coated with chitosan/alginate by layer by layer technology for antitumor applications.

PubMed

Chai, Fujuan; Sun, Linlin; He, Xinyi; Li, Jieli; Liu, Yuanfen; Xiong, Fei; Ge, Liang; Webster, Thomas J; Zheng, Chunli

2017-01-01

Natural polyelectrolyte multilayers of chitosan (CHI) and alginate (ALG) were alternately deposited on doxorubicin (DOX)-loaded poly (lactic-co-glycolic acid) (PLGA) nanoparticles (NPs) with layer by layer self-assembly to control drug release for antitumor activity. Numerous factors which influenced the multilayer growth on nano-colloidal particles were studied: polyelectrolyte concentration, NaCl concentration and temperature. Then the growth regime of the CHI/ALG multilayers was elucidated. The coated NPs were characterized by transmission electron microscopy, atomic force microscopy, X-ray diffraction and a zeta potential analyzer. In vitro studies demonstrated an undesirable initial burst release of DOX-loaded PLGA NPs (DOX-PLGA NPs), which was relieved from 55.12% to 5.78% through the use of the layer by layer technique. The release of DOX increased more than 40% as the pH of media decreased from 7.4 to 5.0. More importantly, DOX-PLGA (CHI/ALG) 3 NPs had superior in vivo tumor inhibition rates at 83.17% and decreased toxicity, compared with DOX-PLGA NPs and DOX in solution. Thus, the presently formulated PLGA-polyelectrolyte NPs have strong potential applications for numerous controlled anticancer drug release applications.

Polyelectrolyte layer-by-layer deposition in cylindrical nanopores.

PubMed

Lazzara, Thomas D; Lau, K H Aaron; Abou-Kandil, Ahmed I; Caminade, Anne-Marie; Majoral, Jean-Pierre; Knoll, Wolfgang

2010-07-27

Layer-by-layer (LbL) deposition of polyelectrolytes within nanopores in terms of the pore size and the ionic strength was experimentally studied. Anodic aluminum oxide (AAO) membranes, which have aligned, cylindrical, nonintersecting pores, were used as a model nanoporous system. Furthermore, the AAO membranes were also employed as planar optical waveguides to enable in situ monitoring of the LbL process within the nanopores by optical waveguide spectroscopy (OWS). Structurally well-defined N,N-disubstituted hydrazine phosphorus-containing dendrimers of the fourth generation, with peripherally charged groups and diameters of approximately 7 nm, were used as the model polyelectrolytes. The pore diameter of the AAO was varied between 30-116 nm and the ionic strength was varied over 3 orders of magnitude. The dependence of the deposited layer thickness on ionic strength within the nanopores is found to be significantly stronger than LbL deposition on a planar surface. Furthermore, deposition within the nanopores can become inhibited even if the pore diameter is much larger than the diameter of the G4-polyelectrolyte, or if the screening length is insignificant relative to the dendrimer diameter at high ionic strengths. Our results will aid in the template preparation of polyelectrolyte multilayer nanotubes, and our experimental approach may be useful for investigating theories regarding the partitioning of nano-objects within nanopores where electrostatic interactions are dominant. Furthermore, we show that the enhanced ionic strength dependence of polyelectrolyte transport within the nanopores can be used to selectively deposit a LbL multilayer atop a nanoporous substrate.

Dual Electrophoresis Detection System for Rapid and Sensitive Immunoassays with Nanoparticle Signal Amplification

NASA Astrophysics Data System (ADS)

Zhang, Fangfang; Ma, Junjie; Watanabe, Junji; Tang, Jinlong; Liu, Huiyu; Shen, Heyun

2017-02-01

An electrophoretic technique was combined with an enzyme-linked immunosorbent assay (ELISA) system to achieve a rapid and sensitive immunoassay. A cellulose acetate filter modified with polyelectrolyte multilayer (PEM) was used as a solid substrate for three-dimensional antigen-antibody reactions. A dual electrophoresis process was used to induce directional migration and local condensation of antigens and antibodies at the solid substrate, avoiding the long diffusion times associated with antigen-antibody reactions in conventional ELISAs. The electrophoretic forces drove two steps in the ELISA process, namely the adsorption of antigen, and secondary antibody-labelled polystyrene nanoparticles (NP-Ab). The total time needed for dual electrophoresis-driven detection was just 4 min, nearly 2 h faster than a conventional ELISA system. Moreover, the rapid NP-Ab electrophoresis system simultaneously achieved amplification of the specific signal and a reduction in noise, leading to a more sensitive NP-Ab immunoassay with a limit of detection (LOD) of 130 fM, and wide range of detectable concentrations from 0.13 to 130 pM. These results suggest that the combination of dual electrophoresis detection and NP-Ab signal amplification has great potential for future immunoassay systems.

Direct evidence of spatially selective iron mineralization using an immobilized ferritin protein cage.

PubMed

Uto, Koichiro; Yamamoto, Kazuya; Kishimoto, Naoko; Muraoka, Masahiro; Aoyagi, Takao; Yamashita, Ichiro

2014-04-01

(Apo)ferritins are cage-shaped proteins which have recently received a great deal of attention because the inner cavity of the protein shell can be used as a size-restricted reaction field for the synthesis of nanomaterials. The biomineralization behavior and inorganic nanoparticle (NP) synthesis mechanism of (apo)ferritin in solution systems have been studied but the mineralization behavior of (apo)ferritin on the substrates has not yet been well studied. Here, we conducted quantitative and kinetic analyses of the mineralization behavior of immobilized (apo)ferritin on a polyelectrolyte multilayer (PEM) using quartz crystal microbalance (QCM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) techniques. We demonstrated that the (apo)ferritin immobilized on a substrate synthesizes a ferrihydrite core within the confines of the protein cage; similar to a solution dispersed system. In addition, we applied a ferritin/apoferritin blended monolayer to the study of iron mineralization and revealed that biomineralization in this system is spatially selective. It is important to understand the mineralization mechanisms for the synthesis of other functional NPs as this approach has potential for a broad range of magnetic, catalytic, and biomedical sensing applications.

(3-aminopropyl)-4-methylpiperazine end-capped poly(1,4-butanediol diacrylate-co-4-amino-1-butanol)-based multilayer films for gene delivery.

PubMed

Li, Cuicui; Tzeng, Stephany Y; Tellier, Liane E; Green, Jordan J

2013-07-10

Biodegradable polyelectrolyte surfaces for gene delivery were created through electrospinning of biodegradable polycations combined with iterative solution-based multilayer coating. Poly(β-amino ester) (PBAE) poly(1,4-butanediol diacrylate-co-4-amino-1-butanol) end-capped with 1-(3-aminopropyl)-4-methylpiperazine was utilized because of its ability to electrostatically interact with anionic molecules like DNA, its biodegradability, and its low cytotoxicity. A new DNA release system was developed for sustained release of DNA over 24 h, accompanied by high exogenous gene expression in primary human glioblastoma (GB) cells. Electrospinning a different PBAE, poly(1,4-butanediol diacrylate-co-4,4'-trimethylenedipiperidine), and its combination with polyelectrolyte 1-(3-aminopropyl)-4-methylpiperazine end-capped poly(1,4-butanediol diacrylate-co-4-amino-1-butanol)-based multilayers are promising for DNA release and intracellular delivery from a surface.

(3-Aminopropyl)-4-methylpiperazine End-capped Poly(1,4-butanediol diacrylate-co-4-amino-1-butanol)-based Multilayer Films for Gene Delivery

PubMed Central

Li, Cuicui; Tzeng, Stephany Y; Tellier, Liane E.; Green, Jordan J

2013-01-01

Biodegradable polyelectrolyte surfaces for gene delivery were created through electrospinning of biodegradable polycations combined with iterative solution-based multilayer coating. Poly(β-amino ester) (PBAE) poly(1,4-butanediol diacrylate-co-4-amino-1-butanol) end-capped with 1-(3-aminopropyl)-4-methylpiperazine was utilized due to its ability to electrostatically interact with anionic molecules like DNA, its biodegradability, and its low cytotoxicity. A new DNA release system was developed for sustained release of DNA over 24 hours, accompanied by high exogenous gene expression in primary human glioblastoma (GB) cells. Electrospinning a different PBAE, poly(1,4-butanediol diacrylate-co-4,4′-trimethylenedipiperidine), and its combination with polyelectrolyte 1-(3-aminopropyl)-4-methylpiperazine end-capped poly(1,4-butanediol diacrylate-co-4-amino-1-butanol)-based multilayers are promising for DNA release and intracellular delivery from a surface. PMID:23755861

Electrical properties of multilayers from low- and high-molecular-weight polyelectrolytes.

PubMed

Radeva, Tsetska; Milkova, Viktoria; Petkanchin, Ivana

2004-11-15

The formation of stable multilayer films by using as constituents sodium poly(4-styrene sulfonate) (PSS) and poly(4-vinyl pyridine) (PVP) was studied by electrooptics. A strong increase in basicity of the pyridine rings in the electrical field of the oppositely charged PSS chains was suggested to be the driving force for multilayer film formation. A linear increase in the film thickness was registered after deposition of the first three layers, with no dependence on the polyelectrolyte molecular weight. The electrooptical effect was found to increase with increasing area of each next layer, but depended on the molecular weights of both polymers. Polarization of "condensed" counterions along the chains of the last-adsorbed layer was suggested to explain this dependence. Following the counterion dynamics, we come to the conclusion that the electrical properties of the top layer govern the electrooptical behavior of the PSS/PVP film.

Chitosan/alginate multilayer film for controlled release of IDM on Cu/LDPE composite intrauterine devices.

PubMed

Tian, Kuan; Xie, Changsheng; Xia, Xianping

2013-09-01

To reduce such side effects as pain and bleeding caused by copper-containing intrauterine device (Cu-IUD), a novel medicated intrauterine device, which is coated with an indomethacin (IDM) delivery system on the surface of copper/low-density polyethylene (Cu/LDPE) composite intrauterine device, has been proposed and developed in the present work. The IDM delivery system is a polyelectrolyte multilayer film, which is composed of IDM containing chitosan and alginate layer by layer, is prepared by using self-assembled polyelectrolyte multilayer method, and the number of the layers of this IDM containing chitosan/alginate multilayer film can be tailored by controlling the cyclic repetition of the deposition process. After the IDM containing chitosan/alginate multilayer film is obtained on the surface of Cu/LDPE composite intrauterine device, its release behavior of both IDM and cupric ion has been studied in vitro. The results show that the release duration of IDM increase with the increasing of thickness of the IDM containing chitosan/alginate multilayer film, and the initial burst release of cupric ion cannot be found in this novel medicated Cu/LDPE composite IUD. These results can be applied to guide the design of novel medicated Cu-IUD with minimal side effects for the future clinical use. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrostatic Interactions and Self-Assembly in Polymeric Systems

NASA Astrophysics Data System (ADS)

Dobrynin, Andrey

Electrostatic interactions between macroions play an important role in different areas ranging from materials science to biophysics. They are main driving forces behind layer-by-layer assembly technique that allows self-assembly of multilayer films from synthetic polyelectrolytes, DNA, proteins and nanoparticles. They are responsible for complexation and reversible gelation between polyelectrolytes and proteins. In this talk, using results of the molecular dynamics simulations and analytical calculations, I will demonstrate what effect electrostatic interactions, counterion condensation and polymer solvent affinity have on a collapse of polyelectrolyte chain in a poor solvent conditions for the polymer backbone, on complexations and reversible gelation between polyelectrolytes and polyamholytes (unstructured proteins), on microphase separation transitions in spherical and planar charged brushes, and on a layer-by-layer assembly of charged nanoparticles and linear polyelectrolytes on charged surfaces. NSF DMR-1004576 DMR-1409710.

Biomolecular strategies for cell surface engineering

NASA Astrophysics Data System (ADS)

Wilson, John Tanner

Islet transplantation has emerged as a promising cell-based therapy for the treatment of diabetes, but its clinical efficacy remains limited by deleterious host responses that underlie islet destruction. In this dissertation, we describe the assembly of ultrathin conformal coatings that confer molecular-level control over the composition and biophysicochemical properties of the islet surface with implications for improving islet engraftment. Significantly, this work provides novel biomolecular strategies for cell surface engineering with broad biomedical and biotechnological applications in cell-based therapeutics and beyond. Encapsulation of cells and tissue offers a rational approach for attenuating deleterious host responses towards transplanted cells, but a need exists to develop cell encapsulation strategies that minimize transplant volume. Towards this end, we endeavored to generate nanothin films of diverse architecture with tunable properties on the extracellular surface of individual pancreatic islets through a process of layer-by-layer (LbL) self assembly. We first describe the formation of poly(ethylene glycol) (PEG)-rich conformal coatings on islets via LbL self assembly of poly(L-lysine)-g-PEG(biotin) and streptavidin. Multilayer thin films conformed to the geometrically and chemically heterogeneous islet surface, and could be assembled without loss of islet viability or function. Significantly, coated islets performed comparably to untreated controls in a murine model of allogenic intraportal islet transplantation, and, to our knowledge, this is the first study to report in vivo survival and function of nanoencapsulated cells or cell aggregates. Based on these findings, we next postulated that structurally similar PLL-g-PEG copolymers comprised of shorter PEG grafts might be used to initiate and propagate the assembly of polyelectrolyte multilayer (PEM) films on pancreatic islets, while simultaneously preserving islet viability. Through control of PLL backbone molecular weight, PEG chain length, and grafting ratio, PLL-g-PEG copolymers were rendered cytocompatible and used to initiate and propagate the growth of cell surface-supported PEM films. Planar characterization of this novel class of PEM films indicated that film thickness and composition may be tailored through appropriate control of layer number and copolymer properties. Furthermore, these investigations have helped establish a conceptual framework for the rational design of cell surface-supported thin films, with the objective of translating the diverse biomedical and biotechnological applications of PEM films to cellular interfaces. Important to the development of effective conformal islet coatings is an inherent strategy through which to incorporate bioactive molecules for directing desired biochemical or cellular responses. Towards this end, PLL-g-PEG copolymers functionalized with biotin, azide, and hydrazide moieties were synthesized and used, either alone or in combination, to capture streptavidin-, triphenylphosphine-, and aldehyde-labeled probes, respectively, on the islet surface. Additionally, PEM films assembled using alginate chemically modified to contain aldehyde groups could be used to introduce hydrazide-functionalized molecules to the islet surface. Hence, modified film constituents may be used as modular elements for controlling the chemical composition cell and tissue surfaces. Finally, we report a strategy for tethering thrombomodulin (TM) to the islet surface. Through site-specific, C-terminal biotinylation of TM and optimization of cell surface biotinylation, TM could be integrated with the islet surface. Re-engineering of islet surfaces with TM resulted in an increased catalytic capacity of islets to generate the powerful anti-inflammatory agent, activated protein C (APC), thereby providing a facile strategy for increasing the local concentration of APC at the site of transplantation.

Multilayered Polyelectrolyte Microcapsules: Interaction with the Enzyme Cytochrome C Oxidase

PubMed Central

Pastorino, Laura; Dellacasa, Elena; Noor, Mohamed R.; Soulimane, Tewfik; Bianchini, Paolo; D'Autilia, Francesca; Antipov, Alexei; Diaspro, Alberto; Tofail, Syed A. M.; Ruggiero, Carmelina

2014-01-01

Cell-sized polyelectrolyte capsules functionalized with a redox-driven proton pump protein were assembled for the first time. The interaction of polyelectrolyte microcapsules, fabricated by electrostatic layer-by-layer assembly, with cytochrome c oxidase molecules was investigated. We found that the cytochrome c oxidase retained its functionality, that the functionalized microcapsules interacting with cytochrome c oxidase were permeable and that the permeability characteristics of the microcapsule shell depend on the shell components. This work provides a significant input towards the fabrication of an integrated device made of biological components and based on specific biomolecular functions and properties. PMID:25372607

pH-responsiveness of multilayered films and membranes made of polysaccharides

PubMed Central

Silva, Joana M.; Caridade, Sofia G.; Costa, Rui R.; Alves, Natália M.; Groth, Thomas; Picart, Catherine; Reis, Rui L.; Mano, João F.

2016-01-01

We investigated the pH-dependent properties of multilayered films made of chitosan (CHI) and alginate (ALG) and focused on their post-assembly response to different pH environments using quartz crystal microbalance with dissipation monitoring (QCM-D), swelling studies, zeta potential measurements and dynamic mechanical analysis (DMA). In an acidic environment, the multilayers presented lower dissipation values and, consequently, higher moduli when compared with the values obtained for the pH used during the assembly (5.5). When the multilayers were exposed to alkaline environments the opposite behavior occurred. These results were further corroborated with the ability of this multilayered system to exhibit a reversible swelling-deswelling behavior within the pH range from 3 to 9. The changes of the physicochemical properties of the multilayer system were gradual and different from the ones of individual solubilized polyelectrolytes. This behavior is related to electrostatic interactions between the ionizable groups combined with hydrogen-bonding and hydrophobic interactions. Beyond the pH range of 3-9 the multilayers were stabilized by genipin cross-linking. The multilayered films also became more rigid while preserving the pH-responsiveness conferred by the ionizable moieties of the polyelectrolytes. This work demonstrates the versatility and feasibility of LbL methodology to generate inherently pH stimuli-responsive nanostructured films. Surface functionalization using pH-repsonsiveness endows abilities for several biomedical applications such as drug delivery, diagnostics, microfluidics, biosensing or biomimetic implantable membranes. PMID:26421873

Influence of salt and rinsing protocol on the structure of PAH/PSS polyelectrolyte multilayers.

PubMed

Feldötö, Zsombor; Varga, Imre; Blomberg, Eva

2010-11-16

A quartz crystal microbalance (QCM) and dual polarization interferometry (DPI) have been utilized to study how the structure of poly(allylamine hydrochloride) (PAH)/poly(styrene sulfonate) (PSS) multilayers is affected by the rinsing method (i.e., the termination of polyelectrolyte adsorption). The effect of the type of counterions used in the deposition solution was also investigated, and the polyelectrolyte multilayers were formed in a 0.5 M electrolyte solution (NaCl and KBr). From the measurements, it was observed that thicker layers were obtained when using KBr in the deposition solution than when using NaCl. Three different rinsing protocols have been studied: (i) the same electrolyte solution as used during multilayer formation, (ii) pure water, and (iii) first a salt solution (0.5 M) and then pure water. When the multilayer with PAH as the outermost layer was exposed to pure water, an interesting phenomenon was discovered: a large change in the energy dissipation was measured with the QCM. This could be attributed to the swelling of the layer, and from both QCM and DPI it is obvious that only the outermost PAH layer swells (to a thickness of 25-30 nm) because of a decrease in ionic strength and hence an increase in intra- and interchain repulsion, whereas the underlying layers retain a very rigid and compact structure with a low water content. Interestingly, the outermost PAH layer seems to obtain very similar thicknesses in water independent of the electrolyte used for the multilayer buildup. Another interesting aspect was that the measured thickness with the DPI evaluated by a single-layer model did not correlate with the estimated thickness from the model calculations performed on the QCM-D data. Thus, we applied a two-layer model to evaluate the DPI data and the results were in excellent agreement with the QCM-D results. To our knowledge, this evaluation of DPI data has not been done previously.

Examination of biogenic selenium-containing nanosystems based on polyelectrolyte complexes by atomic force, Kelvin probe force and electron microscopy methods

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

Sukhanova, T. E., E-mail: tat-sukhanova@mail.ru; Vylegzhanina, M. E.; Valueva, S. V.

The morphology and electrical properties of biogenic selenium-containing nanosystems based on polyelectrolyte complexes (PECs) were examined using AFM, Kelvin Probe Force and electron microscopy methods. It has been found, that prepared nanostructures significantly differed in their morphological types and parameters. In particular, multilayers capsules can be produced via varying synthesis conditions, especially, the selenium–PEC mass ratio ν. At the “special point” (ν = 0.1), filled and hollow nano- and microcapsules are formed in the system. The multilayer character of the capsules walls is visible in the phase images. Kelvin Probe Force images showed the inhomogeneity of potential distribution in capsulesmore » and outside them.« less

Adsorption of IgG on/in a PAH/PSS multilayer film: Layer structure and cell response.

PubMed

Feldötö, Zsombor; Lundin, Maria; Braesch-Andersen, Sten; Blomberg, Eva

2011-02-01

The binding of immunogloblulins (IgG) (mouse monoclonal recognizing IFNγ) on precoated polystyrene or silica surfaces by the layer-by-layer technique has been investigated with QCM-D and DPI. The aim of the work was to increase the sensitivity of the conventional enzyme-linked immunosorbent spot (ELISpot) assay. The polyelectrolytes used to build the multilayers were poly(allylamine hydrochloride) (PAH)/poly(sodium 4-styrenesulfonate) (PSS) alternately adsorbed from 150mM NaCl. The multilayer build up is linear and the internal structure of the PAH/PSS multilayer is compact and rigid as observed by low relative water content (20-25%) and high layer refractive index (n∼1.5) after the formation of five bilayers. Incorporation of IgG within the PAH/PSS multilayer did not give rise to overcharging and did not affect the linear build up. ELISpot test on PAH/PSS multilayer modified polystyrene wells showed that the cytokine response was significantly smaller than on the regular PVDF backed polystyrene wells. This may be due to the compact and rigid nature of the PAH/PSS multilayer, which does not allow formation of the kind of three dimensional support needed to achieve bioactive IgG binding to the surface. Immunological tests of the polyelectrolyte multilayers in the absence of IgG showed that PSS terminated PAH/PSS multilayer did not induce any cytokine response whereas PAH terminated did, which suggests that PSS totally covers the surface from the cells point of view. Copyright © 2010 Elsevier Inc. All rights reserved.

Polyelectrolyte-mediated assembly of copper-phthalocyanine tetrasulfonate multilayers and the subsequent production of nanoparticulate copper oxide thin films.

PubMed

Chickneyan, Zarui Sara; Briseno, Alejandro L; Shi, Xiangyang; Han, Shubo; Huang, Jiaxing; Zhou, Feimeng

2004-07-01

An approach to producing films of nanometer-sized copper oxide particulates, based on polyelectrolyte-mediated assembly of the precursor, copper(II)phthalocyanine tetrasulfonate (CPTS), is described. Multilayered CPTS and polydiallyldimethylammonium chloride (PDADMAC) were alternately assembled on different planar substrates via the layer-by-layer (LbL) procedure. The growth of CPTS multilayers was monitored by UV-visible spectrometry and quartz crystal microbalance (QCM) measurements. Both the UV-visible spectra and the QCM data showed that a fixed amount of CPTS could be attached to the substrate surface for a given adsorption cycle. Cyclic voltammograms at the CPTS/PDADMAC-covered gold electrode exhibited a decrease in peak currents with the layer number, indicating that the permeability of CPTS multilayers on the electrodes had diminished. When these CPTS multilayered films were calcined at elevated temperatures, uniform thin films composed of nanoparticulate copper oxide could be produced. Ellipsometry showed that the thickness of copper oxide nanoparticulate films could be precisely tailored by varying the thickness of CPTS multilayer films. The morphology and roughness of CPTS multilayer and copper oxide thin films were characterized by atomic force microscopy. X-ray diffraction (XRD) measurements indicated that these thin films contained both CuO and Cu2O nanoparticles. The preparation of such copper oxide thin films with the use of metal complex precursors represents a new route for the synthesis of inorganic oxide films with a controlled thickness.

Assembly of luminescent ordered multilayer thin-films based on oppositely-charged MMT and magnetic NiFe-LDHs nanosheets with ultra-long lifetimes

PubMed Central

Liu, Meitang; Wang, Tianlei; Ma, Hongwen; Fu, Yu; Hu, Kunran; Guan, Chao

2014-01-01

In this present report, luminescent ordered multilayer thin films (OMFs) based on oppositely-charged inorganic nanosheets and the different oppositely-charged chromophores were fabricated via layer-by-layer assembly method. Exfoliated layered double hydroxides (LDHs) and montmorillonite (MMT) nanosheets with opposite charges can be expected to provide a pseudo electronic microenvironment (PEM) which has not been declared in previous literatures, and transition metal-bearing LDHs nanosheets can offer an additional ferromagnetic effect (FME) for the chromophores at the same time. Surprisingly, the luminescent lifetimes of those OMFs with PEM and FME are significantly prolonged compared with that of the pristine chromophores, even much longer than those of OMFs without oppositely-charged and ferromagnetic architecture. Therefore, it is highly expected that the PEM and FME formed by oppositely-charged and transition metal-bearing inorganic nanosheets have remarkable influence on obtaining better optical property, which suggests a new potential way to manipulate, control and develop the novel light-emitting materials and optical devices. PMID:25413710

Ion distribution in dry polyelectrolyte multilayers: a neutron reflectometry study

DOE PAGES

Ghoussoub, Yara E.; Zerball, Maximilian; Fares, Hadi M.; ...

2018-02-09

Counterions were found to be uniformly distributed in polycation-terminated films of poly(diallyldimethylammonium) and poly(styrenesulfonate) prepared on silicon wafers using layer-by-layer adsorption.

Layer-by-Layer Self-Assembly of Plexcitonic Nanoparticles

DTIC Science & Technology

2013-08-12

nitrate , trisodium citrate tribasic dihydrate, sodium poly(styrene sulfonate) (PSS, MW ~70,000), poly(diallyldimethyl ammonium chloride ) (PDADMAC...Abstract: Colloidal suspensions of multilayer nanoparticles composed of a silver core, a polyelectrolyte spacer layer (inner shell), and a J-aggregate...multilayer architecture served as a framework for examining the coupling of the localized surface plasmon resonance exhibited by the silver core with

Chain Conformation and Dynamics in Spin-Assisted Weak Polyelectrolyte Multilayers

DOE PAGES

Zhuk, Aliaksandr; Selin, Victor; Zhuk, Iryna; ...

2015-03-13

In this paper, we report on the effect of the deposition technique on film layering, stability, and chain mobility in weak polyelectrolyte layer-by-layer (LbL) films. Ellipsometry and neutron reflectometry (NR) showed that shear forces arising during spin-assisted assembly lead to smaller amounts of adsorbed polyelectrolytes within LbL films, result in a higher degree of internal film order, and dramatically improve stability of assemblies in salt solutions as compared to dip-assisted LbL assemblies. The underlying flattening of polyelectrolyte chains in spin-assisted LbL films was also revealed as an increase in ionization degree of the assembled weak polyelectrolytes. As demonstrated by fluorescencemore » recovery after photobleaching (FRAP), strong binding between spin-deposited polyelectrolytes results in a significant slowdown of chain diffusion in salt solutions as compared to dip-deposited films. Moreover, salt-induced chain intermixing in the direction perpendicular to the substrate is largely inhibited in spin-deposited films, resulting in only subdiffusional (<2 Å) chain displacements even after 200 h exposure to 1 M NaCl solutions. Finally, this persistence of polyelectrolyte layering has important ramifications for multistage drug delivery and optical applications of LbL assemblies.« less

Construction of Compact Polyelectrolyte Multilayers Inspired by Marine Mussel: Effects of Salt Concentration and pH As Observed by QCM-D and AFM.

PubMed

Wang, Weina; Xu, Yisheng; Backes, Sebastian; Li, Ang; Micciulla, Samantha; Kayitmazer, A Basak; Li, Li; Guo, Xuhong; von Klitzing, Regine

2016-04-12

Biomimetic multilayers based on layer-by-layer (LbL) assembly were prepared as functional films with compact structure by incorporating the mussel-inspired catechol cross-linking. Dopamine-modified poly(acrylic acid) (PAADopa) was synthesized as a polyanion to offer electrostatic interaction with the prelayer polyethylenimine (PEI) and consecutively cross-linked by zinc to generate compact multilayers with tunable physicochemical properties. In situ layer-by-layer growth and cross-linking were monitored by a quartz crystal microbalance with dissipation (QCM-D) to reveal the kinetics of the process and the influence of Dopa chemistry. Addition of Dopa enhanced the mass adsorption and led to the formation of a more compact structure. An increase of ionic strength induced an increase in mass adsorption in the Dopa-cross-linked multilayers. This is a universal approach for coating of various surfaces such as Au, SiO2, Ti, and Al2O3. Roughness observed by AFM in both wet and dry conditions was compared to confirm the compact morphology of Dopa-cross-linked multilayers. Because of the pH sensitivity of Dopa moiety, metal-chelated Dopa groups can be turned into softer structure at higher pH as revealed by reduction of Young's modulus determined by MFP-3D AFM. A deeper insight into the growth and mechanical properties of Dopa-cross-linked polyelectrolyte multilayers was addressed in the present study. This allows a better control of these systems for bioapplications.

Controlled enzyme-catalyzed degradation of polymeric capsules templated on CaCO₃: influence of the number of LbL layers, conditions of degradation, and disassembly of multicompartments.

PubMed

Marchenko, Irina; Yashchenok, Alexey; Borodina, Tatiana; Bukreeva, Tatiana; Konrad, Manfred; Möhwald, Helmuth; Skirtach, Andre

2012-09-28

Enzyme-catalyzed degradation of CaCO₃-templated capsules is presented. We investigate a) biodegradable, b) mixed biodegradable/synthetic, and c) multicompartment polyelectrolyte multilayer capsules with different numbers of polymer layers. Using confocal laser scanning microscopy we observed the kinetics of the non-specific protease Pronase-induced degradation of capsules is slowed down on the order of hours by either increasing the number of layers in the wall of biodegradable capsules, or by inserting synthetic polyelectrolyte multilayers into the shell comprised of biodegradable polymers. The degradation rate increases with the concentration of Pronase. Controlled detachment of subcompartments of multicompartment capsules, with potential for intracellular delivery or in-vivo applications, is also shown. Copyright © 2012 Elsevier B.V. All rights reserved.

Layer-by-layer self-assembly in the development of electrochemical energy conversion and storage devices from fuel cells to supercapacitors.

PubMed

Xiang, Yan; Lu, Shanfu; Jiang, San Ping

2012-11-07

As one of the most effective synthesis tools, layer-by-layer (LbL) self-assembly technology can provide a strong non-covalent integration and accurate assembly between homo- or hetero-phase compounds or oppositely charged polyelectrolytes, resulting in highly-ordered nanoscale structures or patterns with excellent functionalities and activities. It has been widely used in the developments of novel materials and nanostructures or patterns from nanotechnologies to medical fields. However, the application of LbL self-assembly in the development of highly efficient electrocatalysts, specific functionalized membranes for proton exchange membrane fuel cells (PEMFCs) and electrode materials for supercapacitors is a relatively new phenomenon. In this review, the application of LbL self-assembly in the development and synthesis of key materials of PEMFCs including polyelectrolyte multilayered proton-exchange membranes, methanol-blocking Nafion membranes, highly uniform and efficient Pt-based electrocatalysts, self-assembled polyelectrolyte functionalized carbon nanotubes (CNTs) and graphenes will be reviewed. The application of LbL self-assembly for the development of multilayer nanostructured materials for use in electrochemical supercapacitors will also be reviewed and discussed (250 references).

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%.

Clay and DOPA containing polyelectrolyte multilayer film for imparting anticorrosion properties to galvanized steel.

PubMed

Faure, Emilie; Halusiak, Emilie; Farina, Fabrice; Giamblanco, Nicoletta; Motte, Cécile; Poelman, Mireille; Archambeau, Catherine; Van de Weerdt, Cécile; Martial, Joseph; Jérôme, Christine; Duwez, Anne-Sophie; Detrembleur, Christophe

2012-02-07

A facile and green approach is developed to impart remarkable protection against corrosion to galvanized steel. A protecting multilayer film is formed by alternating the deposition of a polycation bearing catechol groups, used as corrosion inhibitors, with clay that induces barrier properties. This coating does not affect the esthetical aspect of the surface and does not release any toxic molecules in the environment.

Fabrication and in vitro evaluation of the collagen/hyaluronic acid PEM coating crosslinked with functionalized RGD peptide on titanium.

PubMed

Huang, Ying; Luo, Qiaojie; Li, Xiaodong; Zhang, Feng; Zhao, Shifang

2012-02-01

Surface modification of titanium (Ti) using biomolecules has attracted much attention recently. In this study, a new strategy has been employed to construct a stable and bioactive coating on Ti. To this end, a derivative of hyaluronic acid (HA), i.e. HA-GRGDSPC-(SH), was synthesized. The disulfide-crosslinked Arg-Gly-Asp (RGD)-containing collagen/hyaluronic acid polyelectrolyte membrane (PEM) coating was then fabricated on Ti through the alternate deposition of collagen and HA-GRGDSPC-(SH) with five assembly cycles and subsequent crosslinking via converting free sulphydryl groups into disulfide linkages (RGD-CHC-Ti group). The assembly processes for PEM coating and the physicochemical properties of the coating were carefully characterized. The stability of PEM coating in phosphate-buffered saline solution could be adjusted by the crosslinking degree, while its degradation behaviors in the presence of glutathione were glutathione concentration dependent. The adhesion and proliferation of MC3T3-E1 cells were significantly enhanced in the RGD-CHC-Ti group. Up-regulated bone specific genes, enhanced alkaline phosphatase activity and osteocalcin production, the increased areas of mineralization were also observed in the RGD-CHC-Ti group. These results indicate that the strategy employed herein may function as an effective way to construct stable, RGD-containing bioactive coatings on Ti. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

[Preparation of polyelectrolyte microcapsules contained gold nanoparticles].

PubMed

Sun, Ya-jie; Zhu, Jia-bi; Zheng, Chun-li

2010-03-01

In this work, polyelectrolyte microcapsules containing gold nanoparticles were prepared via layer by layer assembly. Gold nanoparticles and poly (allyamine hydrochloride) (PAH) were coated on the CaCO3 microparticles. And then EDTA was used to remove the CaCO3 core. Scanning electron microscopy (SEM) was used to characterize the surface of microcapsules. SEM images indicate that the microcapsules and the polyelectrolyte multilayer were deposited on the surface of CaCO3 microparticles. FITC-bovine serum albumin (FITC-BSA, 2 mg) was incorporated in the CaCO3 microparticles by co-precipitation. Fluorescence microscopy was used to observe the fluorescence intensity of microcapsules. The encapsulation efficiency was (34.31 +/- 2.44) %. The drug loading was (43.75 +/- 3.12) mg g(-1).

High throughput study of fuel cell proton exchange membranes: Poly(vinylidene fluoride)/acrylic polyelectrolyte blends and nanocomposites with zirconium

NASA Astrophysics Data System (ADS)

Zapata B., Pedro Jose

Sustainability is perhaps one of the most heard buzzwords in the post-20 th century society; nevertheless, it is not without a reason. Our present practices for energy supply are largely unsustainable if we consider their environmental and social impact. In view of this unfavorable panorama, alternative sustainable energy sources and conversion approaches have acquired noteworthy significance in recent years. Among these, proton exchange membrane fuel cells (PEMFCs) are being considered as a pivotal building block in the transition towards a sustainable energy economy in the 21st century. The polyelectrolyte membrane or proton exchange membrane (PEM) is a vital component, as well as a performance-limiting factor, of the PEMFC. Consequently, the development of high-performance PEM materials is of utmost importance for the advance of the PEMFC field. In this work, alternative PEM materials based on semi-interpenetrated networks from blends of poly(vinyledene fluoride) (PVDF) (inert phase) and sulfonated crosslinked acrylic polyelectrolytes (PE) (proton-conducting phase), as well as tri-phase PVDF/PE/zirconium-based composites, are studied. To alleviate the burden resulting from the vast number of possible combinations of the different precursors utilized in the preparation of the membranes (PVDF: 5x, PE: 2x, Nanoparticle: 3x), custom high-throughput (HT) screening systems have been developed for their characterization. By coupling the data spaces obtained via these systems with the appropriate statistical and data analysis tools it was found that, despite not being directly involved in the proton transport process, the inert PVDF phase plays a major role on proton conductivity. Particularly, a univocal inverse correlation between the PVDF crystalline characteristics (i.e., crystallinity and crystallite size) and melt viscosity, and membrane proton conductivity was discovered. Membranes based on highly crystalline and viscous PVDF homopolymers exhibited reduced proton conductivity due to precluded segmental motion and physical blockage of the PE chains during crosslinking. In addition, a maximum effective amount of PE (55-60wt%, neutralized form) beneficial for proton conductivity was revealed. Some of the aforementioned effects may possibly have been overlooked if a high-throughput study including plentiful combinations of multiple precursors hadn't been performed. In the case of composite membranes, despite the fact that nanoparticle dispersion was thermodynamically limited, a general improvement in proton conductivity was evidenced at low to medium nanoparticle loadings (0.5 to 1wt%) in comparison to non-hybrid PVDF/PE references. This beneficial effect was particularly noticeable in membranes based on PVDF homopolymers (7% to 14.3% increment), where the nanoparticles induced a "healing" effect by providing proton-conducting paths between non-crosslinked PE channels separated by dense PVDF areas resulting from large PVDF crystallites. In general, the results presented herein are promising for the development of new cost-effective alternative PEMs.

Electrochemical Analysis of Conducting Polymer Thin Films

PubMed Central

Vyas, Ritesh N.; Wang, Bin

2010-01-01

Polyelectrolyte multilayers built via the layer-by-layer (LbL) method has been one of the most promising systems in the field of materials science. Layered structures can be constructed by the adsorption of various polyelectrolyte species onto the surface of a solid or liquid material by means of electrostatic interaction. The thickness of the adsorbed layers can be tuned precisely in the nanometer range. Stable, semiconducting thin films are interesting research subjects. We use a conducting polymer, poly(p-phenylene vinylene) (PPV), in the preparation of a stable thin film via the LbL method. Cyclic voltammetry and electrochemical impedance spectroscopy have been used to characterize the ionic conductivity of the PPV multilayer films. The ionic conductivity of the films has been found to be dependent on the polymerization temperature. The film conductivity can be fitted to a modified Randle’s circuit. The circuit equivalent calculations are performed to provide the diffusion coefficient values. PMID:20480052

Distance-dependent plasmon-enhanced fluorescence of upconversion nanoparticles using polyelectrolyte multilayers as tunable spacers.

PubMed

Feng, Ai Ling; You, Min Li; Tian, Limei; Singamaneni, Srikanth; Liu, Ming; Duan, Zhenfeng; Lu, Tian Jian; Xu, Feng; Lin, Min

2015-01-14

Lanthanide-doped upconversion nanoparticles (UCNPs) have attracted widespread interests in bioapplications due to their unique optical properties by converting near infrared excitation to visible emission. However, relatively low quantum yield prompts a need for developing methods for fluorescence enhancement. Plasmon nanostructures are known to efficiently enhance fluorescence of the surrounding fluorophores by acting as nanoantennae to focus electric field into nano-volume. Here, we reported a novel plasmon-enhanced fluorescence system in which the distance between UCNPs and nanoantennae (gold nanorods, AuNRs) was precisely tuned by using layer-by-layer assembled polyelectrolyte multilayers as spacers. By modulating the aspect ratio of AuNRs, localized surface plasmon resonance (LSPR) wavelength at 980 nm was obtained, matching the native excitation of UCNPs resulting in maximum enhancement of 22.6-fold with 8 nm spacer thickness. These findings provide a unique platform for exploring hybrid nanostructures composed of UCNPs and plasmonic nanostructures in bioimaging applications.

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.

Polyelectrolyte multilayer-assisted fabrication of non-periodic silicon nanocolumn substrates for cellular interface applications

NASA Astrophysics Data System (ADS)

Lee, Seyeong; Kim, Dongyoon; Kim, Seong-Min; Kim, Jeong-Ah; Kim, Taesoo; Kim, Dong-Yu; Yoon, Myung-Han

2015-08-01

Recent advances in nanostructure-based biotechnology have resulted in a growing demand for vertical nanostructure substrates with elaborate control over the nanoscale geometry and a high-throughput preparation. In this work, we report the fabrication of non-periodic vertical silicon nanocolumn substrates via polyelectrolyte multilayer-enabled randomized nanosphere lithography. Owing to layer-by-layer deposited polyelectrolyte adhesives, uniformly-separated polystyrene nanospheres were securely attached on large silicon substrates and utilized as masks for the subsequent metal-assisted silicon etching in solution. Consequently, non-periodic vertical silicon nanocolumn arrays were successfully fabricated on a wafer scale, while each nanocolumn geometric factor, such as the diameter, height, density, and spatial patterning, could be fully controlled in an independent manner. Finally, we demonstrate that our vertical silicon nanocolumn substrates support viable cell culture with minimal cell penetration and unhindered cell motility due to the blunt nanocolumn morphology. These results suggest that vertical silicon nanocolumn substrates may serve as a useful cellular interface platform for performing a statistically meaningful number of cellular experiments in the fields of biomolecular delivery, stem cell research, etc.Recent advances in nanostructure-based biotechnology have resulted in a growing demand for vertical nanostructure substrates with elaborate control over the nanoscale geometry and a high-throughput preparation. In this work, we report the fabrication of non-periodic vertical silicon nanocolumn substrates via polyelectrolyte multilayer-enabled randomized nanosphere lithography. Owing to layer-by-layer deposited polyelectrolyte adhesives, uniformly-separated polystyrene nanospheres were securely attached on large silicon substrates and utilized as masks for the subsequent metal-assisted silicon etching in solution. Consequently, non-periodic vertical silicon nanocolumn arrays were successfully fabricated on a wafer scale, while each nanocolumn geometric factor, such as the diameter, height, density, and spatial patterning, could be fully controlled in an independent manner. Finally, we demonstrate that our vertical silicon nanocolumn substrates support viable cell culture with minimal cell penetration and unhindered cell motility due to the blunt nanocolumn morphology. These results suggest that vertical silicon nanocolumn substrates may serve as a useful cellular interface platform for performing a statistically meaningful number of cellular experiments in the fields of biomolecular delivery, stem cell research, etc. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02384j

Polyelectrolyte capsules as carriers for growth factor inhibitor delivery to hepatocellular carcinoma.

PubMed

Baldassarre, Francesca; Vergaro, Viviana; Scarlino, Flavia; De Santis, Flavia; Lucarelli, Giovanna; Torre, Antonio Della; Ciccarella, Giuseppe; Rinaldi, Ross; Giannelli, Gianluigi; Leporatti, Stefano

2012-05-01

The efficient internalization of TGF-beta inhibitor-loaded polyelectrolyte capsules and particles is studied in two HCC cell lines. Two polyelectrolyte pairs (biocompatible but not degradable and biodegradable crosslinked with gluteraldehyde) are employed for coating. The capsules are characterized by SEM. LY is successfully loaded inside the core and embedded between polymer layers. MS is used to quantify the loading efficiency by comparing post-loading and core-loading methods, since both coated templates and hollow shells are used as carriers. CLSM confirms dissolution of the pre-formed multilayer upon enzymatic degradation as the method of release, and migration assays demonstrate a higher inhibition efficiency of TGF-beta in tailored biodegradable capsules compared to free LY administration. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox-controlled molecular permeability of composite-wall microcapsules

NASA Astrophysics Data System (ADS)

Ma, Yujie; Dong, Wen-Fei; Hempenius, Mark A.; Möhwald, Helmuth; Julius Vancso, G.

2006-09-01

Many smart materials in bioengineering, nanotechnology and medicine allow the storage and release of encapsulated drugs on demand at a specific location by an external stimulus. Owing to their versatility in material selection, polyelectrolyte multilayers are very promising systems in the development of microencapsulation technologies with permeation control governed by variations in the environmental conditions. Here, organometallic polyelectrolyte multilayer capsules, composed of polyanions and polycations of poly(ferrocenylsilane) (PFS), are introduced. Their preparation involved layer-by-layer self-assembly onto colloidal templates followed by core removal. PFS polyelectrolytes feature redox-active ferrocene units in the main chain. Incorporation of PFS into the capsule walls allowed us to explore the effects of a new stimulus, that is, changing the redox state, on capsule wall permeability. The permeability of these capsules could be sensitively tuned via chemical oxidation, resulting in a fast capsule expansion accompanied by a drastic permeability increase in response to a very small trigger. The substantial swelling could be suppressed by the application of an additional coating bearing common redox-inert species of poly(styrene sulfonate) (PSS-) and poly(allylamine hydrochloride) (PAH+) on the outer wall of the capsules. Hence, we obtained a unique capsule system with redox-controlled permeability and swellability with a high application potential in materials as well as in bioscience.

Coarse-grained simulations of polyelectrolyte complexes: MARTINI models for poly(styrene sulfonate) and poly(diallyldimethylammonium)

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

Vögele, Martin; Department of Theoretical Biophysics, Max Planck Institute of Biophysics, Frankfurt a. M.; Holm, Christian

2015-12-28

We present simulations of aqueous polyelectrolyte complexes with new MARTINI models for the charged polymers poly(styrene sulfonate) and poly(diallyldimethylammonium). Our coarse-grained polyelectrolyte models allow us to study large length and long time scales with regard to chemical details and thermodynamic properties. The results are compared to the outcomes of previous atomistic molecular dynamics simulations and verify that electrostatic properties are reproduced by our MARTINI coarse-grained approach with reasonable accuracy. Structural similarity between the atomistic and the coarse-grained results is indicated by a comparison between the pair radial distribution functions and the cumulative number of surrounding particles. Our coarse-grained models aremore » able to quantitatively reproduce previous findings like the correct charge compensation mechanism and a reduced dielectric constant of water. These results can be interpreted as the underlying reason for the stability of polyelectrolyte multilayers and complexes and validate the robustness of the proposed models.« less

Development of decellularized aortic valvular conduit coated by heparin-SDF-1α multilayer.

PubMed

Zhou, Jingxin; Ye, Xiaofeng; Wang, Zhe; Liu, Jun; Zhang, Busheng; Qiu, Jiapei; Sun, Yanjun; Li, Haiqing; Zhao, Qiang

2015-02-01

Decellularization can reduce the immune response to aortic valve allograft tissue, but the thrombogenicity and in vivo remolding of these grafts remain controversial. The aim of the present study was to modify the surface of decellularized valvular conduits with heparin-stromal cell-derived factor-1α (SDF-1α) polyelectrolyte multilayer film and to test the thrombogenicity and biocompatibility in vitro and recellularization in vivo. The donor aortic valvular conduits were decellularized with a combination of different detergents and were coated with heparin and SDF-1α alternately to form a polyelectrolyte multilayer. Platelet adhesion and lactate dehydrogenase assay were used to evaluate the antiplatelet property. The adhesion, growth, and migration of bone marrow stem cells (BMSCs) to the scaffolds were assessed. For in vivo studies, the grafts were anastomosed to the infrarenal aorta, without or with heparin and SDF-1α multilayer. Functional assessment was performed by Doppler echography and micro-computed tomography at 2-week and 4-week time points after implantation. Explanted grafts were examined histologically and by immunohistochemistry. In vitro studies demonstrated that the heparin-SDF-1α multilayer film improved hemocompatibility with respect to a substantial reduction of platelet adhesion. BMSCs also achieved better adhesion, proliferation, and migration on the modified graft. For in vivo studies, the grafts in both groups remained patent after 4 weeks, but it was demonstrated that the modified decellularized grafts had better self-endothelialization and recruitment of endothelial progenitor cells. These results indicate that heparin-SDF-1α multilayer film can be used to cover the decellularized aortic valvular graft to decrease platelet adhesion while precipitating regeneration of the decellularized aortic valve allograft in vivo. Copyright © 2015 The Society of Thoracic Surgeons. Published by Elsevier Inc. All rights reserved.

Dynamics of polyelectrolyte adsorption on surfaces: Applications in the detection of iron in water

NASA Astrophysics Data System (ADS)

Gammana, Madhira N.

Layer by layer (LbL) self assembly is a simple multilayer thin (nanometer scale) film fabricating technique. The mechanism of film growth remains a topic of much controversy. For example, several models have been proposed to explain the origin of linear and exponential film growth that are attributed to differences in the dynamic processes that occur at the molecular level during film formation. The problem is that there are no methods that directly measure the dynamics of polymer formation during LbL film formation. In this thesis, I describe the essential elements of an ATR-IR spectroscopic method that was developed to enable measurement of the dynamics of the mass adsorbed and polyelectrolyte conformation during the formation of PEM's. In particular, I followed the sequential adsorption of Sodium polyacrylate (NaPA) and Poly (diallyldimethylammonium) chloride (PDADMAC) from deionized (DI) water and as a function of ionic strength to show that polymer diffusion occurs between layers when adsorbed from DI water. In contrast, a denser layer occurs with no polymer interdiffusion for deposition from 0.02M ionic strength solutions of NaPA and PDADMAC. While the mass deposited increased with ionic strength, linear multilayer growth in films were observed in all cases. This finding disputes a common viewpoint that interdiffusion of polymer layers is a key feature of exponential film growth. The theme of polymer layer adsorption was used in the detection of Fe 3+ in seawater. A new approach, developed previously in Tripp's group, utilized "vertical amplification" in which a block copolymer assembled on membranes provided multiple anchoring points extending from the surface for attaching a siderophore, desferrioxamine B (DFB). The Fe3+ chelates with the siderophore producing a red color that can be quantified by visible spectroscopy. However, the rate of Fe3+ uptake was found to be dependent on flow rate. The origin of this flow rate dependence was identified by the work presented in this thesis. It was found that the amount and rate of Fe3+ uptake was dependent on the relative size of each block in the polymer and the degree of reaction of DFB with the adsorbed layer. In particular, higher amounts and higher rates were obtained when the density of DFB was lowered. This shows that the DFB was sterically hindered from forming a hexacoordinate complex with Fe3+ by the presence of neighboring DFB molecules. This is a key factor that needs to be considered in developing Fe3+ detection systems based on siderophores anchored to surfaces.

Layer-by-layer assembled multilayers and polymeric nanoparticles for drug delivery in tissue engineering applications

NASA Astrophysics Data System (ADS)

Mehrotra, Sumit

Tissues and organs in vivo are structured in three dimensional (3-D) ordered assemblies to maintain their metabolic functions. In the case of an injury, certain tissues lack the regenerative abilities without an external supportive environment. In order to regenerate the natural in vivo environment post-injury, there is a need to design three-dimensional (3-D) tissue engineered constructs of appropriate dimensions along with strategies that can deliver growth factors or drugs at a controlled rate from such constructs. This thesis focuses on the applications of hydrogen bonded (H-bonded) nanoscale layer-by-layer (LbL) assembled multilayers for time controlled drug delivery, fabrication of polymeric nanoparticles as drug delivery carriers, and engineering 3-D cellular constructs. Axonal regeneration in the central nervous system after spinal cord injury is often disorganized and random. To support linear axonal growth into spinal cord lesion sites, certain growth factors, such as brain-derived neurotrophic factor (BDNF), needs to be delivered at a controlled rate from an array of uniaxial channels patterned in a scaffold. In this study, we demonstrate for the first time that H-bonded LbL assembled degradable thin films prepared over agarose hydrogel, whereby the protein was loaded separately from the agarose fabrication, provided sustained release of protein under physiological conditions for more than four weeks. Further, patterned agarose scaffolds implanted at the site of a spinal cord injury forms a reactive cell layer of leptomeningeal fibroblasts in and around the scaffold. This limits the ability of axons to reinnervate the spinal cord. To address this challenge, we demonstrate the time controlled release of an anti-mitotic agent from agarose hydrdgel to control the growth of the reactive cell layer of fibroblasts. Challenges in tissue engineering can also be addressed using gene therapy approaches. Certain growth factors in the body are known to inhibit axonal growth and nerve repair. Therefore, another possible method to promote axonal growth is to silence the genes to inhibit the production of such growth factors. Small interfering RNA (siRNA) is a powerful therapeutic tool which knocks-down the gene function. Gene therapy approaches to knock-down a gene in mammalian cells, requires optimal selection of a transfection carrier for the siRNA. In this study, 25 kDa linear polyethylenimine (LPEI) was shown as a promising transfection carrier for siRNA delivery in-vitro. LPEI-siRNA complex nanoparticles were optimized for efficient siRNA delivery. Further, effort was made to fabricate LPEI particles of novel shapes, as particle shapes potentially have an impact on gene delivery efficiency. Finally, LbL assembled polyelectrolyte multilayers (PEMs) were engineered to tune surface properties to modulate the cell adhesion on a surface, to stamp and fabricate self-standing thin PEMs to create 3-D cellular constructs.

Sustained, Controlled and Stimuli-Responsive Drug Release Systems Based on Nanoporous Anodic Alumina with Layer-by-Layer Polyelectrolyte

NASA Astrophysics Data System (ADS)

Porta-i-Batalla, Maria; Eckstein, Chris; Xifré-Pérez, Elisabet; Formentín, Pilar; Ferré-Borrull, J.; Marsal, Lluis F.

2016-08-01

Controlled drug delivery systems are an encouraging solution to some drug disadvantages such as reduced solubility, deprived biodistribution, tissue damage, fast breakdown of the drug, cytotoxicity, or side effects. Self-ordered nanoporous anodic alumina is an auspicious material for drug delivery due to its biocompatibility, stability, and controllable pore geometry. Its use in drug delivery applications has been explored in several fields, including therapeutic devices for bone and dental tissue engineering, coronary stent implants, and carriers for transplanted cells. In this work, we have created and analyzed a stimuli-responsive drug delivery system based on layer-by-layer pH-responsive polyelectrolyte and nanoporous anodic alumina. The results demonstrate that it is possible to control the drug release using a polyelectrolyte multilayer coating that will act as a gate.

Spectroscopic properties of triangular silver nanoplates immobilized on polyelectrolyte multilayer-modified glass substrates

NASA Astrophysics Data System (ADS)

Rabor, Janice B.; Kawamura, Koki; Muko, Daiki; Kurawaki, Junichi; Niidome, Yasuro

2017-07-01

Fabrication of surface-immobilized silver nanostructures with reproducible plasmonic properties by dip-coating technique is difficult due to shape alteration. To address this challenge, we used a polyelectrolyte multilayer to promote immobilization of as-received triangular silver nanoplates (TSNP) on a glass substrate through electrostatic interaction. The substrate-immobilized TSNP were characterized by absorption spectrophotometry and scanning electron microscopy. The bandwidth and peak position of localized surface plasmon resonance (LSPR) bands can be tuned by simply varying the concentration of the colloidal solution and immersion time. TSNP immobilized from a higher concentration of colloidal solution with longer immersion time produced broadened LSPR bands in the near-IR region, while a lower concentration with shorter immersion time produced narrower bands in the visible region. The shape of the nanoplates was retained even at long immersion time. Analysis of peak positions and bandwidths also revealed the point at which the main species of the immobilization had been changed from isolates to aggregates.

Distance-Dependent Plasmon-Enhanced Fluorescence of Upconversion Nanoparticles using Polyelectrolyte Multilayers as Tunable Spacers

PubMed Central

Feng, Ai Ling; You, Min Li; Tian, Limei; Singamaneni, Srikanth; Liu, Ming; Duan, Zhenfeng; Lu, Tian Jian; Xu, Feng; Lin, Min

2015-01-01

Lanthanide-doped upconversion nanoparticles (UCNPs) have attracted widespread interests in bioapplications due to their unique optical properties by converting near infrared excitation to visible emission. However, relatively low quantum yield prompts a need for developing methods for fluorescence enhancement. Plasmon nanostructures are known to efficiently enhance fluorescence of the surrounding fluorophores by acting as nanoantennae to focus electric field into nano-volume. Here, we reported a novel plasmon-enhanced fluorescence system in which the distance between UCNPs and nanoantennae (gold nanorods, AuNRs) was precisely tuned by using layer-by-layer assembled polyelectrolyte multilayers as spacers. By modulating the aspect ratio of AuNRs, localized surface plasmon resonance (LSPR) wavelength at 980 nm was obtained, matching the native excitation of UCNPs resulting in maximum enhancement of 22.6-fold with 8 nm spacer thickness. These findings provide a unique platform for exploring hybrid nanostructures composed of UCNPs and plasmonic nanostructures in bioimaging applications. PMID:25586238

Highly magneto-responsive multilayer microcapsules for controlled release of insulin.

PubMed

Zheng, Chunli; Ding, Yafei; Liu, Xiaoqing; Wu, Yunkai; Ge, Liang

2014-11-20

In this study, magneto-responsive polyelectrolyte multilayer microcapsules were successfully prepared by the formation of shell with biocompatible iron oxide nanoparticles (Fe₃O₄ NPs) and polyallylamine hydrochloride (PAH) by layer-by-layer (LbL) self-assembly technique. The self-assembled microcapsules were characterized by SEM, TEM and zeta-potential analyzer. According to the pH sensitivity of the microcapsule membrane permeability, insulin was encapsulated, with the encapsulation efficiency of 92.08±5.57%. The in vitro release behavior in an external alternating magnetic field indicated that once the magnetic field was applied, the drug release was greatly accelerated. In addition, according to the observed pulse release upon cyclic on-off operations of magnetic field, it could be assumed that the magneto-responsive microcapsules had an excellent "switching on" effect, which might be attributed to the rearrangement of shell structure caused by magnetic nanoparticles twisting and polyelectrolyte chains shaking, hence the increase of microcapsule membrane permeability and the enhancement of insulin release. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of Protamine Functionalization on the Colloidal Stability of 1D and 2D Titanium Oxide Nanostructures.

PubMed

Rouster, Paul; Pavlovic, Marko; Horváth, Endre; Forró, László; Dey, Sandwip K; Szilagyi, Istvan

2017-09-26

The colloidal stability of titanium oxide nanosheets (TNS) and nanowires (TiONW) was studied in the presence of protamine (natural polyelectrolyte) in aqueous dispersions, where the nanostructures possessed negative net charge, and the protamine was positively charged. Regardless of their shape, similar charging and aggregation behaviors were observed for both TNS and TiONW. Electrophoretic experiments performed at different protamine loadings revealed that the adsorption of protamine led to charge neutralization and charge inversion depending on the polyelectrolyte dose applied. Light scattering measurements indicated unstable dispersions once the surface charge was close to zero or slow aggregation below and above the charge neutralization point with negatively or positively charged nanostructures, respectively. These stability regimes were confirmed by the electron microscopy images taken at different polyelectrolyte loadings. The protamine dose and salt-dependent colloidal stability confirmed the presence of DLVO-type interparticle forces, and no experimental evidence was found for additional interactions (e.g., patch-charge, hydrophobic, or steric forces), which are usually present in similar polyelectrolyte-particle systems. These findings indicate that the polyelectrolyte adsorbs on the TNS and TiONW surfaces in a flat and extended conformation giving rise to the absence of surface heterogeneities. Therefore, protamine is an excellent biocompatible candidate to form smooth surfaces, for instance in multilayers composed of polyelectrolytes and particles to be used in biomedical applications.

Human mesenchymal stem cell osteoblast differentiation, ECM deposition, and biomineralization on PAH/PAA polyelectrolyte multilayers.

PubMed

Pattabhi, Sudhakara Rao; Lehaf, Ali M; Schlenoff, Joseph B; Keller, Thomas C S

2015-05-01

Polyelectrolyte multilayer (PEMU) coatings built layer by layer with alternating pairs of polyelectrolytes can be tuned to improve cell interactions with surfaces and may be useful as biocompatible coatings to improve fixation between implants and tissues. Here, we show that human mesenchymal stromal cells (hMSCs) induced with bone differentiation medium (BDM) to become osteoblasts biomineralize crosslinked PEMUs built with the polycation poly(allylamine hydrochloride) (PAH) and the polyanion poly(acrylic acid) (PAA). Degrees of hMSC osteoblast differentiation and surface biomineralization on the smooth PAH-terminated PEMUs (PAH-PEMUs) and microstructured PAA-terminated PEMUs (PAA-PEMUs) reflect differences in cell-deposited extracellular matrix (ECM). BDM-induced hMSCs expressed higher levels of the early osteoblast differentiation marker alkaline phosphatase and collagen 1 (COL1) sooner on PAA-PEMUs than on PAH-PEMUs. Cells on both types of PEMUs proceeded to express the later stage osteoblast differentiation marker bone sialoprotein (BSP), but the BDM-induced cells organized a more amorphous Collagen I and denser BSP localization on PAA-PEMUs than on PAH-PEMUs. These ECM properties correlated with greater biomineralization on the PAA-PEMUs than on PAH-PEMUs. Together, these results confirm the suitability of PAH/PAA PEMUs as a substrate for hMSC osteogenesis and highlight the importance of substrate effects on ECM organization and BSP presentation on biomineralization. © 2014 Wiley Periodicals, Inc.

Elasticity, biodegradability and cell adhesive properties of chitosan/hyaluronan multilayer films

NASA Astrophysics Data System (ADS)

Schneider, Aurore; Richert, Ludovic; Francius, Gregory; Voegel, Jean-Claude; Picart, Catherine

2007-03-01

In the bioengineering field, a recent and promising approach to modifying biomaterial surfaces is the layer-by-layer (LbL) technique used to build thin polyelectrolyte multilayer films. In this work, we focused on polyelectrolyte multilayer films made of two polysaccharides, chitosan (CHI) and hyaluronan (HA), and on the control of their physico-chemical and cell adhesive properties by chemical cross-linking. CHI/HA films were cross-linked using a water soluble carbodiimide and observed by confocal laser scanning microscopy (CLSM) with a fluorescently labeled CHI. Film thicknesses were similar for native and cross-linked films. The film nanometer roughness was measured by atomic force microscopy and was found to be higher for cross-linked films. Cross-linking the films also leads to a drastic change in film stiffness. The elastic modulus of the films (Young's modulus) as measured by AFM nano-indentation was about tenfold increased for cross-linked films as compared to native ones. From a biological point of view, cross-liked films are more resistant to enzymatic degradation by hyaluronidase. Furthermore, the increase in film stiffness has a favorable effect on the adhesion and spreading of chondrosarcoma cells. Thus, the CHI/HA cross-linked films could be used for various applications due to their adhesive properties and to their mechanical properties (including stability in enzymatic media).

Comparative study of cytotoxicity of ferromagnetic nanoparticles and magnetitecontaining polyelectrolyte microcapsules

NASA Astrophysics Data System (ADS)

Minaeva, O. V.; Brodovskaya, E. P.; Pyataev, M. A.; Gerasimov, M. V.; Zharkov, M. N.; Yurlov, I. A.; Kulikov, O. A.; Kotlyarov, A. A.; Balykova, L. A.; Kokorev, A. V.; Zaborovskiy, A. V.; Pyataev, N. A.; Sukhorukov, G. B.

2017-01-01

The cytotoxicity of magnetite nanoparticles (MNP) stabilized with citrate acidand polyelectrolyte multilayer microcapsules containing these particles in the shell is analyzed. Microcapsules were prepared by co-precipitation of iron (II) and (III) chlorides. Polyelectrolyte microcapsules synthesized by the layer-by-layer method from biodegradable polymers polyarginine and dextran sulfate. Cytotoxicity of the synthesized objects was studied on the L929 cells culture and human leucocytes. It was also investigated the phagocytic activity of leukocytes for the MNP and magnetite containing polyelectrolyte microcapsules (MCPM). A set of tests (MTT assay, neutral red uptake assay, lactate dehydrogenase release assay) was used to study the cytotoxicity in vitro. All the tests have shown that the magnetic nanoparticles have a greater cytotoxicity in comparison with microcapsules containing an equivalent amount of magnetite. In contrast to the mouse fibroblast culture, human leukocytes were more resistant to the toxic effects of magnetite. At the concentrations used in our studies no significant reduction in the viability of leukocytes has been registered. Both MNP and MCPM undergo phagocytosis, however, the phagocytic activity of leukocytes for these particles was lower than for the standard objects (latex microparticles).

Formation and Properties of Multilayer Films Based on Polyethyleneimine and Bovine Serum Albumin

NASA Astrophysics Data System (ADS)

Kulikouskaya, V. I.; Lazouskaya, M. E.; Kraskouski, A. N.; Agabekov, V. E.

2018-01-01

(Polyethyleneimine/bovine serum albumin) n ((PEI/BSA) n) multilayer films ( n = 1-10) are produced via the layer-by-later deposition of polyelectrolytes. It is shown that thickness and morphology of the formed coatings can be controlled by varying the solution's ionic strength during alternating adsorption of the components. (PEI/BSA)10 multilayer systems that contain up to 0.6 mg of antiseptic miramistin per 1 cm2 of film were created. It is established that the kinetics of miramistin release from (PEI/BSA)10 films in phosphate buffers and physiological solutions obey the Korsmeyer-Peppas equation with a high degree of accuracy ( R 2 > 0.95).

Multilayer Films and Capsules of Sodium Carboxymethylcellulose and Polyhexamethylenguanidine Hydrochloride

NASA Astrophysics Data System (ADS)

Guzenko, Nataliia; Gabchak, Oleksandra; Pakhlov, Evgenij

The complexation of polyhexamethylenguanidine hydrochloride (PHMG) and sodium carboxymethylcellulose (CMC) was investigated for different conditions. Mixing of equiconcentrated aqueous solutions of the polyelectrolytes was found to result in the formation of an insoluble interpolyelectrolyte complex with an overweight of carboxymethylcellulose. A step-by-step formation of stable, irreversibly adsorbed multilayer film of the polymers was demonstrated using the quartz crystal microbalance method. Unusually thick polymer shells with a large number of loops and tails of the polyanion were formed by the method of layer-by-layer self-assembly of PHMG and CMC on spherical CaCO3 particles. Hollow multilayer capsules stable in neutral media were obtained by dissolution of the inorganic matrix in EDTA solution.

Modeling the growth processes of polyelectrolyte multilayers using a quartz crystal resonator.

PubMed

Salomäki, Mikko; Kankare, Jouko

2007-07-26

The layer-by-layer buildup of chitosan/hyaluronan (CH/HA) and poly(l-lysine)/hyaluronan (PLL/HA) multilayers was followed on a quartz crystal resonator (QCR) in different ionic strengths and at different temperatures. These polyelectrolytes were chosen to demonstrate the method whereby useful information is retrieved from acoustically thick polymer layers during their buildup. Surface acoustic impedance recorded in these measurements gives a single or double spiral when plotted in the complex plane. The shape of this spiral depends on the viscoelasticity of the layer material and regularity of the growth process. The polymer layer is assumed to consist of one or two zones. A mathematical model was devised to represent the separation of the layer to two zones with different viscoelastic properties. Viscoelastic quantities of the layer material and the mode and parameters of the growth process were acquired by fitting a spiral to the experimental data. In all the cases the growth process was mainly exponential as a function of deposition cycles, the growth exponent being between 0.250 and 0.275.

Self-Healing Textile: Enzyme Encapsulated Layer-by-Layer Structural Proteins.

PubMed

Gaddes, David; Jung, Huihun; Pena-Francesch, Abdon; Dion, Genevieve; Tadigadapa, Srinivas; Dressick, Walter J; Demirel, Melik C

2016-08-10

Self-healing materials, which enable an autonomous repair response to damage, are highly desirable for the long-term reliability of woven or nonwoven textiles. Polyelectrolyte layer-by-layer (LbL) films are of considerable interest as self-healing coatings due to the mobility of the components comprising the film. In this work mechanically stable self-healing films were fabricated through construction of a polyelectrolyte LbL film containing squid ring teeth (SRT) proteins. SRTs are structural proteins with unique self-healing properties and high elastic modulus in both dry and wet conditions (>2 GPa) due to their semicrystalline architecture. We demonstrate LbL construction of multilayers containing native and recombinant SRT proteins capable of self-healing defects. Additionally, we show these films are capable of utilizing functional biomolecules by incorporating an enzyme into the SRT multilayer. Urease was chosen as a model enzyme of interest to test its activity via fluorescence assay. Successful construction of the SRT films demonstrates the use of mechanically stable self-healing coatings, which can incorporate biomolecules for more complex protective functionalities for advanced functional fabrics.

Assessment of a polyelectrolyte multilayer film coating loaded with BMP-2 on titanium and PEEK implants in the rabbit femoral condyle

PubMed Central

Guillot, R.; Pignot-Paintrand, I.; Lavaud, J.; Decambron, A.; Bourgeois, E.; Josserand, V.; Logeart-Avramoglou, D.; Viguier, E.; Picart, C.

2016-01-01

The aim of this study was to evaluate the osseointegration of titanium implants (Ti-6Al-4V, noted here TA6V) and poly(etheretherketone) PEEK implants induced by a BMP-2-delivering surface coating made of polyelectrolyte multilayer films. The in vitro bioactivity of the polyelectrolyte film-coated implants was assessed using the alkaline phosphatase assay. BMP-2-coated TA6V and PEEK implants with a total dose of 9.3 µg of BMP-2 were inserted into the femoral condyles of New Zealand white rabbits and compared to uncoated implants. Rabbits were sacrificed 4 and 8 weeks after implantation. Histomorphometric analyses on TA6V and PEEK implants and microcomputed tomography on PEEK implants revealed that the bone-to-implant contact and bone area around the implants were significantly lower for the BMP-2-coated implants than for the bare implants. This was confirmed by scanning electron microscopy imaging. This difference was more pronounced at 4 weeks in comparison to the 8-week time point. However, bone growth inside the hexagonal upper hollow cavity of the screws was higher in the case of the BMP-2 coated implants. Overall, this study shows that a high dose of BMP-2 leads to localized and temporary bone impairment, and that the dose of BMP-2 delivered at the surface of an implant needs to be carefully optimized. PMID:26965394

Structure of Protein Layers in Polyelectrolyte Matrices Studied by Neutron Reflectivity

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

Kozlovskaya, Veronika; Ankner, John Francis; O'Neill, Hugh Michael

2011-01-01

Polyelectrolyte multilayer films obtained by localized incorporation of Green Fluorescent Protein (GFP) within electrostatically assembled matrices of poly(styrene sulfonate)/poly(allylamine hydrochloride) (PSS/PAH) via spin-assisted layer-by-layer growth were discovered to be highly structured, with closely packed monomolecular layers of the protein within the bio-hybrid films. The structure of the films was evaluated in both vertical and lateral directions with neutron reflectometry, using deuterated GFP as a marker for neutron scattering contrast. Importantly, the GFP preserves its structural stability upon assembly as confirmed by circular dichroism (CD) and in situ attenuated total reflection Fourier Transform Infrared spectroscopy (ATR-FTIR). Atomic force microscopy was complimentedmore » with X-ray reflectometry to characterize the external roughness of the biohybrid films. Remarkably, films assembled with a single GFP layer confined at various distances from the substrate exhibit a strong localization of the GFP layer without intermixing into the LbL matrix. However, partial intermixing of the GFP layers with polymeric material is evidenced in multiple-GFP layer films with alternating protein-rich and protein-deficient regions. We hypothesize that the polymer-protein exchange observed in the multiple-GFP layer films suggests the existence of a critical protein concentration which can be accommodated by the multilayer matrix. Our results yield new insights into the mechanism of GFP interaction with a polyelectrolyte matrix and open opportunities for fabrication of bio-hybrid films with well-organized structure and controllable function, a crucial requirement for advanced sensing applications.« less

Ionically Paired Layer-by-Layer Hydrogels: Water and Polyelectrolyte Uptake Controlled by Deposition Time

DOE PAGES

Selin, Victor; Ankner, John Francis; Sukhishvili, Svetlana

2018-01-11

Despite intense recent interest in weakly bound nonlinear (“exponential”) multilayers, the underlying structure-property relationships of these films are still poorly understood. This study explores the effect of time used for deposition of individual layers of nonlinearly growing layer-by-layer (LbL) films composed of poly(methacrylic acid) (PMAA) and quaternized poly-2-(dimethylamino)ethyl methacrylate (QPC) on film internal structure, swelling, and stability in salt solution, as well as the rate of penetration of invading polyelectrolyte chains. Thicknesses of dry and swollen films were measured by spectroscopic ellipsometry, film internal structure—by neutron reflectometry (NR), and degree of PMAA ionization—by Fourier-transform infrared spectroscopy (FTIR). The results suggestmore » that longer deposition times resulted in thicker films with higher degrees of swelling (up to swelling ratio as high as 4 compared to dry film thickness) and stronger film intermixing. The stronger intermixed films were more swollen in water, exhibited lower stability in salt solutions, and supported a faster penetration rate of invading polyelectrolyte chains. These results can be useful in designing polyelectrolyte nanoassemblies for biomedical applications, such as drug delivery coatings for medical implants or tissue engineering matrices.« less

Ionically Paired Layer-by-Layer Hydrogels: Water and Polyelectrolyte Uptake Controlled by Deposition Time

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

Selin, Victor; Ankner, John Francis; Sukhishvili, Svetlana

Despite intense recent interest in weakly bound nonlinear (“exponential”) multilayers, the underlying structure-property relationships of these films are still poorly understood. This study explores the effect of time used for deposition of individual layers of nonlinearly growing layer-by-layer (LbL) films composed of poly(methacrylic acid) (PMAA) and quaternized poly-2-(dimethylamino)ethyl methacrylate (QPC) on film internal structure, swelling, and stability in salt solution, as well as the rate of penetration of invading polyelectrolyte chains. Thicknesses of dry and swollen films were measured by spectroscopic ellipsometry, film internal structure—by neutron reflectometry (NR), and degree of PMAA ionization—by Fourier-transform infrared spectroscopy (FTIR). The results suggestmore » that longer deposition times resulted in thicker films with higher degrees of swelling (up to swelling ratio as high as 4 compared to dry film thickness) and stronger film intermixing. The stronger intermixed films were more swollen in water, exhibited lower stability in salt solutions, and supported a faster penetration rate of invading polyelectrolyte chains. These results can be useful in designing polyelectrolyte nanoassemblies for biomedical applications, such as drug delivery coatings for medical implants or tissue engineering matrices.« less

Palladium-bacterial cellulose membranes for fuel cells.

PubMed

Evans, Barbara R; O'Neill, Hugh M; Malyvanh, Valerie P; Lee, Ida; Woodward, Jonathan

2003-07-01

Bacterial cellulose is a versatile renewable biomaterial that can be used as a hydrophilic matrix for the incorporation of metals into thin, flexible, thermally stable membranes. In contrast to plant cellulose, we found it catalyzed the deposition of metals within its structure to generate a finely divided homogeneous catalyst layer. Experimental data suggested that bacterial cellulose possessed reducing groups capable of initiating the precipitation of palladium, gold, and silver from aqueous solution. Since the bacterial cellulose contained water equivalent to at least 200 times the dry weight of the cellulose, it was dried to a thin membranous structure suitable for the construction of membrane electrode assemblies (MEAs). Results of our study with palladium-cellulose showed that it was capable of catalyzing the generation of hydrogen when incubated with sodium dithionite and generated an electrical current from hydrogen in an MEA containing native cellulose as the polyelectrolyte membrane (PEM). Advantages of using native and metallized bacterial cellulose membranes in an MEA over other PEMs such as Nafion 117 include its higher thermal stability to 130 degrees C and lower gas crossover.

Robust Guar Gum/Cellulose Nanofibrils Multilayer Films with Good Barrier Properties.

PubMed

Dai, Lei; Long, Zhu; Chen, Jie; An, Xingye; Cheng, Dong; Khan, Avik; Ni, Yonghao

2017-02-15

The pursuit of sustainable functional materials requires development of materials based on renewable resources and efficient fabrication methods. Hereby, we fabricated all-polysaccharides multilayer films using cationic guar gum (CGG) and anionic cellulose nanofibrils (i.e., TEMPO-oxidized cellulose nanofibrils, TOCNs) through a layer-by-layer casting method. This technique is based on alternate depositions of oppositely charged water-based CGG and TOCNs onto laminated films. The resultant polyelectrolyte multilayer films were transparent, ductile, and strong. More importantly, the self-standing films exhibited excellent gas (water vapor and oxygen) and oil barrier performances. Another outstanding feature of these resultant films was their resistance to various organic solvents including methanol, acetone, N,N-dimethylacetamide (DMAc) and tetrahydrofuran (THF). The proposed film fabrication process is environmentally benign, cost-effective, and easy to scale-up. The developed CGG/TOCNs multilayer films can be used as a renewable material for industrial applications such as packaging.

Biocolloids with ordered urease multilayer shells as enzymatic reactors.

PubMed

Lvov, Y; Caruso, F

2001-09-01

The preparation of biocolloids with organized enzyme-containing multilayer shells for exploitation as colloidal enzymatic nanoreactors is described. Urease multilayers were assembled onto submicrometer-sized polystyrene spheres by the sequential adsorption of urease and polyelectrolyte, in a predetermined order, utilizing electrostatic interactions for layer growth. The catalytic activity of the biocolloids increased proportionally with the number of urease layers deposited on the particles, demonstrating that biocolloid particles with tailored enzymatic activities can be produced. It was further found that precoating the latex spheres with nanoparticles (40-nm silica or 12-nm magnetite) enhanced both the stability (with respect to adsorption) and enzymatic activity of the urease multilayers. The presence of the magnetite nanoparticle coating also provided a magnetic function that allowed the biocolloids to be easily and rapidly separated with a permanent magnet. The fabrication of such colloids opens new avenues for the application of bioparticles and represents a promising route for the creation of complex catalytic particles.

Synthesis of size-controlled acid-resistant hybrid calcium carbonate microparticles as templates for fabricating "micelles-enhanced" polyelectrolyte capsules by the LBL technique.

PubMed

Li, Xiaodong; Hu, Qiaoling; Yue, Linhai; Shen, Jiacong

2006-07-24

Size-controlled, low-dispersed calcium carbonate microparticles were synthesized in the presence of the amphiphilic block copolymer polystyrene-b-poly(acrylic acid) (PS-b-PAA) by modulating the concentration of block copolymer in the reactive system. This type of hybrid microparticles have acid-resistant properties. By investigating the aggregation behaviors of PS-b-PAA micelles by transmission electron microscopy (TEM), the mechanism of hybrid calcium carbonate formation illustrated that the block copolymer served not only as "pseudonuclei" for the growth of calcium carbonate nanocrystals, but also forms the supramicelle congeries, a spherical framework, as templates for calcium carbonate nanocrystal growth into hybrid CaCO(3) particles. Moreover, this pilot study shows that the hybrid microparticle is a novel candidate as a template for fabricating multilayer polyelectrolyte capsules, in which the block copolymer is retained within the capsule interior after core removal under soft conditions. This not only facilitates the encapsulation of special materials, but also provides "micelles-enhanced" polyelectrolyte capsules.

Imatinib-loaded polyelectrolyte microcapsules for sustained targeting of BCR-ABL+ leukemia stem cells.

PubMed

Palamà, Ilaria E; Leporatti, Stefano; de Luca, Emanuela; Di Renzo, Nicola; Maffia, Michele; Gambacorti-Passerini, Carlo; Rinaldi, Ross; Gigli, Giuseppe; Cingolani, Roberto; Coluccia, Addolorata M L

2010-04-01

The lack of sensitivity of chronic myeloid leukemia (CML) stem cells to imatinib mesylate (IM) commonly leads to drug dose escalation or early disease relapses when therapy is stopped. Here, we report that packaging of IM into a biodegradable carrier based on polyelectrolyte microcapsules increases drug retention and antitumor activity in CML stem cells, also improving the ex vivo purging of malignant progenitors from patient autografts. Microparticles/capsules were obtained by layer-by-layer (LbL) self-assembly of oppositely charged polyelectrolyte multilayers on removable calcium carbonate (CaCO(3)) templates and loaded with or without IM. A leukemic cell line (KU812) and CD34(+) cells freshly isolated from healthy donors or CML patients were tested. Polyelectrolyte microcapsules (PMCs) with an average diameter of 3 microm, fluorescently labelled multilayers sensitive to the action of intracellular proteases and 95-99% encapsulation efficiency of IM, were prepared. Cell uptake efficiency of such biodegradable carriers was quantified in KU812, leukemic and normal CD34(+) stem cells (range: 70-85%), and empty PMCs did not impact cell viability. IM-loaded PMCs selectively targeted CML cells, by promoting apoptosis at doses that exert only cytostatic effects by IM alone. More importantly, residual CML cells from patient leukapheresis products were reduced or eliminated more efficiently by using IM-loaded PMCs compared with freely soluble IM, with a purging efficiency of several logs. No adverse effects on normal CD34(+) stem-cell survival and their clonogenic potential was noticed in long-term cultures of hematopoietic progenitors in vitro. This pilot study provides the proof-of-principle for the clinical application of biodegradable IM-loaded PMC as feasible, safe and effective ex vivo purging agents to target CML stem cells, in order to improve transplant outcome of resistant/relapsed patients or reduce IM dose escalation.

Chemosensors and biosensors based on polyelectrolyte microcapsules containing fluorescent dyes and enzymes.

PubMed

Kazakova, Lyubov I; Shabarchina, Lyudmila I; Anastasova, Salzitsa; Pavlov, Anton M; Vadgama, Pankaj; Skirtach, Andre G; Sukhorukov, Gleb B

2013-02-01

The concept of enzyme-assisted substrate sensing based on use of fluorescent markers to detect the products of enzymatic reaction has been investigated by fabrication of micron-scale polyelectrolyte capsules containing enzymes and dyes in one entity. Microcapsules approximately 5 μm in size entrap glucose oxidase or lactate oxidase, with peroxidase, together with the corresponding markers Tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) dichloride (Ru(dpp)) complex and dihydrorhodamine 123 (DHR123), which are sensitive to oxygen and hydrogen peroxide, respectively. These capsules are produced by co-precipitation of calcium carbonate particles with the enzyme followed by layer-by-layer assembly of polyelectrolytes over the surface of the particles and incorporation of the dye in the capsule interior or in the multilayer shell. After dissolution of the calcium carbonate the enzymes and dyes remain in the multilayer capsules. In this study we produced enzyme-containing microcapsules sensitive to glucose and lactate. Calibration curves based on fluorescence intensity of Ru(dpp) and DHR123 were linearly dependent on substrate concentration, enabling reliable sensing in the millimolar range. The main advantages of using these capsules with optical recording is the possibility of building single capsule-based sensors. The response from individual capsules was observed by confocal microscopy as increasing fluorescence intensity of the capsule on addition of lactate at millimolar concentrations. Because internalization of the micron-sized multi-component capsules was feasible, they could be further optimized for in-situ intracellular sensing and metabolite monitoring on the basis of fluorescence reporting.

Robust lanthanide emitters in polyelectrolyte thin films for photonic applications

NASA Astrophysics Data System (ADS)

Greenspon, Andrew S.; Marceaux, Brandt L.; Hu, Evelyn L.

2018-02-01

Trivalent lanthanides provide stable emission sources at wavelengths spanning the ultraviolet through the near infrared with uses in telecommunications, lighting, and biological sensing and imaging. We describe a method for incorporating an organometallic lanthanide complex within polyelectrolyte multilayers, producing uniform, optically active thin films on a variety of substrates. These films demonstrate excellent emission with narrow linewidths, stable over a period of months, even when bound to metal substrates. Utilizing different lanthanides such as europium and terbium, we are able to easily tune the resulting wavelength of emission of the thin film. These results demonstrate the suitability of this platform as a thin film emitter source for a variety of photonic applications such as waveguides, optical cavities, and sensors.

Thermal treatment of galactose-branched polyelectrolyte microcapsules to improve drug delivery with reserved targetability.

PubMed

Zhang, Fu; Wu, Qi; Liu, Li-Jun; Chen, Zhi-Chun; Lin, Xian-Fu

2008-06-05

A novel multilayered drug delivery system by LbL assembly of galactosylated polyelectrolyte, which is possible to have the potential in hepatic targeting by the presence of galactose residues at the microcapsule's surface, is designed. Thermal treatment was performed on the capsules and a dramatic thermal shrinkage up to 60% decrease of capsule diameter above 50 degrees C was observed. This thermal behavior was then used to manipulate drug loading capacity and release rate. Heating after drug loading could seal the capsule shell, enhancing the loading capacity and reducing the release rate significantly. Excellent affinity between galactose-binding lectin and heated galactose-containing microcapsules were observed, indicating a stable targeting potential even after high temperature elevating up to 90 degrees C.

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

PubMed

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

2004-10-01

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

Silica Encapsulation of Ferrimagnetic Zinc Ferrite Nanocubes Enabled by Layer-by-layer Polyelectrolyte Deposition

PubMed Central

Park, Jooneon; Porter, Marc D.; Granger, Michael C.

2016-01-01

Stable suspensions of magnetic nanoparticles (MNPs) with large magnetic moment, m, per particle have tremendous utility in a wide range of biological applications. However, due to the strong magnetic coupling interactions often present in these systems, it is challenging to stabilize individual, high moment, ferro- and ferrimagnetic nanoparticles. A novel approach to encapsulate large, i.e., >100 nm, ferrimagnetic zinc ferrite nanocubes (ZFNCs) with silica after an intermediary layer-by-layer polyelectrolyte deposition step is described in this paper. The seed ZFNCs are uniform in shape and size and have high saturation mass magnetic moment (σs ~100 emu/g, m~4×10−13 emu/particle at 150 Oe). For the MNP system described within, successful silica encapsulation and creation of discrete ZFNCs were realized only after depositing polyelectrolyte multilayers composed of alternating polyallylamine and polystyrene sulfonate. Without the intermediary polyelectrolyte layers, magnetic dipole-dipole interactions led to the formation of linearly chained ZFNCs embedded in a silica matrix. Characterization of particle samples was performed by electron microscopy, energy-dispersive X-ray spectroscopy, infrared spectroscopy, powder X-ray diffraction, dynamic light scattering (hydrodynamic size and ζ-potential), and vibrating sample magnetometry. The results of these characterizations, which were performed after each of the synthetic steps, and synthetic details are presented. PMID:25756216

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.

[Liposomes: support for the formation of stable capsules made of reticulated polyelectrolytes or silicum].

PubMed

Germain, M; Paquereau, L; Winterhalter, M; Hochepied, J-F; Fournier, D

2007-03-01

Uses of enzymes for therapeutic purpose or for biosensing require a well-controlled nanoenvironnement to avoid degradation by proteolytic agents, pH variations or dilution effects. A solution is encapsulation under undenaturating conditions into a nanometer sized and stable capsule. The nanometer scall decreases recognition by the reticulo-endothelial system recognition and subsequent immune reaction. Liposomes are the method of choice since they allow protein encapsulation under mild conditions. However they lack in stability. In contrast, other type of capsules exhibit strong stability but with conditions required for formation that are incompatible with enzyme integrity. Here we combine different capsule formation techniques and use liposomes as templates for further stabilization. Here we demonstrate two types of multicomposite capsules. The first type is to coat the liposome surface with polyelectrolytes followed by secondary covalent crosslinking of the polyelectrolytes multilayer. In the second type of capsules we used silica to build an inorganic shell around liposome. Both techniques allow the formation of detergent stable nanocapsules which exhibits properties protective against acetylcholinesterase protein degradation, an enzyme of much interest for pesticide detection.

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

PubMed Central

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

2015-01-01

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

Nitric oxide assisted C60 secondary ion mass spectrometry for molecular depth profiling of polyelectrolyte multilayers.

PubMed

Zappalà, G; Motta, V; Tuccitto, N; Vitale, S; Torrisi, A; Licciardello, A

2015-12-15

Secondary ion mass spectrometry (SIMS) with polyatomic primary ions provides a successful tool for molecular depth profiling of polymer systems, relevant in many technological applications. Widespread C60 sources, however, cause in some polymers extensive damage with loss of molecular information along depth. We study a method, based on the use of a radical scavenger, for inhibiting ion-beam-induced reactions causing sample damage. Layered polystyrene sulfonate and polyacrylic acid based polyelectrolyte films, behaving differently towards C60 beam-induced damage, were selected and prepared as model systems. They were depth profiled by means of time-of-flight (TOF)-SIMS in dual beam mode, using fullerene ions for sputtering. Nitric oxide was introduced into the analysis chamber as a radical scavenger. The effect of sample cooling combined with NO-dosing on the quality of depth profiles was explored. NO-dosing during C60-SIMS depth profiling of >1 micrometer-thick multilayered polyelectrolytes allows detection, along depth, of characteristic fragments from systems otherwise damaged by C60 bombardment, and increases sputtering yield by more than one order of magnitude. By contrast, NO has little influence on those layers that are well profiled with C60 alone. Such leveling effect, more pronounced at low temperature, leads to a dramatic improvement of profile quality, with a clear definition of interfaces. NO-dosing provides a tool for extending the applicability, in SIMS depth profiling, of the widely spread fullerene ion sources. In view of the acceptable erosion rates on inorganics, obtainable with C60, the method could be of relevance also in connection with the 3D-imaging of hybrid polymer/inorganic systems. Copyright © 2015 John Wiley & Sons, Ltd.

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.

Suitable combination of noble/ferromagnetic metal multilayers for enhanced magneto-plasmonic biosensing.

PubMed

Regatos, David; Sepúlveda, Borja; Fariña, David; Carrascosa, Laura G; Lechuga, Laura M

2011-04-25

We present a theoretical and experimental study on the biosensing sensitivity of Au/Co/Au multilayers as transducers of the magneto-optic surface-plasmon-resonance (MOSPR) sensor. We demonstrate that the sensing response of these magneto-plasmonic (MP) transducers is a trade-off between the optical absorption and the magneto-optical activity, observing that the MP multilayer with larger MO effect does not provide the best sensing response. We show that it is possible to design highly-sensitive MP transducers able to largely surpass the limit of detection of the conventional surface-plasmon-resonance (SPR) sensor. This was proved comparing the biosensing performance of both sensors for the label-free detection of short DNA chains hybridization. For this purpose, we used and tested a novel label-free biofunctionalization protocol based on polyelectrolytes, which increases the resistance of MP transducers in aqueous environments.

Polymer multilayer tattooing for enhanced DNA vaccination

NASA Astrophysics Data System (ADS)

Demuth, Peter C.; Min, Younjin; Huang, Bonnie; Kramer, Joshua A.; Miller, Andrew D.; Barouch, Dan H.; Hammond, Paula T.; Irvine, Darrell J.

2013-04-01

DNA vaccines have many potential benefits but have failed to generate robust immune responses in humans. Recently, methods such as in vivo electroporation have demonstrated improved performance, but an optimal strategy for safe, reproducible, and pain-free DNA vaccination remains elusive. Here we report an approach for rapid implantation of vaccine-loaded polymer films carrying DNA, immune-stimulatory RNA, and biodegradable polycations into the immune-cell-rich epidermis, using microneedles coated with releasable polyelectrolyte multilayers. Films transferred into the skin following brief microneedle application promoted local transfection and controlled the persistence of DNA and adjuvants in the skin from days to weeks, with kinetics determined by the film composition. These ‘multilayer tattoo’ DNA vaccines induced immune responses against a model HIV antigen comparable to electroporation in mice, enhanced memory T-cell generation, and elicited 140-fold higher gene expression in non-human primate skin than intradermal DNA injection, indicating the potential of this strategy for enhancing DNA vaccination.

Generic delivery of payload of nanoparticles intracellularly via hybrid polymer capsules for bioimaging applications.

PubMed

Sami, Haider; Maparu, Auhin K; Kumar, Ashok; Sivakumar, Sri

2012-01-01

Towards the goal of development of a generic nanomaterial delivery system and delivery of the 'as prepared' nanoparticles without 'further surface modification' in a generic way, we have fabricated a hybrid polymer capsule as a delivery vehicle in which nanoparticles are loaded within their cavity. To this end, a generic approach to prepare nanomaterials-loaded polyelectrolyte multilayered (PEM) capsules has been reported, where polystyrene sulfonate (PSS)/polyallylamine hydrochloride (PAH) polymer capsules were employed as nano/microreactors to synthesize variety of nanomaterials (metal nanoparticles; lanthanide doped inorganic nanoparticles; gadolinium based nanoparticles, cadmium based nanoparticles; different shapes of nanoparticles; co-loading of two types of nanoparticles) in their hollow cavity. These nanoparticles-loaded capsules were employed to demonstrate generic delivery of payload of nanoparticles intracellularly (HeLa cells), without the need of individual nanoparticle surface modification. Validation of intracellular internalization of nanoparticles-loaded capsules by HeLa cells was ascertained by confocal laser scanning microscopy. The green emission from Tb(3+) was observed after internalization of LaF(3):Tb(3+)(5%) nanoparticles-loaded capsules by HeLa cells, which suggests that nanoparticles in hybrid capsules retain their functionality within the cells. In vitro cytotoxicity studies of these nanoparticles-loaded capsules showed less/no cytotoxicity in comparison to blank capsules or untreated cells, thus offering a way of evading direct contact of nanoparticles with cells because of the presence of biocompatible polymeric shell of capsules. The proposed hybrid delivery system can be potentially developed to avoid a series of biological barriers and deliver multiple cargoes (both simultaneous and individual delivery) without the need of individual cargo design/modification.

Generic Delivery of Payload of Nanoparticles Intracellularly via Hybrid Polymer Capsules for Bioimaging Applications

PubMed Central

Sami, Haider; Maparu, Auhin K.; Kumar, Ashok; Sivakumar, Sri

2012-01-01

Towards the goal of development of a generic nanomaterial delivery system and delivery of the ‘as prepared’ nanoparticles without ‘further surface modification’ in a generic way, we have fabricated a hybrid polymer capsule as a delivery vehicle in which nanoparticles are loaded within their cavity. To this end, a generic approach to prepare nanomaterials-loaded polyelectrolyte multilayered (PEM) capsules has been reported, where polystyrene sulfonate (PSS)/polyallylamine hydrochloride (PAH) polymer capsules were employed as nano/microreactors to synthesize variety of nanomaterials (metal nanoparticles; lanthanide doped inorganic nanoparticles; gadolinium based nanoparticles, cadmium based nanoparticles; different shapes of nanoparticles; co-loading of two types of nanoparticles) in their hollow cavity. These nanoparticles-loaded capsules were employed to demonstrate generic delivery of payload of nanoparticles intracellularly (HeLa cells), without the need of individual nanoparticle surface modification. Validation of intracellular internalization of nanoparticles-loaded capsules by HeLa cells was ascertained by confocal laser scanning microscopy. The green emission from Tb3+ was observed after internalization of LaF3:Tb3+(5%) nanoparticles-loaded capsules by HeLa cells, which suggests that nanoparticles in hybrid capsules retain their functionality within the cells. In vitro cytotoxicity studies of these nanoparticles-loaded capsules showed less/no cytotoxicity in comparison to blank capsules or untreated cells, thus offering a way of evading direct contact of nanoparticles with cells because of the presence of biocompatible polymeric shell of capsules. The proposed hybrid delivery system can be potentially developed to avoid a series of biological barriers and deliver multiple cargoes (both simultaneous and individual delivery) without the need of individual cargo design/modification. PMID:22649489

A parametric model order reduction technique for poroelastic finite element models.

PubMed

Lappano, Ettore; Polanz, Markus; Desmet, Wim; Mundo, Domenico

2017-10-01

This research presents a parametric model order reduction approach for vibro-acoustic problems in the frequency domain of systems containing poroelastic materials (PEM). The method is applied to the Finite Element (FE) discretization of the weak u-p integral formulation based on the Biot-Allard theory and makes use of reduced basis (RB) methods typically employed for parametric problems. The parametric reduction is obtained rewriting the Biot-Allard FE equations for poroelastic materials using an affine representation of the frequency (therefore allowing for RB methods) and projecting the frequency-dependent PEM system on a global reduced order basis generated with the proper orthogonal decomposition instead of standard modal approaches. This has proven to be better suited to describe the nonlinear frequency dependence and the strong coupling introduced by damping. The methodology presented is tested on two three-dimensional systems: in the first experiment, the surface impedance of a PEM layer sample is calculated and compared with results of the literature; in the second, the reduced order model of a multilayer system coupled to an air cavity is assessed and the results are compared to those of the reference FE model.

Organic Electronic Devices Using Crosslinked Polyelectrolyte Multilayers as an Ultra-Thin Dielectric Material

DTIC Science & Technology

2006-09-01

energy band diagram illustrating the allowed energies for valence and conducting electrons. The dashes within the band gap (Eg) represent localized ...allowed energies for valence and conducting electrons. The dashes within the band gap (Eg) represent localized electron energy states, or traps, that...been observed with the formation of alternating bond lengths along the backbone.43 The localization of the π-electrons while forming the shorter double

Electrochemical monitoring of chlorhexidine digluconate effect on polyelectrolyte immobilized bacteria and kinetic cell adhesion.

PubMed

Borghol, N; Mora, L; Sakly, N; Lejeune, P; Jouenne, T; Jaffrézic-Renault, N; Othmane, A

2011-01-10

The electrochemical impedance spectroscopy (EIS) technique has been used as a sensitive method to explore the effect of antibacterial molecules on immobilized bacteria and biofilm formation. In this work, we describe the electrochemical spectroscopy as a powerful method to monitor the effect of chlorhexidine digluconate (CHX-Dg) on polyelectrolyte immobilized Escherichia coli K12 MG1655 and the kinetics of cell adhesion on gold electrodes. The experimental impedance data were modeled with a Zview program to find the best equivalent electrical circuit and analyse its parameter's properties. Polyelectrolyte multilayer formation on the electrode surface and bacteria immobilization greatly increased the electron-transfer resistance (R(et)) and reduced the constant phase element (CPE(dl)). The effect of CHX-Dg was studied in a 0.5 x 10⁻⁴ mmol l⁻¹ to 0.5 mmol l⁻¹ range. The relation between the evolution of R(et) and CHX-Dg concentration was found to be negatively correlated. When CHX-Dg was added, the electrochemical monitoring of the bacterial kinetic adhesion showed that the electrode's capacity (C(P)) variation remained stable, demonstrating that the addition of CHX-Dg in the broth inhibited bacterial adhesion. © 2010 Elsevier B.V. All rights reserved.

Co-encapsulation of enzyme and sensitive dye as a tool for fabrication of microcapsule based sensor for urea measuring.

PubMed

Kazakova, Lyubov I; Shabarchina, Lyudmila I; Sukhorukov, Gleb B

2011-06-21

Enzyme based micron sized sensing system with optical readout was fabricated by co-encapsulation of urease and dextran couple with pH sensitive dye SNARF-1 into polyelectrolyte multilayer capsules. Co-precipitation of calcium carbonate, urease and dextran followed up by multilayer film coating and Ca-extracting by EDTA resulted in the formation of 3.5-4 micron capsules, what enable the calibrated fluorescence response to urea in concentration range from 10(-6) to 10(-1) M. The presence of urea can be monitored on a single capsule level as illustrated by confocal fluorescent microscopy. Variations in urease:dye ratio in capsules, applicability and limits of use of that type multi-component microencapsulated sensors are discussed.

Surfactant-stable and pH-sensitive liposomes coated with N-succinyl-chitosan and chitooligosaccharide for delivery of quercetin.

PubMed

Seong, Joon Seob; Yun, Mid Eum; Park, Soo Nam

2018-02-01

Layer-by-layer (LbL) self-assembly of multilayered liposomes is used to improve the stability of conventional liposomes. In this study, the LbL technology was used to prepare novel multilayered liposomes from chitooligosaccharide and N-succinyl-chitosan. We propose that this preparation can be used as a transdermal drug delivery system (TDDS) to enhance stability against surfactants and control drug release. Particle size increased with the number of layers in the multilayer and the zeta potential varied between positive and negative values with alternate deposition of polyelectrolytes. Finally, approximately 300-400nm-thick four-layered liposomes were prepared. These liposomes were more stable against surfactants and showed a relatively high release of quercetin at pH 5.5 than the uncoated liposomes as assessed via in vitro drug release and skin permeation studies. In summary, the multilayered liposomes showed potential for use as a surfactant-stable TDDS that effectively enhanced the permeation of quercetin, a poorly soluble drug, into the skin. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

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

2018-02-28

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

Characterization of casein and poly-L-arginine multilayer films.

PubMed

Szyk-Warszyńska, Lilianna; Kilan, Katarzyna; Socha, Robert P

2014-06-01

Thin films containing casein appear to be a promising material for coatings used in the medical area to promote biomineralization. α- and β-casein and poly-L-arginine multilayer films were formed by the layer-by layer technique and their thickness and mass were analyzed by ellipsometry and quartz crystal microbalance with dissipation monitoring (QCM-D). (PLArg/casein) films deposited in 0.15M NaCl exhibit fast (exponential-like) growth of the film thickness with the number of layers. The resulting films were c.a. 10 times thicker than obtained for poly-L-arginine and natural polyanions. We investigated the effect of the type of casein used for the film formation, finding that films with α-casein were slightly thicker than ones with β-casein. The effect of polyethylene imine anchoring layer on the thickness and mass of adsorbed films was similar as for linear polyelectrolyte pairs. Thickness of "wet" films was c.a. two times larger than measured after drying that suggests their large hydration. The analysis of the mass of films during their post-treatment with the solutions of various ionic strength and pH provided the information concerning films stability. Films remain stable in the neutral and weakly basic conditions that includes HEPES buffer, which is widely used in cell culture and biomedical experiments. At the conditions of high ionic strength films swell but their swelling is reversible. Films containing caseins as polyanion appear to be more elastic and the same time more viscous than one formed with polyelectrolyte pairs. XPS elemental analysis confirmed binding of calcium ions by the casein embedded in the multilayers. Copyright © 2014 Elsevier Inc. All rights reserved.

Multicolor Layer-by-Layer films using weak polyelectrolyte assisted synthesis of silver nanoparticles

NASA Astrophysics Data System (ADS)

Rivero, Pedro Jose; Goicoechea, Javier; Urrutia, Aitor; Matias, Ignacio Raul; Arregui, Francisco Javier

2013-10-01

In the present study, we show that silver nanoparticles (AgNPs) with different shape, aggregation state and color (violet, green, orange) have been successfully incorporated into polyelectrolyte multilayer thin films using the layer-by-layer (LbL) assembly. In order to obtain colored thin films based on AgNPs is necessary to maintain the aggregation state of the nanoparticles, a non-trivial aspect in which this work is focused on. The use of Poly(acrylic acid, sodium salt) (PAA) as a protective agent of the AgNPs is the key element to preserve the aggregation state and makes possible the presence of similar aggregates (shape and size) within the LbLcolored films. This approach based on electrostatic interactions of the polymeric chains and the immobilization of AgNPs with different shape and size into the thin films opens up a new interesting perspective to fabricate multicolornanocomposites based on AgNPs.

UV and NIR-Responsive Layer-by-Layer Films Containing 6-Bromo-7-hydroxycoumarin Photolabile Groups

PubMed Central

2017-01-01

This paper describes polyelectrolyte multilayer films prepared by the layer-by-layer (LbL) technique capable of undergoing dissolution upon exposure to either ultraviolet or near-infrared light. Film dissolution is driven by photochemical deprotection of a random methacrylic copolymer with two types of side chains: (i) 6-bromo-7-hydroxycoumarinyl esters, photocleavable groups that are known to have substantial two-photon photolysis cross sections, and (ii) cationic residues from the commercially available monomer N,N-dimethylaminoethyl methacrylate (DMAEMA). In addition, the dependence of stability of both unirradiated and irradiated films on pH provides experimental evidence for the necessity of disrupting both ion-pairing and hydrophobic interactions between polyelectrolytes to realize film dissolution. This work therefore provides both new fundamental insight regarding photolabile LbL films and expands their applied capabilities to nonlinear photochemical processes. PMID:28967754

Multicolor Layer-by-Layer films using weak polyelectrolyte assisted synthesis of silver nanoparticles

PubMed Central

2013-01-01

In the present study, we show that silver nanoparticles (AgNPs) with different shape, aggregation state and color (violet, green, orange) have been successfully incorporated into polyelectrolyte multilayer thin films using the layer-by-layer (LbL) assembly. In order to obtain colored thin films based on AgNPs is necessary to maintain the aggregation state of the nanoparticles, a non-trivial aspect in which this work is focused on. The use of Poly(acrylic acid, sodium salt) (PAA) as a protective agent of the AgNPs is the key element to preserve the aggregation state and makes possible the presence of similar aggregates (shape and size) within the LbLcolored films. This approach based on electrostatic interactions of the polymeric chains and the immobilization of AgNPs with different shape and size into the thin films opens up a new interesting perspective to fabricate multicolornanocomposites based on AgNPs. PMID:24148227

Photoinduced charge-transfer materials for nonlinear optical applications

DOEpatents

McBranch, Duncan W.

2006-10-24

A method using polyelectrolyte self-assembly for preparing multi-layered organic molecular materials having individual layers which exhibit ultrafast electron and/or energy transfer in a controlled direction occurring over the entire structure. Using a high molecular weight, water-soluble, anionic form of poly-phenylene vinylene, self-assembled films can be formed which show high photoluminescence quantum efficiency (QE). The highest emission QE is achieved using poly(propylene-imine) (PPI) dendrimers as cationic binders. Self-quenching of the luminescence is observed as the solid polymer film thickness is increased and can be reversed by inserting additional spacer layers of transparent polyelectrolytes between each active conjugated layer, such that the QE grows with thickness. A red shift of the luminescence is also observed as additional PPV layers are added. This effect persists as self-quenching is eliminated. Charge transfer superlattices can be formed by additionally incorporating C.sub.60 acceptor layers.

Encapsulation of basic fibroblast growth factor by polyelectrolyte multilayer microcapsules and its controlled release for enhancing cell proliferation.

PubMed

She, Zhen; Wang, Chunxia; Li, Jun; Sukhorukov, Gleb B; Antipina, Maria N

2012-07-09

Basic fibroblast growth factor (FGF2) is an important protein for cellular activity and highly vulnerable to environmental conditions. FGF2 protected by heparin and bovine serum albumin was loaded into the microcapsules by a coprecipitation-based layer-by-layer encapsulation method. Low cytotoxic and biodegradable polyelectrolytes dextran sulfate and poly-L-arginine were used for capsule shell assembly. The shell thickness-dependent encapsulation efficiency was measured by enzyme-linked immunosorbent assay. A maximum encapsulation efficiency of 42% could be achieved by microcapsules with a shell thickness of 14 layers. The effects of microcapsule concentration and shell thickness on cytotoxicity, FGF2 release kinetics, and L929 cell proliferation were evaluated in vitro. The advantage of using microcapsules as the carrier for FGF2 controlled release for enhancing L929 cell proliferation was analyzed.

Halloysite clay nanotubes for resveratrol delivery to cancer cells.

PubMed

Vergaro, Viviana; Lvov, Yuri M; Leporatti, Stefano

2012-09-01

Halloysite is natural aluminosilicate clay with hollow tubular structure which allows loading with low soluble drugs using their saturated solutions in organic solvents. Resveratrol, a polyphenol known for having antioxidant and antineoplastic properties, is loaded inside these clay nanotubes lumens. Release time of 48 h is demonstrated. Spectroscopic and ζ-potential measurements are used to study the drug loading/release and for monitoring the nanotube layer-by-layer (LbL) coating with polyelectrolytes for further release control. Resveratrol-loaded clay nanotubes are added to breast cell cultures for toxicity tests. Halloysite functionalization with LbL polyelectrolyte multilayers remarkably decrease nanotube self-toxicity. MTT measurements performed with a neoplastic cell lines model system (MCF-7) as function of the resveratrol-loaded nanotubes concentration and incubation time indicate that drug-loaded halloysite strongly increase of cytotoxicity leading to cell apoptosis. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved Photon-Emission-Microscope System

NASA Technical Reports Server (NTRS)

Vu, Duc

2006-01-01

An improved photon-emission-microscope (PEM) instrumentation system has been developed for use in diagnosing failure conditions in semiconductor devices, including complex integrated circuits. This system is designed primarily to image areas that emit photons, at wavelengths from 400 to 1,100 nm, associated with device failures caused by leakage of electric current through SiO2 and other dielectric materials used in multilayer semiconductor structures. In addition, the system is sensitive enough to image areas that emit photons during normal operation.

Polymer multilayer tattooing for enhanced DNA vaccination

PubMed Central

DeMuth, Peter C.; Min, Younjin; Huang, Bonnie; Kramer, Joshua A.; Miller, Andrew D.; Barouch, Dan H.; Hammond, Paula T.; Irvine, Darrell J.

2014-01-01

DNA vaccines have many potential benefits but have failed to generate robust immune responses in humans. Recently, methods such as in vivo electroporation have demonstrated improved performance, but an optimal strategy for safe, reproducible, and pain-free DNA vaccination remains elusive. Here we report an approach for rapid implantation of vaccine-loaded polymer films carrying DNA, immune-stimulatory RNA, and biodegradable polycations into the immune-cell-rich epidermis, using microneedles coated with releasable polyelectrolyte multilayers. Films transferred into the skin following brief microneedle application promoted local transfection and controlled the persistence of DNA and adjuvants in the skin from days to weeks, with kinetics determined by the film composition. These “multilayer tattoo” DNA vaccines induced immune responses against a model HIV antigen comparable to electroporation in mice, enhanced memory T-cell generation, and elicited 140-fold higher gene expression in non-human primate skin than intradermal DNA injection, indicating the potential of this strategy for enhancing DNA vaccination. PMID:23353628

Distribution of PEG-coated hollow polyelectrolyte microcapsules after introduction into the circulatory system and muscles of zebrafish

PubMed Central

2018-01-01

ABSTRACT The use of polyelectrolyte multilayer microcapsules as carriers for fluorescent molecular probes is a prospective technique for monitoring the physiological characteristics of animal vasculature and interstitial environment in vivo. Polyelectrolyte microcapsules have many features that favor their use as implantable carriers of optical sensors, but little information is available on their interactions with complex living tissues, distribution or residence time following different routes of administration in the body of vertebrates. Using the common fish model, the zebrafish Danio rerio, we studied in vivo the distribution of non-biodegradable microcapsules covered with polyethylene glycol (PEG) over time in the adults and evaluated potential side effects of their delivery into the fish bloodstream and muscles. Fluorescent microcapsules administered into the bloodstream and interstitially (in concentrations that were sufficient for visualization and spectral signal recording) both showed negligible acute toxicity to the fishes during three weeks of observation. The distribution pattern of microcapsules delivered into the bloodstream was stable for at least one week, with microcapsules prevalent in capillaries-rich organs. However, after intramuscular injection, the phagocytosis of the microcapsules by immune cells was manifested, indicating considerable immunogenicity of the microcapsules despite PEG coverage. The long-term negative effects of chronic inflammation were also investigated in fish muscles by histological analysis. PMID:29305467

Layer-by-layer polyelectrolyte-polyester hybrid microcapsules for encapsulation and delivery of hydrophobic drugs.

PubMed

Luo, Rongcong; Venkatraman, Subbu S; Neu, Björn

2013-07-08

A two-step process is developed to form layer-by-layer (LbL) polyelectrolyte microcapsules, which are able to encapsulate and deliver hydrophobic drugs. Spherical porous calcium carbonate (CaCO3) microparticles were used as templates and coated with a poly(lactic acid-co-glycolic acid) (PLGA) layer containing hydrophobic compounds via an in situ precipitation gelling process. PLGA layers that precipitated from N-methyl-2-pyrrolidone (NMP) had a lower loading and smoother surface than those precipitated from acetone. The difference may be due to different viscosities and solvent exchange dynamics. In the second step, the successful coating of multilayer polyelectrolytes poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS) onto the PLGA coated CaCO3 microparticles was confirmed with AFM and ζ-potential studies. The release of a model hydrophobic drug, ibuprofen, from these hybrid microcapsules with different numbers of PAH/PSS layers was investigated. It was found that the release of ibuprofen decreases with increasing layer numbers demonstrating the possibility to control the release of ibuprofen with these novel hybrid microcapsules. Besides loading of hydrophobic drugs, the interior of these microcapsules can also be loaded with hydrophilic compounds and functional nanoparticles as demonstrated by loading with Fe3O4 nanoparticles, forming magnetically responsive dual drug releasing carriers.

Nanostructured 3D constructs based on chitosan and chondroitin sulphate multilayers for cartilage tissue engineering.

PubMed

Silva, Joana M; Georgi, Nicole; Costa, Rui; Sher, Praveen; Reis, Rui L; Van Blitterswijk, Clemens A; Karperien, Marcel; Mano, João F

2013-01-01

Nanostructured three-dimensional constructs combining layer-by-layer technology (LbL) and template leaching were processed and evaluated as possible support structures for cartilage tissue engineering. Multilayered constructs were formed by depositing the polyelectrolytes chitosan (CHT) and chondroitin sulphate (CS) on either bidimensional glass surfaces or 3D packet of paraffin spheres. 2D CHT/CS multi-layered constructs proved to support the attachment and proliferation of bovine chondrocytes (BCH). The technology was transposed to 3D level and CHT/CS multi-layered hierarchical scaffolds were retrieved after paraffin leaching. The obtained nanostructured 3D constructs had a high porosity and water uptake capacity of about 300%. Dynamical mechanical analysis (DMA) showed the viscoelastic nature of the scaffolds. Cellular tests were performed with the culture of BCH and multipotent bone marrow derived stromal cells (hMSCs) up to 21 days in chondrogenic differentiation media. Together with scanning electronic microscopy analysis, viability tests and DNA quantification, our results clearly showed that cells attached, proliferated and were metabolically active over the entire scaffold. Cartilaginous extracellular matrix (ECM) formation was further assessed and results showed that GAG secretion occurred indicating the maintenance of the chondrogenic phenotype and the chondrogenic differentiation of hMSCs.

Building a road map for tailoring multilayer polyelectrolyte films

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

Ankner, John Francis; Bardoel, Agatha A; Sukishvili, Svetlana

2012-01-01

Researchers are moving a step closer to a definite road map for building layer-by-layer (LbL) assembled polyelectrolyte films, with the assistance of the Liquids Reflectometer at Oak Ridge National Laboratory's Spallation Neutron Source, in Oak Ridge, Tennessee. Scientists using the liquids reflectometer have successfully taken snapshots in close to real time of these multilayered structures for different applications when they modify the structure and function parameters. Polyelecrolytes are polymers that carry charge in aqueous solutions. They contain chemical groups that dissociate in water, making such polymers charged. Most polyelectrolytes are water soluble. They are important components in foods, soaps, shampoos,more » and cosmetics products. They show promise for such environmental work as oil recovery and water treatment. Polyelectrolytes are compelling because researchers can chemically modify how they interact with water for multiple applications. When two types of polyelectrolytes of opposite charge are assembled at a surface in a sequential way using the LbL assembly technique, 'the result is the forming of surface films, useful for coatings, biomedical implants and devices, controlling adhesion of biological molecules, and controlling delivery of therapeutic molecules from surfaces,' said Svetlana Sukhishvili of the Stevens Institute of Technology in New Jersey, the lead chemist on the collaboration. 'Medical doctors often prefer to deliver multiple therapeutic compounds from the coatings in a time-resolved manner,' Sukhishvili said. 'To assist them, material scientists need to learn how to build coatings in which polymer layering will not be compromised when exposed to normal physiological conditions.' 'Being able to control these properties, understanding how what you do to the materials affects their properties, this allows you to apply them to situations where interacting with an environment is very helpful, whether in a biological context or any other kind of water soluble context,' said John Ankner, lead instrument scientist for the Liquids Reflectometer. Ankner said that when several parameters are systematically altered, that allows researchers to map out the whole range of structures in the polymer. 'This work really sets a road map for how to get started with synthesizing polyelectrolyte materials for specific applications. Then, one can say, ok, this methylated material, the one that is 30% charged, is going to be what we want to use for a particular application.' The ORNL collaboration with the Stevens Institute has been conducting a series of experiments at the SNS to study layered film stratification in these polymers. Researchers stitch the polyelectrolyte chains in the LbL films together through what is called ionic pairing and arrange them within fuzzy, ultrathin layers that lie parallel to a solid surface substrate. Exposure of these films to aqueous solutions that contain salt (i.e., conditions that imitate real life) can compromise this film layering, as the salt ions act to weaken the ionic pairing that binds such layers together. So salt solutions are of key interest in studying how to make such layers for use in human applications. In the first research, Ankner, Sukhishvili and her student Li Xu looked at the effects of the layering of two types of LbL films of changing the charge density with a salt solution, and of blocking access to a charged site by nearby groups. The films were composed of positively charged variants of PDMA, a methyl polymer, and PDEA, an ethyl polymer. The other component of both systems is the ion exchanger polystyrene sulfonate (PSS) which features a fixed negative charge. First, a silicon substrate was dipped into solutions of PDMA and PDEA in dilute sodium chloride for a fixed time. Depending on the deposition time and the concentration of the solution, a nanometer-thick monolayer of the polymer adsorbs to the silicon surface. The film buildup is then continued by depositing a layer of PSS, and the cycle is repeated. The PDMA (methyl)/PSS and PDEA (ethyl)/PSS films were then annealed in varying concentrations of aqueous salt solutions. The chemists wanted to know if in these multi-layer cake-like assemblies, the structure can be systematically altered by varying the salt concentration, time in solution, and ultimately other environmental parameters, such as temperature or pH. Neutron reflectivity of the layered films exhibits the quality of the layering, in particular the concentration of the layers and how intermixed they are with adjacent layers. In this research, neutron reflectivity data from films built from 10%, 40%, and 100% charged PDMA or PDEA polyelectrolytes and 100% charged PSS were quantitatively compared to predicted, layered arrangements until the models produced reflectivity patterns matching those of the data.« less

The Effectiveness of the Controlled Release of Gentamicin from Polyelectrolyte Multilayers in the Treatment of Staphylococcus aureus Infection in a Rabbit Bone Model

PubMed Central

Moskowitz, Joshua; Blaisse, Michael; Samuel, Raymond; Hsu, Hu-Ping; Harris, Mitchel; Martin, Scott; Lee, Jean; Spector, Myron; Hammond, Paula

2010-01-01

While the infection rate of orthopedic implants is low, the required treatment, which can involve six weeks of antibiotic therapy and two additional surgical operations, is life threatening and expensive, and thus motivates the development of a one-stage re-implantation procedure. Polyelectrolyte multilayers incorporating gentamicin were fabricated using the layer-by-layer deposition process for use as a device coating to deal with an existing bone infection in a direct implant exchange operation. The films eluted about 70% of their payload in vitro during the first three days and subsequently continued to release drug for more than four additional weeks, reaching a total average release of over 550 μg/cm2. The coatings were demonstrated to be bactericidal against Staphylococcus aureus, and degradation products were generally nontoxic towards MC3T3-E1 murine preosteoblasts. Film-coated titanium implants were compared to uncoated implants in an in vivo S. aureus bone infection model. After a direct exchange procedure, the antimicrobial-coated devices yielded bone homogenates with a significantly lower degree of infection than uncoated devices at both day four (p < 0.004) and day seven (p < 0.03). This study has demonstrated that a self-assembled ultrathin film coating is capable of effectively treating an experimental bone infection in vivo and lays the foundation for development of a multi-therapeutic film for optimized, synergistic treatment of pain, infection, and osteomyelitis. PMID:20488534

Functionalized gold nanoparticles: a detailed in vivo multimodal microscopic brain distribution study

NASA Astrophysics Data System (ADS)

Sousa, Fernanda; Mandal, Subhra; Garrovo, Chiara; Astolfo, Alberto; Bonifacio, Alois; Latawiec, Diane; Menk, Ralf Hendrik; Arfelli, Fulvia; Huewel, Sabine; Legname, Giuseppe; Galla, Hans-Joachim; Krol, Silke

2010-12-01

In the present study, the in vivo distribution of polyelectrolyte multilayer coated gold nanoparticles is shown, starting from the living animal down to cellular level. The coating was designed with functional moieties to serve as a potential nano drug for prion disease. With near infrared time-domain imaging we followed the biodistribution in mice up to 7 days after intravenous injection of the nanoparticles. The peak concentration in the head of mice was detected between 19 and 24 h. The precise particle distribution in the brain was studied ex vivo by X-ray microtomography, confocal laser and fluorescence microscopy. We found that the particles mainly accumulate in the hippocampus, thalamus, hypothalamus, and the cerebral cortex.In the present study, the in vivo distribution of polyelectrolyte multilayer coated gold nanoparticles is shown, starting from the living animal down to cellular level. The coating was designed with functional moieties to serve as a potential nano drug for prion disease. With near infrared time-domain imaging we followed the biodistribution in mice up to 7 days after intravenous injection of the nanoparticles. The peak concentration in the head of mice was detected between 19 and 24 h. The precise particle distribution in the brain was studied ex vivo by X-ray microtomography, confocal laser and fluorescence microscopy. We found that the particles mainly accumulate in the hippocampus, thalamus, hypothalamus, and the cerebral cortex. Electronic supplementary information (ESI) available: Fig. S1-S6. See DOI: 10.1039/c0nr00345j

Polyelectrolyte multilayer capsules as vehicles with tunable permeability.

PubMed

Antipov, Alexei A; Sukhorukov, Gleb B

2004-11-29

This review is devoted to a novel type of polymer micro- and nanocapsules. The shell of the capsule is fabricated by alternate adsorption of oppositely charged polyelectrolytes (PEs) onto the surface of colloidal particles. Cores of different nature (organic or inorganic) with size varied from 0.1 to 10 mum can be used for templating such PE capsules. The shell thickness can be tuned in nanometer range by assembling of defined number of PE layers. The permeability of capsules depends on the pH, ionic strength, solvent, polymer composition, and shell thickness; it can be controlled and varied over wide range of substances regarding their molecular weight and charge. Including functional polymers into capsule wall, such as weak PEs or thermosensitive polymers, makes the capsule permeability sensitive to correspondent external stimuli. Permeability of the capsules is of essential interest in diverse areas related to exploitation of systems with controlled and sustained release properties. The envisaged applications of such capsules/vesicles cover biotechnology, medicine, catalysis, food industry, etc.

Molecular lego for the assembly of biosensing layers.

PubMed

Mano, N; Kuhn, A

2005-03-31

We propose a procedure to assemble monolayers of redox mediator, coenzyme, enzyme and stabilizing polyelectrolyte on an electrode surface using essentially electrostatic and complexing interactions. In a first step a monolayer of redox mediator, substituted nitrofluorenones, is adsorbed. In a second step, a layer of calcium cations is immobilized at the interface. It establishes a bridge between the redox mediator and the subsequently adsorbed coenzyme NAD(+). In the next step we use the intrinsic affinity of the NAD(+) monolayer for dehydrogenases to build up a multilayer composed of mediator/Ca(2+)/NAD(+)/dehydrogenase. The so obtained modified electrode can be used as a biosensor. Quartz crystal microbalance measurements allowed us to better understand the different parameters responsible for the adsorption. A more detailed investigation of the system made it possible to finally stabilize the assembly sufficiently by the adsorption of a polyelectrolyte layer in order to perform rotating disk electrode measurements with the whole supramolecular architecture on the electrode surface.

Fabrication of dopamine-modified hyaluronic acid/chitosan multilayers on titanium alloy by layer-by-layer self-assembly for promoting osteoblast growth

NASA Astrophysics Data System (ADS)

Zhang, Xinming; Li, Zhaoyang; Yuan, Xubo; Cui, Zhenduo; Yang, Xianjin

2013-11-01

The bare inert surface of titanium (Ti) alloy typically causes early failures in implants. Layer-by-layer self-assembly is one of the simple methods for fabricating bioactive multilayer coatings on titanium implants. In this study, a dopamine-modified hyaluronic acid/chitosan (DHA/CHI) bioactive multilayer was built on the surface of Ti-24Nb-2Zr (TNZ) alloy. Zeta potential oscillated between -2 and 17 mV for DHA- and CHI-ending layers during the assembly process, respectively. The DHA/CHI multilayer considerably decreased the contact angle and dramatically improved the wettability of TNZ alloy. Atomic force microscopy results revealed a rough surface on the original TNZ alloy, while the surface became smoother and more homogeneous after the deposition of approximately 5 bilayers (TNZ/(DHA/CHI)5). X-ray photoelectron spectroscopy analysis indicated that the TNZ/(DHA/CHI)5 sample was completely covered by polyelectrolytes. Pre-osteoblast MC3T3-E1 cells were cultured on the original TNZ alloy and TNZ/(DHA/CHI)5 to evaluate the effects of DHA/CHI multilayer on osteoblast proliferation in vitro. The proliferation of osteoblasts on TNZ/(DHA/CHI)5 was significantly higher than that on the original TNZ alloy. The results of this study indicate that the proposed technique improves the biocompatibility of TNZ alloy and can serve as a potential modification method in orthopedic applications.

Super Oxygen and Improved Water Vapor Barrier of Polypropylene Film with Polyelectrolyte Multilayer Nanocoatings.

PubMed

Song, Yixuan; Tzeng, Ping; Grunlan, Jaime C

2016-06-01

Biaxially oriented polypropylene (BOPP) is widely used in packaging. Although its orientation increases mechanical strength and clarity, BOPP suffers from a high oxygen transmission rate (OTR). Multilayer thin films are deposited from water using layer-by-layer (LbL) assembly. Polyethylenimine (PEI) is combined with either poly(acrylic acid) (PAA) or vermiculite (VMT) clay to impart high oxygen barrier. A 30-bilayer PEI/VMT nanocoating (226 nm thick) improves the OTR of 17.8 μm thick BOPP by more than 30X, rivaling most inorganic coatings. PEI/PAA multilayers achieve comparable barrier with only 12 bilayers due to greater thickness, but these films exhibit increased oxygen permeability at high humidity. The PEI/VMT coatings actually exhibit improved oxygen barrier at high humidity (and also improve moisture barrier by more than 40%). This high barrier BOPP meets the criteria for sensitive food and some electronics packaging applications. Additionally, this water-based coating technology is cost effective and provides an opportunity to produce high barrier polypropylene film on an industrial scale. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of nanocapsule carriers from multilayer-coated vaterite calcium carbonate nanoparticles.

PubMed

Biswas, Aniket; Nagaraja, Ashvin T; McShane, Michael J

2014-12-10

Nanosized luminescent sensors were prepared as reagents for optical sensing and imaging of oxygen using ratiometric emission properties of a two-dye system. Polymeric capsules were fabricated utilizing poly(vinylsulfonic acid) (PVSA)-stabilized vaterite CaCO3 nanoparticles (CCNPs) as sacrificial templates. The buffer and polymeric surfactant requirements of the layer-by-layer (LbL) process were evaluated toward deposition of multilayer coatings and, ultimately, formation of hollow capsules using these interesting materials. CCNPs were found to be more stable in alkaline NaHCO3 buffer after repeated cycles of washing under sonication and resuspension. An intermediate PVSA concentration was required to maximize the loading of oxygen-sensitive porphyrin and oxygen-insensitive fluorescent nanoparticles in the CCNPs while maintaining minimal nanoparticle size. The CCNPs were then coated with polyelectrolyte multilayers and subsequent removal of the CaCO3 core yielded nanocapsules containing dye and fluorescent nanoparticles. The resulting nanocapsules with encapsulated luminophores functioned effectively as oxygen sensors with a quenching response of 89.28 ± 2.59%, and O2 (S = 1/2) = 20.91 μM of dissolved oxygen.

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

Petrova, V. A.; Orekhov, A. S.; Chernyakov, D. D.

A method for preparing multilayer film composites based on chitosan has been developed by the example of polymer pairs: chitosan–hyaluronic acid, chitosan–alginic acid, and chitosan–carrageenan. The structure of the composite films is characterized by X-ray diffractometry and scanning electron microscopy. It is shown that the deposition of a solution of hyaluronic acid, alginic acid, or carrageenan on a chitosan gel film leads to the formation of a polyelectrolyte complex layer at the interface, which is accompanied by the ordering of chitosan chains in the surface region; the microstructure of this layer depends on the nature of contacting polymer pairs.

Ionochromic 4,4 '-azobispyridinium salt-incorporated polymer: synthesis and optical properties

NASA Astrophysics Data System (ADS)

Lee, Taek Seung; Ahn, Heungki; Lee, Jin Kyun; Park, Won Ho

2003-01-01

Azobispyridinium-bearing polyelectrolyte linked with flexible alkyl chain was synthesized and characterized. The polymer showed absorption changes upon addition of hydroxide anion with an isobestic point in UV-visible spectrum. It is presumed that conformational change of the azo group in the main chain is responsible for the point. Transduction of physical information (hydroxide concentration) into an optical signal from azo group was related to the ionochromic effect. Electrostatic self-assembled multilayer of the polymer with appropriate polyanion was carried out via layer-by-layer deposition.

The Structures of Fibronectin Adsorbed on Polyelectrolyte Thin Films

NASA Astrophysics Data System (ADS)

Shin, Kwanwoo; Satija, Sushil; Fang, Xiao-Hua; Li, Bin-Quan; Nadine, Pernodet; Miriam, Rafailovich; Sokolov, Jonathan; Arach, Goldar; Roser, Steve

2002-03-01

We have shown that it is possible to form a fibrilar network of fibronectin on a polyelectrolyte polymer film whose dimensions are similar to those reported on the extra cellular matrix. The fibronectin network was observed to form only when the charge density of the polymer was in excess of the natural charge density of the cell wall. Furthermore, the self-organized fibronectin layer was much thicker than the polymer film, indicating that long ranged interaction may play a key role in the assembly process. It is therefore important to understand the structure of the polymer layer/protein interface. Here we report on a neutron reflectivity study where we explore the structure of the polyelectrolyte layer, in this case sulfonated polystyrene (PSS_x.), with varying degree of sulfonation (x<30%), as a function of sulfur content and counter ion concentration. These results are then correlated with systemic study of the adsorption and the multilayer formation of fibronectin as a function of incubation time for various sulfonation levels of PSS_x. Furthermore, the surface charge on the substrates can be strongly influenced by the presence of salt ions, it is important to understand changes due to electrostatic interactions occurring in the various salt conditions. Complementary X-ray reflection was used to determine the salt density profile associating with the internal ionic polymer matrix. This work was funded in part of the NSF-MRSEC program.

Characterisation of capacitive field-effect sensors with a nanocrystalline-diamond film as transducer material for multi-parameter sensing.

PubMed

Abouzar, M H; Poghossian, A; Razavi, A; Williams, O A; Bijnens, N; Wagner, P; Schöning, M J

2009-01-01

The feasibility of a capacitive field-effect EDIS (electrolyte-diamond-insulator-semiconductor) platform for multi-parameter sensing is demonstrated by realising EDIS sensors with an O-terminated nanocrystalline-diamond (NCD) film as transducer material for the detection of pH and penicillin concentration as well as for the label-free electrical monitoring of adsorption and binding of charged macromolecules, like polyelectrolytes. The NCD films were grown on p-Si-SiO(2) substrates by microwave plasma-enhanced chemical vapour deposition. To obtain O-terminated surfaces, the NCD films were treated in an oxidising medium. The NCD-based field-effect sensors have been characterised by means of constant-capacitance method. The average pH sensitivity of the O-terminated NCD film was 40 mV/pH. A low detection limit of 5 microM and a high penicillin G sensitivity of 65-70 mV/decade has been obtained for an EDIS penicillin biosensor with the adsorptively immobilised enzyme penicillinase. Alternating potential changes, having tendency to decrease with increasing the number of adsorbed polyelectrolyte layers, have been observed after the layer-by-layer deposition of polyelectrolyte multilayers, using positively charged PAH (poly (allylamine hydrochloride)) and a negatively charged PSS (poly (sodium 4-styrene sulfonate)) as a model system. The response mechanism of the developed EDIS sensors is discussed.

Delivery of Plasmid DNA to Vascular Tissue in vivo using Catheter Balloons Coated with Polyelectrolyte Multilayers

PubMed Central

Saurer, Eric M.; Yamanouchi, Dai; Liu, Bo; Lynn, David M.

2010-01-01

We report an approach for the localized delivery of plasmid DNA to vascular tissue from the surfaces of inflatable embolectomy catheter balloons. Using a layer-by-layer approach, ultrathin multilayered polyelectrolyte films were fabricated on embolectomy catheter balloons by alternately adsorbing layers of a hydrolytically degradable poly(β-amino ester) and plasmid DNA. Fluorescence microscopy revealed that the films coated the surfaces of the balloons uniformly. Coated balloons that were incubated in phosphate-buffered saline at 37 °C released ~25 μg DNA/cm2 over 24 hours. Analysis of the DNA by gel electrophoresis showed that the DNA was released in open-circular (‘nicked’) and supercoiled conformations, and in vitro cell transfection assays confirmed that the released DNA was transcriptionally active. Arterial injury was induced in the internal carotid arteries of Sprague-Dawley rats using uncoated balloons, followed by treatment with film-coated balloons for 20 minutes. X-gal, immunohistochemical, and immunofluorescence staining of sectioned arteries indicated high levels of β-galactosidase or enhanced green fluorescent protein (EGFP) expression in arteries treated with film-coated balloons. β-galactosidase and EGFP expression were observed throughout the medial layers of arterial tissue, and around approximately two-thirds of the circumference of the treated arteries. The layer-by-layer approach reported here provides a general platform for the balloon-mediated delivery of DNA to vascular tissue. Our results suggest the potential of this approach to deliver therapeutically relevant DNA to prevent complications such as intimal hyperplasia that arise after vascular interventions. PMID:20933275

Adaptive growth factor delivery from a polyelectrolyte coating promotes synergistic bone tissue repair and reconstruction

PubMed Central

Shah, Nisarg J.; Hyder, Md. Nasim; Quadir, Mohiuddin A.; Dorval Courchesne, Noémie-Manuelle; Seeherman, Howard J.; Nevins, Myron; Spector, Myron; Hammond, Paula T.

2014-01-01

Traumatic wounds and congenital defects that require large-scale bone tissue repair have few successful clinical therapies, particularly for craniomaxillofacial defects. Although bioactive materials have demonstrated alternative approaches to tissue repair, an optimized materials system for reproducible, safe, and targeted repair remains elusive. We hypothesized that controlled, rapid bone formation in large, critical-size defects could be induced by simultaneously delivering multiple biological growth factors to the site of the wound. Here, we report an approach for bone repair using a polyelectrolye multilayer coating carrying as little as 200 ng of bone morphogenetic protein-2 and platelet-derived growth factor-BB that were eluted over readily adapted time scales to induce rapid bone repair. Based on electrostatic interactions between the polymer multilayers and growth factors alone, we sustained mitogenic and osteogenic signals with these growth factors in an easily tunable and controlled manner to direct endogenous cell function. To prove the role of this adaptive release system, we applied the polyelectrolyte coating on a well-studied biodegradable poly(lactic-co-glycolic acid) support membrane. The released growth factors directed cellular processes to induce bone repair in a critical-size rat calvaria model. The released growth factors promoted local bone formation that bridged a critical-size defect in the calvaria as early as 2 wk after implantation. Mature, mechanically competent bone regenerated the native calvaria form. Such an approach could be clinically useful and has significant benefits as a synthetic, off-the-shelf, cell-free option for bone tissue repair and restoration. PMID:25136093

Tailored adhesion behavior of polyelectrolyte thin films deposited on plasma-treated poly(dimethylsiloxane) for functionalized membranes

NASA Astrophysics Data System (ADS)

Bassil, Joelle; Alem, Halima; Henrion, Gérard; Roizard, Denis

2016-04-01

Completely homogenous films formed via the layer-by-layer assembly of poly(diallyldimethylammonium chloride) (PDADMAC) and the poly(styrene sulfonate) were successfully obtained on plasma-treated poly(dimethylsiloxane) (PDMS) substrates. To modify the hydrophobicity of the PDMS surface, a cold plasma treatment was previously applied to the membrane, which led to the creation of hydrophilic groups on the surface of the membrane. PDMS wettability and surface morphology were successfully correlated with the plasma parameters. A combination of contact angle measurements, scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis was used to demonstrate that homogeneous and hydrophilic surfaces could be achieved on PDMS cold-plasma-treated membranes. The stability of the assembled PEL layer on the PDMS was evaluated using a combination of pull-off testing and X-ray photoelectron spectroscopy (XPS), which confirmed the relevance of a plasma pre-treatment as the adhesion of the polyelectrolyte multilayers was greatly enhanced when the deposition was completed on an activated PDMS surface at 80 W for 5 min.

Localized entrapment of green fluorescent protein within nanostructured polymer films

NASA Astrophysics Data System (ADS)

Ankner, John; Kozlovskaya, Veronika; O'Neill, Hugh; Zhang, Qiu; Kharlampieva, Eugenia

2012-02-01

Protein entrapment within ultrathin polymer films is of interest for applications in biosensing, drug delivery, and bioconversion, but controlling protein distribution within the films is difficult. We report on nanostructured protein/polyelectrolyte (PE) materials obtained through incorporation of green fluorescent protein (GFP) within poly(styrene sulfonate)/poly(allylamine hydrochloride) multilayer films assembled via the spin-assisted layer-by-layer method. By using deuterated GFP as a marker for neutron scattering contrast we have inferred the architecture of the films in both normal and lateral directions. We find that films assembled with a single GFP layer exhibit a strong localization of the GFP without intermixing into the PE matrix. The GFP volume fraction approaches the monolayer density of close-packed randomly oriented GFP molecules. However, intermixing of the GFP with the PE matrix occurs in multiple-GFP layer films. Our results yield new insight into the organization of immobilized proteins within polyelectrolyte matrices and open opportunities for fabrication of protein-containing films with well-organized structure and controllable function, a crucial requirement for advanced sensing applications.

Molecular Origins of Thermal Transitions in Polyelectrolyte Assemblies

NASA Astrophysics Data System (ADS)

Yildirim, Erol; Zhang, Yanpu; Antila, Hanne S.; Lutkenhaus, Jodie L.; Sammalkorpi, Maria; Aalto Team; Texas A&M Team

2015-03-01

Polyelectrolyte (PE) multilayers and complexes formed from oppositely charged polymers can exhibit extraordinary superhydrophobicity, mechanical strength and responsiveness resulting in applications ranging functional membranes, optics, sensors and drug delivery. Depending on the assembly conditions, PE assemblies may undergo a thermal transition from glassy to soft behavior under heating. Our earlier work using thermal analysis measurements shows a distinct thermal transition for PE layer-by-layer (LbL) systems assembled with added salt but no analogous transition in films assembled without added salt or dry systems. These findings raise interesting questions on the nature of the thermal transition; here, we explore its molecular origins through characterization of the PE aggregates by temperature-controlled all-atom molecular dynamics simulations. We show via molecular simulations the thermal transition results from the existence of an LCST (lower critical solution temperature) in the PE systems: the diffusion behavior, hydrogen bond formation, and bridging capacity of water molecules plasticizing the complex changes at the transition temperature. We quantify the behavior, map its chemistry specificity through comparison of strongly and weakly charged PE complexes, and connect the findings to our interrelated QCM-D experiments.

Avidin/PSS membrane microcapsules with biotin-binding activity.

PubMed

Endo, Yoshihiro; Sato, Katsuhiko; Sugimoto, Kentaro; Anzai, Jun-ichi

2011-08-15

Polyelectrolyte microcapsules with avidin-poly(styrene sulfonate) (PSS) membrane were prepared by a layer-by-layer deposition technique. The uptake and release of biotin-labeled fluorescein (b-FITC) as well as immobilization of biotin-labeled glucose oxidase (b-GOx) to the microcapsule were studied. The polyelectrolyte microcapsules were prepared by coating the surface of calcium carbonate (CaCO(3)) microparticles with an avidin/PSS multilayer membrane, followed by dissolution of CaCO(3) core in an ethylenediaminetetraacetic acid solution. Inner and outer poly(allylamine)/PSS films were required to isolate the microcapsules, whereas microcapsules could not be formed without the support. The uptake of b-FITC into the microcapsule was highly enhanced through a strong binding of b-FITC to avidin as compared with the uptake of biotin-free FITC. Release of b-FITC from the microcapsule was accelerated upon addition of biotin due to a competitive binding of the added biotin to the binding site of avidin. Similarly, the surface of microcapsule was modified with b-GOx with retaining its catalytic activity. Copyright © 2011 Elsevier Inc. All rights reserved.

Collective epithelial cell sheet adhesion and migration on polyelectrolyte multilayers with uniform and gradients of compliance

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

Martinez, Jessica S.; Schlenoff, Joseph B.; Keller, Thomas C.S., E-mail: tkeller@bio.fsu.edu

Polyelectrolyte multilayers (PEMUs) are tunable thin films that could serve as coatings for biomedical implants. PEMUs built layer by layer with the polyanion poly(acrylic acid) (PAA) modified with a photosensitive 4-(2-hydroxyethoxy) benzophenone (PAABp) group and the polycation poly(allylamine hydrochloride) (PAH) are mechanically tunable by UV irradiation, which forms covalent bonds between the layers and increases PEMU stiffness. PAH-terminated PEMUs (PAH-PEMUs) that were uncrosslinked, UV-crosslinked to a uniform stiffness, or UV-crosslinked with an edge mask or through a neutral density optical gradient filter to form continuous compliance gradients were used to investigate how differences in PEMU stiffness affect the adhesion andmore » migration of epithelial cell sheets from scales of the fish Poecilia sphenops (Black Molly) and Carassius auratus (Comet Goldfish). During the progressive collective cell migration, the edge cells (also known as ‘leader’ cells) in the sheets on softer uncrosslinked PEMUs and less crosslinked regions of the gradient formed more actin filaments and vinculin-containing adherens junctions and focal adhesions than formed in the sheet cells on stiffer PEMUs or glass. During sheet migration, the ratio of edge cell to internal cell (also known as ‘follower’ cells) motilities were greater on the softer PEMUs than on the stiffer PEMUs or glass, causing tension to develop across the sheet and periods of retraction, during which the edge cells lost adhesion to the substrate and regions of the sheet retracted toward the more adherent internal cell region. These retraction events were inhibited by the myosin II inhibitor Blebbistatin, which reduced the motility velocity ratios to those for sheets on the stiffer PEMUs. Blebbistatin also caused disassembly of actin filaments, reorganization of focal adhesions, increased cell spreading at the leading edge, as well as loss of edge cell-cell connections in epithelial cell sheets on all surfaces. Interestingly, cells throughout the interior region of the sheets on uncrosslinked PEMUs retained their actin and vinculin organization at adherens junctions after treatment with Blebbistatin. Like Blebbistatin, a Rho-kinase (ROCK) inhibitor, Y27632, promoted loss of cell-cell connections between edge cells, whereas a Rac1 inhibitor, NSC23766, primarily altered the lamellipodial protrusion in edge cells. Compliance gradient PAH-PEMUs promoted durotaxis of the cell sheets but not of individual keratocytes, demonstrating durotaxis, like plithotaxis, is an emergent property of cell sheet organization. - Highlights: • Fish scale cell sheets migrate on PAH-PAABp polyelectrolyte multilayers. • Sheets migrating on softer PEMUs periodically retract. • Sheets durotax on modulus gradients. • Myosin II inhibitors inhibit sheet integrity and migration.« less

Porous PLGA microspheres tailored for dual delivery of biomolecules via layer-by-layer assembly.

PubMed

Go, Dewi P; Palmer, Jason A; Mitchell, Geraldine M; Gras, Sally L; O'Connor, Andrea J

2015-05-01

Tissue engineering is a complex and dynamic process that requires varied biomolecular cues to promote optimal tissue growth. Consequently, the development of delivery systems capable of sequestering more than one biomolecule with controllable release profiles is a key step in the advancement of this field. This study develops multilayered polyelectrolyte films incorporating alpha-melanocyte stimulating hormone (α-MSH), an anti-inflammatory molecule, and basic fibroblast growth factor (bFGF). The layers were successfully formed on macroporous poly lactic-co-glycolic acid microspheres produced using a combined inkjet and thermally induced phase separation technique. Release profiles could be varied by altering layer properties including the number of layers and concentrations of layering molecules. α-MSH and bFGF were released in a sustained manner and the bioactivity of α-MSH was shown to be preserved using an activated macrophage cell assay in vitro. The system performance was also tested in vivo subcutaneously in rats. The multilayered microspheres reduced the inflammatory response induced by a carrageenan stimulus 6 weeks after implantation compared to the non-layered microspheres without the anti-inflammatory and growth factors, demonstrating the potential of such multilayered constructs for the controlled delivery of bioactive molecules. © 2014 Wiley Periodicals, Inc.

Adjusting the Ion Permeability of Polyelectrolyte Multilayers through Layer-by-Layer Assembly under a High Gravity Field.

PubMed

Jiang, Chao; Luo, Caijun; Liu, Xiaolin; Shao, Lei; Dong, Youqing; Zhang, Yingwei; Shi, Feng

2015-05-27

The layer-by-layer (LbL) assembled multilayer has been widely used as good barrier film or capsule due to the advantages of its flexible tailoring of film permeability and compactness. Although many specific systems have been proposed for film design, developing a versatile strategy to control film compactness remains a challenge. We introduced the simple mechanical energy of a high gravity field to the LbL assembly process to tailor the multilayer permeability through adjusting film compactness. By taking poly(diallyldimethylammonium chloride) (PDDA) and poly{1-4[4-(3-carboxy-4-hydroxyphenylazo)benzenesulfonamido]-1,2-ethanediyl sodium salt} (PAzo) as a model system, we investigated the LbL assembly process under a high gravity field. The results showed that the high gravity field introduced effectively accelerated the multilayer deposition process by 20-fold compared with conventional dipping assembly; the adsorption rate was positively dependent on the rotating speed of the high gravity equipment and the concentration of the building block solutions. More interestingly, the film compactness of the PDDA/PAzo multilayer prepared under the high gravity field increased remarkably with the growing rotational speed of the high gravity equipment, as demonstrated through comparisons of surface morphology, cyclic voltammetry curves, and photoisomerization kinetics of PDDA/PAzo multilayers fabricated through the conventional dipping method and through LbL assembly under a high gravity field, respectively. In this way, we have introduced a simple and versatile external form of mechanical energy into the LbL assembling process to improve film compactness, which should be useful for further applications in controlled ion permeability, anticorrosion, and drug loading.

Macromolecular shape and interactions in layer-by-layer assemblies within cylindrical nanopores.

PubMed

Lazzara, Thomas D; Lau, K H Aaron; Knoll, Wolfgang; Janshoff, Andreas; Steinem, Claudia

2012-01-01

Layer-by-layer (LbL) deposition of polyelectrolytes and proteins within the cylindrical nanopores of anodic aluminum oxide (AAO) membranes was studied by optical waveguide spectroscopy (OWS). AAO has aligned cylindrical, nonintersecting pores with a defined pore diameter d(0) and functions as a planar optical waveguide so as to monitor, in situ, the LbL process by OWS. The LbL deposition of globular proteins, i.e., avidin and biotinylated bovine serum albumin was compared with that of linear polyelectrolytes (linear-PEs), both species being of similar molecular weight. LbL deposition within the cylindrical AAO geometry for different pore diameters (d(0) = 25-80 nm) for the various macromolecular species, showed that the multilayer film growth was inhibited at different maximum numbers of LbL steps (n(max)). The value of n(max) was greatest for linear-PEs, while proteins had a lower value. The cylindrical pore geometry imposes a physical limit to LbL growth such that n(max) is strongly dependent on the overall internal structure of the LbL film. For all macromolecular species, deposition was inhibited in native AAO, having pores of d(0) = 25-30 nm. Both, OWS and scanning electron microscopy showed that LbL growth in larger AAO pores (d(0) > 25-30 nm) became inhibited when approaching a pore diameter of d(eff,n_max) = 25-35 nm, a similar size to that of native AAO pores, with d(0) = 25-30 nm. For a reasonable estimation of d(eff,n_max), the actual volume occupied by a macromolecular assembly must be taken into consideration. The results clearly show that electrostatic LbL allowed for compact macromolecular layers, whereas proteins formed loosely packed multilayers.

Layer-by-layer hollow photosensitizer microcapsule design via a manganese carbonate hard template for photodynamic therapy in cells.

PubMed

Simioni, Andreza Ribeiro; de Jesus, Priscila Costa Carvalho; Tedesco, Antonio Claudio

2018-06-01

Microcapsules fabricated using layer-by-layer self-assembly have unique properties, making them attractive for drug delivery applications. The technique has been improved, allowing the deposition of multiple layers of oppositely charged polyelectrolytes on spherical, colloidal templates. These templates can be decomposed by coating multiple layers, resulting in hollow shells. In this paper, we describe a novel drug delivery system for loading photosensitizer drugs into hollow multilayered microcapsules for photoprocess applications. Manganese carbonate particles were prepared by mixing NH 4 HCO 3 and MnSO 4 and performing consecutive polyelectrolyte adsorption processes onto these templates using poly-(sodium 4-styrene sulfonate) and poly-(allylamine hydrocholoride). A photosensitizer was also incorporated into the layers. Hollow spheres were fabricated by removing the cores in the acidic solution. The hollow, multilayered microcapsules were studied by scanning electron microscopy, steady-state, and time-resolved techniques. Their biological activity was evaluated in vitro with cancer cells using a conventional MTT assay. The synthesized CaCO 3 microparticles were uniform, non-aggregated, and highly porous spheres. The phthalocyanine derivatives loaded in the microcapsules maintained their photophysical behaviour after encapsulation. The spectroscopic results presented here showed excellent photophysical behaviour of the studied drug. We observed a desirable increase in singlet oxygen production, which is favourable for the PDT protocol. Cell viability after treatment was determined and the proposed microcapsules caused 80% cell death compared to the control. The results demonstrate that photosensitizer adsorption into the CaCO 3 microparticle voids together with the layer-by-layer assembly of biopolymers provide a method for the fabrication of biocompatible microcapsules for use as biomaterials. Copyright © 2018 Elsevier B.V. All rights reserved.

Bioinspired assembly of surface-roughened nanoplatelets.

PubMed

Lin, Tzung-Hua; Huang, Wei-Han; Jun, In-Kook; Jiang, Peng

2010-04-15

Here we report a novel electrophoretic deposition technology for assembling surface-roughened inorganic nanoplatelets into ordered multilayers that mimic the brick-and-mortar nanostructure found in the nacreous layer of mollusk shells. A thin layer of sol-gel silica is coated on smooth gibbsite nanoplatelets in order to increase the surface roughness to mimic the asperity of aragonite platelets found in nacres. To avoid the severe cracking caused by the shrinkage of sol-gel silica during drying, polyelectrolyte polyethyleneimine is used to reverse the surface charge of silica-coated-gibbsite nanoplatelets and increase the adherence and strength of the electrodeposited films. Polymer nanocomposites can then be made by infiltrating the interstitials of the aligned nanoplatelet multilayers with photocurable monomer followed by photopolymerization. The resulting self-standing films are highly transparent and exhibit nearly three times higher tensile strength and one-order-of-magnitude higher toughness than those of pure polymer. The measured tensile strength agrees with that predicted by a simple shear lag model. Published by Elsevier Inc.

Fabrication of complex free-standing nanostructures with concave and convex curvature via the layer-by-layer approach.

PubMed

Raoufi, Mohammad; Schönherr, Holger

2014-02-18

We report on the fabrication of unprecedented free-standing complex polymeric nanoobjects, which possess both concave and convex curvatures, by exploiting the layer-by-layer (LBL) deposition of polyelectrolytes. In a combined top-down/bottom-up replication approach pore diameter-modulated anodic aluminum oxide (AAO) templates, fabricated by temperature modulation hard anodization (TMHA), were replicated with multilayers of poly(styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) to yield open nanotubes with diameters in the wide and narrow segments of 210 and 150 nm, respectively. To obtain stable pore diameter-modulated nanopores, which possess segment lengths between 1 and 5 μm and 5 and 10 μm in the narrow and wide pore portion, respectively, conventional hard anodization of aluminum was followed by a subsequent temperature-modulated anodization. After removing the backside aluminum electrode, silanizing the aluminum oxide, and passivating the exposed membrane surface with a thin layer of gold, PSS and PAH were deposited alternatingly to yield LBL multilayers. For optimized LBL multilayer thicknesses and compactness, established in separate experiments on silicon substrates and nanoporous AAO with straight pores, free-standing polymeric nanoobjects with concave and convex curvatures, were obtained. These were stable for wall thickness to pore diameter ratios of ≥0.08.

Establishing Antibacterial Multilayer Films on the Surface of Direct Metal Laser Sintered Titanium Primed with Phase-Transited Lysozyme

PubMed Central

Guan, Binbin; Wang, Haorong; Xu, Ruiqing; Zheng, Guoying; Yang, Jie; Liu, Zihao; Cao, Man; Wu, Mingyao; Song, Jinhua; Li, Neng; Li, Ting; Cai, Qing; Yang, Xiaoping; Li, Yanqiu; Zhang, Xu

2016-01-01

Direct metal laser sintering is a technology that allows the fabrication of titanium (Ti) implants with a functional gradation of porosity and surface roughness according to three-dimensional (3D) computer data. The surface roughness of direct metal laser sintered titanium (DMLS-Ti) implants may provide abundant binding sites for bacteria. Bacterial colonization and subsequent biofilm formation can cause unsatisfactory cell adhesion and implant-related infections. To prevent such infections, a novel phase-transited lysozyme (PTL) was utilized as an initial functional layer to simply and effectively prime DMLS-Ti surfaces for subsequent coating with antibacterial multilayers. The purpose of the present study was to establish a surface with dual biological functionality. The minocycline-loaded polyelectrolyte multilayers of hyaluronic acid (HA) and chitosan (CS) formed via a layer-by-layer (LbL) self-assembly technique on PTL-functionalized DMLS-Ti were designed to inhibit pathogenic microbial infections while allowing the DMLS-Ti itself and the modified coatings to retain acceptable biocompatibility. The experimental results indicate that the DMLS-Ti and the hydrogel treated surfaces can inhibit early bacterial adhesion while completely preserving osteoblast functions. This design is expected to gain considerable interest in the medical field and to have good potential for applications in multifunctional DMLS-Ti implants. PMID:27821857

Establishing Antibacterial Multilayer Films on the Surface of Direct Metal Laser Sintered Titanium Primed with Phase-Transited Lysozyme.

PubMed

Guan, Binbin; Wang, Haorong; Xu, Ruiqing; Zheng, Guoying; Yang, Jie; Liu, Zihao; Cao, Man; Wu, Mingyao; Song, Jinhua; Li, Neng; Li, Ting; Cai, Qing; Yang, Xiaoping; Li, Yanqiu; Zhang, Xu

2016-11-08

Direct metal laser sintering is a technology that allows the fabrication of titanium (Ti) implants with a functional gradation of porosity and surface roughness according to three-dimensional (3D) computer data. The surface roughness of direct metal laser sintered titanium (DMLS-Ti) implants may provide abundant binding sites for bacteria. Bacterial colonization and subsequent biofilm formation can cause unsatisfactory cell adhesion and implant-related infections. To prevent such infections, a novel phase-transited lysozyme (PTL) was utilized as an initial functional layer to simply and effectively prime DMLS-Ti surfaces for subsequent coating with antibacterial multilayers. The purpose of the present study was to establish a surface with dual biological functionality. The minocycline-loaded polyelectrolyte multilayers of hyaluronic acid (HA) and chitosan (CS) formed via a layer-by-layer (LbL) self-assembly technique on PTL-functionalized DMLS-Ti were designed to inhibit pathogenic microbial infections while allowing the DMLS-Ti itself and the modified coatings to retain acceptable biocompatibility. The experimental results indicate that the DMLS-Ti and the hydrogel treated surfaces can inhibit early bacterial adhesion while completely preserving osteoblast functions. This design is expected to gain considerable interest in the medical field and to have good potential for applications in multifunctional DMLS-Ti implants.

Establishing Antibacterial Multilayer Films on the Surface of Direct Metal Laser Sintered Titanium Primed with Phase-Transited Lysozyme

NASA Astrophysics Data System (ADS)

Guan, Binbin; Wang, Haorong; Xu, Ruiqing; Zheng, Guoying; Yang, Jie; Liu, Zihao; Cao, Man; Wu, Mingyao; Song, Jinhua; Li, Neng; Li, Ting; Cai, Qing; Yang, Xiaoping; Li, Yanqiu; Zhang, Xu

2016-11-01

Direct metal laser sintering is a technology that allows the fabrication of titanium (Ti) implants with a functional gradation of porosity and surface roughness according to three-dimensional (3D) computer data. The surface roughness of direct metal laser sintered titanium (DMLS-Ti) implants may provide abundant binding sites for bacteria. Bacterial colonization and subsequent biofilm formation can cause unsatisfactory cell adhesion and implant-related infections. To prevent such infections, a novel phase-transited lysozyme (PTL) was utilized as an initial functional layer to simply and effectively prime DMLS-Ti surfaces for subsequent coating with antibacterial multilayers. The purpose of the present study was to establish a surface with dual biological functionality. The minocycline-loaded polyelectrolyte multilayers of hyaluronic acid (HA) and chitosan (CS) formed via a layer-by-layer (LbL) self-assembly technique on PTL-functionalized DMLS-Ti were designed to inhibit pathogenic microbial infections while allowing the DMLS-Ti itself and the modified coatings to retain acceptable biocompatibility. The experimental results indicate that the DMLS-Ti and the hydrogel treated surfaces can inhibit early bacterial adhesion while completely preserving osteoblast functions. This design is expected to gain considerable interest in the medical field and to have good potential for applications in multifunctional DMLS-Ti implants.

Multilayer engineered nanoliposomes as a novel tool for oral delivery of lipopeptide-based vaccines against group A Streptococcus.

PubMed

Marasini, Nirmal; Giddam, Ashwini K; Ghaffar, Khairunnisa A; Batzloff, Michael R; Good, Michael F; Skwarczynski, Mariusz; Toth, Istvan

2016-05-01

To develop an oral nanovaccine delivery system for lipopeptide-based vaccine candidate against group A Streptococcus. Lipid-core peptide-1-loaded nanoliposomes were prepared as a template and coated with opposite-charged polyelectrolytes to produce particles with size <200 nm. Efficacy of this oral nanovaccine delivery system was evaluated in mice model. Polymer-coated liposomes produced significantly higher antigen-specific mucosal IgA and systemic IgG titers in comparison to vaccine formulated with a strong mucosal adjuvant upon oral immunization in mice. Moreover, high levels of systemic antibody titers were retained even at day 185 postprimary immunization. Efficient oral delivery platform for lipopeptide-based vaccines has been developed.

pH dependent growth of poly( L-lysine)/poly( L-glutamic) acid multilayer films and their cell adhesion properties

NASA Astrophysics Data System (ADS)

Richert, Ludovic; Arntz, Youri; Schaaf, Pierre; Voegel, Jean-Claude; Picart, Catherine

2004-10-01

The short-term interaction of chondrosarcoma cells with (PGA/PLL) polyelectrolyte multilayers was investigated in a serum-containing medium for films built at different pHs and subsequently exposed to the culture medium. The buildup of the films and their stability was first investigated by means of optical waveguide lightmode spectroscopy, quartz crystal microbalance, streaming potential measurements and atomic force microscopy. While film growth is linear at all pHs, after a few layers have been deposited the growth is much larger for the films built at basic pH and even more pronounced for those built at acidic pH. However, these latter films remain stable in the culture medium only if they have been crosslinked prior to the ionic strength and pH jumps. The films built at acidic pH were found to swell in water by about 200% whereas those built at other pHs did not swell in a physiological buffer. For thin films (≈20 nm) built at pH = 7.4, the detachment forces were dependent on the outermost layer, the forces being significantly higher on PLL-ending films than on PGA-ending ones. In contrast, for the thick films built at pH = 4.4 and at pH = 10.4 (thickness of the order of few hundred of nanometers), the detachment forces were independent of the outermost layer of the film. The films built at pH = 10.4, which shrink in contact with salt containing solutions, were highly cell adhesive whereas those built at acidic pH were highly cell resistant. Protein adsorption and film roughness (as measured by AFM) could not explain these striking differences. The high adhesion observed on the film built at pH 10.4 may rather be related to the secondary structure of the film and to its relatively low swellability in water, whereas the cell resistance of the films built at pH 4.4 may be linked to their high swellability. Therefore, for the PGA/PLL films, the cell adhesion properties can be tuned depending on the deposition pH of the polyelectrolyte solutions. This study reveals the importance of the multilayer structure and architecture to control the detachment force of cells onto such films.

Linear and Star Poly(ionic liquid) Assemblies: Surface Monolayers and Multilayers.

PubMed

Erwin, Andrew J; Xu, Weinan; He, Hongkun; Matyjaszewski, Krzysztof; Tsukruk, Vladimir V

2017-04-04

The surface morphology and organization of poly(ionic liquid)s (PILs), poly[1-(4-vinylbenzyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] are explored in conjunction with their molecular architecture, adsorption conditions, and postassembly treatments. The formation of stable PIL Langmuir and Langmuir-Blodgett (LB) monolayers at the air-water and air-solid interfaces is demonstrated. The hydrophobic bis(trifluoromethylsulfonyl)imide (Tf 2 N - ) is shown to be a critical agent governing the assembly morphology, as observed in the reversible condensation of LB monolayers into dense nanodroplets. The PIL is then incorporated as an unconventional polyelectrolyte component in the layer-by-layer (LbL) films of hydrophobic character. We demonstrate that the interplay of capillary forces, macromolecular mobility, and structural relaxation of the polymer chains influence the dewetting mechanisms in the PIL multilayers, thereby enabling access to a diverse set of highly textured, porous, and interconnected network morphologies for PIL LbL films that would otherwise be absent in conventional LbL films. Their compartmentalized internal structure is relevant to molecular separation membranes, ultrathin hydrophobic coatings, targeted cargo delivery, and highly conductive films.

Xylella fastidiosa plasmid-encoded PemK toxin is an endoribonuclease.

USDA-ARS?s Scientific Manuscript database

Stable inheritance of pXF-RIV11 in Xylella fastidiosa is conferred by the pemI/pemK plasmid addiction system. PemK serves as a toxin inhibiting bacterial growth; PemI is the corresponding antitoxin that blocks activity of PemK toxin by direct binding. PemK toxin and PemI antitoxin were over-expre...

Layer-by-layer self-assembly of micro-capsules for the magnetic activation of semi-permeable nano-shells

NASA Astrophysics Data System (ADS)

Prouty, Malcolm D.

2007-12-01

Layer-by-layer (LbL) self-assembly has demonstrated broad perspectives for encapsulating, and the controllable delivery, of drugs. The nano-scale polymer layers have the capability of material protection. Magnetic nanoparticles have great potential to be applied with LbL technology to achieve both "focusing" of the encapsulated drugs to a specific location followed by "switching" them on to release the encapsulated drugs. In this work, Phor21-betaCG(ala), dextran, and dexamethasone were used as model drugs. Encapsulation of these drugs with layer-by-layer self-assembly formed biolnano robotic capsules for controlled delivery and drug release. Silica nanoparticles coated with polyelectrolyte layers of sodium carboxymethyl cellulose (CMC) or gelatin B, along with an oppositely charged peptide drug (Phor2l-betaCG(ala)), were prepared using LbL self-assembly and confirmed using QCM and zeta potential measurements. The peptide drug was assembled as a component of the multilayer walls. The release kinetics of the embedded peptide were determined. Up to 18% of the embedded Phor21-betaCG(ala) was released from the CMC multilayers over a period of 28 hours. The release was based on physiological conditions, and an external control mechanism using magnetic nanoparticles needed to be developed. Magnetic permeability control experiments were setup by applying LbL self-assembly on MnCO3 micro-cores to fabricate polyelectrolyte microcapsules embedded with superparamagnetic gold coated cobalt (Co Au) nanoparticles. An alternating magnetic field was applied to the microcapsules to check for changes in permeability. Permeability experiments were achieved by adding fluorescein isothiocyanate (FITC) labeled dextran to the microcapsule solution. Before an alternating magnetic field was applied, the capsules remained impermeable to the FITC-dextran; however, after an alternating magnetic field was applied for 30 minutes, approximately 99% of the capsules were filled with FITC-dextran, showing that the Co Au embedded microcapsules were indeed "switched on" using an alternating magnetic field. LbL assembly was then applied to encapsulate micronized dexamethasone with biocompatible polyelectrolytes such as protamine sulfate C, chondroitin sulfate sodium salt, and gelatin B, along with a layer of superparamagnetic nanoparticles. The biocompatible polymers were used to retain and protect the vulnerable drug. In vitro drug release kinetics were investigated according to different environmental factors such as temperature and pH. An external oscillating magnetic field was applied to "switch on" and accelerate the drug release. The results were compared to those without applying a magnetic field.

Imprinting of metal receptors into multilayer polyelectrolyte films: fabrication and applications in marine antifouling† †Electronic supplementary information (ESI) available: FTIR, NMR spectra of synthesized polymers, XPS spectra and AFM images of non-cross linked and cross linked LBLA and LBLB films, UV-Visible absorption spectra of copper complexation with PAH-His, QCM data of LBLA and LBLB films and stability of the films are provided in the electronic supplementary information. See DOI: 10.1039/c4sc02367f Click here for additional data file.

PubMed Central

Puniredd, Sreenivasa Reddy; Go, Dewi Pitrasari; Zhu, Xiaoying; Guo, Shifeng; Ming Teo, Serena Lay; Chen Lee, Serina Siew

2015-01-01

Polymeric films constructed using the layer-by-layer (LbL) fabrication process were employed as a platform for metal ion immobilization and applied as a marine antifouling coating. The novel Cu2+ ion imprinting process described is based on the use of metal ion templates and LbL multilayer covalent cross-linking. Custom synthesized, peptide mimicking polycations composed of histidine grafted poly(allylamine) (PAH) to bind metal ions, and methyl ester containing polyanions for convenient cross-linking were used in the fabrication process. Two methods of LbL film formation have been investigated using alternate polyelectrolyte deposition namely non-imprinted LbLA, and imprinted LbLB. Both LbL films were cross linked at mild temperature to yield covalent bridging of the layers for improved stability in a sea water environment. A comparative study of the non-imprinted LbLA films and imprinted LbLB films for Cu2+ ion binding capacity, leaching rate and stability of the films was performed. The results reveal that the imprinted films possess enhanced affinity to retain metal ions due to the preorganization of imidazole bearing histidine receptors. As a result the binding capacity of the films for Cu2+ could be improved by seven fold. Antifouling properties of the resulting materials in a marine environment have been demonstrated against the settlement of barnacle larvae, indicating that controlled release of Cu ions was achieved. PMID:28966763

PemK toxin encoded by the Xylella fastidiosa IncP-1 plasmid pXF-RIV11 is a ribonuclease

USDA-ARS?s Scientific Manuscript database

Stable inheritance of the IncP-1 plasmid pXF-RIV11 in Xylella fastidiosa is conferred by the pemI/pemK plasmid addiction system. PemK serves as a toxin inhibiting bacterial growth; PemI is the corresponding antitoxin that blocks activity of PemK toxin by direct binding. Here, PemK toxin and PemI ant...

Removal of copper ions from aqueous solution by adsorption onto novel polyelectrolyte film-coated nanofibrous silk fibroin non-wovens

NASA Astrophysics Data System (ADS)

Zhou, Weitao; Huang, Haitao; Du, Shan; Huo, Yingdong; He, Jianxin; Cui, Shizhong

2015-08-01

In this approach, polyelectrolyte film-coated nanofibrous silk fibroin (SF) nonwovens were prepared from the alternate deposition of positively charged polyethylenimine (PEI) and negatively charged SF using electrostatic layer-by-layer (LBL) self-assembled technology. The composite membranes were characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectrometer. The SF-PEI multilayer-assembled nanofibers (less than five layers) were fine and uniform with the fiber diameter from 400 nm to 600 nm, and had very large surface area and high porosity (more than 70%). The amino groups of PEI were proved to be deposited onto SF nonwovens, which granted the coated nonwovens with potential applicability for copper ions adsorption. The PEI films coated SF substrate showed much higher copper ions adsorption capacity than that of ethanol treated SF nanofibers. Adding the number of PEI coated could enhance the Cu2+ adsorption capacity significantly. The maximum milligrams per gram of copper ions adsorbed reached 59.7 mg/g when the SF substrate was coated with 5 bilayers of SF-PEI. However, the copper ions adsorption capacity had no obvious change as the number of PEI continued to increase. These results suggest potential for PEL film-coated nanofibrous nonwovens as a new adsorbent for metal ions.

Physical deposition behavior of stiff amphiphilic polyelectrolytes in an external electric field

NASA Astrophysics Data System (ADS)

Hu, Dongmei; Zuo, Chuncheng; Cao, Qianqian; Chen, Hongli

2017-08-01

Coarse-grained molecular dynamics simulations are conducted to study the physical deposition behavior of stiff amphiphilic polyelectrolytes (APEs) in an external electric field. The effects of chain stiffness, the charge distribution of a hydrophilic block, and electric field strength are investigated. Amphiphilic multilayers, which consist of a monolayer of adsorbed hydrophilic monomers (HLMs), a hydrophobic layer, and another hydrophilic layer, are formed in a selective solvent. All cases exhibit locally ordered hydrophilic monolayers. Two kinds of hydrophobic micelles are distinguished based on local structures. Stripe and network hydrophobic patterns are formed in individual cases. Increasing the chain stiffness decreases the thickness of the deposited layer, the lateral size of the hydrophobic micelles, and the amount of deposition. Increasing the number of positively charged HLMs in a single chain has the same effect as increasing chain stiffness. Moreover, when applied normally to the substrate, the electric field compresses the deposited structures and increases the amount of deposition by pulling more PEs toward the substrate. A stronger electric field also facilitates the formation of a thinner and more ordered hydrophilic adsorption layer. These estimates help us explore how to tailor patterned nano-surfaces, nano-interfaces, or amphiphilic nanostructures by physically depositing semi-flexible APEs which is of crucial importance in physical sciences, life sciences and nanotechnology.

Shape-Morphing Nanocomposite Origami

PubMed Central

2015-01-01

Nature provides a vast array of solid materials that repeatedly and reversibly transform in shape in response to environmental variations. This property is essential, for example, for new energy-saving technologies, efficient collection of solar radiation, and thermal management. Here we report a similar shape-morphing mechanism using differential swelling of hydrophilic polyelectrolyte multilayer inkjets deposited on an LBL carbon nanotube (CNT) composite. The out-of-plane deflection can be precisely controlled, as predicted by theoretical analysis. We also demonstrate a controlled and stimuli-responsive twisting motion on a spiral-shaped LBL nanocomposite. By mimicking the motions achieved in nature, this method offers new opportunities for the design and fabrication of functional stimuli-responsive shape-morphing nanoscale and microscale structures for a variety of applications. PMID:24689908

Cellulose fiber-enzyme composites fabricated through layer-by-layer nanoassembly.

PubMed

Xing, Qi; Eadula, Sandeep R; Lvov, Yuri M

2007-06-01

Cellulose microfibers were coated with enzymes, laccase and urease, through layer-by-layer assembly by alternate adsorption with oppositely charged polycations. The formation of organized polyelectrolyte and enzyme multilayer films of 15-20 nm thickness was demonstrated by quartz crystal microbalance, zeta-potential analysis, and confocal laser scanning microscopy. These biocomposites retained enzymatic catalytic activity, which was proportional to the number of coated enzyme layers. For laccase-fiber composites, around 50% of its initial activity was retained after 2 weeks of storage at 4 degrees C. The synthesis of calcium carbonate microparticles on urease-fiber composites confirmed urease functionality and demonstrated its possible applications. This strategy could be employed to fabricate fiber-based composites with novel biological functions.

[An electron microscopy study of the structure of polyelectrolyte microcapsules containing protein and containing no protein].

PubMed

Kazakova, L I; Dubrovskiĭ, A V; Moshkov, D A; Shabarchina, L I; Sukhorukov, B I

2007-01-01

Electron micrographs of ultrathin sections of polyelectrolyte microparticles containing protein and free from protein for the formation of which CaCO3 spherulites served as a core basis have been obtained and analyzed. Polyelectrolyte microparticles with the number of alternately layered polyelectrolyte layers of polystyrene sulfonate and polyallylamine from 6 to 11 have been studied. It follows from the data obtained that protein-free polyelectrolyte particles having the dimensions 4.5-5 mm are formations of an intricate internal organization, which consist of a set of threadlike and closed nanoelements of polyelectrolyte nature with a thickness of 20-30 nm. The particles containing six to eight polyelectrolyte layers lack the external envelope; therefore, they were called polyelectrolyte microspherulites. With the number of layers nine and more, when a polyelectrolyte envelope appears on the surface, they transfer into polyelectrolyte microcapsules. It was found that, in a protein-containing polyelectrolyte microcapsule, as distinct from protein-free polyelectrolyte microspherulite and microcapsule, polyelectrolytes are located only in the nearsurface layer, and the external spatially organized envelope restricts the internal volume filled with protein solution. As the number of polyelectrolyte layers increases, the thickness of the envelope increases. The reasons for such substantial differences in the structures of polyelectrolyte microcapsules formed on protein-containing and protein-free CaCO3 spherulite are discussed.

Effect of Molecular Weight on Mechanical and Electrochemical Performance of All Solid-State Polymer Electrolyte Membranes

NASA Astrophysics Data System (ADS)

He, Ruixuan; Ward, Daniel; Echeverri, Mauricio; Kyu, Thein

2015-03-01

Guided by ternary phase diagrams of polyethylene glycol diacrylate (PEGDA), succinonitrile plasticizer, and LiTFSI salt, completely amorphous solid-state transparent polymer electrolyte membranes (ss-PEM) were fabricated by UV irradiation in the isotropic melt state. Effects of PEGDA molecular weight (700 vs 6000 g/mol) on ss-PEM performance were investigated. These amorphous PEMs have superionic room temperature ionic conductivity of ~10-3 S/cm, whereby PEGDA6000-PEM outperforms its PEGDA700 counterpart, which may be ascribed to lower crosslinking density and greater segmental mobility. The longer chain between crosslinked points of PEGDA6000-PEM is responsible for greater extensibility of ~80% versus ~7% of PEGDA700-PEM. Besides, both PEMs exhibited thermal stability up to 120 °C and electrochemical stability versus Li+/Li up to 4.7V. LiFePO4/PEM/Li and Li4Ti5O12 /PEM/Li half-cells exhibited stable cyclic behavior up to 50 cycles tested with a capacity of ~140mAh/g, suggesting that LiFePO4/PEM/Li4Ti5O12 may be a promising full-cell for all solid-state lithium battery. We thank NSF-DMR 1161070 for providing funding of this project.

Functionalization of calcium carbonate microparticles as a combined sensor and transport system for active agents in cells.

PubMed

Reibetanz, Uta; Chen, Min Hui Averil; Mutukumaraswamy, Shaillender; Liaw, Zi Yen; Oh, Bernice Hui Lin; Donath, Edwin; Neu, Björn

2011-01-01

In recent years colloidal particles and capsules, layer-by-layer (LbL) coated with biocompatible polyelectrolytes, have received much attention as drug-delivery systems. In this study an LbL-assembled, biopolymer-based multilayer system was established as a combined transporter and sensor for monitoring intracellular degradation and processing. CaCO(3) cores were functionalized with fluorescein isothiocyanatelabelled poly(allylamine hydrochloride) (FITC-PAH). This pH-sensitive fluorescent dye allows identifying the location of these LbL-coated particles in cell compartments of different pH, like the endo-lysosome and cytoplasm. The labelled core was then coated with consecutive layers of protamine (PRM) and dextran sulfate (DXS). Finally, plasmid DNA (pEGFP-C1) as a reporter agent for drug release in the cytoplasm was integrated into the biocompatible and degradable PRM/DXS multilayer. The system was tested regarding its long-term stability and interaction with HEK 293T/17 cells. These multifunctional microparticles allow the simultaneous investigation of particle localization and processing within cells, and should thus provide a valuable tool for studying and improving the controlled LbL-based release of active agents into cells. © Koninklijke Brill NV, Leiden, 2011

Method of monitoring CO concentrations in hydrogen feed to a PEM fuel cell

DOEpatents

Grot, Stephen Andreas; Meltser, Mark Alexander; Gutowski, Stanley; Neutzler, Jay Kevin; Borup, Rodney Lynn; Weisbrod, Kirk

2000-01-01

The CO concentration in the H.sub.2 feed stream to a PEM fuel cell stack is monitored by measuring current and/or voltage behavior patterns from a PEM-probe communicating with the reformate feed stream. Pattern recognition software may be used to compare the current and voltage patterns from the PEM-probe to current and voltage telltale outputs determined from a reference cell similar to the PEM-probe and operated under controlled conditions over a wide range of CO concentrations in the H.sub.2 fuel stream. The PEM-probe is intermittently purged of any CO build-up on the anode catalyst (e.g., by (1) flushing the anode with air, (2) short circuiting the PEM-probe, or (3) reverse biasing the PEM-probe) to keep the PEM-probe at peak performance levels.

Gating capacitive field-effect sensors by the charge of nanoparticle/molecule hybrids.

PubMed

Poghossian, Arshak; Bäcker, Matthias; Mayer, Dirk; Schöning, Michael J

2015-01-21

The semiconductor field-effect platform is a powerful tool for chemical and biological sensing with direct electrical readout. In this work, the field-effect capacitive electrolyte-insulator-semiconductor (EIS) structure - the simplest field-effect (bio-)chemical sensor - modified with citrate-capped gold nanoparticles (AuNPs) has been applied for a label-free electrostatic detection of charged molecules by their intrinsic molecular charge. The EIS sensor detects the charge changes in AuNP/molecule inorganic/organic hybrids induced by the molecular adsorption or binding events. The feasibility of the proposed detection scheme has been exemplarily demonstrated by realizing capacitive EIS sensors consisting of an Al-p-Si-SiO2-silane-AuNP structure for the label-free detection of positively charged cytochrome c and poly-d-lysine molecules as well as for monitoring the layer-by-layer formation of polyelectrolyte multilayers of poly(allylamine hydrochloride)/poly(sodium 4-styrene sulfonate), representing typical model examples of detecting small proteins and macromolecules and the consecutive adsorption of positively/negatively charged polyelectrolytes, respectively. For comparison, EIS sensors without AuNPs have been investigated, too. The adsorption of molecules on the surface of AuNPs has been verified via the X-ray photoelectron spectroscopy method. In addition, a theoretical model of the functioning of the capacitive field-effect EIS sensor functionalized with AuNP/charged-molecule hybrids has been discussed.

Proton exchange membrane and electrode surface areas as factors that affect power generation in microbial fuel cells.

PubMed

Oh, Sang-Eun; Logan, Bruce E

2006-03-01

Power generation in microbial fuel cells (MFCs) is a function of the surface areas of the proton exchange membrane (PEM) and the cathode relative to that of the anode. To demonstrate this, the sizes of the anode and cathode were varied in two-chambered MFCs having PEMs with three different surface areas (A (PEM)=3.5, 6.2, or 30.6 cm(2)). For a fixed anode and cathode surface area (A (An)=A (Cat)=22.5 cm(2)), the power density normalized to the anode surface area increased with the PEM size in the order 45 mW/m(2) (A (PEM)=3.5 cm(2)), 68 mW/m(2) (A (PEM)=6.2 cm(2)), and 190 mW/m(2) (A (PEM)=30.6 cm(2)). PEM surface area was shown to limit power output when the surface area of the PEM was smaller than that of the electrodes due to an increase in internal resistance. When the relative cross sections of the PEM, anode, and cathode were scaled according to 2A (Cat)=A(PEM)=2A (An), the maximum power densities of the three different MFCs, based on the surface area of the PEM (A (PEM)=3.5, 6.2, or 30.6 cm(2)), were the same (168+/-4.53 mW/m(2)). Increasing the ionic strength and using ferricyanide at the cathode also increased power output.

A membrane film sensor with encapsulated fluorescent dyes towards express freshness monitoring of packaged food.

PubMed

Kiryukhin, Maxim V; Lau, Hooi Hong; Goh, Seok Hong; Teh, Cathleen; Korzh, Vladimir; Sadovoy, Anton

2018-05-15

A new Membrane Film Sensor (MFS) has been developed to measure pH of fluids. MFS comprises a polyelectrolyte multilayer film with uniformly distributed compartments (microchambers) where a fluorescent sensing dye is encapsulated. Fabricated film is sealed onto a polyethylene film for a future use. MFS was applied to report changes in golden pomfret fillet upon its storage at 5 °C. MFS pH readings were correlated to bacteriological analysis of fish samples. A hike in pH of fish juices happens after 10 days of storage signaling bacterial spoilage of fish. The design of developed MFS allows easy integration with transparent packaging materials for future development of "SMART" packaging sensing food freshness. Copyright © 2018 Elsevier B.V. All rights reserved.

Stiffness-dependent cellular internalization of matrix-bound BMP-2 and its relation to Smad and non-Smad signaling.

PubMed

Gilde, Flora; Fourel, Laure; Guillot, Raphael; Pignot-Paintrand, Isabelle; Okada, Takaharu; Fitzpatrick, Vincent; Boudou, Thomas; Albiges-Rizo, Corinne; Picart, Catherine

2016-12-01

Surface coatings delivering BMP are a promising approach to render biomaterials osteoinductive. In contrast to soluble BMPs which can interact with their receptors at the dorsal side of the cell, BMPs presented as an insoluble cue physically bound to a biomimetic matrix, called here matrix-bound (bBMP-2), are presented to cells by their ventral side. To date, BMP-2 internalization and signaling studies in cell biology have always been performed by adding soluble (sBMP-2) to cells adhered on cell culture plates or glass slides, which will be considered here as a "reference" condition. However, whether and how matrix-bound BMP-2 can be internalized by cells and its relation to canonical (SMAD) and non-canonical signaling (ALP) remain open questions. In this study, we investigated the uptake and processing of BMP-2 by C2C12 myoblasts. This BMP-2 was presented either embedded in polyelectrolyte multilayer films (matrix-bound presentation) or as soluble form. Using fluorescently labeled BMP-2, we showed that the amount of matrix-bound BMP-2 internalized is dependent on the level of crosslinking of the polyelectrolyte films. Cav-1-mediated internalization is related to both SMAD and ALP signaling, while clathrin-mediated is only related to ALP signaling. BMP-2 internalization was independent of the presentation mode (sBMP-2 versus bBMP-2) for low crosslinked films (soft, EDC10) in striking contrast with high crosslinked (stiff, EDC70) films where internalization was much lower and slower for bBMP-2. As anticipated, internalization of sBMP-2 barely depended on the underlying matrix. Taken together, these results indicate that BMP-2 internalization can be tuned by the underlying matrix and activates downstream BMP-2 signaling, which is key for the effective formation of bone tissue. The presentation of growth factors from material surfaces currently presents significant challenges in academic research, clinics and industry. Being able to deliver efficiently these growth factors by a biomaterial will open new perspectives for regenerative medicine. However, to date, very little is known about how matrix-bound growth factors are delivered to cells, especially whether they are internalized and how they are signaling to drive key differentiation events. These initial steps are crucial as they will guide the subsequent processes leading to tissue regeneration. In this work, we investigate the uptake and processing by cells of BMP-2 ligands embedded in polyelectrolyte multilayer films in comparison to soluble BMP-2. We show that BMP-2 responsive cells can internalize matrix-bound BMP-2 and that internalization is dependent on the cross-linking level of the polyelectrolyte films. In addition, we show that internalization is mediated by both clathrin- and caveolin-dependent pathways. While inhibiting clathrin-dependent endocytosis affects only non-canonical signaling, blocking caveolin-1-dependent endocytosis reduces both canonical and non-canonical BMP signaling. The signaling pathways found for matrix-bound BMP-2 are similar to those found for soluble BMP-2. These results highlight that BMP-2 presented by a biomaterial at the ventral side of the cell can trigger major endocytic and associated signaling pathways leading to bone regeneration. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Simulating the thermodynamics of charging in weak polyelectrolytes: the Debye-Hückel limit

NASA Astrophysics Data System (ADS)

Rathee, Vikramjit S.; Sikora, Benjamin J.; Sidky, Hythem; Whitmer, Jonathan K.

2018-01-01

The coil-globule transition in weak (annealed) polyelectrolytes involves a subtle balance of pH, charge strength, and solvation forces. In this work, we utilize a coarse-grained hybrid grand-canonical Monte Carlo and molecular dynamics approach to explore the swelling behavior of weak linear and star polyelectrolytes under different ionic screening conditions and pH. Importantly, we are able to quantify topology-dependent effects in charging which arise at the core of star polymers. Our results are suggestive of suppression of charging in star weak polyelectrolytes in comparison to linear weak polyelectrolytes. Furthermore, we characterize the coil-globule transition in linear and star weak polyelectrolyte through expanded ensemble density-of-states simulations which suggest a change from a first order to second order phase transition moving from linear to star polyelectrolytes. Lastly, we characterize the inhomogeneous charging across the weak star polyelectrolyte through observed shifts in {{Δ }}{{{pK}}}{{o}}, and compare with experimental work. We discuss these results in relation to surfaces functionalized by weak polyelectrolyte brushes and weak polyelectrolyte-based drug delivery applications.

Availability and Readability of Online Patient Education Materials Regarding Regional Anesthesia Techniques for Perioperative Pain Management.

PubMed

Kumar, Gunjan; Howard, Steven K; Kou, Alex; Kim, T Edward; Butwick, Alexander J; Mariano, Edward R

2017-10-01

Patient education materials (PEM) should be written at a sixth-grade reading level or lower. We evaluated the availability and readability of online PEM related to regional anesthesia and compared the readability and content of online PEM produced by fellowship and nonfellowship institutions. With IRB exemption, we constructed a cohort of online regional anesthesia PEM by searching Websites from North American academic medical centers supporting a regional anesthesiology and acute pain medicine fellowships and used a standardized Internet search engine protocol to identify additional nonfellowship Websites with regional anesthesia PEM based on relevant keywords. Readability metrics were calculated from PEM using the TextStat 0.1.4 textual analysis package for Python 2.7 and compared between institutions with and without a fellowship program. The presence of specific descriptive PEM elements related to regional anesthesia was also compared between groups. PEM from 17 fellowship and 15 nonfellowship institutions were included in analyses. The mean (SD) Flesch-Kincaid Grade Level for PEM from the fellowship group was 13.8 (2.9) vs 10.8 (2.0) for the nonfellowship group (p = 0.002). We observed no other differences in readability metrics between fellowship and nonfellowship institutions. Fellowship-based PEM less commonly included descriptions of the following risks: local anesthetic systemic toxicity (p = 0.033) and injury due to an insensate extremity (p = 0.003). Available online PEM related to regional anesthesia are well above the recommended reading level. Further, fellowship-based PEM posted are at a higher reading level than PEM posted by nonfellowship institutions and are more likely to omit certain risk descriptions. 2016 American Academy of Pain Medicine. This work is written by US Government employees and is in the public domain in the US.

Bi-polarized translation of ascidian maternal mRNA determinant pem-1 associated with regulators of the translation machinery on cortical Endoplasmic Reticulum (cER).

PubMed

Paix, Alexandre; Le Nguyen, Phuong Ngan; Sardet, Christian

2011-09-01

Polarized cortical mRNA determinants such as maternal macho-1 and pem-1 in ascidians, like budding yeast mating factor ASH1 reside on the cER-mRNA domain a subdomain of cortical Endoplasmic Reticulum(ER) and are translated in its vicinity. Using high resolution imaging and isolated cortical fragments prepared from eggs and embryos we now find that macho-1 and pem-1 RNAs co-localize with phospho-protein regulators of translation initiation (MnK/4EBP/S6K). Translation of cortical pem-1 RNA follows its bi-polarized relocalization. About 10 min after fertilization or artificial activation with a calcium ionophore, PEM1 protein is detected in the vegetal cortex in the vicinity of pem-1 RNA. About 40 min after fertilization-when pem-1 RNA and P-MnK move to the posterior pole-PEM1 protein remains in place forming a network of cortical patches anchored at the level of the zygote plasma membrane before disappearing. Cortical PEM1 protein is detected again at the 4 cell stage in the posterior centrosome attracting body (CAB) region where the cER-mRNA domain harboring pem-1/P-MnK/P-4EBP/P-S6K is concentrated. Bi-polarized PEM1 protein signals are not detected when pem-1 morpholinos are injected into eggs or zygotes or when MnK is inhibited. We propose that localized translation of the pem-1 RNA determinant is triggered by the fertilization/calcium wave and that the process is controlled by phospho-protein regulators of translation initiation co-localized with the RNA determinant on a sub-domain of the cortical Endoplasmic Reticulum. Copyright © 2011 Elsevier Inc. All rights reserved.

Post-Exertional Malaise in Patients with ME and CFS with Comorbid Fibromyalgia.

PubMed

McManimen, Stephanie L; Jason, Leonard A

2017-01-01

Myalgic encephalomyelitis (ME) and chronic fatigue syndrome (CFS) share some similar symptoms with fibromyalgia (FM). Prior research has found increased illness severity when patients have FM that is comorbid with ME and CFS. For example, post-exertional malaise (PEM) has been shown to be more severe in those with comorbid FM. However, PEM can be separated into two factors, Muscle and General PEM. It is unknown if the more severe PEM findings in comorbid FM are due to the Muscle or General PEM factor. The purpose of this study was to determine if the PEM differences seen between patients with and without comorbid FM exist for the Muscle or General PEM factors. An international convenience sample was collected via an online questionnaire. The questionnaire assessed the frequency and severity of several PEM-related symptoms. Additionally, participants provided information regarding the course and characteristics of their illness. Participants that indicated a comorbid diagnosis of FM displayed significantly more frequent and severe PEM symptoms in the Muscle and General PEM factors. The FM group also indicated significantly worse physical functioning compared to the group without comorbid FM. The secondary diagnosis of FM in addition to ME and CFS appears to amplify the PEM symptomatology and worsen patients' physical functioning. The findings of this study have notable implications on the inclusion of patients with comorbid FM in ME and CFS research studies.

Reliability analysis and utilization of PEMs in space application

NASA Astrophysics Data System (ADS)

Jiang, Xiujie; Wang, Zhihua; Sun, Huixian; Chen, Xiaomin; Zhao, Tianlin; Yu, Guanghua; Zhou, Changyi

2009-11-01

More and more plastic encapsulated microcircuits (PEMs) are used in space missions to achieve high performance. Since PEMs are designed for use in terrestrial operating conditions, the successful usage of PEMs in space harsh environment is closely related to reliability issues, which should be considered firstly. However, there is no ready-made methodology for PEMs in space applications. This paper discusses the reliability for the usage of PEMs in space. This reliability analysis can be divided into five categories: radiation test, radiation hardness, screening test, reliability calculation and reliability assessment. One case study is also presented to illuminate the details of the process, in which a PEM part is used in a joint space program Double-Star Project between the European Space Agency (ESA) and China. The influence of environmental constrains including radiation, humidity, temperature and mechanics on the PEM part has been considered. Both Double-Star Project satellites are still running well in space now.

Antimicrobial coatings on polyethylene terephthalate based on curcumin/cyclodextrin complex embedded in a multilayer polyelectrolyte architecture.

PubMed

Shlar, Ilya; Droby, Samir; Rodov, Victor

2018-04-01

Bacterial contamination is a growing concern worldwide. The aim of this work was to develop an antimicrobial coating based on curcumin-cyclodextrin inclusion complex and using polyethylene terephthalate (PET) film as a support matrix. After a pre-treatment aimed to provide sufficient electric charge to the PET surface, it was electrostatically coated with repeated multilayers comprising alternately deposited positively-charged poly-l-lysine (PLL) and negatively-charged poly-l-glutamic acid (PLGA) and carboxymethyl-β-cyclodextrin (CMBCD). The coatings had an architecture (PLL-PLGA) 6 -(PLL-PLGA-PLL-CMBCD) n , with the number of repeated multilayers n varying from 5 to 20. The CMBCD molecules were either covalently cross-linked using carbodiimide crosslinker chemistry or left unbound. The surface morphology, structure and elemental composition of the coatings were analysed by scanning electron microscopy and energy dispersive x-ray spectroscopy. To impart antimicrobial properties to the coatings they were loaded with a natural phenolic compound curcumin forming inclusion complexes with β-cyclodextrin. The non-cross-linked coatings showed bactericidal activity towards Escherichia coli in the dark, and this activity was further enhanced upon illumination with white light. Curcumin was released from the non-cross-linked coatings into an aqueous medium in the form of cyclodextrin inclusion complex. After the cross-linking, the coating lost its dark antimicrobial activity but retained the photodynamic properties. Stabilized cross-linked curcumin-loaded coatings can serve a basis for developing photoactivated antimicrobial surfaces controlling bacterial contamination and spread. Copyright © 2018 Elsevier B.V. All rights reserved.

Galactosylated electrospun membranes for hepatocyte sandwich culture.

PubMed

Chien, Hsiu-Wen; Lai, Juin-Yih; Tsai, Wei-Bor

2014-04-01

In this work, we developed a galactocylated electrospun polyurethane membrane for sandwich culture of hepatocyte sandwich culture. The electrospun fibrous membranes were bio-functionalized with galactose molecules by a UV-crosslinked layer-by-layer polyelectrolyte multilayer deposition technique. The galactosylated electrospun membranes were employed as a top support membrane for the sandwich culture of HepG2/C3A cells on a collagen substrate. Our results demonstrate that HepG2/C3A cells covered by the galactosylated PU membranes form multi-cellular aggregates and lead to improved albumin secretion ability compared to the control membranes (unmodified PU or poly(ethylene imine)-modified PU). Our study reveals the potential of galactosylated electrospun membranes in the application of liver tissue engineering and the regeneration of liver-tissue substitutes. Copyright © 2014 Elsevier B.V. All rights reserved.

Additive controlled synthesis of gold nanorods (GNRs) for two-photon luminescence imaging of cancer cells

NASA Astrophysics Data System (ADS)

Zhu, Jing; Yong, Ken-Tye; Roy, Indrajit; Hu, Rui; Ding, Hong; Zhao, Lingling; Swihart, Mark T.; He, Guang S.; Cui, Yiping; Prasad, Paras N.

2010-07-01

Gold nanorods (GNRs) with a longitudinal surface plasmon resonance peak that is tunable from 600 to 1100 nm have been fabricated in a cetyl trimethylammoniumbromide (CTAB) micellar medium using hydrochloric acid and silver nitrate as additives to control their shape and size. By manipulating the concentrations of silver nitrate and hydrochloric acid, the aspect ratio of the GNRs was reliably and reproducibly tuned from 2.5 to 8. The GNRs were first coated with polyelectrolyte multilayers and then bioconjugated to transferrin (Tf) to target pancreatic cancer cells. Two-photon imaging excited from the bioconjugated GNRs demonstrated receptor-mediated uptake of the bioconjugates into Panc-1 cells, overexpressing the transferrin receptor (TfR). The bioconjugated GNR formulation exhibited very low toxicity, suggesting that it is biocompatible and potentially suitable for targeted two-photon bioimaging.

Self-recovery of stressed nanomembranes

NASA Astrophysics Data System (ADS)

Jiang, Chaoyang; Rybak, Beth M.; Markutsya, Sergiy; Kladitis, Paul E.; Tsukruk, Vladimir V.

2005-03-01

Long-term stability and self-recovery properties were studied for the compliant nanomembranes with a thickness of 55nm free suspended over openings of several hundred microns across. These nanomembranes were assembled with spin-assisted layer-by-layer routines and were composed of polymer multilayers and gold nanoparticles. In a wide pressure range, the membranes behave like completely elastic freely suspended plates. Temporal stability was tested under extreme deformational conditions close to ultimate strain and very modest creep behavior was observed. A unique "self-recovery" ability of these nanomembranes was revealed in these tests. We observed a complete restoration of the initial nanomembrane shape and properties after significant inelastic deformation. These unique micromechanical properties are suggested to be the result of strong Coulombic interaction between the polyelectrolyte layers combined with a high level of biaxial orientation of polymer chains and in-plane prestretching stresses.

Satellite-based terrestrial production efficiency modeling

PubMed Central

McCallum, Ian; Wagner, Wolfgang; Schmullius, Christiane; Shvidenko, Anatoly; Obersteiner, Michael; Fritz, Steffen; Nilsson, Sten

2009-01-01

Production efficiency models (PEMs) are based on the theory of light use efficiency (LUE) which states that a relatively constant relationship exists between photosynthetic carbon uptake and radiation receipt at the canopy level. Challenges remain however in the application of the PEM methodology to global net primary productivity (NPP) monitoring. The objectives of this review are as follows: 1) to describe the general functioning of six PEMs (CASA; GLO-PEM; TURC; C-Fix; MOD17; and BEAMS) identified in the literature; 2) to review each model to determine potential improvements to the general PEM methodology; 3) to review the related literature on satellite-based gross primary productivity (GPP) and NPP modeling for additional possibilities for improvement; and 4) based on this review, propose items for coordinated research. This review noted a number of possibilities for improvement to the general PEM architecture - ranging from LUE to meteorological and satellite-based inputs. Current PEMs tend to treat the globe similarly in terms of physiological and meteorological factors, often ignoring unique regional aspects. Each of the existing PEMs has developed unique methods to estimate NPP and the combination of the most successful of these could lead to improvements. It may be beneficial to develop regional PEMs that can be combined under a global framework. The results of this review suggest the creation of a hybrid PEM could bring about a significant enhancement to the PEM methodology and thus terrestrial carbon flux modeling. Key items topping the PEM research agenda identified in this review include the following: LUE should not be assumed constant, but should vary by plant functional type (PFT) or photosynthetic pathway; evidence is mounting that PEMs should consider incorporating diffuse radiation; continue to pursue relationships between satellite-derived variables and LUE, GPP and autotrophic respiration (Ra); there is an urgent need for satellite-based biomass measurements to improve Ra estimation; and satellite-based soil moisture data could improve determination of soil water stress. PMID:19765285

Inkjet Deposition of Layer by Layer Assembled Films

PubMed Central

Andres, Christine M.; Kotov, Nicholas A.

2010-01-01

Layer-by-layer assembly (LBL) can create advanced composites with exceptional properties unavailable by other means, but the laborious deposition process and multiple dipping cycles hamper their utilization in microtechnologies and electronics. Multiple rinse steps provide both structural control and thermodynamic stability to LBL multilayers but they significantly limit their practical applications and contribute significantly to the processing time and waste. Here we demonstrate that by employing inkjet technology one can deliver the necessary quantities of LBL components required for film build-up without excess, eliminating the need for repetitive rinsing steps. This feature differentiates this approach from all other recognized LBL modalities. Using a model system of negatively charged gold nanoparticles and positively charged poly(diallyldimethylammonium) chloride, the material stability, nanoscale control over thickness and particle coverage offered by the inkjet LBL technique are shown to be equal or better than the multilayers made with traditional dipping cycles. The opportunity for fast deposition of complex metallic patterns using a simple inkjet printer was also shown. The additive nature of LBL deposition based on the formation of insoluble nanoparticle-polyelectrolyte complexes of various compositions provides an excellent opportunity for versatile, multi-component, and non-contact patterning for the simple production of stratified patterns that are much needed in advanced devices. PMID:20863114

Directed assembly of three-dimensional structures with micron-scale features

DOEpatents

Gratson, Gregory; Lewis, Jennifer A.

2006-11-28

The invention provides polyelectrolyte inks comprising a solvent, a cationic polyelectrolyte, dissolved in the solvent, and an anionic polyelectrolyte, dissolved in the solvent. The concentration of at least one of the polyelectrolytes in the solvent is in a semidilute regime.

Fuel cell CO sensor

DOEpatents

Grot, Stephen Andreas; Meltser, Mark Alexander; Gutowski, Stanley; Neutzler, Jay Kevin; Borup, Rodney Lynn; Weisbrod, Kirk

1999-12-14

The CO concentration in the H.sub.2 feed stream to a PEM fuel cell stack is monitored by measuring current and/or voltage behavior patterns from a PEM-probe communicating with the reformate feed stream. Pattern recognition software may be used to compare the current and voltage patterns from the PEM-probe to current and voltage telltale outputs determined from a reference cell similar to the PEM-probe and operated under controlled conditions over a wide range of CO concentrations in the H.sub.2 fuel stream. A CO sensor includes the PEM-probe, an electrical discharge circuit for discharging the PEM-probe to monitor the CO concentration, and an electrical purging circuit to intermittently raise the anode potential of the PEM-probe's anode to at least about 0.8 V (RHE) to electrochemically oxidize any CO adsorbed on the probe's anode catalyst.

Casein Aggregates Built Step-by-Step on Charged Polyelectrolyte Film Surfaces Are Calcium Phosphate-cemented*

PubMed Central

Nagy, Krisztina; Pilbat, Ana-Maria; Groma, Géza; Szalontai, Balázs; Cuisinier, Frédéric J. G.

2010-01-01

The possible mechanism of casein aggregation and micelle buildup was studied in a new approach by letting α-casein adsorb from low concentration (0.1 mg·ml−1) solutions onto the charged surfaces of polyelectrolyte films. It was found that α-casein could adsorb onto both positively and negatively charged surfaces. However, only when its negative phosphoseryl clusters remained free, i.e. when it adsorbed onto a negative surface, could calcium phosphate (CaP) nanoclusters bind to the casein molecules. Once the CaP clusters were in place, step-by-step building of multilayered casein architectures became possible. The presence of CaP was essential; neither Ca2+ nor phosphate could alone facilitate casein aggregation. Thus, it seems that CaP is the organizing motive in the casein micelle formation. Atomic force microscopy revealed that even a single adsorbed casein layer was composed of very small (in the range of tens of nanometers) spherical forms. The stiffness of the adsorbed casein layer largely increased in the presence of CaP. On this basis, we can imagine that casein micelles emerge according to the following scheme. The amphipathic casein monomers aggregate into oligomers via hydrophobic interactions even in the absence of CaP. Full scale, CaP-carrying micelles could materialize by interlocking these casein oligomers with CaP nanoclusters. Such a mechanism would not contradict former experimental results and could offer a synthesis between the submicelle and the block copolymer models of casein micelles. PMID:20921229

Microcapsules functionalized with neuraminidase can enter vascular endothelial cells in vitro

PubMed Central

Liu, Weizhi; Wang, Xiaocong; Bai, Ke; Lin, Miao; Sukhorukov, Gleb; Wang, Wen

2014-01-01

Microcapsules made of polyelectrolyte multilayers exhibit no or low toxicity, appropriate mechanical stability, variable controllable degradation and can incorporate remote release mechanisms triggered by various stimuli, making them well suited for targeted drug delivery to live cells. This study investigates interactions between microcapsules made of synthetic (i.e. polystyrenesulfonate sodium salt/polyallylamine hydrochloride) or natural (i.e. dextran sulfate/poly-l-arginine) polyelectrolyte and human umbilical vein endothelial cells with particular focus on the effect of the glycocalyx layer on the intake of microcapsules by endothelial cells. Neuraminidase cleaves N-acetyl neuraminic acid residues of glycoproteins and targets the sialic acid component of the glycocalyx on the cell membrane. Three-dimensional confocal images reveal that microcapsules, functionalized with neuraminidase, can be internalized by endothelial cells. Capsules without neuraminidase are blocked by the glycocalyx layer. Uptake of the microcapsules is most significant in the first 2 h. Following their internalization by endothelial cells, biodegradable DS/PArg capsules rupture by day 5; however, there is no obvious change in the shape and integrity of PSS/PAH capsules within the period of observation. Results from the study support our hypothesis that the glycocalyx functions as an endothelial barrier to cross-membrane movement of microcapsules. Neuraminidase-loaded microcapsules can enter endothelial cells by localized cleavage of glycocalyx components with minimum disruption of the glycocalyx layer and therefore have high potential to act as drug delivery vehicles to reach tissues beyond the endothelial barrier of blood vessels. PMID:25339691

[Preparation of polyelectrolyte microcapsules containing ferrosoferric oxide nanoparticles].

PubMed

Liu, Xiao-Qing; Zheng, Chun-Li; Zhu, Jia-Bi

2011-01-01

In this study, polyelectrolyte microcapsules have been fabricated by biocompatible ferrosoferric oxide nanoparticles (Fe3O4 NPs) and poly allyamine hydrochloride (PAH) using layer by layer assembly technique. The Fe3O4 NPs were prepared by chemical co-precipitation, and characterized by transmission electron microscopy (TEM) and infrared spectrum (IR). Quartz cell also was used as a substrate for building multilayer films to evaluate the capability of forming planar film. The result showed that Fe3O4 NPs were selectively deposited on the surface of quartz cell. Microcapsules containing Fe3O4 NPs were fabricated by Fe3O4 NPs and PAH alternately self-assembly on calcium carbonate microparticles firstly, then 0.2 molL(-1) EDTA was used to remove the calcium carbonate. Scanning electron microscopy (SEM), Zetasizer and vibrating sample magnetometer (VSM) were used to characterize the microcapsule's morphology, size and magnetic properties. The result revealed that Fe3O4 NPs and PAH were successfully deposited on the surface of CaCO3 microparticles, the microcapsule manifested superparamagnetism, size and saturation magnetization were 4.9 +/- 1.2 microm and 8.94 emu x g(-1), respectively. As a model drug, Rhodamin B isothiocyanate labeled bovine serum albumin (RBITC-BSA) was encapsulated in microcapsule depended on pH sensitive of the microcapsule film. When pH 5.0, drug add in was 2 mg, the encapsulation efficiency was (86.08 +/- 3.36) % and the drug loading was 8.01 +/- 0.30 mg x m(L-1).

Systematic Assessment Reveals Lack of Understandability for Prostate Biopsy Online Patient Education Materials.

PubMed

Maciolek, Kimberly A; Jarrard, David F; Abel, E Jason; Best, Sara L

2017-11-01

To evaluate the accuracy, readability, understandability, and actionability of Internet patient education materials (PEM) about transrectal ultrasound-guided prostate biopsy. A comprehensive Internet search was performed to find PEM with pre- or postbiopsy instructions. PEM that were duplicates, government affiliated, international, or video based were excluded. Biopsy instructions were evaluated for accuracy and presence of essential topics. Readability was assessed via word count and Flesch-Kincaid Grade Level. Understandability and actionability were measured using the Patient Education Materials Assessment Tool (PEMAT). Effects of authorship and geographical variation were determined using Fischer exact and Kruskal-Wallis tests. We identified 148 unique PEM. Only 31 (21%) sites adhered to the recommended <8th grade reading level. Most PEM did not contain recommended graphics (14%), checklists (2%), or summaries (6%). The PEMAT understandability score for academic PEM was higher than private (P = .02) and unaffiliated PEM (P = .01). No websites had inaccurate content. Only 2 PEM sites (1%) included all essential content (stop anticoagulants, antibiotics, need for urinalysis, biopsy pain, when to resume activity, and bleeding complications). Few significant differences based on geographic region were observed for word count, readability, PEMAT scores, or content. Transrectal ultrasound-guided prostate biopsy PEM adhere poorly to guidelines for easy-to-understand materials. Most PEM lack vital information and are written at a reading level that is too complex for patient comprehension. The urology community can construct better websites by consulting PEM advisory materials and providing nontechnical language, figures, and specific instructions. Published by Elsevier Inc.

Freestanding and Reactive Thin Films Fabricated by Covalent Layer-by-Layer Assembly and Subsequent Lift-Off of Azlactone-Containing Polymer Multilayers

PubMed Central

Buck, Maren E.

2010-01-01

We report an approach to the fabrication of freestanding and amine-reactive thin films that is based on the reactive layer-by-layer assembly and subsequent lift-off of azlactone-containing polymer multilayers. We demonstrate that covalently crosslinked multilayers fabricated using the azlactone-functionalized polymer poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) and a primary amine-containing polymer [poly(ethyleneimine) (PEI)] can be delaminated from planar glass and silicon surfaces by immersion in mildly acidic aqueous environments to yield flexible freestanding membranes. These freestanding membranes are robust and can withstand exposure to strong acid, strong base, or incubation in high ionic strength solutions that typically lead to the disruption and erosion of polymer multilayers assembled by reversible weak interactions (e.g., ‘polyelectrolyte multilayers’ assembled by electrostatic interactions or hydrogen bonding). We demonstrate further that these PEI/PVDMA assemblies contain residual reactive azlactone functionality that can be exploited to chemically modify the films (either directly after fabrication or after they have been lifted off of the substrates on which they were fabricated) using a variety of amine-functionalized small molecules. These freestanding membranes can also be transferred readily onto other objects (for example, onto the surfaces of planar substrates containing holes or pores) to fabricate suspended polymer membranes and other film-functionalized interfaces. In addition to planar, two-dimensional freestanding films, this approach can be used to fabricate and isolate three-dimensional freestanding membranes (e.g., curved films or tubes) by layer-by-layer assembly on, and subsequent lift-off from, the surfaces of topologically complex substrates (e.g., the curved ends of glass tubing, etc.). The results of this investigation, when combined, suggest the basis of methods for the fabrication of stable, chemically-reactive, and flexible polymer thin films and membranes of potential utility in a variety of fundamental and applied contexts. PMID:20857952

Scaling Theory of Polyelectrolyte Nanogels

NASA Astrophysics Data System (ADS)

Qu, Li-Jian

2017-08-01

The present paper develops the scaling theory of polyelectrolyte nanogels in dilute and semidilute solutions. The dependencies of the nanogel dimension on branching topology, charge fraction, subchain length, segment number, solution concentration are obtained. For a single polyelectrolyte nanogel in salt free solution, the nanogel may be swelled by the Coulombic repulsion (the so-called polyelectrolyte regime) or the osmotic counterion pressure (the so-called osmotic regime). Characteristics and boundaries between different regimes of a single polyelectrolyte nanogel are summarized. In dilute solution, the nanogels in polyelectrolyte regime will distribute orderly with the increase of concentration. While the nanogels in osmotic regime will always distribute randomly. Different concentration dependencies of the size of a nanogel in polyelectrolyte regime and in osmotic regime are also explored. Supported by China Earthquake Administration under Grant No. 20150112 and National Natural Science Foundation of China under Grant No. 21504014

Thermal stability control system of photo-elastic interferometer in the PEM-FTs

NASA Astrophysics Data System (ADS)

Zhang, M. J.; Jing, N.; Li, K. W.; Wang, Z. B.

2018-01-01

A drifting model for the resonant frequency and retardation amplitude of a photo-elastic modulator (PEM) in the photo-elastic modulated Fourier transform spectrometer (PEM-FTs) is presented. A multi-parameter broadband-matching driving control method is proposed to improve the thermal stability of the PEM interferometer. The automatically frequency-modulated technology of the driving signal based on digital phase-locked technology is used to track the PEM's changing resonant frequency. Simultaneously the maximum optical-path-difference of a laser's interferogram is measured to adjust the amplitude of the PEM's driving signal so that the spectral resolution is stable. In the experiment, the multi-parameter broadband-matching control method is applied to the driving control system of the PEM-FTs. Control of resonant frequency and retardation amplitude stabilizes the maximum optical-path-difference to approximately 236 μm and results in a spectral resolution of 42 cm-1. This corresponds to a relative error smaller than 2.16% (4.28 standard deviation). The experiment shows that the method can effectively stabilize the spectral resolution of the PEM-FTs.

Compendium of NASA data base for the Global Tropospheric Experiment's Pacific Exploratory Mission West-A (PEM West-A)

NASA Technical Reports Server (NTRS)

Gregory, G. L.; Scott, A. D., Jr.

1995-01-01

This compendium describes aircraft data that are available from NASA's Pacific Exploratory Mission West-A (PEM West-A). PEM West is a component of the International Global Atmospheric Chemistry's (IGAC) East Asia/North Pacific Regional Study (APARE) project. The PEM- West program encompassed two expeditions to study contrasting meteorological regimes in the Pacific. Objectives of PEM West are to investigate the atmospheric chemistry of ozone over the northwest Pacific -- natural budgets and the impact of anthropogenic sources; and to investigate sulfur chemistry -- continental versus marine sulfur sources. PEM West-A was conducted in September 1991 during which the predominance of tropospheric air is from the mid-Pacific (marine) regions, but (at times) is modified/mixed with Asian continental outflow. PEM West-B was conducted during February 1994, a period characterized by maximum continental outflow. PEM-B data (not included) will become public domain during the Summer of 1995. PEM West-A flight experiments were based at Japan, Hong Kong, and Guam. This document provides a representation of NASA DC-8 aircraft data that are available from NASA Langley's Distributed Active Archive Center (DAAC), which include numerous data such as meteorological observations, modeling products, results from surface studies, satellite observations, and sonde releases.

Compendium of NASA data base for the global tropospheric experiment's Pacific Exploratory Mission West-B (PEM West-B)

NASA Technical Reports Server (NTRS)

Gregory, Gerald L.; Scott, A. Donald, Jr.

1995-01-01

This compendium describes aircraft data that are available from NASA's Pacific Exploratory Mission West-B (PEM West-B). PEM West is a component of the International Global Atmospheric Chemistry's (IGAC) East Asia/North Pacific Regional Study (APARE) project. Objectives of PEM West are to investigate the atmospheric chemistry of ozone over the northwest Pacific -- natural budgets and the impact of anthropogenic/continental sources; and to investigate sulfur chemistry -- continental and marine sulfur sources. The PEM West program encompassed two expeditions. PEM West-A was conducted in September 1991 during which the predominance of tropospheric air was from mid-Pacific (marine) regions, but (at times) was modified by Asian outflow. PEM West-B was conducted during February 1994, a period characterized by maximum Asian outflow. Results from PEM West-A and B are public domain. PEM West-A data are summarized in NASA TM 109177 (published February 1995). Flight experiments were based at Guam, Hong Kong, and Japan. This document provides a representation of NASA DC-8 aircraft data that are available from NASA Langley's Distributed Active Archive Center (DAAC). The DAAC includes numerous other data such as meteorological and modeling products, results from surface studies, satellite observations, and sonde releases.

[Organizational forms of emergency medicine in international comparison].

PubMed

Lipp, M

1993-09-01

The tasks of preclinical emergency medicine systems (PEMS) are to stabilize and maintain the vital functions and to guarantee qualified transport to the hospital. Worldwide, different structures exist as a result of historical developments. Legal regulations for PEMS have been introduced in most of the industrialized countries since 1960. More and more aspects have been subject to detailed regulations. PEMS are provided either by state-owned or by state-controlled (private) organisations. In most of the "underdeveloped" countries legal regulations do not exist and PEMS is often provided by social workers, by the army or by volunteers. In most countries, PEMS are financed by the state with a charge on the patient. In a few states PEMS are totally financed by the public health structure. Modern PEMS are controlled from dispatch centres which receive emergency calls (mostly by telephone) and send the appropriate rescue unit. In most states the staff of dispatch centres are paramedics; in some countries and in some urban areas physicians control the dispatch centre. In PEMS without physicians on the scene, an information exchange between the scene and the hospital can be observed frequently, in contrast to systems with physicians on the scene. Worldwide, ground-based PEMS are preferred, but in most countries an additional air rescue system has been established. The quality and quantity of the technical equipment of the ground-based PEMS differ widely: nationwide regulations exist, however, in the USA and Germany. Generally, there are two main concepts concerning the personnel structure: PEMS are either physician based or not. Requirements for emergency physicians differ greatly: in some countries no formal requirements exist, in others extensive practical and theoretical training is required.(ABSTRACT TRUNCATED AT 250 WORDS)

Large Scale PEM Electrolysis to Enable Renewable Hydrogen Fuel Production

DTIC Science & Technology

2010-02-10

PEM Fuel Cell Anode + -Cathode e- e- e- e- Electric load...BOP system. • Enables new product launch (C- Series) Proton PEM cell stack for UK Vanguard subs 18UNCLASSIFIED: Dist A. Approved for public release...UNCLASSIFIED: Dist A. Approved for public release “Large Scale PEM Electrolysis to Enable Renewable Hydrogen Fuel Production” Alternative Energy

A photoelastic modulator-based birefringence imaging microscope for measuring biological specimens

NASA Astrophysics Data System (ADS)

Freudenthal, John; Leadbetter, Andy; Wolf, Jacob; Wang, Baoliang; Segal, Solomon

2014-11-01

The photoelastic modulator (PEM) has been applied to a variety of polarimetric measurements. However, nearly all such applications use point-measurements where each point (spot) on the sample is measured one at a time. The main challenge for employing the PEM in a camera-based imaging instrument is that the PEM modulates too fast for typical cameras. The PEM modulates at tens of KHz. To capture the specific polarization information that is carried on the modulation frequency of the PEM, the camera needs to be at least ten times faster. However, the typical frame rates of common cameras are only in the tens or hundreds frames per second. In this paper, we report a PEM-camera birefringence imaging microscope. We use the so-called stroboscopic illumination method to overcome the incompatibility of the high frequency of the PEM to the relatively slow frame rate of a camera. We trigger the LED light source using a field-programmable gate array (FPGA) in synchrony with the modulation of the PEM. We show the measurement results of several standard birefringent samples as a part of the instrument calibration. Furthermore, we show results observed in two birefringent biological specimens, a human skin tissue that contains collagen and a slice of mouse brain that contains bundles of myelinated axonal fibers. Novel applications of this PEM-based birefringence imaging microscope to both research communities and industrial applications are being tested.

Young Children's Participation and Environment Measure: Swedish Cultural Adaptation.

PubMed

Åström, Frida Marie; Khetani, Mary; Axelsson, Anna Karin

2018-08-01

To culturally adapt and evaluate the psychometric properties of the Young Children's Participation and Environment Measure (YC-PEM) for use by caregivers of Swedish children with and without disabilities, aged 2-5 years. Thirteen cognitive interviews and two focus groups with caregivers of children with and without disabilities were conducted to evaluate the cultural relevance of YC-PEM content for use in Sweden. Per participant feedback, a revised version of the Swedish YC-PEM was created and pilot tested with caregivers of children with disabilities (n = 11) and children with typical development (n = 22). User feedback informed content revisions to 7% of items. Internal consistency estimates of the Swedish YC-PEM pilot version were acceptable and ranged from .70 to .92 for all but two of the YC-PEM scales. Mean percentage agreement between raters ranged from 47% to 93% across YC-PEM scales for inter-rater, and 44% to 86% for test-retest. One of twelve YC-PEM scales revealed significant group differences between young children with and without disabilities. This study contributes preliminary evidence for the use of some scales within a culturally adapted YC-PEM in Sweden. Further validation with larger samples will allow for parametric testing to evaluate its psychometric properties.

Assessing the reading level of online sarcoma patient education materials.

PubMed

Patel, Shaan S; Sheppard, Evan D; Siegel, Herrick J; Ponce, Brent A

2015-01-01

Cancer patients rely on patient education materials (PEMs) to gather information regarding their disease. Patients who are better informed about their illness have better health outcomes. The National Institutes of Health (NIH) recommends that PEMs be written at a sixth- to seventh-grade reading level. The purpose of this study was to evaluate the readability of online PEMs of bone and soft-tissue sarcomas and related conditions. We identified relevant online PEMs from the following websites: American Academy of Orthopaedic Surgeons, academic training centers, sarcoma specialists, Google search hits, Bonetumor.org, Sarcoma Alliance, Sarcoma Foundation of America, and Medscape. We used 10 different readability instruments to evaluate the reading level of each website's PEMs. In assessing 72 websites and 774 articles, we found that none of the websites had a mean readability score at or below 7 (seventh grade). Collectively, all websites had a mean readability score of 11.4, and the range of scores was grade level 8.9 to 15.5. None of the PEMs in this study of bone and soft-tissue sarcomas and related conditions met the NIH recommendation for PEM reading levels. Concerted efforts to improve the reading level of orthopedic oncologic PEMs are necessary.

Influence of polymeric electron injection layers on the electrical properties of solution-processed multilayered polymer light-emitting diodes

NASA Astrophysics Data System (ADS)

Itoh, Eiji; Kurami, Kazuhiko

2016-02-01

In this study, we fabricated multilayered polymer-based light-emitting diodes (pLEDs) with various solution-processed electron-injection layers (EILs), and investigated the influence of the EILs on the electrical properties of pLEDs in indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonic acid) (PEDOT:PSS)/poly[(9,9-dioctylfluorene-alt-(1,4-phenylene((4-sec-butylphenyl)amino)-1,4-phenylene))] (TFB) (HTL)/poly(9,9-dioctylfluorene-alt-1,4-benzothiadiazole) (F8BT) (EML)/EIL/Al structures. We have used the quaternized ammonium π-conjugated polyelectrolyte derivative (poly[(9,9-di(3,3‧-N,N‧-trimethylammonium)propylfluorenyl-2,7-diyl)-co-(1,4-phenylene)]diiodide salt) (PF-PDTA), a mixture of PF-PDTA and CS2CO3, and the aliphatic-amine-based polymer poly(ethylene imine) (PEI) as solution-processed EILs, and compared them with LiF as a solvent-free EIL. The EILs enhanced the electron injection and improve the pLED performance. High external quantum efficiencies of nearly 4% were obtained in the pLEDs with the combination of a multilayered structure fabricated by a transfer printing technique and EILs of a PF-PDTA:CS2CO3 mixture and PEI. On the other hand, the device with PF-PDTA exhibited lower efficiency, higher driving voltage, and larger leakage current at lower voltage. The migration of ionic charges was suggested from the abnormal dielectric behaviors, and serious damage on the electrode material occurred when both an acid hole-injection layer (PEDOT:PSS) and PF-PDTA were used. On the other hand, the pLEDs with ultrathin PEI showed high performance and stable device operation in terms of the influence of ionic charges.

Engineering the Structure and Properties of DNA-Nanoparticle Superstructures Using Polyvalent Counterions.

PubMed

Chou, Leo Y T; Song, Fayi; Chan, Warren C W

2016-04-06

DNA assembly of nanoparticles is a powerful approach to control their properties and prototype new materials. However, the structure and properties of DNA-assembled nanoparticles are labile and sensitive to interactions with counterions, which vary with processing and application environment. Here we show that substituting polyamines in place of elemental counterions significantly enhanced the structural rigidity and plasmonic properties of DNA-assembled metal nanoparticles. These effects arose from the ability of polyamines to condense DNA and cross-link DNA-coated nanoparticles. We further used polyamine wrapped DNA nanostructures as structural templates to seed the growth of polymer multilayers via layer-by-layer assembly, and controlled the degree of DNA condensation, plasmon coupling efficiency, and material responsiveness to environmental stimuli by varying polyelectrolyte composition. These results highlight counterion engineering as a versatile strategy to tailor the properties of DNA-nanoparticle assemblies for various applications, and should be applicable to other classes of DNA nanostructures.

Measurement and Control of Electroosmotic Flow in Plastic Microchannels

NASA Astrophysics Data System (ADS)

Ross, David; Barker, Susan; Waddell, Emanuel; Johnson, Tim; Locascio, Laurie

2000-11-01

We have measured electroosmotic flow profiles in microchannels fabricated in a variety of commercially available plastics by imprinting using a silicon template and by UV laser ablation. It is possible to achieve nearly ideal plug flow profiles in straight imprinted channels made entirely of one material. In contrast, electroosmotic flow in imprinted channels constructed from two different materials and in channels fabricated using laser ablation show deviations from ideal plug flow resulting from non-uniformity of the surface charge density on the walls of the channels. We have also explored strategies for controlling electroosmotic flow through modification of the surface charge density. The techniques used to alter surface charge include the deposition of polyelectrolyte multilayers on channel surfaces and the use of combinations of imprinting and laser ablation in the fabrication of the channels. We will discuss the effectiveness of these strategies for controlling flow, sample dispersion, and mixing.

Fabrication of triple-labeled polyelectrolyte microcapsules for localized ratiometric pH sensing.

PubMed

Song, Xiaoxue; Li, Huanbin; Tong, Weijun; Gao, Changyou

2014-02-15

Encapsulation of pH sensitive fluorophores as reporting molecules provides a powerful approach to visualize the transportation of multilayer capsules. In this study, two pH sensitive dyes (fluorescein and oregon green) and one pH insensitive dye (rhodamine B) were simultaneously labeled on the microcapsules to fabricate ratiometric pH sensors. The fluorescence of the triple-labeled microcapsule sensors was robust and nearly independent of other intracellular species. With a dynamic pH measurement range of 3.3-6.5, the microcapsules can report their localized pH at a real time. Cell culture experiments showed that the microcapsules could be internalized by RAW 246.7 cells naturally and finally accumulated in acidic organelles with a pH value of 5.08 ± 0.59 (mean ± s.d.; n=162). Copyright © 2013 Elsevier Inc. All rights reserved.

Interfaces and thin films as seen by bound electromagnetic waves.

PubMed

Knoll, W

1998-01-01

This contribution summarizes the use of plasmon surface polaritons and guided optical waves for the characterization of interfaces and thin organic films. After a short introduction to the theoretical background of evanescent wave optics, examples are given that show how this interfacial "light" can be employed to monitor thin coatings at a solid/air or solid/liquid interface. Examples are given for a very sensitive thickness determination of samples ranging from self-assembled monolayers, to multilayer assemblies prepared by the Langmuir/Blodgett/Kuhn technique or by the alternate polyelectrolyte deposition. These are complemented by the demonstration of the potential of the technique to also monitor time-dependent processes in a kinetic mode. Here, we put an emphasis on the combination set-up of surface plasmon optics with electrochemical techniques, allowing for the on-line characterization of various surface functionalization strategies, e.g. for (bio-) sensor purposes.

Capillary electrochromatography and preconcentration of neutral compounds on poly(dimethylsiloxane) microchips.

PubMed

Ro, Kyung Won; Chang, Woo-Jin; Kim, Ho; Koo, Yoon-Mo; Hahn, Jong Hoon

2003-09-01

Capillary electrochromatography (CEC) and preconcentration of neutral compounds have been realized on poly(dimethylsiloxane) (PDMS) microchips. The channels are coated with polyelectrolyte multilayers to avoid absorption of hydrophobic analytes into PDMS. The structures of a microchip include an injector and a bead chamber with integrated frits, where the particles of the stationary phase are completely retained. Dimensions of the frit structures are 25 micro mx20 micro m, and the space between the structures is 3 micro m. A neutral compound, BODIPY, that is strongly absorbed into native PDMS, is successfully and selectively retained on octadecylsilane-coated silica beads in the bead chamber with a concentration enhancement of up to 100 times and eluted with elution buffer solution containing 70% acetonitrile. Preconcentrations and CEC separations of coumarins have been conducted with the same device and achieved complete separations in less than 50 s.

Multicolor quantum dot-encoded microspheres for the fluoroimmunoassays of chicken newcastle disease and goat pox virus.

PubMed

Yuan, Pingfan; Ma, Qiang; Meng, Rizeng; Wang, Chao; Dou, Wenchao; Wang, Guannan; Su, Xingguang

2009-05-01

Semiconductor nanocrystals (or quantum dots, QDs) have the potential to overcome some of the limitations encountered by traditional fluorophores in fluorescence labeling applications. The unique spectroscopic properties of QDs make them hold immense promise as versatile labels for biological applications. In this work, we employ the layer-by-layer (LbL) method for the construction of bio-functional multicolor QD-encoded microspheres. Polystyrene microspheres with diameter of 3 microm were used as templates for the deposition of different sized CdTe QDs/polyelectrolyte multilayers. Two different antigens, Chicken newcastle disease (CND) antigen and goat pox virus (GPV) antigen, were conjugated to two kinds of biofunctional multicolor microspheres with different optical encoding. The multicolor microspheres can capture corresponding antibodies labeled with QDs, QDs-CND antibody and QDs-GPV antibody in the fluoroimmunoassays. The microspheres can be distinguished from each other based on their optical encoding.

Towards Theranostic Multicompartment Microcapsules: in-situ Diagnostics and Laser-induced Treatment

PubMed Central

Xiong, Ranhua; Soenen, Stefaan J.; Braeckmans, Kevin; Skirtach, Andre G.

2013-01-01

Paving the way towards the application of polyelectrolyte multilayer capsules in theranostics, we describe diagnostic multi-functionality and drug delivery using multicompartment polymeric capsules which represent the next generation of drug delivery carriers. Their versatility is particularly important for potential applications in the area of theranostics wherein the carriers are endowed with the functionality for both diagnostics and therapy. Responsiveness towards external stimuli is attractive for providing controlled and on-demand release of encapsulated materials. An overview of external stimuli is presented with an emphasis on light as a physical stimulus which has been widely used for activation of microcapsules and release of their contents. In this article we also describe existing and new approaches to build multicompartment microcapsules as well as means available to achieve controlled and triggered release from their subcompartments, with a focus on applications in theranostics. Outlook for future directions in the area are highlighted. PMID:23471141

Construction of flame retardant nanocoating on ramie fabric via layer-by-layer assembly of carbon nanotube and ammonium polyphosphate.

PubMed

Zhang, Tao; Yan, Hongqiang; Peng, Mao; Wang, Lili; Ding, Hongliang; Fang, Zhengping

2013-04-07

A new flame retardant nanocoating has been constructed by the alternate adsorption of polyelectrolyte amino-functionalized multiwall carbon nanotube (MWNT-NH2) and ammonium polyphosphate (APP) onto flexible and porous ramie fabric. Scanning electron microscopy indicates that the adsorbed carbon nanotube coating is a randomly oriented and overlapped network structure, which is a promising candidate for flame retardancy applications. Attenuated total reflection Fourier transform infrared spectroscopy and energy-dispersive X-ray analysis confirm that the APP is successfully incorporated into the multilayers sequentially. Assessment of the thermal and flammability properties for the pristine and nanocoated ramie fabrics shows that the thermal stability, flame retardancy and residual char are enhanced as the concentration of MWNT-NH2 suspension and number of deposition cycles increases. The enhancements are mostly attributed to the barrier effect of intumescent network structure, which is composed of MWNT-NH2 and the absorbed APP.

Development of ClearPEM-Sonic, a multimodal mammography system for PET and Ultrasound

NASA Astrophysics Data System (ADS)

Cucciati, G.; Auffray, E.; Bugalho, R.; Cao, L.; Di Vara, N.; Farina, F.; Felix, N.; Frisch, B.; Ghezzi, A.; Juhan, V.; Jun, D.; Lasaygues, P.; Lecoq, P.; Mensah, S.; Mundler, O.; Neves, J.; Paganoni, M.; Peter, J.; Pizzichemi, M.; Siles, P.; Silva, J. C.; Silva, R.; Tavernier, S.; Tessonnier, L.; Varela, J.

2014-03-01

ClearPEM-Sonic is an innovative imaging device specifically developed for breast cancer. The possibility to work in PEM-Ultrasound multimodality allows to obtain metabolic and morphological information increasing the specificity of the exam. The ClearPEM detector is developed to maximize the sensitivity and the spatial resolution as compared to Whole-Body PET scanners. It is coupled with a 3D ultrasound system, the SuperSonic Imagine Aixplorer that improves the specificity of the exam by providing a tissue elasticity map. This work describes the ClearPEM-Sonic project focusing on the technological developments it has required, the technical merits (and limits) and the first multimodal images acquired on a dedicated phantom. It finally presents selected clinical case studies that confirm the value of PEM information.

Essentials of PEM Fellowship Part 2: The Profession in Entrustable Professional Activities.

PubMed

Hsu, Deborah; Nypaver, Michele; Fein, Daniel M; McAneney, Constance; Santen, Sally; Nagler, Joshua; Zuckerbraun, Noel; Roskind, Cindy Ganis; Reynolds, Stacy; Zaveri, Pavan; Stankovic, Curt; House, Joseph B; Langhan, Melissa; Titus, M Olivia; Dahl-Grove, Deanna; Klasner, Ann E; Ramirez, Jose; Chang, Todd; Jacobs, Elizabeth; Chapman, Jennifer; Lumba-Brown, Angela; Thompson, Tonya; Mittiga, Matthew; Eldridge, Charles; Heffner, Viday; Herman, Bruce E; Kennedy, Christopher; Madhok, Manu; Kou, Maybelle

2016-06-01

This article is the second in a 7-part series that aims to comprehensively describe the current state and future directions of pediatric emergency medicine (PEM) fellowship training from the essential requirements to considerations for successfully administering and managing a program to the careers that may be anticipated upon program completion. This article describes the development of PEM entrustable professional activities (EPAs) and the relationship of these EPAs with existing taxonomies of assessment and learning within PEM fellowship. It summarizes the field in concepts that can be taught and assessed, packaging the PEM subspecialty into EPAs.

Electricity generation using an air-cathode single chamber microbial fuel cell in the presence and absence of a proton exchange membrane.

PubMed

Liu, Hong; Logan, Bruce E

2004-07-15

Microbial fuel cells (MFCs) are typically designed as a two-chamber system with the bacteria in the anode chamber separated from the cathode chamber by a polymeric proton exchange membrane (PEM). Most MFCs use aqueous cathodes where water is bubbled with air to provide dissolved oxygen to electrode. To increase energy output and reduce the cost of MFCs, we examined power generation in an air-cathode MFC containing carbon electrodes in the presence and absence of a polymeric proton exchange membrane (PEM). Bacteria present in domestic wastewater were used as the biocatalyst, and glucose and wastewater were tested as substrates. Power density was found to be much greater than typically reported for aqueous-cathode MFCs, reaching a maximum of 262 +/- 10 mW/m2 (6.6 +/- 0.3 mW/L; liquid volume) using glucose. Removing the PEM increased the maximum power density to 494 +/- 21 mW/m2 (12.5 +/- 0.5 mW/L). Coulombic efficiency was 40-55% with the PEM and 9-12% with the PEM removed, indicating substantial oxygen diffusion into the anode chamber in the absence of the PEM. Power output increased with glucose concentration according to saturation-type kinetics, with a half saturation constant of 79 mg/L with the PEM-MFC and 103 mg/L in the MFC without a PEM (1000 omega resistor). Similar results on the effect of the PEM on power density were found using wastewater, where 28 +/- 3 mW/m2 (0.7 +/- 0.1 mW/L) (28% Coulombic efficiency) was produced with the PEM, and 146 +/- 8 mW/m2 (3.7 +/- 0.2 mW/L) (20% Coulombic efficiency) was produced when the PEM was removed. The increase in power output when a PEM was removed was attributed to a higher cathode potential as shown by an increase in the open circuit potential. An analysis based on available anode surface area and maximum bacterial growth rates suggests that mediatorless MFCs may have an upper order-of-magnitude limit in power density of 10(3) mW/m2. A cost-effective approach to achieving power densities in this range will likely require systems that do not contain a polymeric PEM in the MFC and systems based on direct oxygen transfer to a carbon cathode.

Building a Predictive Capability for Decision-Making that Supports MultiPEM

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

Carmichael, Joshua Daniel

Multi-phenomenological explosion monitoring (multiPEM) is a developing science that uses multiple geophysical signatures of explosions to better identify and characterize their sources. MultiPEM researchers seek to integrate explosion signatures together to provide stronger detection, parameter estimation, or screening capabilities between different sources or processes. This talk will address forming a predictive capability for screening waveform explosion signatures to support multiPEM.

Tuning the properties of conjugated polyelectrolytes and application in a biosensor platform

DOEpatents

Chen, Liaohai

2004-05-18

The present invention provides a method of detecting a biological agent including contacting a sample with a sensor including a polymer system capable of having an alterable measurable property from the group of luminescence, anisotropy, redox potential and uv/vis absorption, the polymer system including an ionic conjugated polymer and an electronically inert polyelectrolyte having a biological agent recognition element bound thereto, the electronically inert polyelectrolyte adapted for undergoing a conformational structural change upon exposure to a biological agent having affinity for binding to the recognition element bound to the electronically inert polyelectrolyte, and, detecting the detectable change in the alterable measurable property. A chemical moiety being the reaction product of (i) a polyelectrolyte monomer and (ii) a biological agent recognition element-substituted polyelectrolyte monomer is also provided.

Validity of the Participation and Environment Measure for Children and Youth (PEM-CY) for Health Impact Assessment (HIA) in sustainable development projects.

PubMed

Khetani, Mary; Marley, Jenifer; Baker, Megan; Albrecht, Erin; Bedell, Gary; Coster, Wendy; Anaby, Dana; Law, Mary

2014-04-01

Participation in home, school, and community activities is an important indicator of child health and well-being. Evaluating environmental influences on children's participation can inform efforts to develop sustainable built environments, but few validated measures exist. To examine the concurrent validity and utility of the Participation and Environment Measure for Children and Youth (PEM-CY) for Health Impact Assessment in non-urban sustainable development projects affecting children with disabilities. Eighty-nine parents of children and youth with disabilities who identified as residing in a small town or rural community were sampled. Sixty-six caregivers completed the PEM-CY online, and 23 caregivers completed the PEM-CY and CHIEF-CP paper forms. Spearman correlational analyses were conducted to establish the concurrent validity of the PEM-CY environment sections against the CHIEF-CP. Group comparisons by child's age, number of functional limitations, and annual household income were used to examine differences in summary and item-level responses on the PEM-CY community section. Moderate to strong associations were found between CHIEF-CP Total Product and Magnitude Scores and all PEM-CY Environment Summary Scores. CHIEF-CP Physical/Structural and Policies Subscale Scores were most consistently associated with PEM-CY Environment Summary Scores. Group differences by household income were found for participation frequency and number of supports, including perceived availability and adequacy of money and information about programs and services, even when controlling child's age and number of functional limitations. Study results lend support to the use of the PEM-CY in HIA to reliably assess for environmental impact on children's participation. Implications for using the PEM-CY to inform decision-making in non-urban sustainable development projects affecting families of children and youth with disabilities are discussed. Published by Elsevier Inc.

Nonhumidified High-Temperature Membranes Developed for Proton Exchange Membrane Fuel Cells

NASA Technical Reports Server (NTRS)

Kinder, James D.

2005-01-01

Fuel cells are being considered for a wide variety of aerospace applications. One of the most versatile types of fuel cells is the proton-exchange-membrane (PEM) fuel cell. PEM fuel cells can be easily scaled to meet the power and space requirements of a specific application. For example, small 100-W PEM fuel cells are being considered for personal power for extravehicular activity suit applications, whereas larger PEM fuel cells are being designed for primary power in airplanes and in uninhabited air vehicles. Typically, PEM fuel cells operate at temperatures up to 80 C. To increase the efficiency and power density of the fuel cell system, researchers are pursuing methods to extend the operating temperature of the PEM fuel cell to 180 C. The most widely used membranes in PEM fuel cells are Nafion 112 and Nafion 117--sulfonated perfluorinated polyethers that were developed by DuPont. In addition to their relatively high cost, the properties of these membranes limit their use in a PEM fuel cell to around 80 C. The proton conductivity of Nafion membranes significantly decreases above 80 C because the membrane dehydrates. The useful operating range of Nafion-based PEM fuel cells can be extended to over 100 C if ancillary equipment, such as compressors and humidifiers, is added to maintain moisture levels within the membrane. However, the addition of these components reduces the power density and increases the complexity of the fuel cell system.

Two modulator generalized ellipsometer for complete mueller matrix measurement

DOEpatents

Jellison, Jr., Gerald E.; Modine, Frank A.

1999-01-01

A two-modulator generalized ellipsometer (2-MGE) comprising two polarizer-photoelastic modulator (PEM) pairs, an optical light source, an optical detection system, and associated data processing and control electronics, where the PEMs are free-running. The input light passes through the first polarizer-PEM pair, reflects off the sample surface or passes through the sample, passes through the second PEM-polarizer pair, and is detected. Each PEM is free running and operates at a different resonant frequency, e.g., 50 and 60 kHz. The resulting time-dependent waveform of the light intensity is a complicated function of time, and depends upon the exact operating frequency and phase of each PEM, the sample, and the azimuthal angles of the polarizer-PEM pairs, but can be resolved into a dc component and eight periodic components. In one embodiment, the waveform is analyzed using a new spectral analysis technique that is similar to Fourier analysis to determine eight sample Mueller matrix elements (normalized to the m.sub.00 Mueller matrix element). The other seven normalized elements of the general 4.times.4 Mueller matrix can be determined by changing the azimuthal angles of the PEM-polarizer pairs with respect to the plane of incidence. Since this instrument can measure all elements of the sample Mueller matrix, it is much more powerful than standard ellipsometers.

Nanoparticle modification by weak polyelectrolytes for pH-sensitive pickering emulsions.

PubMed

Haase, Martin F; Grigoriev, Dmitry; Moehwald, Helmuth; Tiersch, Brigitte; Shchukin, Dmitry G

2011-01-04

The affinity of weak polyelectrolyte coated oxide particles to the oil-water interface can be controlled by the degree of dissociation and the thickness of the weak polyelectrolyte layer. Thereby the oil in water (o/w) emulsification ability of the particles can be enabled. We selected the weak polyacid poly(methacrylic acid sodium salt) and the weak polybase poly(allylamine hydrochloride) for the surface modification of oppositely charged alumina and silica colloids, respectively. The isoelectric point and the pH range of colloidal stability of both particle-polyelectrolyte composites depend on the thickness of the weak polyelectrolyte layer. The pH-dependent wettability of a weak polyelectrolyte-coated oxide surface is characterized by contact angle measurements. The o/w emulsification properties of both particles for the nonpolar oil dodecane and the more polar oil diethylphthalate are investigated by measurements of the droplet size distributions. Highly stable emulsions can be obtained when the degree of dissociation of the weak polyelectrolyte is below 80%. Here the average droplet size depends on the degree of dissociation, and a minimum can be found when 15 to 45% of the monomer units are dissociated. The thickness of the adsorbed polyelectrolyte layer strongly influences the droplet size of dodecane/water emulsion droplets but has a less pronounced impact on the diethylphthalate/water droplets. We explain the dependency of the droplet size on the emulsion pH value and the polyelectrolyte coating thickness with arguments based on the particle-wetting properties, the particle aggregation state, and the oil phase polarity. Cryo-SEM visualization shows that the regularity of the densely packed particles on the oil-water interface correlates with the degree of dissociation of the corresponding polyelectrolyte.

Fluctuation-Noise Model for PEM Fuel Cell

NASA Astrophysics Data System (ADS)

Denisov, E. S.; Salakhova, A. Sh.; Adiutantov, N. A.; Evdokimov, Yu. K.

2017-08-01

The fluctuation-noise model is presented. This model allows to describe the power spectral density of PEM fuel cell electrical fluctuation. The proposed model can be used for diagnostics of PEM fuel cell state of health.

The electrochemistry of "solid/water" interfaces involved in PEM-H2O reactors: part I. The "Pt/water" interfaces.

PubMed

Wang, Qiang; Cha, Chuan-Sin; Lu, Juntao; Zhuang, Lin

2009-01-28

The nature and properties of Pt surfaces in contact with pure water in PEM-H2O reactors were mimetically studied by employing CV measurements with microelectrode techniques. These "Pt/water" interfaces were found to be electrochemically polarizable, and the local interfacial potential relative to reversible hydrogen electrode (RHE) potential in pure water is numerically the same as the potential value measured against a RHE in contact with PEM as the reference electrode. However, the structural parameters of the electric double layer at the "Pt/water" interfaces can be quite different from those at the "Pt/PEM" interfaces, and the kinetics of electrode processes could be seriously affected by the structure of electric double layer in pure water media. Besides, there is active diffusional flow of intermediates of electrode reactions between the "Pt/water" and the "Pt/PEM" interfaces, thus facilitating the active involvement of the "Pt/water" interfaces in the current-generation mechanism of PEM fuel cells and other types of PEM-H2O reactors.

Post-marketing studies: the work of the Drug Safety Research Unit.

PubMed

Mackay, F J

1998-11-01

The Drug Safety Research Unit (DSRU) is the centre for prescription-event monitoring (PEM) in England. PEM studies are noninterventional observational cohort studies which monitor the safety of newly marketed drugs. The need for post-marketing surveillance is well recognised in the UK and general practice is an ideal source of data. PEM studies are general practitioner (community)-based and exposure is based on dispensed prescription data in England. To date, 65 PEM studies have been completed with a mean cohort size of 10 979 patients and the DSRU database has clinical information on over 700000 patients prescribed new drugs. Unlike spontaneous reporting schemes, PEM produces incidence rates for events reported during treatment. Comparative studies can be conducted for drugs in the same class. The DSRU aggregates outcome data for pregnancies exposed to new drugs. Data for children and the elderly can also be specifically examined. PEM data have a number of advantages over data from computerised general practice databases in the UK. PEM is the only technique within the UK capable of monitoring newly marketed drugs in such a comprehensive and systematic way.

Redox responsive nanotubes from organometallic polymers by template assisted layer by layer fabrication

NASA Astrophysics Data System (ADS)

Song, Jing; Jańczewski, Dominik; Guo, Yuanyuan; Xu, Jianwei; Vancso, G. Julius

2013-11-01

Redox responsive nanotubes were fabricated by the template assisted layer-by-layer (LbL) assembly method and employed as platforms for molecular payload release. Positively and negatively charged organometallic poly(ferrocenylsilane)s (PFS) were used to construct the nanotubes, in combination with other polyions. During fabrication, multilayers of these polyions were deposited onto the inner pores of template porous membranes, followed by subsequent removal of the template. Anodized porous alumina and track-etched polycarbonate membranes were used as templates. The morphology, electrochemistry, composition and other properties of the obtained tubular structure were characterized by fluorescence microscopy, scanning (SEM) and transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) spectroscopy. Composite nanotubes, consisting of poly(acrylic acid) anions with PFS+ and nanoparticles including fluorophore labelled dextran and decorated quantum dots, with PFS polyelectrolytes were also fabricated, broadening the scope of the structures. Cyclic voltammograms of PFS containing nanotubes showed similar redox responsive behaviour to thin LbL assembled films. Redox triggered release of labelled macromolecules from these tubular structures demonstrated application potential in controlled molecular delivery.Redox responsive nanotubes were fabricated by the template assisted layer-by-layer (LbL) assembly method and employed as platforms for molecular payload release. Positively and negatively charged organometallic poly(ferrocenylsilane)s (PFS) were used to construct the nanotubes, in combination with other polyions. During fabrication, multilayers of these polyions were deposited onto the inner pores of template porous membranes, followed by subsequent removal of the template. Anodized porous alumina and track-etched polycarbonate membranes were used as templates. The morphology, electrochemistry, composition and other properties of the obtained tubular structure were characterized by fluorescence microscopy, scanning (SEM) and transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) spectroscopy. Composite nanotubes, consisting of poly(acrylic acid) anions with PFS+ and nanoparticles including fluorophore labelled dextran and decorated quantum dots, with PFS polyelectrolytes were also fabricated, broadening the scope of the structures. Cyclic voltammograms of PFS containing nanotubes showed similar redox responsive behaviour to thin LbL assembled films. Redox triggered release of labelled macromolecules from these tubular structures demonstrated application potential in controlled molecular delivery. Electronic supplementary information (ESI) available: Nanotube wall thickness determination protocol. See DOI: 10.1039/c3nr03927g

Biointerfacing polymeric microcapsules for in vivo near-infrared light-triggered drug release

NASA Astrophysics Data System (ADS)

Shao, Jingxin; Xuan, Mingjun; Si, Tieyan; Dai, Luru; He, Qiang

2015-11-01

Seeking safe and effective water-soluble drug carriers is of great significance in nanomedicine. To achieve this goal, we present a novel drug delivery system based on biointerfacing hollow polymeric microcapsules for effectively encapsulating water-soluble antitumor drug and gold nanorod (GNR) functionalization for triggered release of therapeutic drugs on-demand using low power near-infrared (NIR) radiation. The surface of polymeric microcapsules is covered with fluidic lipid bilayers to decrease the permeability of the wall of polymeric capsules. The temperature increase upon NIR illumination deconstructs the structure of the lipid membrane and polyelectrolyte multilayers, which in turn results in the rapid release of encapsulated water-soluble drug. In vivo antitumor tests demonstrate that this microcapsule has the effective ability of inhibiting tumor growth and preventing metastases. Real time in vivo fluorescence imaging results confirm that capsules can be excreted gradually from the animal body which in turn demonstrates the biocompatibility and biodegradation of these biointerfacing GNR-microcapsules. This intelligent system provides a novel anticancer platform with the advantages of controlled release, biological friendliness and credible biosafety.Seeking safe and effective water-soluble drug carriers is of great significance in nanomedicine. To achieve this goal, we present a novel drug delivery system based on biointerfacing hollow polymeric microcapsules for effectively encapsulating water-soluble antitumor drug and gold nanorod (GNR) functionalization for triggered release of therapeutic drugs on-demand using low power near-infrared (NIR) radiation. The surface of polymeric microcapsules is covered with fluidic lipid bilayers to decrease the permeability of the wall of polymeric capsules. The temperature increase upon NIR illumination deconstructs the structure of the lipid membrane and polyelectrolyte multilayers, which in turn results in the rapid release of encapsulated water-soluble drug. In vivo antitumor tests demonstrate that this microcapsule has the effective ability of inhibiting tumor growth and preventing metastases. Real time in vivo fluorescence imaging results confirm that capsules can be excreted gradually from the animal body which in turn demonstrates the biocompatibility and biodegradation of these biointerfacing GNR-microcapsules. This intelligent system provides a novel anticancer platform with the advantages of controlled release, biological friendliness and credible biosafety. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06350g

Protein adsorption and biomimetic mineralization behaviors of PLL-DNA multilayered films assembled onto titanium

NASA Astrophysics Data System (ADS)

Gao, Wenli; Feng, Bo; Ni, Yuxiang; Yang, Yongli; Lu, Xiong; Weng, Jie

2010-11-01

Titanium and its alloys are frequently used as surgical implants in load bearing situations, such as hip prostheses and dental implants, owing to their biocompatibility, mechanical and physical properties. In this paper, a layer-by-layer (LBL) self-assembly technique, based on the polyelectrolyte-mediated electrostatic adsorption of poly-L-lysine (PLL) and DNA, was used to the formation of multilayer on titanium surfaces. Then bovine serum albumin (BSA) adsorption and biomimetic mineralization of modified surfaces were studied. The chemical composition and wettability of assembled substrates were investigated by X-ray photoelectron spectroscopy (XPS), fluorescence microscopy and water contact angle measurement, respectively. The XPS analysis indicated that the layers were assembled successfully through electrostatic attractions. The measurement with ultraviolet (UV) spectrophotometer revealed that the LBL films enhanced ability of BSA adsorption onto titanium. The adsorption quantity of BSA on the surface terminated with PLL was higher than that of the surface terminated with DNA, and the samples of TiOH/P/D/P absorbed BSA most. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) showed that samples of assembled PLL or/and DNA had better bioactivity in inducing HA formation. Thus the assembling of PLL and DNA onto the surface of titanium in turn via a layer-by-layer self-assembly technology can improve the bioactivity of titanium.

Calcium Binding-Mediated Sustained Release of Minocycline from Hydrophilic Multilayer Coatings Targeting Infection and Inflammation

PubMed Central

Zhang, Zhiling; Nix, Camilla A.; Ercan, Utku K.; Gerstenhaber, Jonathan A.; Joshi, Suresh G.; Zhong, Yinghui

2014-01-01

Infection and inflammation are common complications that seriously affect the functionality and longevity of implanted medical implants. Systemic administration of antibiotics and anti-inflammatory drugs often cannot achieve sufficient local concentration to be effective, and elicits serious side effects. Local delivery of therapeutics from drug-eluting coatings presents a promising solution. However, hydrophobic and thick coatings are commonly used to ensure sufficient drug loading and sustained release, which may limit tissue integration and tissue device communications. A calcium-mediated drug delivery mechanism was developed and characterized in this study. This novel mechanism allows controlled, sustained release of minocycline, an effective antibiotic and anti-inflammatory drug, from nanoscale thin hydrophilic polyelectrolyte multilayers for over 35 days at physiologically relevant concentrations. pH-responsive minocycline release was observed as the chelation between minocycline and Ca2+ is less stable at acidic pH, enabling ‘smart’ drug delivery in response to infection and/or inflammation-induced tissue acidosis. The release kinetics of minocycline can be controlled by varying initial loading, Ca2+ concentration, and Ca2+ incorporation into different layers, enabling facile development of implant coatings with versatile release kinetics. This drug delivery platform can potentially be used for releasing any drug that has high Ca2+ binding affinity, enabling its use in a variety of biomedical applications. PMID:24409292

Effect of pH on the structure and drug release profiles of layer-by-layer assembled films containing polyelectrolyte, micelles, and graphene oxide.

PubMed

Han, Uiyoung; Seo, Younghye; Hong, Jinkee

2016-04-07

Layer by layer (lbl) assembled multilayer thin films are used in drug delivery systems with attractive advantages such as unlimited selection of building blocks and free modification of the film structure. In this paper, we report the fundamental properties of lbl films constructed from different substances such as PS-b-PAA amphiphilic block copolymer micelles (BCM) as nano-sized drug vehicles, 2D-shaped graphene oxide (GO), and branched polyethylenimine (bPEI). These films were fabricated by successive lbl assembly as a result of electrostatic interactions between the carboxyl group of BCM and amine group of functionalized GO or bPEI under various pH conditions. We also compared the thickness, roughness, morphology and degree of adsorption of the (bPEI/BCM) films to those in the (GO/BCM) films. The results showed significant difference because of the distinct pH dependence of each material. In addition, drug release rates of the GO/BCM film were more rapid those of the (bPEI/BCM) film in pH 7.4 and pH 2 PBS buffer solutions. In (bPEI/BCM/GO/BCM) film, the inserted GO layers into bPEI/BCM multilayer induced rapid drug release. We believe that these materials &pH dependent film properties allow developments in the control of coating techniques for biological and biomedical applications.

Composite Magnetite and Protein Containing CaCO3 Crystals. External Manipulation and Vaterite → Calcite Recrystallization-Mediated Release Performance.

PubMed

Sergeeva, Alena; Sergeev, Roman; Lengert, Ekaterina; Zakharevich, Andrey; Parakhonskiy, Bogdan; Gorin, Dmitry; Sergeev, Sergey; Volodkin, Dmitry

2015-09-30

Biocompatibility and high loading capacity of mesoporous CaCO3 vaterite crystals give an option to utilize the polycrystals for a wide range of (bio)applications. Formation and transformations of calcium carbonate polymorphs have been studied for decades, aimed at both basic and applied research interests. Here, composite multilayer-coated calcium carbonate polycrystals containing Fe3O4 magnetite nanoparticles and model protein lysozyme are fabricated. The structure of the composite polycrystals and vaterite → calcite recrystallization kinetics are studied. The recrystallization results in release of both loaded protein and Fe3O4 nanoparticles (magnetic manipulation is thus lost). Fe3O4 nanoparticles enhance the recrystallization that can be induced by reduction of the local pH with citric acid and reduction of the polycrystal crystallinity. Oppositely, the layer-by-layer assembled poly(allylamine hydrochloride)/poly(sodium styrenesulfonate) polyelectrolyte coating significantly inhibits the vaterite → calcite recrystallization (from hours to days) most likely due to suppression of the ion exchange giving an option to easily tune the release kinetics for a wide time scale, for example, for prolonged release. Moreover, the recrystallization of the coated crystals results in formulation of multilayer capsules keeping the feature of external manipulation. This study can help to design multifunctional microstructures with tailor-made characteristics for loading and controlled release as well as for external manipulation.

Enzyme-polyelectrolyte multilayer assemblies on reduced graphene oxide field-effect transistors for biosensing applications.

PubMed

Piccinini, Esteban; Bliem, Christina; Reiner-Rozman, Ciril; Battaglini, Fernando; Azzaroni, Omar; Knoll, Wolfgang

2017-06-15

We present the construction of layer-by-layer (LbL) assemblies of polyethylenimine and urease onto reduced-graphene-oxide based field-effect transistors (rGO FETs) for the detection of urea. This versatile biosensor platform simultaneously exploits the pH dependency of liquid-gated graphene-based transistors and the change in the local pH produced by the catalyzed hydrolysis of urea. The use of an interdigitated microchannel resulted in transistors displaying low noise, high pH sensitivity (20.3µA/pH) and transconductance values up to 800 µS. The modification of rGO FETs with a weak polyelectrolyte improved the pH response because of its transducing properties by electrostatic gating effects. In the presence of urea, the urease-modified rGO FETs showed a shift in the Dirac point due to the change in the local pH close to the graphene surface. Markedly, these devices operated at very low voltages (less than 500mV) and were able to monitor urea in the range of 1-1000µm, with a limit of detection (LOD) down to 1µm, fast response and good long-term stability. The urea-response of the transistors was enhanced by increasing the number of bilayers due to the increment of the enzyme surface coverage onto the channel. Moreover, quantification of the heavy metal Cu 2+ (with a LOD down to 10nM) was performed in aqueous solution by taking advantage of the urease specific inhibition. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Polyelectrolyte Multilayer Film Coated Silver Nanorods: An Effective Carrier System for Externally Activated Drug Delivery

NASA Astrophysics Data System (ADS)

Paramasivam, Gokul; Sharma, Varsha; Sundaramurthy, Anandhakumar

2017-08-01

Nanoparticle anisotropy offers unique functions and features in comparison with spherical nanoparticles (NPs) and makes anisotropic nanoparticles (ANPs) promising candidates in applications like drug delivery, imaging, biosensing and theranostics. Presence of surface active groups (e.g. amine, and carboxylate groups) on their surface provides binding sites for ligands or other biomolecules, and hence, this could be targeted for specific part or cells in our body. In the quest of such surface modification, functionalization of ANPs along Layer-by-Layer (LbL) coating of oppositely charged polyelectrolytes (PE) reduces cellular toxicity and promotes easy encapsulation of drugs. In this work, we report the silver nanorods (AgNRs) synthesis by adsorbate directed synthetic approach using cetyltrimethyl ammonium bromide (CTAB). The formed ANPs is investigated by scanning electron microscopy (SEM) and UV-Visible (UV-Vis) spectroscopy revealing the shaping of AgNRs of 3-16 nm aspect ratio with some presence of triangles. These NRs were further coated with bio polymers of chitosan (CH) and dextran sulphate (DS) through LbL approach and used for encapsulation of water soluble anti-bacterial drugs like ciprofloxacin hydrochloride (CFH). The encapsulation of drugs and profiles of drug release were investigated and compared to that of spherical silver nanoparticles (AgNPs). The added advantages of the proposed drug delivery system (DDS) can be externally activated to release the loaded drug and used as contrast agents for biological imaging under exposure to NIR light. Such system shows unique and attractive characteristics required for drug delivery and bioimaging thus offering the scope for further development as theranostic material.

Different Approaches for Ensuring Performance/Reliability of Plastic Encapsulated Microcircuits (PEMs) in Space Applications

NASA Technical Reports Server (NTRS)

Gerke, R. David; Sandor, Mike; Agarwal, Shri; Moor, Andrew F.; Cooper, Kim A.

1999-01-01

This paper presents viewgraphs on Plastic Encapsulated Microcircuits (PEMs). Different approaches are addressed to ensure good performance and reliability of PEMs. The topics include: 1) Mitigating Risk; and 2) Program results.

Nanostructure-based proton exchange membrane for fuel cell applications at high temperature.

PubMed

Li, Junsheng; Wang, Zhengbang; Li, Junrui; Pan, Mu; Tang, Haolin

2014-02-01

As a clean and highly efficient energy source, the proton exchange membrane fuel cell (PEMFC) has been considered an ideal alternative to traditional fossil energy sources. Great efforts have been devoted to realizing the commercialization of the PEMFC in the past decade. To eliminate some technical problems that are associated with the low-temperature operation (such as catalyst poisoning and poor water management), PEMFCs are usually operated at elevated temperatures (e.g., > 100 degrees C). However, traditional proton exchange membrane (PEM) shows poor performance at elevated temperature. To achieve a high-performance PEM for high temperature fuel cell applications, novel PEMs, which are based on nanostructures, have been developed recently. In this review, we discuss and summarize the methods for fabricating the nanostructure-based PEMs for PEMFC operated at elevated temperatures and the high temperature performance of these PEMs. We also give an outlook on the rational design and development of the nanostructure-based PEMs.

Utilization of pectin-enriched materials from apple pomace as a fat replacer in a model food system.

PubMed

Min, Bockki; Bae, In Young; Lee, Hyeon Gyu; Yoo, Sang-Ho; Lee, Suyong

2010-07-01

Water soluble pectin-enriched materials (PEMs) from apple pomace, were evaluated as a fat replacer in a model food system. When PEM solutions were subjected to steady-shear measurements, shear-thinning behavior was observed. The flow behaviors could be described by the Cross model (R(2)=0.99), and temperature effects were investigated by the Arrhenius equation. The addition of PEMs significantly increased the pasting parameters of wheat flour as measured by a starch pasting rheometer. Gelatinization temperature and enthalpy increased with increasing PEM concentrations. When PEMs were incorporated into cookie formulations in place of shortening (semisolid fat generally used in baked foods) up to 30% by the weight of shortening, the cookie spread diameter was reduced while an increase in the moisture content was observed. Moreover, replacement of shortening with PEMs contributed to a more tender texture and lighter surface color. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

PEM-INST-001: Instructions for Plastic Encapsulated Microcircuit (PEM) Selection, Screening, and Qualification

NASA Technical Reports Server (NTRS)

Teverovsky, Alexander; Sahu, Kusum

2003-01-01

Potential users of plastic encapsulated microcircuits (PEMs) need to be reminded that unlike the military system of producing robust high-reliability microcircuits that are designed to perform acceptably in a variety of harsh environments, PEMs are primarily designed for use in benign environments where equipment is easily accessed for repair or replacement. The methods of analysis applied to military products to demonstrate high reliability cannot always be applied to PEMs. This makes it difficult for users to characterize PEMs for two reasons: 1. Due to the major differences in design and construction, the standard test practices used to ensure that military devices are robust and have high reliability often cannot be applied to PEMs that have a smaller operating temperature range and are typically more frail and susceptible to moisture absorption. In contrast, high-reliability military microcircuits usually utilize large, robust, high-temperature packages that are hermetically sealed. 2. Unlike the military high-reliability system, users of PEMs have little visibility into commercial manufacturers proprietary design, materials, die traceability, and production processes and procedures. There is no central authority that monitors PEM commercial product for quality, and there are no controls in place that can be imposed across all commercial manufacturers to provide confidence to high-reliability users that a common acceptable level of quality exists for all PEMs manufacturers. Consequently, there is no guaranteed control over the type of reliability that is built into commercial product, and there is no guarantee that different lots from the same manufacturer are equally acceptable. And regarding application, there is no guarantee that commercial products intended for use in benign environments will provide acceptable performance and reliability in harsh space environments. The qualification and screening processes contained in this document are intended to detect poor-quality lots and screen out early random failures from use in space flight hardware. However, since it cannot be guaranteed that quality was designed and built into PEMs that are appropriate for space applications, users cannot screen in quality that may not exist. It must be understood that due to the variety of materials, processes, and technologies used to design and produce PEMs, this test process may not accelerate and detect all failure mechanisms. While the tests herein will increase user confidence that PEMs with otherwise unknown reliability can be used in space environments, such testing may not guarantee the same level of reliability offered by military microcircuits. PEMs should only be used where due to performance needs there are no alternatives in the military high-reliability market, and projects are willing to accept higher risk.

Transient charge-masking effect of applied voltage on electrospinning of pure chitosan nanofibers from aqueous solutions.

PubMed

Terada, Dohiko; Kobayashi, Hisatoshi; Zhang, Kun; Tiwari, Ashutosh; Yoshikawa, Chiaki; Hanagata, Nobutaka

2012-02-01

The processing of a polyelectrolyte (whose functionality is derived from its ionized functional groups) into a nanofiber may improve its functionality and yield multiple functionalities. However, the electrospinning of nanofibers from polyelectrolytes is imperfect because polyelectrolytes differ considerably from neutral polymers in their rheological properties. In our study, we attempt to solve this problem by applying a voltage of opposite polarity to charges on a polyelectrolyte. The application of this 'countervoltage' can temporarily mask or screen a specific rheological property of the polyelectrolyte, making it behave as a neutral polymer. This approach can significantly contribute to the development of new functional nanofiber materials.

[Inclusion of proteins into polyelectrolyte microcapsules by coprecipitation and adsorption].

PubMed

Kochetkova, O Iu; Kazakova, L I; Moshkov, D A; Vinokurov, M G; Shabarchina, L I

2013-01-01

In present study microcapsules composed of synthetic (PSS and PAA) and biodegradable (DS and PAr) polyelectrolytes on calcium carbonate microparticles were obtained. The ultrastructural organization of biodegradable microcapsules was studied using transmission electron microscopy. The envelope of such capsules consisting of six polyelectrolyte layers is already well-formed, having the average thickness of 44 ± 3.0 nm, and their internal polyelectrolyte matrix is sparser compared to the synthetic microcapsules. Spectroscopy was employed to evaluate the efficiency of incorporation of FITC-labeled BSA into synthetic microcapsules by adsorption, depending on the number of polyelectrolyte layers. It was shown that the maximal amount of protein incorporated into the capsules with 6 or 7 polyelectrolyte layers (4 and 2 pg/capsule, correspondingly). As a result we conclude that, in comparison with co-precipitation, the use of adsorption allows to completely avoid the loss of protein upon encapsulation.

Born energy, acid-base equilibrium, structure and interactions of end-grafted weak polyelectrolyte layers.

PubMed

Nap, R J; Tagliazucchi, M; Szleifer, I

2014-01-14

This work addresses the effect of the Born self-energy contribution in the modeling of the structural and thermodynamical properties of weak polyelectrolytes confined to planar and curved surfaces. The theoretical framework is based on a theory that explicitly includes the conformations, size, shape, and charge distribution of all molecular species and considers the acid-base equilibrium of the weak polyelectrolyte. Namely, the degree of charge in the polymers is not imposed but it is a local varying property that results from the minimization of the total free energy. Inclusion of the dielectric properties of the polyelectrolyte is important as the environment of a polymer layer is very different from that in the adjacent aqueous solution. The main effect of the Born energy contribution on the molecular organization of an end-grafted weak polyacid layer is uncharging the weak acid (or basic) groups and consequently decreasing the concentration of mobile ions within the layer. The magnitude of the effect increases with polymer density and, in the case of the average degree of charge, it is qualitatively equivalent to a small shift in the equilibrium constant for the acid-base equilibrium of the weak polyelectrolyte monomers. The degree of charge is established by the competition between electrostatic interactions, the polymer conformational entropy, the excluded volume interactions, the translational entropy of the counterions and the acid-base chemical equilibrium. Consideration of the Born energy introduces an additional energetic penalty to the presence of charged groups in the polyelectrolyte layer, whose effect is mitigated by down-regulating the amount of charge, i.e., by shifting the local-acid base equilibrium towards its uncharged state. Shifting of the local acid-base equilibrium and its effect on the properties of the polyelectrolyte layer, without considering the Born energy, have been theoretically predicted previously. Account of the Born energy leads to systematic, but in general small, corrections to earlier theoretical predictions describing the behavior of weak polyelectrolyte layers. However, polyelectrolyte uncharging results in a decrease in the concentration of counterions and inclusion of the Born Energy can result in a substantial decrease of the counterion concentration. The effect of considering the Born energy contribution is explored for end-grafted weak polyelectrolyte layers by calculating experimental observables which are known to depend on the presence of charges within the polyelectrolyte layer: inclusion of the Born energy contribution leads to a decrease in the capacitance of polyelectrolyte-modified electrodes, a decrease of conductivity of polyelectrolyte-modified nanopores and an increase in the repulsion exerted by a planar polyelectrolyte layer confined by an opposing wall.

Enhancing the Chemical and Mechanical Durability of Polymer Electrolyte Membranes for Fuel Cell Applications

NASA Astrophysics Data System (ADS)

Baker, Andrew M.

Polymer electrolyte membrane (PEM) fuel cells are energy conversion devices which generate electricity from the electrochemical reaction of hydrogen and oxygen. Currently, widespread adoption of PEM fuel cell technology is hindered by low component durability and high costs. In this work, strategies were investigated to improve the mechanical and chemical durability of the ion conducting polymer, or ionomer, which comprises the PEM, in order to directly address these limitations. Owing to their exceptional mechanical properties, carbon nanotubes (CNTs) were investigated for mechanical reinforcement of the PEM. Because of their electronic conductivity, which diminishes cell performance, two strategies were developed to enable the use of CNTs as PEM reinforcement. These systems result in enhanced mechanical properties without sacrificing performance of the PEM during operation. Further, when coated with ceria (CeO2), which scavenges radicals that are generated during operation and cause PEM chemical degradation by attacking vulnerable chemical groups in the ionomer, MWCNTs further improved PEM chemical durability. During cell fabrication, conditioning, and discharge, Ce rapidly migrates between the PEM and catalyst layers (CLs), which reduces catalyst efficiency and leaves areas of the cell defenseless against radical attacks. Therefore, in order to stabilize Ce and localize it to areas of highest radical generation, it is critical to understand and identify the relative influences of different migration mechanisms. Using a novel elemental analysis technique, Ce migration was characterized due to potential and concentration gradients, water flux, and degradation of Ce-exchanged sulfonic acid groups within the PEM. Additionally, Zr-doped ceria was employed to resist migration due to ionomer degradation which improved cell durability, without reducing performance, resulting in PEM Ce stabilization near its initial concentrations after > 1,400 hours of testing. Ce was not observed to leave the cell during stress testing, however, it does irreversibly accumulate in the CLs, which reduces its scavenging efficacy in the system. In order to model Ce migration during fuel cell operation, the relevant Ce transport coefficients were determined under a range of conditions. This knowledge enables the development of additional system control and material engineering strategies to mitigate Ce migration in order to reduce performance losses and improve cell durability.

Prevalence of protein-energy malnutrition in hospital patients over 75 years of age admitted for hip fracture.

PubMed

Drevet, S; Bioteau, C; Mazière, S; Couturier, P; Merloz, P; Tonetti, J; Gavazzi, G

2014-10-01

One percent of falls in over-75 years old cause hip fracture (HF). Protein-energy malnutrition (PEM) is associated with falls and fracture. PEM screening and perioperative nutritional management are recommended by the European Society of Parenteral and Enteral Nutrition, yet data on nutritional status in elderly HF patients are sparse. The Mini Nutritional Assessment (MNA) score is presently the most effective screening tool for PEM in over-75 years old. The principal objective of the present study was to determine the prevalence on MNA of PEM in patients aged over 75 years admitted for HF. Secondary objectives were to identify factors associated with PEM and its role as a factor of evolution. A prospective observational epidemiological study included 50 patients aged over 75 years admitted for HF in an 8-bed orthopedic surgery department with a geriatric follow-up unit. PEM was defined by MNA<17/30. Assessment systematically comprised associated comorbidity (Cumulative Illness Rating Scale-Geriatric [CIRS-G]), cognitive status on the Mini Mental State Examination (MMSE), functional status on activities of daily life (ADL), and mean hospital stay (MHS). Scores were compared on quantitative tests (Student t) with the significance threshold set at P<0.05. Mean age for the 50 patients was 86.1 years (range, 77-94 years). Prevalence of PEM was 28%; a further 58% of patients were at risk for PEM. PEM was associated with elevated CIRS-G (P<0.006), greater numbers of severe comorbidities (P=0.006), more severe cognitive disorder (P=0.005) and functional dependence (P=0.002), and 8 days' longer MHS (P=0.012). The present study confirmed the high prevalence of PEM in HF patients aged over 75 years, supporting longer hospital stay. MNA is a diagnostic gold standard, not to be replaced by albuminemia or body-mass index in this perioperative clinical situation. Given the present economic stakes relating to geriatric trauma patients' hospital stay, it is essential to prevent, diagnose and treat PEM in elderly subjects. Level IV; prospective cohort study. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

Characterization of PM-PEMS for in-use measurements conducted during validation testing for the PM-PEMS measurement allowance program

NASA Astrophysics Data System (ADS)

Khan, M. Yusuf; Johnson, Kent C.; Durbin, Thomas D.; Jung, Heejung; Cocker, David R.; Bishnu, Dipak; Giannelli, Robert

2012-08-01

This study provides an evaluation of the latest Particulate Matter-Portable Emissions Measurement Systems (PM-PEMS) under different environmental and in-use conditions. It characterizes four PM measurement systems based on different measurement principles. At least three different units were tested for each PM-PEMS to account for variability. These PM-PEMS were compared with a UC Riverside's mobile reference laboratory (MEL). PM measurements were made from a class 8 truck with a 2008 Cummins diesel engine with a diesel particulate filter (DPF). A bypass around the DPF was installed in the exhaust to achieve a brake specific PM (bsPM) emissions level of 25 mg hp-1h-1. PM was dominated by elemental carbon (EC) during non-regeneration conditions and by hydrated sulfate (H2SO4.6H2O) during regeneration. The photo-acoustic PM-PEMS performed best, with a linear regression slope of 0.90 and R2 of 0.88 during non-regenerative conditions. With the addition of a filter, the photo-acoustic PM-PEMS slightly over reported than the total PM mass (slope = 1.10, R2 = 0.87). Under these same non-regeneration conditions, a PM-PEMS equipped with a quartz crystal microbalance (QCM) technology performed the poorest, and had a slope of 0.22 and R2 of 0.13. Re-tests performed on upgraded QCM PM-PEMS showed a better slope (0.66), and a higher R2 of 0.25. In the case of DPF regeneration, all PM-PEMS performed poorly, with the best having a slope of 0.20 and R2 of 0.78. Particle size distributions (PSD) showed nucleation during regeneration, with a shift of particle size to smaller diameters (˜64 nm to ˜13 nm) with elevated number concentrations when compared to non-regeneration conditions.

LASERS, ACTIVE MEDIA: The aqueous-polyelectrolyte dye solution as an active laser medium

NASA Astrophysics Data System (ADS)

Akimov, A. I.; Saletskii, A. M.

2000-11-01

The spectral, luminescent, and lasing properties of aqueous solutions of a cationic dye rhodamine 6G with additions of anion polyelectrolytes — polyacrylic and polymethacrylic acids — are studied. It is found that the energy and spectral properties of lasing of these solutions depend on the ratio of concentrations of polyelectrolyte and molecules. It is also found that the lasing parameters of aqueous-polyelectrolyte dye solutions can be controlled by changing the structure of the molecular system. The variation in the structure of aqueous-polyelectrolyte dye solutions of rhodamine 6G resulted in an almost five-fold increase in the lasing efficiency compared to that in aqueous dye solutions.

Employment of Gibbs-Donnan-based concepts for interpretation of the properties of linear polyelectrolyte solutions

USGS Publications Warehouse

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

1991-01-01

Earlier research has shown that the acid dissociation and metal ion complexation equilibria of linear, weak-acid polyelectrolytes and their cross-linked gel analogues are similarly sensitive to the counterion concentration levels of their solutions. Gibbs-Donnan-based concepts, applicable to the gel, are equally applicable to the linear polyelectrolyte for the accommodation of this sensitivity to ionic strength. This result is presumed to indicate that the linear polyelectrolyte in solution develops counterion-concentrating regions that closely resemble the gel phase of their analogues. Advantage has been taken of this description of linear polyelectrolytes to estimate the solvent uptake by these regions. ?? 1991 American Chemical Society.

Design of flexible polyphenylene proton-conducting membrane for next-generation fuel cells.

PubMed

Miyake, Junpei; Taki, Ryunosuke; Mochizuki, Takashi; Shimizu, Ryo; Akiyama, Ryo; Uchida, Makoto; Miyatake, Kenji

2017-10-01

Proton exchange membrane fuel cells (PEMFCs) are promising devices for clean power generation in automotive, stationary, and portable applications. Perfluorosulfonic acid (PFSA) ionomers (for example, Nafion) have been the benchmark PEMs; however, several problems, including high gas permeability, low thermal stability, high production cost, and environmental incompatibility, limit the widespread dissemination of PEMFCs. It is believed that fluorine-free PEMs can potentially address all of these issues; however, none of these membranes have simultaneously met the criteria for both high performance (for example, proton conductivity) and durability (for example, mechanical and chemical stability). We present a polyphenylene-based PEM (SPP-QP) that fulfills the required properties for fuel cell applications. The newly designed PEM exhibits very high proton conductivity, excellent membrane flexibility, low gas permeability, and extremely high stability, with negligible degradation even under accelerated degradation conditions, which has never been achieved with existing fluorine-free PEMs. The polyphenylene PEM also exhibits reasonably high fuel cell performance, with excellent durability under practical conditions. This new PEM extends the limits of existing fluorine-free proton-conductive materials and will help to realize the next generation of PEMFCs via cost reduction as well as the performance improvement compared to the present PFSA-based PEMFC systems.

Investigation of polymer electrolyte membrane fuel cell internal behaviour during long term operation and its use in prognostics

NASA Astrophysics Data System (ADS)

Mao, Lei; Jackson, Lisa; Jackson, Tom

2017-09-01

This paper investigates the polymer electrolyte membrane (PEM) fuel cell internal behaviour variation at different operating condition, with characterization test data taken at predefined inspection times, and uses the determined internal behaviour evolution to predict the future PEM fuel cell performance. For this purpose, a PEM fuel cell behaviour model is used, which can be related to various fuel cell losses. By matching the model to the collected polarization curves from the PEM fuel cell system, the variation of fuel cell internal behaviour can be obtained through the determined model parameters. From the results, the source of PEM fuel cell degradation during its lifetime at different conditions can be better understood. Moreover, with determined fuel cell internal behaviour, the future fuel cell performance can be obtained by predicting the future model parameters. By comparing with prognostic results using adaptive neuro fuzzy inference system (ANFIS), the proposed prognostic analysis can provide better predictions for PEM fuel cell performance at dynamic condition, and with the understanding of variation in PEM fuel cell internal behaviour, mitigation strategies can be designed to extend the fuel cell performance.

Polyelectrolyte/Graphene Oxide Barrier Film for Flexible OLED.

PubMed

Yang, Seung-Yeol; Park, Jongwhan; Kim, Yong-Seog

2015-10-01

Ultra-thin flexible nano-composite barrier layer consists of graphene oxide and polyelectrolyte was prepared using the layer-by-layer processing method. Microstructures of the barrier layer was optimized via modifying coating conditions and inducing chemical reactions. Although the barrier layer consists of hydrophilic polyelectrolyte was not effective in blocking the water vapor permeation, the chemical reduction of graphene oxide as well as conversion of polyelectrolyte to hydrophobic nature were very effective in reducing the permeation.

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.

Investigation of low glass transition temperature on COTS PEMs reliability

NASA Technical Reports Server (NTRS)

Sandor, M.; Agarwal, S.

2002-01-01

Many factors influence PEM component reliability.One of the factors that can affect PEM performance and reliability is the glass transition temperature (Tg) and the coefficient of thermal expansion (CTE) of the encapsulant or underfill. JPL/NASA is investigating how the Tg and CTE for PEMs affect device reliability under different temperature and aging conditions. Other issues with Tg are also being investigated. Some preliminary data will be presented on glass transition temperature test results conducted at JPL.

The use of experimental design to find the operating maximum power point of PEM fuel cells

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

Crăciunescu, Aurelian; Pătularu, Laurenţiu; Ciumbulea, Gloria

2015-03-10

Proton Exchange Membrane (PEM) Fuel Cells are difficult to model due to their complex nonlinear nature. In this paper, the development of a PEM Fuel Cells mathematical model based on the Design of Experiment methodology is described. The Design of Experiment provides a very efficient methodology to obtain a mathematical model for the studied multivariable system with only a few experiments. The obtained results can be used for optimization and control of the PEM Fuel Cells systems.

Plastic packaged microcircuits: Quality, reliability, and cost issues

NASA Astrophysics Data System (ADS)

Pecht, Michael G.; Agarwal, Rakesh; Quearry, Dan

1993-12-01

Plastic encapsulated microcircuits (PEMs) find their main application in commercial and telecommunication electronics. The advantages of PEMs in cost, size, weight, performance, and market lead-time, have attracted 97% of the market share of worldwide microcircuit sales. However, PEMs have always been resisted in US Government and military applications due to the perception that PEM reliability is low. This paper surveys plastic packaging with respect to the issues of reliability, market lead-time, performance, cost, and weight as a means to guide part-selection and system-design.

Myalgic Encephalomyelitis (ME), Chronic Fatigue Syndrome (CFS), and Chronic Fatigue (CF) are distinguished accurately: results of supervised learning techniques applied on clinical and inflammatory data.

PubMed

Maes, Michael; Twisk, Frank N M; Johnson, Cort

2012-12-30

There is much debate on the diagnostic classification of Myalgic Encephalomyelitis (ME), Chronic Fatigue Syndrome (CFS) and chronic fatigue (CF). Post-exertional malaise (PEM) is stressed as a key feature. This study examines whether CF and CFS, with and without PEM, are distinct diagnostic categories. Fukuda's criteria were used to diagnose 144 patients with chronic fatigue and identify patients with CFS and CF, i.e. those not fulfilling the Fukuda's criteria. PEM was rated by means of a scale with defined scale steps between 0 and 6. CFS patients were divided into those with PEM lasting more than 24h (labeled: ME) and without PEM (labeled: CFS). The 12-item Fibromyalgia and Chronic Fatigue Syndrome (FF) Rating Scale was used to measure severity of illness. Plasma interleukin-1 (IL-1), tumor necrosis factor (TNF)α, and lysozyme, and serum neopterin were employed as external validating criteria. Using fatigue, a subjective feeling of infection and PEM we found that ME, CFS, and CF were distinct categories. Patients with ME had significantly higher scores on concentration difficulties and a subjective experience of infection, and higher levels of IL-1, TNFα, and neopterin than patients with CFS. These biomarkers were significantly higher in ME and CFS than in CF patients. PEM loaded highly on the first two factors subtracted from the data set, i.e. "malaise-sickness" and "malaise-hyperalgesia". Fukuda's criteria are adequate to make a distinction between ME/CFS and CF, but ME/CFS patients should be subdivided into ME (with PEM) and CFS (without PEM). Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

The Communication AssessmenT Checklist in Health (CATCH): a tool for assessing the quality of printed educational materials for clinicians.

PubMed

Genova, Juliana; Nahon-Serfaty, Isaac; Dansokho, Selma Chipenda; Gagnon, Marie-Pierre; Renaud, Jean-Sébastien; Giguère, Anik M C

2014-01-01

There is little guidance available on strategies to improve the communication quality of printed educational materials (PEMs) for clinicians. The purposes of this study were to conceptualize PEM communication quality, develop a checklist based on this conceptualization, and validate the checklist with a selection of PEMs. From a literature review of the strategies influencing communication quality, we generated a conceptual map and developed the Communication AssessmenT Checklist in Health (CATCH) consisting of 55 items nested in 12 concepts. Two raters independently applied CATCH to 45 PEMs evaluated in the studies included in a Cochrane systematic review. From these results, we conducted an item analysis and assessed content validity of CATCH using a hierarchical cluster analysis to explore the extent to which our CATCH operationalization truly represented the communication quality concepts. Some concepts were better covered in the studied PEMs, whereas others were not covered consistently. We observed 3 contrasting PEM clusters. A first cluster (n = 22) was characterized by longer PEMs and comprised mostly high-impact peer-reviewed scientific articles or clinical practice guidelines. A second cluster (n = 22) consisted of PEMs shorter than 4 pages that used special fonts, color, pictures, and graphics. A third cluster consisted of a single brief PEM. With CATCH it is possible to categorize and understand the mechanisms that can trigger a change in behavior in health care providers. Additional research is needed to validate CATCH before it can be recommended for use. © 2014 The Alliance for Continuing Education in the Health Professions, the Society for Academic Continuing Medical Education, and the Council on Continuing Medical Education, Association for Hospital Medical Education.

A Survey of Graduates of Combined Emergency Medicine-Pediatrics Residency Programs: An Update.

PubMed

Strobel, Ashley M; Chasm, Rose M; Woolridge, Dale P

2016-10-01

In 1998, emergency medicine-pediatrics (EM-PEDS) graduates were no longer eligible for the pediatric emergency medicine (PEM) sub-board certification examination. There is a paucity of guidance regarding the various training options for medical students who are interested in PEM. We sought to to determine attitudes and personal satisfaction of graduates from EM-PEDS combined training programs. We surveyed 71 graduates from three EM-PEDS residences in the United States. All respondents consider their combined training to be an asset when seeking a job, 92% find it to be an asset to their career, and 88% think it provided added flexibility to job searches. The most commonly reported shortcoming was their ineligibility for the PEM sub-board certification. The lack of this designation was perceived to be a detriment to securing academic positions in dedicated children's hospitals. When surveyed regarding which training offers the better skill set for the practice of PEM, 90% (44/49) stated combined EM-PEDS training. When asked which training track gives them the better professional advancement in PEM, 52% (23/44) chose combined EM-PEDS residency, 27% (12/44) chose a pediatrics residency followed by a PEM fellowship, and 25% (11/44) chose an EM residency then a PEM fellowship. No EM-PEDS respondents considered PEM fellowship training after the completion of the dual training program. EM-PEDS graduates found combined training to be an asset in their career. They felt that it provided flexibility in job searches, and that it was ideal training for the skill set required for the practice of PEM. EM-PEDS graduates' practices varied, including mixed settings, free-standing children's hospitals, and community emergency departments. Copyright © 2016 Elsevier Inc. All rights reserved.

Assessment of printed patient-educational materials for chronic kidney disease

PubMed Central

Tuot, Delphine S; Davis, Elizabeth; Velasquez, Alexandra; Banerjee, Tanushree; Powe, Neil R

2013-01-01

Background Awareness of chronic kidney disease (CKD) is suboptimal among patients with CKD, perhaps due to poor readability of patient education materials (PEMs). We reviewed the suitability and readability of common PEMs that focused on 5 content areas: basics of CKD, risk factors for CKD development, risk factors for CKD progression, complications of CKD and self-management strategies to improve kidney health. Methods Three reviewers (nephrologist, primary care physician, patient) used the Suitability Assessment of Materials to rate PEMs on message content/stimulation of learning, typography, visuals and layout and determined literacy level. Mean ratings were calculated for each PEM by content area and overall (Superior=70–100; Adequate=40–69; Inadequate=<40). Linear regression was used to determine the impact of literacy level on mean rating. Results We reviewed 69 PEMs from 19 organizations, divided into 113 content area sections. Most (79%) PEM sections were “Adequate” (mean rating, 58.3%). Inclusion of patient-centered content and opportunities for patient interaction were associated with “Superior” ratings. Mean ratings (SD) were similar across content areas: basics of CKD, 58.9% [9.1]; risk factors for CKD development, 57.0% [12.3]; risk factors for CKD progression, 58.5% [12.0]; CKD complications, 62.3% [15.7] and self-management strategies, 62.2% [12.3]. ≤ 6th grade literacy level (vs >6th grade) was associated with an 11.7 point higher mean rating. Conclusion Most PEMs for kidney disease were adequate. Outstanding PEMs shared characteristics of patient centeredness, a low literacy level, and patient interaction. Providers should be aware of strengths and limitations of PEMs when educating their patients about CKD. PMID:23970127

Assessment of printed patient-educational materials for chronic kidney disease.

PubMed

Tuot, Delphine S; Davis, Elizabeth; Velasquez, Alexandra; Banerjee, Tanushree; Powe, Neil R

2013-01-01

Awareness of chronic kidney disease (CKD) is suboptimal among patients with CKD, perhaps due to poor readability of patient education materials (PEMs). We reviewed the suitability and readability of common PEMs that focused on 5 content areas: basics of CKD, risk factors for CKD development, risk factors for CKD progression, complications of CKD and self-management strategies to improve kidney health. Three reviewers (nephrologist, primary care physician, patient) used the Suitability Assessment of Materials to rate PEMs on message content/stimulation of learning, typography, visuals and layout and determined literacy level. Mean ratings were calculated for each PEM by content area and overall (superior = 70-100; adequate = 40-69; inadequate = <40). Linear regression was used to determine the impact of literacy level on mean rating. We reviewed 69 PEMs from 19 organizations, divided into 113 content area sections. Most (79%) PEM sections were 'adequate' (mean rating, 58.3%). Inclusion of patient-centered content and opportunities for patient interaction were associated with 'superior' ratings. Mean ratings (SD) were similar across content areas: basics of CKD, 58.9% (9.1); risk factors for CKD development, 57.0% (12.3); risk factors for CKD progression, 58.5% (12.0); CKD complications, 62.3% (15.7), and self-management strategies, 62.2% (12.3). ≤6th grade literacy level (vs. >6th grade) was associated with an 11.7 point higher mean rating. Most PEMs for kidney disease were adequate. Outstanding PEMs shared characteristics of patient centeredness, a low literacy level, and patient interaction. Providers should be aware of strengths and limitations of PEMs when educating their patients about CKD. Copyright © 2013 S. Karger AG, Basel.

Protein–energy malnutrition increases activation of the transcription factor, nuclear factor κB, in the gerbil hippocampus following global ischemia☆

PubMed Central

Ji, Liang; Nazarali, Adil J.; Paterson, Phyllis G.

2013-01-01

Protein–energy malnutrition (PEM) exacerbates functional impairment caused by brain ischemia. This is correlated with reactive gliosis, which suggests an increased inflammatory response. The objective of the current study was to investigate if PEM increases hippocampal activation of nuclear factor κB (NFκB), a transcription factor that amplifies the inflammatory response involved in ischemic brain injury. Mongolian gerbils (11–12 weeks old) were randomly assigned to control diet (12.5% protein) or protein-deficient diet (2%) for 4 weeks. The 2% protein group had a 15% decrease in voluntary food intake (P<.001; unpaired t test), resulting in PEM. Body weight after 4 weeks was 20% lower in the PEM group (P<.001). Gerbils were then exposed to sham surgery or global ischemia induced by 5-min bilateral common carotid artery occlusion. PEM independently increased hippocampal NFκB activation detected by electrophoretic mobility shift assay at 6 h after surgery (P=.014; 2-factor ANOVA). Ischemia did not significantly affect NFκB activation nor was there interaction between diet and ischemia. Serum glucose and cortisol concentrations at 6 h postischemia were unaltered by diet or ischemia. A second experiment using gerbils of the same age and feeding paradigm demonstrated that PEM also increases hippocampal NFκB activation in the absence of surgery. These findings suggest that PEM, which exists in 16% of elderly patients at admission for stroke, may worsen outcome by increasing activation of NFκB. Since PEM increased NFκB activation independent of ischemia or surgery, the data also have implications for the inflammatory response of the many individuals affected globally by PEM. PMID:18430555

Development of Highly-Conductive Polyelectrolytes for Lithium Batteries

NASA Technical Reports Server (NTRS)

Shriver, D. F.; Ratner, M. A.; Vaynman, S.; Annan, K. O.; Snyder, J. F.

2003-01-01

Future NASA and Air Force missions require reliable and safe sources of energy with high specific energy and energy density that can provide thousands of charge-discharge cycles at more than 40% depth- of-discharge and that can operate at low temperatures. All solid-state batteries have substantial advantages with respect to stability, energy density, storage fife and cyclability. Among all solid-state batteries, those with flexible polymer electrolytes offer substantial advantages in cell dimensionality and commensurability, low temperature operation and thin film design. The above considerations suggest that lithium-polymer electrolyte systems are promising for high energy density batteries and should be the systems of choice for NASA and US Air Force applications. Polyelectrolytes (single ion conductors) are among most promising avenues for achieving a major breakthrough 'in the applicability of polymer- based electrolyte systems. Their major advantages include unit transference number for the cation, reduced cell polarization, minimal salt precipitation, and favorable electrolyte stability at interfaces. Our research is focused on synthesis, modeling and cell testing of single ion carriers, polyelectrolytes. During the first year of this project we attempted the synthesis of two polyelectrolytes. The synthesis of the first one, the poly(ethyleneoxide methoxy acrylateco-lithium 1,1,2-trifluorobutanesulfonate acrylate, was attempted few times and it was unsuccessful. We followed the synthetic route described by Cowie and Spence. The yield was extremely low and the final product could not be separated from the impurities. The synthesis of this polyelectrolyte is not described in this report. The second polyelectrolyte, comb polysiloxane polyelectrolyte containing oligoether and perfluoroether sidechains, was synthesized in sufficient quantity to study the range of properties such as thermal stability, Li- ion- conductivity and stability toward lithium metal. Also, the batteries containing this polyelectrolyte were assembled and tested. The results are detailed below. The synthesis of another polyelectrolyte similar to polysiloxane polyelectrolyte has been started, however, the synthesis was not completed due to termination of the project.

The environmental applications and implications of nanotechnology in membrane-based separations for water treatment

NASA Astrophysics Data System (ADS)

Shan, Wenqian

This dissertation presents results of three related projects focused on the applications of membrane separation technology to water treatment: 1) Experimental design and evaluation of polyelectrolyte multilayer films as regenerable membrane coatings with controllable surface properties; 2) Modeling of the interactions of nanoscale TiO2 and NOM molecules in aqueous solutions of environmentally relevant compositions; 3) Experimental design and preliminary testing of a membrane-based crossflow filtration hydrocyclone process for the separation of oil-in-water dispersions. Chapter 2 describes the design of polyelectrolyte multilayers as nanoscale membrane coatings and their application in nanofiltration of feed waters that contain suspended colloids and dissolved species. Layer-by-layer deposition of anionic and cationic polyelectrolytes was employed to prepare membrane coatings allowing for a fine control over their surface properties. This approach to membrane design also affords a possibility of regenerating coatings after they are fouled by colloids. This project demonstrated, for first time, the possibility of designing nanofiltration membranes with regenerable skin. Chapter 3 describes a study on the mechanisms of natural organic matter (NOM) adsorption onto the surface of titania nanoparticles. Titainia (TiO 2) is often used in the fabrication of ceramic membranes and understanding how NOM interacts with TiO2 can help to better predict ceramic membrane fouling by NOM-containing waters. The combined effect of pH and calcium on the interactions of nonozonated and ozonated NOM with nanoscale TiO 2 was investigated by applying extended Derjaguin --- Landau --- Verwey - Overbeek (XDLVO) modeling. XDLVO surface energy analysis predicted NOM adsorption onto TiO2 in the ozone-controlled regime but not in the calcium-controlled regime. In both regimes, short range NOM-NOM and NOM-TiO2 interactions were governed by acid-base and van der Waals forces, whereas the role of electrostatic forces was found to be relatively insignificant. Ozonation increased the surface energy of NOM, contributing to the hydrophilic repulsion component of the NOM-NOM and NOM-TiO2 interactions. In the calcium-controlled regime, non-XDLVO interactions such as intermolecular bridging by calcium were hypothesized to be responsible for the observed adsorption behavior. Chapter 4 describes research on the crossflow filtration hydrocyclone separation of oil-in-water dispersions wherein a ceramic tubular membrane was used as the permeable wall of the hydrocyclone. Air sparging was applied to mitigate oil fouling. A dual membrane system consisting of an outer hydrophilic ceramic membrane and an inner hydrophobic polymeric membrane was evaluated to test the possibility of separating the dispersion into two streams: 1) oil with zero or very low concentration of water and 2) water with zero or very low concentration of oil. The performance of the dual membrane system indicated the possibility of using membranes with different chemical affinities to cost-effectively separate the oil-water dispersion into two separate phases. The incorporation of air sparging to membrane filtration was found to be effective in mitigating oil fouling with improved permeate flux.

Monte Carlo simulations of polyelectrolytes inside viral capsids.

PubMed

Angelescu, Daniel George; Bruinsma, Robijn; Linse, Per

2006-04-01

Structural features of polyelectrolytes as single-stranded RNA or double-stranded DNA confined inside viral capsids and the thermodynamics of the encapsidation of the polyelectrolyte into the viral capsid have been examined for various polyelectrolyte lengths by using a coarse-grained model solved by Monte Carlo simulations. The capsid was modeled as a spherical shell with embedded charges and the genome as a linear jointed chain of oppositely charged beads, and their sizes corresponded to those of a scaled-down T=3 virus. Counterions were explicitly included, but no salt was added. The encapisdated chain was found to be predominantly located at the inner capsid surface, in a disordered manner for flexible chains and in a spool-like structure for stiff chains. The distribution of the small ions was strongly dependent on the polyelectrolyte-capsid charge ratio. The encapsidation enthalpy was negative and its magnitude decreased with increasing polyelectrolyte length, whereas the encapsidation entropy displayed a maximum when the capsid and polyelectrolyte had equal absolute charge. The encapsidation process remained thermodynamically favorable for genome charges ca. 3.5 times the capsid charge. The chain stiffness had only a relatively weak effect on the thermodynamics of the encapsidation.

Investigation of low glass transition temperature on COTS PEM's reliability for space applications

NASA Technical Reports Server (NTRS)

Sandor, M.; Agarwal, S.; Peters, D.; Cooper, M. S.

2003-01-01

Plastic Encapsulated Microelectronics (PEM) reliability is affected by many factors. Glass transition temperature (Tg) is one such factor. In this presentation issues relating to PEM reliability and the effect of low glass transition temperature epoxy mold compounds are presented.

Energy Systems Integration Partnerships: NREL + Giner

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

2017-03-22

This fact sheet highlights work done at the ESIF in partnership with Giner. Giner, a developer of proton-exchange membrane (PEM) technologies, has contracted with NREL to validate the performance of its large-scale PEM electrolyzer stacks. PEM electrolyzers work much like fuel cells run in reverse.

Advances in proton-exchange membranes for fuel cells: an overview on proton conductive channels (PCCs).

PubMed

Wu, Liang; Zhang, Zhenghui; Ran, Jin; Zhou, Dan; Li, Chuanrun; Xu, Tongwen

2013-04-14

Proton-exchange membranes (PEM) display unique ion-selective transport that has enabled a breakthrough in high-performance proton-exchange membrane fuel cells (PEMFCs). Elemental understanding of the morphology and proton transport mechanisms of the commercially available Nafion® has promoted a majority of researchers to tune proton conductive channels (PCCs). Specifically, knowledge of the morphology-property relationship gained from statistical and segmented copolymer PEMs has highlighted the importance of the alignment of PCCs. Furthermore, increasing efforts in fabricating and aligning artificial PCCs in field-aligned copolymer PEMs, nanofiber composite PEMs and mesoporous PEMs have set new paradigms for improvement of membrane performances. This perspective profiles the recent development of the channels, from the self-assembled to the artificial, with a particular emphasis on their formation and alignment. It concludes with an outlook on benefits of highly aligned PCCs for fuel cell operation, and gives further direction to develop new PEMs from a practical point of view.

Polyelectrolyte-modified cowpea mosaic virus for the synthesis of gold nanoparticles.

PubMed

Aljabali, Alaa A A; Evans, David J

2014-01-01

Polyelectrolyte surface-modified cowpea mosaic virus (CPMV) can be used for the templated synthesis of narrowly dispersed gold nanoparticles. Cationic polyelectrolyte, poly(allylamine) hydrochloride, is electrostatically bound to the external surface of the virus capsid. The polyelectrolyte-coated CPMV promotes adsorption of aqueous gold hydroxide anionic species, prepared from gold(III) chloride and potassium carbonate, that are easily reduced to form CPMV-templated gold nanoparticles. The process is simple and environmentally benign using only water as solvent at ambient temperature.

User-Centered Design and Printed Educational Materials: A Focus Group Study of Primary Care Physician Preferences.

PubMed

Grudniewicz, Agnes; Bhattacharyya, Onil; McKibbon, K Ann; Straus, Sharon E

2016-01-01

It is challenging for primary care physicians (PCPs) to review and apply the growing amount of clinical evidence available. Printed educational materials (PEMs), which synthesize evidence, are often ineffective at improving knowledge, possibly due to poor design and limited uptake. In this study, we collected PCP preferences for the design and content of physician-oriented PEMs and determined key attributes that may increase their usability and uptake. We held 90-minute focus groups with PCPs in Toronto, ON, Canada. Focus groups included discussion about whether and how participants use PEMs, feedback on three examples of PEMs, and a discussion on general format and design preferences in PEMs. We analyzed focus group transcripts using a thematic analysis and summarized results in a list of user preferences. Four focus groups were held with 13 PCPs. We found that participants only read PEMs relevant to their patients and prefer short, concise documents, with links to sources that can provide more detailed information. Simplicity of materials was important, with many participants preferring PEMs without lengthy backgrounds or scientific explanations. Most participants wanted to see key messages highlighted to easily assess the relevance of the materials to their practice. Some participants shared physician-oriented PEMs with patients. This study shows that PCPs may prefer shorter, simpler, and more concise documents that have less scientific detail but provide references to further information sources. It is important to understand end user preferences for the design and content of these materials to enhance their uptake.

Economics of Direct Hydrogen Polymer Electrolyte Membrane Fuel Cell Systems

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

Mahadevan, Kathyayani

Battelle's Economic Analysis of PEM Fuel Cell Systems project was initiated in 2003 to evaluate the technology and markets that are near-term and potentially could support the transition to fuel cells in automotive markets. The objective of Battelle?s project was to assist the DOE in developing fuel cell systems for pre-automotive applications by analyzing the technical, economic, and market drivers of direct hydrogen PEM fuel cell adoption. The project was executed over a 6-year period (2003 to 2010) and a variety of analyses were completed in that period. The analyses presented in the final report include: Commercialization scenarios for stationarymore » generation through 2015 (2004); Stakeholder feedback on technology status and performance status of fuel cell systems (2004); Development of manufacturing costs of stationary PEM fuel cell systems for backup power markets (2004); Identification of near-term and mid-term markets for PEM fuel cells (2006); Development of the value proposition and market opportunity of PEM fuel cells in near-term markets by assessing the lifecycle cost of PEM fuel cells as compared to conventional alternatives used in the marketplace and modeling market penetration (2006); Development of the value proposition of PEM fuel cells in government markets (2007); Development of the value proposition and opportunity for large fuel cell system application at data centers and wastewater treatment plants (2008); Update of the manufacturing costs of PEM fuel cells for backup power applications (2009).« less

Polyelectrolytes and Their Biological Interactions

PubMed Central

Katchalsky, A.

1964-01-01

Polyelectrolytes are water-soluble electrically charged polymers. Their properties are determined by the interplay of the electrical forces, the Brownian motion of the macromolecular chain, and intermolecular Van der Waals forces. Charged polyacids or polybases are stretched by the electrostatic forces, as evidenced by increase in solution viscosity, or by the stretching of polyelectrolyte gels. The electrical field of the polyions is neutralized by a dense atmosphere of counter-ions. The counter-ion attraction to the polyions is expressed by a reduction of the osmotic activity of the polyion—the osmotic pressure being only 15 to 20 per cent of the ideal in highly charged polyelectrolytes neutralized by monovalent counter-ions, and as low as 1 to 3 per cent of the ideal for polyvalent counter-ions. Since the ionic atmosphere is only slightly dependent on added low molecular salt, the osmotic pressure of polyelectrolyte salt mixtures is approximately equal to the sum of the osmotic pressure of polyelectrolyte and salt alone. Acidic and basic polyelectrolytes interact electrostatically with precipitation at the point of polymeric electroneutrality. At higher salt concentrations the interaction is inhibited by the screening of polymeric fixed charges. The importance of these interactions in enzymatic processes is discussed. The electrical double layer is polarizable as may be deduced from dielectric and conductometric studies. The polarizability leads to strong dipole formation in an electrical field. These macromolecular dipoles may play a role in the adsorption of polyelectrolytes on charged surfaces. The final part of the paper is devoted to interactions of polyelectrolytes with cell membranes and the gluing of cells to higher aggregates by charged biocolloids. ImagesFigure 17Figure 18Figure 19Figure 20 PMID:14104085

40 CFR 1065.920 - PEMS calibrations and verifications.

Code of Federal Regulations, 2014 CFR

2014-07-01

....920 PEMS calibrations and verifications. (a) Subsystem calibrations and verifications. Use all the... verifications and analysis. It may also be necessary to limit the range of conditions under which the PEMS can... additional information or analysis to support your conclusions. (b) Overall verification. This paragraph (b...

GREENHOUSE GAS (GHG) VERIFICATION GUIDELINE SERIES: ANR Pipeline Company PARAMETRIC EMISSIONS MONITORING SYSTEM (PEMS) VERSION 1.0

EPA Science Inventory

The Environmental Technology Verification report discusses the technology and performance of the Parametric Emissions Monitoring System (PEMS) manufactured by ANR Pipeline Company, a subsidiary of Coastal Corporation, now El Paso Corporation. The PEMS predicts carbon doixide (CO2...

Nanocomplexes of Photolabile Polyelectrolyte and Upconversion Nanoparticles for Near-Infrared Light-Triggered Payload Release.

PubMed

Xiang, Jun; Ge, Feijie; Yu, Bing; Yan, Qiang; Shi, Feng; Zhao, Yue

2018-06-07

A new approach to encapsulating charged cargo molecules into a nanovector and subsequently using near-infrared (NIR) light to trigger the release is demonstrated. NIR light-responsive nanovector was prepared through electrostatic interaction-driven complexation between negatively charged silica-coated upconversion nanoparticles (UCNP@silica, 87 nm hydrodynamic diameter, polydispersity index ∼0.05) and a positively charged UV-labile polyelectrolyte bearing pendants of poly(ethylene glycol) and o-nitrobenzyl side groups; whereas charged fluorescein (FLU) was loaded through a co-complexation process. By controlling the amount of polyelectrolyte, UCNP@silica can be covered by the polymer, whereas remaining dispersed in aqueous solution. Under 980 nm laser excitation, UV light emitted by UCNP is absorbed by photolytic side groups within polyelectrolyte, which results in cleavage of o-nitrobenzyl groups and formation of carboxylic acid groups. Such NIR light-induced partial reversal of positive charge to negative charge on the polyelectrolyte layer disrupts the equilibrium among UCNP@silica, polyelectrolyte, and FLU and, consequently, leads to release of FLU molecules.

Ion transferring in polyelectrolyte networks in electric fields

NASA Astrophysics Data System (ADS)

Li, Honghao; Erbas, Aykut; Zwanikken, Jos; Olvera de La Cruz, Monica

Ion-conducting polyelectrolyte gels have drawn the attention of many researchers in the last few decades as they have wide applications not only in lithium batteries but also as stretchable, transparent ionic conductor or ionic cables devices. However, ion dynamics in polyelectrolyte gels has been much less studied analytically or computationally due to the complicated interplay of long-range electrostatic and short-range interactions. Here we propose a coarse-grained non-equilibrium molecular dynamics simulation to study the ion dynamics in polyelectrolyte gels under external electric fields. We found a nonlinear response region where the molar conductivity of polyelectrolyte gels increases with external fields. We propose counterion redistribution under electric fields as the driving mechanism. We also found the ionic conductivity to be modulated by changing polylelectrolyte network topology such as the chain length. Our discovery reveals the essential difference of ion dynamics between electrolytes and polyelectrolyte gels. These results will expand our understanding in charged polymeric systems and help in designing ion-conducting devices with higher conductivity.

Reversible Adhesion with Polyelectrolyte Brushes Tailored via the Uptake and Release of Trivalent Lanthanum Ions

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

Farina, Robert; Laugel, Nicolas; Yu, Jing

Applications of end-tethered polyelectrolyte “brushes” to modify solid surfaces have been developed and studied for their colloidal stabilization and high lubrication properties. Current efforts have expanded into biological realms and stimuli-responsive materials. Our work explores responsive and reversible aspects of polyelectrolyte brush behavior when polyelectrolyte chains interact with oppositely charged multivalent ions and complexes, which act as counterions. There is a significant void in the polyelectrolyte literature regarding interactions with multivalent species. This paper demonstrates that interactions between solid surfaces bearing negatively charged polyelectrolyte brushes are highly sensitive to the presence of trivalent lanthanum, La3+. Lanthanum cations have unique interactionsmore » with polyelectrolyte chains, in part due to their small size and hydration radius which results in a high local charge density. Using La3+ in conjunction with the surface forces apparatus (SFA), adhesion has been observed to reversibly appear and disappear upon the uptake and release, respectively, of these multivalent cations acting as counterions. In media of fixed ionic strength set by monovalent sodium salt, at I0 = 0.003 M and I0 = 0.3 M, the sign of the interaction forces between overlapping brushes changes from repulsive to attractive when La3+ concentrations reach 0.1 mol % of the total ion concentration. These results are also shown to be generally consistent with, but subtlety different from, previous polyelectrolyte brush experiments using trivalent ruthenium hexamine in the role of the multivalent counterion.« less

PEM Electrolysis H2A Production Case Study Documentation

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

James, Brian; Colella, Whitney; Moton, Jennie

2013-12-31

This report documents the development of four DOE Hydrogen Analysis (H2A) case studies for polymer electrolyte membrane (PEM) electrolysis. The four cases characterize PEM electrolyzer technology for two hydrogen production plant sizes (Forecourt and Central) and for two technology development time horizons (Current and Future).

Development of PEM fuel cell technology at international fuel cells

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

Wheeler, D.J.

1996-04-01

The PEM technology has not developed to the level of phosphoric acid fuel cells. Several factors have held the technology development back such as high membrane cost, sensitivity of PEM fuel cells to low level of carbon monoxide impurities, the requirement to maintain full humidification of the cell, and the need to pressurize the fuel cell in order to achieve the performance targets. International Fuel Cells has identified a hydrogen fueled PEM fuel cell concept that leverages recent research advances to overcome major economic and technical obstacles.

Design of flexible polyphenylene proton-conducting membrane for next-generation fuel cells

PubMed Central

Miyake, Junpei; Taki, Ryunosuke; Mochizuki, Takashi; Shimizu, Ryo; Akiyama, Ryo; Uchida, Makoto; Miyatake, Kenji

2017-01-01

Proton exchange membrane fuel cells (PEMFCs) are promising devices for clean power generation in automotive, stationary, and portable applications. Perfluorosulfonic acid (PFSA) ionomers (for example, Nafion) have been the benchmark PEMs; however, several problems, including high gas permeability, low thermal stability, high production cost, and environmental incompatibility, limit the widespread dissemination of PEMFCs. It is believed that fluorine-free PEMs can potentially address all of these issues; however, none of these membranes have simultaneously met the criteria for both high performance (for example, proton conductivity) and durability (for example, mechanical and chemical stability). We present a polyphenylene-based PEM (SPP-QP) that fulfills the required properties for fuel cell applications. The newly designed PEM exhibits very high proton conductivity, excellent membrane flexibility, low gas permeability, and extremely high stability, with negligible degradation even under accelerated degradation conditions, which has never been achieved with existing fluorine-free PEMs. The polyphenylene PEM also exhibits reasonably high fuel cell performance, with excellent durability under practical conditions. This new PEM extends the limits of existing fluorine-free proton-conductive materials and will help to realize the next generation of PEMFCs via cost reduction as well as the performance improvement compared to the present PFSA-based PEMFC systems. PMID:29075671

Detection of enteropathogens in diarrhoeal diseases among malnourished Egyptian infant and children.

PubMed

Hassan, E M; el-Meneza, S A; el-Rashidy, Z; Rashad, R; Rabie, S; Fahmy, S A

1989-01-01

The influence of the Pre-existing malnutrition (PEM) on the severity of diarrhoea as well as the causative organisms was studied on 60 cases. The duration of diarrhoea was prolonged in cases with PEM. The stool purgative rate ranged from 4-15 times/day in PEM infant while it was 3-6 times in well nourished cases (WNC) (P less than 0.05). Also vomiting and dehydration was more marked among PEM cases (52.9% and 32.4% of cases than in WNC cases (31.3% and 12.5% of cases) (P less than 0.05). Rota virus and Candida albicans were the Commonest identified organisms in the stools of the PEM cases, they were detected in 52% and 38.2% of cases respectively while 25% of WNC had rota virus in their stool and non of them had Candida (P less than 0.02). Giardia lamblia was detected in 23.5% and 18.8% of PEM and WNC while 10% of healthy controls had Giardia. Other bacterial enteropathogen were also found less frequently including Salmonella, Shigella, E. coli, Pseudomonas and Campylobacter. There was no statistical difference in the incidence between both groups. Multiple infections were detected in 47% and 18.7% of PEM cases and WNC (P less than 0.05) and correlated with the severity of illness.

Cerium migration during PEM fuel cell accelerated stress testing

DOE PAGES

Baker, Andrew M.; Mukundan, Rangachary; Borup, Rodney L.; ...

2016-01-01

Cerium is a radical scavenger which improves polymer electrolyte membrane (PEM) fuel cell durability. During operation, however, cerium rapidly migrates in the PEM and into the catalyst layers (CLs). In this work, membrane electrode assemblies (MEAs) were subjected to accelerated stress tests (ASTs) under different humidity conditions. Cerium migration was characterized in the MEAs after ASTs using X-ray fluorescence. During fully humidified operation, water flux from cell inlet to outlet generated in-plane cerium gradients. Conversely, cerium profiles were flat during low humidity operation, where in-plane water flux was negligible, however, migration from the PEM into the CLs was enhanced. Humiditymore » cycling resulted in both in-plane cerium gradients due to water flux during the hydration component of the cycle, and significant migration into the CLs. Fluoride and cerium emissions into effluent cell waters were measured during ASTs and correlated, which signifies that ionomer degradation products serve as possible counter-ions for cerium emissions. Fluoride emission rates were also correlated to final PEM cerium contents, which indicates that PEM degradation and cerium migration are coupled. Lastly, it is proposed that cerium migrates from the PEM due to humidification conditions and degradation, and is subsequently stabilized in the CLs by carbon catalyst supports.« less

Applicability of the PEMS technique for simplified NO X monitoring on board ships

NASA Astrophysics Data System (ADS)

Cooper, D. A.; Ekström, M.

The performance of a predictive emission monitoring system (PEMS) as a technique for NO x monitoring on medium speed marine diesel engines has been evaluated for 16 similar engines on four different ships. The PEMS function tested measured O 2 concentration in the exhaust gas, engine load, combustion air temperature and humidity, and barometric pressure to calculate the NO x concentration. Emission measurements were carried out by means of a conventional continuous emission monitoring system (CEMS) and the measured NO x concentrations were compared with those calculated by the PEMS function. For 11 of the 16 engines, the average error between measured and calculated NO x concentration was <10% of the calibration range (1725 ppm). In addition, 10 of the engines displayed correlation coefficients between measured and calculated NO x as 0.90 or higher. For two of the ships, the predicted NO x concentrations from all engines on board gave good agreement with those measured (2.6-4.7% and 2.6-8.0% average error). In other cases however, the performance of the PEMS function was poor e.g. the four engines of ship D showed average errors of 10.3-17.7%. Although similar engine models, fuel and load characteristics were compared in the tests, the specific NO x emissions at steady-state loads used varied from 12.6 up to 15.8 g k -1Wh corr. Although a single PEMS function may prove universal and adequate for calculating NO x emissions from similar engines on board the same ship, an engine specific PEMS function is recommended. The form of the PEMS function, i.e. using exhaust O 2 and engine load as inputs, is however likely to be applicable to most propeller-law diesel engines. Bearing in mind the performance criteria for using PEMS at land-based installations, the results from this study are promising. Viewed as a single data set of 56 h with 16 separate engine comparisons between CEMS and PEMS, the data set shows a relative accuracy of 14.5% i.e. within the 20% requirement of the US Environmental Protection Agency. In light of the increased interest and international guidelines for continuous NO x monitoring on board ships, the PEMS technique can offer a simple but cost-effective option.

Encapsulation of Bacterial Spores in Nanoorganized Polyelectrolyte Shells (Postprint)

DTIC Science & Technology

2009-05-27

Nanoorganized polyelectrolyte shells have already found applica- tions in drug microencapsulation as a result of the tunable properties of the...polyelectrolyte shell.19 The same LbL technology allowed the introduction of enzymatic activity onto yeast cell shells in order to promote the conversion of

Counterion adsorption and desorption rate of a charged macromolecule

NASA Astrophysics Data System (ADS)

Shi, Yu; Yang, Jingfa; Zhao, Jiang

The rate constant of counterion adsorption to and desorption from a synthetic polyelectrolyte, polystyrene sulfonate (PSS-), is measured in aqueous solution by single molecule fluorescence spectroscopy. The results show that both adsorption and desorption rate of counterions have strong dependence on polymer concentration, salt concentration as well as the molecular weight of polyelectrolytes. The results clearly demonstrate that the contribution of electrostatic interaction and the translational entropy to the distribution of counterions of a polyelectrolyte molecule. The information is helpful to the understanding of polyelectrolyte physics. National Natural Science Foundation of China.

Modeling pH-Responsive Adsorption of Polyelectrolytes at Oil-Water Interfaces

NASA Astrophysics Data System (ADS)

Qin, Shiyi; Yong, Xin

We use dissipative particle dynamics (DPD) to discover the interfacial adsorption of pH-responsive polyelectrolytes in oil-water binary systems under different pH values. The electrostatic interactions between charged beads and the dielectric discontinuity across the interface are modeled by exploiting a modified Particle-Particle-Particle-Mesh (PPPM) method, which uses an iterative method to solve the Poisson equation on a uniform grid. We first model the adsorption behavior of a single linear polyelectrolyte from the aqueous phase. The Henderson-Hasselbalch equation describes the relation between pH and the degree of ionization of the modeled polyelectrolytes. Through changing the degree of ionization, we explore the influence of pH on the adsorption behavior and show that the electrostatic interactions significantly modulate the adsorption. Time evolutions of the position and conformation of the polyelectrolytes and the variation in the oil-water surface tension will be measured to characterize the adsorption behavior. Furthermore, we model the pH-dependent adsorption behavior of polyelectrolytes with more complicated structures, namely, branched polyelectrolytes with hydrophobic backbones and hydrophilic side chains. We also find that the addition of salts in the medium and the lengths of the backbone and ionized side chain affect the adsorption. This research supported by the American Chemical Society Petroleum Research Fund (Award 56884-DNI9).

Mitochondrially-targeted bacterial phosphatidylethanolamine methyltransferase sustained phosphatidylcholine synthesis of a Saccharomyces cerevisiae Δpem1 Δpem2 double mutant without exogenous choline supply.

PubMed

Kobayashi, Shingo; Mizuike, Aya; Horiuchi, Hiroyuki; Fukuda, Ryouichi; Ohta, Akinori

2014-09-01

In eukaryotic cells, phospholipids are synthesized exclusively in the defined organelles specific for each phospholipid species. To explain the reason for this compartmental specificity in the case of phosphatidylcholine (PC) synthesis, we constructed and characterized a Saccharomyces cerevisiae strain that lacked endogenous phosphatidylethanolamine (PE) methyltransferases but had a recombinant PE methyltransferase from Acetobacter aceti, which was fused with a mitochondrial targeting signal from yeast Pet100p and a 3×HA epitope tag. This fusion protein, which we named as mitopmt, was determined to be localized to the mitochondria by fluorescence microscopy and subcellular fractionation. The expression of mitopmt suppressed the choline auxotrophy of a double deletion mutant of PEM1 and PEM2 (pem1Δpem2Δ) and enabled it to synthesize PC in the absence of choline. This growth suppression was observed even if the Kennedy pathway was inactivated by the repression of PCT1 encoding CTP:phosphocholine cytidylyltransferase, suggesting that PC synthesized in the mitochondria is distributed to other organelles without going through the salvage pathway. The pem1Δpem2Δ strain deleted for PSD1 encoding the mitochondrial phosphatidylserine decarboxylase was able to grow because of the expression of mitopmt in the presence of ethanolamine, implying that PE from other organelles, probably from the ER, was converted to PC by mitopmt. These results suggest that PC could move out of the mitochondria, and raise the possibility that its movement is not under strict directional limitations. Copyright © 2014 Elsevier B.V. All rights reserved.

[Research of dual-photoelastic-modulator-based beat frequency modulation and Fourier-Bessel transform imaging spectrometer].

PubMed

Wang, Zhi-Bin; Zhang, Rui; Wang, Yao-Li; Huang, Yan-Fei; Chen, You-Hua; Wang, Li-Fu; Yang, Qiang

2014-02-01

As the existing photoelastic-modulator(PEM) modulating frequency in the tens of kHz to hundreds of kHz between, leading to frequency of modulated interference signal is higher, so ordinary array detector cannot effectively caprure interference signal..A new beat frequency modulation method based on dual-photoelastic-modulator (Dual-PEM) and Fourier-Bessel transform is proposed as an key component of dual-photoelastic-modulator-based imaging spectrometer (Dual-PEM-IS) combined with charge coupled device (CCD). The dual-PEM are operated as an electro-optic circular retardance modulator, Operating the PEMs at slightly different resonant frequencies w1 and w2 respectively, generates a differential signal at a much lower heterodyne frequency that modulates the incident light. This method not only retains the advantages of the existing PEM, but also the frequency of modulated photocurrent decreased by 2-3 orders of magnitude (10-500 Hz) and can be detected by common array detector, and the incident light spectra can be obtained by Fourier-Bessel transform of low frequency component in the modulated signal. The method makes the PEM has the dual capability of imaging and spectral measurement. The basic principle is introduced, the basic equations is derived, and the feasibility is verified through the corresponding numerical simulation and experiment. This method has' potential applications in imaging spectrometer technology, and analysis of the effect of deviation of the optical path difference. This work provides the necessary theoretical basis for remote sensing of new Dual-PEM-IS and for engineering implementation of spectra inversion.

Effects of proton exchange membrane on the performance and microbial community composition of air-cathode microbial fuel cells.

PubMed

Lee, Yun-Yeong; Kim, Tae Gwan; Cho, Kyung-Suk

2015-10-10

This study investigated the effects of proton exchange membranes (PEMs) on performance and microbial community of air-cathode microbial fuel cells (MFCs). Air-cathode MFCs with reactor volume of 1L were constructed in duplicate with or without PEM (designated as ACM-MFC and AC-MFC, respectively) and fed with a mixture of glucose and acetate (1:1, w:w). The maximum power density and coulombic efficiency did not differ between MFCs in the absence or presence of a PEM. However, PEM use adversely affected maximum voltage production and the rate of organic compound removal (p<0.05). Quantitative droplet digital PCR indicated that AC-MFCs had a greater bacterial population than ACM-MFCs (p<0.05). Likewise, ribosomal tag pyrosequencing revealed that the diversity index of bacterial communities was greater for AC-MFCs (p<0.05). Network analysis revealed that the most abundant genus was Enterococcus, which comprised ≥62% of the community and was positively associated with PEM and negatively associated with the rate of chemical oxygen demand (COD) removal (Pearson correlation>0.9 and p<0.05). Geobacter, which is known as an exoelectrogen, was positively associated with maximum power density and negatively associated with PEM. Thus, these results suggest that the absence of PEM favored the growth of Geobacter, a key player for electricity generation in MFC systems. Taken together, these findings demonstrate that MFC systems without PEM are more efficient with respect to power production and COD removal as well as exoelectrogen growth. Copyright © 2015 Elsevier B.V. All rights reserved.

40 CFR 1065.915 - PEMS instruments.

Code of Federal Regulations, 2010 CFR

2010-07-01

... max 0.5 % of max. Engine torque estimator, BSFC (This is a signal from an engine's ECM) T or BSFC 1 s... standards to account for ambient effects on PEMS. (d) ECM signals. You may use signals from the engine's electronic control module (ECM) in place of values measured by individual instruments within a PEMS, subject...

Durability of PEM Fuel Cell Membranes

NASA Astrophysics Data System (ADS)

Huang, Xinyu; Reifsnider, Ken

Durability is still a critical limiting factor for the commercialization of polymer electrolyte membrane (PEM) fuel cells, a leading energy conversion technology for powering future hydrogen fueled automobiles, backup power systems (e.g., for base transceiver station of cellular networks), portable electronic devices, etc. Ionic conducting polymer (ionomer) electrolyte membranes are the critical enabling materials for the PEM fuel cells. They are also widely used as the central functional elements in hydrogen generation (e.g., electrolyzers), membrane cell for chlor-alkali production, etc. A perfluorosulfonic acid (PFSA) polymer with the trade name Nafion® developed by DuPont™ is the most widely used PEM in chlor-alkali cells and PEM fuel cells. Similar PFSA membranes have been developed by Dow Chemical, Asahi Glass, and lately Solvay Solexis. Frequently, such membranes serve the dual function of reactant separation and selective ionic conduction between two otherwise separate compartments. For some applications, the compromise of the "separation" function via the degradation and mechanical failure of the electrolyte membrane can be the life-limiting factor; this is particularly the case for PEM in hydrogen/oxygen fuel cells.

Adsorption of surfactants and polymers at interfaces

NASA Astrophysics Data System (ADS)

Rojas, Orlando Jose

Surface tension and high-resolution laser light scattering experiments were used to investigate the adsorption of isomeric sugar-based surfactants at the air/liquid interface in terms of surfactant surface packing and rheology. Soluble monolayers of submicellar surfactant solutions exhibited a relatively viscous behavior. It was also proved that light scattering of high-frequency thermally-induced capillary waves can be utilized to study surfactant exchange between the surface and the bulk solution. Such analysis revealed the existence of a diffusional relaxation mechanism. A procedure based on XPS was developed for quantification, on an absolute basis, of polymer adsorption on mica and Langmuir-Blodgett cellulose films. The adsorption of cationic polyelectrolytes on negatively-charged solid surfaces was highly dependent on the polymer ionicity. It was found that the adsorption process is driven by electrostatic mechanisms. Charge overcompensation (or charge reversal) of mica occurred after adsorption of polyelectrolytes of ca. 50% charge density, or higher. It was demonstrated that low-charge-density polyelectrolytes adsorb on solid surfaces with an extended configuration dominated by loops and tails. In this case the extent of adsorption is limited by steric constraints. The conformation of the polyelectrolyte in the adsorbed layer is dramatically affected by the presence of salts or surfactants in aqueous solution. The phenomena which occur upon increasing the ionic strength are consistent with the screening of the electrostatic attraction between polyelectrolyte segments and solid surface. This situation leads to polyelectrolyte desorption accompanied by both an increase in the layer thickness and the range of the steric force. Adsorbed polyelectrolytes and oppositely charged surfactants readily associate at the solid/liquid interface. Such association induces polyelectrolyte desorption at a surfactant concentration which depends on the polyelectrolyte charge density. In practical systems the adsorption phenomena were found to be far more complex. Electrostatic and hydrogen bonding interactions play a major role in the adsorption of cationic polyelectrolytes on cellulosic substrates. Cationic and underivatized guar gum macromolecules form complexes with fines and dissolved and colloidal carbohydrates which are then retained on the cellulose fibers. The extent of the adsorption and association depends on the charge and nature of all the components present in pulp suspensions.

Recent progress in the applications of layer-by-layer assembly to the preparation of nanostructured ion-rejecting water purification membranes.

PubMed

Sanyal, Oishi; Lee, Ilsoon

2014-03-01

Reverse osmosis (RO) and nanofiltration (NF) are the two dominant membrane separation processes responsible for ion rejection. While RO is highly efficient in removal of ions it needs a high operating pressure and offers very low selectivity between ions. Nanofiltration on the other hand has a comparatively low operating pressure and most commercial membranes offer selectivity in terms of ion rejection. However in many nanofiltration operations rejection of monovalent ions is not appreciable. Therefore a high flux high rejection membrane is needed that can be applied to water purification systems. One such alternative is the usage of polyelectrolyte multilayer membranes that are prepared by the deposition of alternately charged polyelectrolytes via layer-by-layer (LbL) assembly method. LbL is one of the most common self-assembly techniques and finds application in various areas. It has a number of tunable parameters like deposition conditions, number of bilayers deposited etc. which can be manipulated as per the type of application. This technique can be applied to make a nanothin membrane skin which gives high rejection and at the same time allow a high water flux across it. Several research groups have applied this highly versatile technique to prepare membranes that can be employed for water purification. Some of these membranes have shown better performance than the commercial nanofiltration and reverse osmosis membranes. These membranes have the potential to be applied to various different aspects of water treatment like water softening, desalination and recovery of certain ions. Besides the conventional method of LbL technique other alternative methods have also been suggested that can make the technique fast, more efficient and thereby make it more commercially acceptable.

A partial exponential lumped parameter model to evaluate groundwater age distributions and nitrate trends in long-screened wells

USGS Publications Warehouse

Jurgens, Bryant; Böhlke, John Karl; Kauffman, Leon J.; Belitz, Kenneth; Esser, Bradley K.

2016-01-01

A partial exponential lumped parameter model (PEM) was derived to determine age distributions and nitrate trends in long-screened production wells. The PEM can simulate age distributions for wells screened over any finite interval of an aquifer that has an exponential distribution of age with depth. The PEM has 3 parameters – the ratio of saturated thickness to the top and bottom of the screen and mean age, but these can be reduced to 1 parameter (mean age) by using well construction information and estimates of the saturated thickness. The PEM was tested with data from 30 production wells in a heterogeneous alluvial fan aquifer in California, USA. Well construction data were used to guide parameterization of a PEM for each well and mean age was calibrated to measured environmental tracer data (3H, 3He, CFC-113, and 14C). Results were compared to age distributions generated for individual wells using advective particle tracking models (PTMs). Age distributions from PTMs were more complex than PEM distributions, but PEMs provided better fits to tracer data, partly because the PTMs did not simulate 14C accurately in wells that captured varying amounts of old groundwater recharged at lower rates prior to groundwater development and irrigation. Nitrate trends were simulated independently of the calibration process and the PEM provided good fits for at least 11 of 24 wells. This work shows that the PEM, and lumped parameter models (LPMs) in general, can often identify critical features of the age distributions in wells that are needed to explain observed tracer data and nonpoint source contaminant trends, even in systems where aquifer heterogeneity and water-use complicate distributions of age. While accurate PTMs are preferable for understanding and predicting aquifer-scale responses to water use and contaminant transport, LPMs can be sensitive to local conditions near individual wells that may be inaccurately represented or missing in an aquifer-scale flow model.

The Pacific Exploratory Mission-West Phase B: February-March, 1994

NASA Astrophysics Data System (ADS)

Hoell, J. M.; Davis, D. D.; Liu, S. C.; Newell, R. E.; Akimoto, H.; McNeal, R. J.; Bendura, R. J.

1997-12-01

The NASA Pacific Exploratory Mission in the Western Pacific Ocean (PEM-West) is a major component of the East Asia/North Pacific Regional Study (APARE), a project within the International Global Atmospheric Chemistry (IGAC) Program. The broad objectives of the PEM-West/APARE initiative are to study chemical processes and long-range transport of atmospheric trace species over the north-west Pacific Ocean and to estimate the magnitude of the human impact on these species over this region. The first phase of PEM-West (PEM-West A) was conducted in September-October 1991, a period characterized by minimum outflow from the Asian continent. The second phase of this mission, PEM-West B, was conducted during February-March 1994, a period characterized by enhanced outflow from the Asian continent. Both field campaigns of PEM-West included intensive airborne measurements of trace gases and aerosols from the NASA DC-8 aircraft coordinated with measurements at surface sites. This paper reports the experimental design for PEM-West B and provides a brief summary of the salient results of the PEM-West B campaign with particular emphases on the difference/similarities between phases A and B. Results from the two campaigns clearly quantify, from a trace gas perspective, the seasonal differences in the continental outflow that were qualitatively anticipated based upon meteorological considerations, and show the impact of major meteorological features within the region on the quality of tropospheric air over the North Pacific Ocean regions. The PEM-West database provides a "baseline" tool by which future assessments of a continuing impact of Asian emissions on remote Pacific regions can be judged. [These data are currently available through the Global Troposhperic Experiment Data Archive at NASA's Langley Research Center (http://www-gte.larc.nasa.gov) and the Langley Distributed Archive Center (http://eosdis.larc.nasa.gov)].

Establishing the cultural equivalence of the Young Children’s Participation and Environment Measure (YC-PEM) for use in Singapore

PubMed Central

Lim, Chun Yi; Law, Mary; Khetani, Mary; Pollock, Nancy; Rosenbaum, Peter

2016-01-01

Aims Establishing the cultural equivalence of clinical assessments is critical to ensuring culturally competent care. Developed in North America, the Young Children’s Participation and Environment Measure (YC-PEM) is a caregiver questionnaire of participation in home, preschool, and community activities and perceptions of environmental impact on participation. The purpose of this study is to establish the cultural equivalence of YC-PEM content for use in Singapore. Methods We conducted semi-structured interviews with 10 early childhood and healthcare providers and cognitive interviews with 10 parents in Singapore to examine the relevance of original YC-PEM content (activities, environmental factors, item wording). Interviews were transcribed, summarized and categorized according to item, semantic, conceptual, and operational dimensions of the Applied Cultural Framework that served as a decision-making guide to keep, modify or delete the items. Results Providers and parents agreed on conceptual, item and semantic changes but less on operational changes. Significant changes were made to improve comprehension of the YC-PEM. Conclusions Despite using the same language, the majority of the YC-PEM items needed modification to be relevant to the Singapore culture. Cultural adaptation of the YC-PEM is important because there are cultural differences in children’s participation, their environments as well as the way people understand words. PMID:26642891

Characterization of Rhodamine Self-Assembled Films Using Desorption Electrospray Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Shi, Ruixia; Na, Na; Jiang, Fubin; Ouyang, Jin

2013-06-01

Growth process information and molecular structure identification are very important for characterization of self-assembled films. Here, we explore the possible application of desorption electrospray ionization mass spectrometry (DESI-MS) that provides the assembled information of rhodamine B (Rh B) and rhodamine 123 (Rh 123) films. With the help of lab-made DESI source, two characteristic ions [Rh B]+ and [Rh 123]+ are observed directly in the open environment. To evaluate the reliability of this technique, a comparative study of ultraviolet-visible (UV-vis) spectroscopy and our method is carried out, and the result shows good correlation. According to the signal intensity of characteristic ions, the layer-by-layer adsorption process of dyes can be monitored, and the thicknesses of multilayer films can also be comparatively determined. Combining the high sensitivity, selectivity, and speed of mass spectrometry, the selective adsorption of similar structure molecules under different pH is recognized easily from extracted ion chronograms. The variation trend of dyes signalling intensity with concentration of polyelectrolyte is studied as well, which reflects the effect of surface charge on dyes deposition. Additionally, the desorption area, surface morphology, and thicknesses of multilayer films are investigated using fluorescence microscope, scanning electron microscope (SEM), and atomic force microscopy (AFM), respectively. Because the desorption area was approximately as small as 2 mm2, the distribution situation of organic dyes in an arbitrary position could be gained rapidly, which means DESI-MS has advantages on in situ analysis.

Lipophilic polyelectrolyte gel derived from phosphonium borate can absorb a wide range of organic solvents.

PubMed

Sunaga, Sokuro; Kokado, Kenta; Sada, Kazuki

2018-01-24

Herein, we demonstrate a polyelectrolyte gel which can absorb a wide range of organic solvents from dimethylsulfoxide (DMSO, permittivity: ε = 47.0) to tetrahydrofuran (ε = 5.6). The gel consists of polystyrene chains with small amounts (∼5 mol%) of lipophilic electrolytes derived from triphenylphosphonium tetraaryl borate. The swelling ability of the polyelectrolyte gel was higher than that of the alkyl ammonium tetraaryl borate previously reported by us, and this is attributed to the higher compatibility with organic solvents, as well as the higher dissociating ability, of the triphenyl phosphonium salt. The role of the ionic moieties was additionally confirmed by post modification of the polyelectrolyte gel via a conventional Wittig reaction, resulting in a nonionic gel. Our findings introduced here will lead to a clear-cut molecular design for polyelectrolyte gels which absorb all solvents.

Biomaterials based on photosynthetic membranes as potential sensors for herbicides.

PubMed

Ventrella, Andrea; Catucci, Lucia; Placido, Tiziana; Longobardi, Francesco; Agostiano, Angela

2011-08-15

In this study, ultrathin film multilayers of Photosystem II-enriched photosynthetic membranes (BBY) were prepared and immobilized on quartz substrates by means of a Layer by Layer procedure exploiting electrostatic interactions with poly(ethylenimine) as polyelectrolyte. The biomaterials thus obtained were characterized by means of optical techniques and Atomic Force Microscopy, highlighting the fact that the Layer by Layer approach allowed the BBYs to be immobilized with satisfactory results. The activity of these hybrid materials was evaluated by means of optical assays based on the Hill Reaction, indicating that the biosamples, which preserved about 65% of their original activity even ten weeks after preparation, were both stable and active. Furthermore, an investigation of the biochips' sensitivity to the herbicide terbutryn, as a model analyte, gave interesting results: inhibition of photosynthetic activity was observed at terbutryn concentrations higher than 10(-7)M, thus evidencing the potential of such biomaterials in the environmental biosensor field. Copyright © 2011 Elsevier B.V. All rights reserved.

Layer-by-layer assembled biopolymer microcapsule with separate layer cavities generated by gas-liquid microfluidic approach.

PubMed

Wang, Yifeng; Zhou, Jing; Guo, Xuecheng; Hu, Qian; Qin, Chaoran; Liu, Hui; Dong, Meng; Chen, Yanjun

2017-12-01

In this work, a layer-by-layer (LbL) assembled biopolymer microcapsule with separate layer cavities is generated by a novel and convenient gas-liquid microfluidic approach. This approach exhibits combined advantages of microfluidic approach and LbL assembly method, and it can straightforwardly build LbL-assembled capsules in mild aqueous environments at room temperature. In particular, using this approach we can build the polyelectrolyte multilayer capsule with favorable cavities in each layer, and without the need for organic solvent, emulsifying agent, or sacrificial template. Various components (e.g., drugs, proteins, fluorescent dyes, and nanoparticles) can be respectively encapsulated in the separate layer cavities of the LbL-assembled capsules. Moreover, the encapsulated capsules present the ability as colorimetric sensors, and they also exhibit the interesting release behavior. Therefore, the LbL-assembled biopolymer capsule is a promising candidate for biomedical applications in targeted delivery, controlled release, and bio-detection. Copyright © 2017 Elsevier B.V. All rights reserved.

Surface Modification of Dental Titanium Implant by Layer-by-Layer Electrostatic Self-Assembly

PubMed Central

Shi, Quan; Qian, Zhiyong; Liu, Donghua; Liu, Hongchen

2017-01-01

In vivo implants that are composed of titanium and titanium alloys as raw materials are widely used in the fields of biology and medicine. In the field of dental medicine, titanium is considered to be an ideal dental implant material. Good osseointegration and soft tissue closure are the foundation for the success of dental implants. Therefore, the enhancement of the osseointegration and antibacterial abilities of titanium and its alloys has been the focus of much research. With its many advantages, layer-by-layer (LbL) assembly is a self-assembly technique that is used to develop multilayer films based on complementary interactions between differently charged polyelectrolytes. The LbL approach provides new methods and applications for the surface modification of dental titanium implant. In this review, the application of the LbL technique to surface modification of titanium including promoting osteogenesis and osseointegration, promoting the formation and healing of soft tissues, improving the antibacterial properties of titanium implant, achieving local drug delivery and sustained release is summarized. PMID:28824462

Comprehensive overview of recent preparation and application trends of various open tubular capillary columns in separation science.

PubMed

Cheong, Won Jo; Ali, Faiz; Kim, Yune Sung; Lee, Jin Wook

2013-09-20

Open tubular (OT) capillary columns have been increasingly used in a variety of fields of separation science such as CEC, LC, and SPE. Especially their application in CEC has attracted a lot of attention for their outstanding separation performance. Various forms of OT stationary phase materials have been employed such as in-situ prepared polymers, molecular imprinted polymers (MIPs), brush ligands, host ligands, block copolymers, aptamers, carbon nanotubes, polysaccharides, proteins, tentacles, nanoparticles, monoliths, and polyelectrolyte multi-layers. They have been prepared either in the chemically bound format or physically adsorbed format. Sol-gel technologies and nanoparticles have been sometimes involved in their preparation. There have been also some unique miscellaneous studies, for example, adopting preferentially adsorbed mobile phase components as stationary phases. In this review, recent progresses since mostly 2007 will be critically discussed in detail with some summarized descriptions for the work before the date. Copyright © 2013 Elsevier B.V. All rights reserved.

Recent Advances in Gas Barrier Thin Films via Layer-by-Layer Assembly of Polymers and Platelets.

PubMed

Priolo, Morgan A; Holder, Kevin M; Guin, Tyler; Grunlan, Jaime C

2015-05-01

Layer-by-layer (LbL) assembly has emerged as the leading non-vacuum technology for the fabrication of transparent, super gas barrier films. The super gas barrier performance of LbL deposited films has been demonstrated in numerous studies, with a variety of polyelectrolytes, to rival that of metal and metal oxide-based barrier films. This Feature Article is a mini-review of LbL-based multilayer thin films with a 'nanobrick wall' microstructure comprising polymeric mortar and nano-platelet bricks that impart high gas barrier to otherwise permeable polymer substrates. These transparent, water-based thin films exhibit oxygen transmission rates below 5 × 10(-3) cm(3) m(-2) day(-1) atm(-1) and lower permeability than any other barrier material reported. In an effort to put this technology in the proper context, incumbent technologies such as metallized plastics, metal oxides, and flake-filled polymers are briefly reviewed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interplay of polyelectrolytes with different adsorbing surfaces

NASA Astrophysics Data System (ADS)

Xie, Feng

We study the adsorption of polyelectrolytes from solution onto different adsorbing surfaces, focusing on the electrostatic interactions. Measurements of the surface excess, fractional ionization of chargeable groups, segmental orientation, and adsorption kinetics were made using Fourier transform infrared spectroscopy in the mode of attenuated total reflection. Different adsorbing surfaces, from single solid surfaces, solid surfaces modified with adsorbed polymer layer, to fluid-like surfaces-biomembranes were adopted. Both atomic force microscopy (AFM) and fluorescent techniques were employed to investigate the fluid-like surfaces in the absence and in the presence of polyelectrolytes. The work focuses on three primary issues: (i) the charge regulation of weak polyelectrolytes on both homogeneous and heterogeneous surfaces, (ii) the dynamics of adsorption when the surface possesses reciprocal mobility, i.e., biomembrane surface, and (iii) the structural and dynamical properties of the fluid-like surfaces interacting with polyelectrolytes. We find that the ionization of chargeable groups in weak polyelectrolytes is controlled by the charge balance between the adsorbates and the surfaces. A new interpretation of ionization in the adsorbed layer provides a new insight into the fundamental problem of whether ions of opposite charge associate or remain separate. Bjerrum length is found to be a criterion for the onset of surface ionization suppression, which helps to predict and control the conformation transition of proteins. In addition to the effect of different surfaces on the adsorption behavior of polyelectrolytes, we also focused on the response of the surfaces to the adsorbates. Chains that encountered sparsely-covered surfaces spread to maximize the number of segment-surface contacts at rates independent of the molar mass. Surface reconstruction rather than molar mass of the adsorbing molecules appeared to determine the rate of spreading. This contrasts starkly with traditional polymer adsorption onto surfaces whose structure is "frozen" and unresponsive. Finally, preliminary studies on dynamical properties of biomembrane surfaces interacting with polyelectrolytes are presented, using fluorescence correlation spectroscopy (FCS). The significance is to characterize domains induced by polyelectrolyte binding.

The JPL Direct Methanol Liquid-feed PEM Fuel Cell

NASA Technical Reports Server (NTRS)

Halpert, G.; Surampudi, S.

1994-01-01

Recently, there has been a breakthrough in fuel cell technology in the Energy Storage Systems Group at the Jet Propulsion Laboratory with the develpment of a direct methanol, liquid-feed, solid polymer electrolyte membrane (PEM) fuel cell... The methanol liquid-feed, solid polymer electrolyte (PEM) design has numerous system level advantages over the gas-feed design. These include:...

Zero-CO2 emission and low-crossover 'rechargeable' PEM fuel cells using cyclohexane as an organic hydrogen reservoir.

PubMed

Kariya, Nobuko; Fukuoka, Atsushi; Ichikawa, Masaru

2003-03-21

High performance (open circuit voltage = 920 mV, maximum power density = 14-15 mW cm(-2)) of the PEM fuel cell was achieved by using cyclohexane as a fuel with zero-CO2 emission and lower-crossover through PEM than with a methanol-based fuel cell.

Studies on Ionic Conductivity and Electrochemical Stability of Plasticized Photopolymerized Polymer Electrolyte Membranes for Solid State Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

He, Ruixuan

In pursuit of safer and more flexible solid-state lithium ion batteries, solid polymer electrolytes have emerged as a promising candidate. The present dissertation entails exploration of solid plasticized, photopolymerized (i.e. ultraviolent-cured) polymer electrolyte membranes (PEM) for fulfilling the critical requirements of electrolytes, such as high ionic conductivity and good thermal and electrochemical stability, among others. Electrochemical performance of PEMs containing lithium ion half-cells was also investigated at different two temperatures. Phase diagram approach was adopted to guide the fabrication of two types of plasticized PEMs. Prepolymer poly (ethylene glycol) diacrylate (PEGDA) was used as a matrix for building an ionic conductive and mechanically sturdy network. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was incorporated as a source of lithium ions, while a solid plasticizer succinonitrile (SCN) and a liquid plasticizer tetraethylene glycol dimethyl ether (TEGDME) were incorporated in the respective systems. The important role of plasticizer on the enhancement of ionic conductivity (sigma) to the superionic conductive level (10-3 S/cm) was revealed in both systems. It is worth noting that photopolymerization induced crystallization (PIC) occurred during UV-curing in the SCN-rich region of the ternary PEGDA/LiTFSI/SCN ternary mixtures. The PEM thus formed contained a plastic crystal phase, which showed lower σ relative to their amorphous PEGDA/LiTFSI/TEGDME counterpart. Comparisons on other thermal and electrochemical properties of the two types of PEMs are presented in Chapter IV. For the PEGDA/LiTFSI/SCN PEMs, fundamental study was carried out to clarify the relationship between σ and glass transition temperature (T g). In lithium salt/polymer binary PEMs, increase in Tg and reduction in σ were observed; these may be attributed to ion-dipole complexation between dissociated lithium cations and ether oxygen upon salt addition. Notably, above the threshold salt concentration of 7 mol %, dual loss tangent peaks were observed in dynamic mechanical studies. These might be ascribed to segmental relaxations of ion-dipole complexed networks and that of polymer chains surrounding the undissociated lithium salt acting like "fillers". Upon SCN incorporation, these two peaks merged into one that was further suppressed below the Tg of the pure network, whereas σ improved to the superionic conductor level. The role of SCN on the σ enhancement as both plasticizer for the polymer network and ionizer for the salt is discussed in Chapter V. In order to improve the mechanical toughness of the highly conductive PEGDA/LiTFSI/SCN PEM, effects of prepolymer molecular weight on mechanical and electrochemical properties of PEMs were further investigated. By increasing molecular weight of PEGDA from 700 to 6000 g/mol, toughness and elongation at break were enhanced as expected. Interestingly, improved ionic conductivity was achieved simultaneously. The dual improvement may be attributed to the less chemical crosslinked points and the more flexible chain motion in the looser network of PEGDA6000-PEM relative to its PEGDA700 counterpart. Subsequently, high thermal stability and electrochemical stability of both types of PEMs, as well as the satisfactory room temperature charge/discharge cycling performance of PEM containing lithium ion half-cells were observed. The pertinent information is documented in Chapter VI. Finally, the investigation of the charge/discharge cycling performance of solid-state LiFePO4 half-cells at an elevated temperature of 60°C is discussed in Chapter VII. In the half-cells, particularly, SCN plasticized PEMs with and without electrolyte modifier lithium bis(oxalato)borate (LiBOB) were respectively employed. Rapid decline of capacity and increase of cell resistance were found in the unmodified PEM containing cell; however, these deteriorations were greatly suppressed upon LiBOB modification. Electrochemical and thermal compatibility of PEMs towards different electrodes were examined in several symmetric cells and half-cells. Detailed characterization on LiFePO 4 electrodes and PEMs retrieved from these cells implied that the observed battery failure might be triggered by an amide-forming side reaction that took place at the interface of a SCN plasticized PEM and a lithium electrode at high temperature. Of particular importance is the fact that this detrimental side reaction was effectively suppressed upon LiBOB electrolyte modifier addition. Plausible mechanisms are discussed.

Polyelectrolyte Bundles: Finite size at thermodynamic equilibrium?

NASA Astrophysics Data System (ADS)

Sayar, Mehmet

2005-03-01

Experimental observation of finite size aggregates formed by polyelectrolytes such as DNA and F-actin, as well as synthetic polymers like poly(p-phenylene), has created a lot of attention in recent years. Here, bundle formation in rigid rod-like polyelectrolytes is studied via computer simulations. For the case of hydrophobically modified polyelectrolytes finite size bundles are observed even in the presence of only monovalent counterions. Furthermore, in the absence of a hydrophobic backbone, we have also observed formation of finite size aggregates via multivalent counterion condensation. The size distribution of such aggregates and the stability is analyzed in this study.

Reduced activities of thiamine-dependent and cytochrome c oxidase enzymes in cerebral cortex of cattle affected by sulfur-induced polioencephalomalacia

PubMed Central

Amat, Samat; Hendrick, Steve; Moshynskyy, Igor; Simko, Elemir

2017-01-01

Sulfur-induced polioencephalomalacia (PEM) is an important disease affecting cattle in certain geographical regions. However, the pathogenesis of brain damage is not completely understood. We previously observed that excess dietary sulfur may influence thiamine status and altered thiamine metabolism may be involved in the pathogenesis of sulfur-induced PEM in cattle. In this study, we evaluated the activities of thiamine-dependent enzymes [α-ketogluterate dehydrogenase (α-KGDH) and pyruvate dehydrogenase (PDH)] and cytochrome c oxidase (COX) in the cerebral cortex of sulfur-induced PEM-affected cattle (n = 9) and clinically normal cattle (n = 8, each group) exposed to low or high dietary sulfur [LS = 0.30% versus HS = 0.67% sulfur on a dry matter (DM) basis]. Enzyme activities in PEM brains were measured from the brain tissue regions and examined using ultraviolent (UV) light illumination to show fluorescence or non-fluorescence regions. No gross changes under regular or UV light, or histopathological changes indicative of PEM were detected in the brains of cattle exposed to LS or HS diets. The PDH, α-KGDH, and COX activities did not differ between LS and HS brains, but all enzymes showed significantly lower (P < 0.05) activities in UV-positive region of PEM brains compared with LS and HS brains. The UV-negative regions of PEM brain had similar PDH activities to LS and HS brains, but the activities of α-KGDH and COX were significantly lower than in LS and HS brains. The results of this study suggest that reduced enzyme activities of brain PHD, α-KGDH, and COX are associated with the pathogenesis of sulfur-induced PEM. PMID:29081580

A Novel Marking Reader for Progressive Addition Lenses Based on Gabor Holography.

PubMed

Perucho, Beatriz; Picazo-Bueno, José Angel; Micó, Vicente

2016-05-01

Progressive addition lenses (PALs) are marked with permanent engraved marks (PEMs) at standardized locations. Permanent engraved marks are very useful through the manufacturing and mounting processes, act as locator marks to re-ink the removable marks, and contain useful information about the PAL. However, PEMs are often faint and weak, obscured by scratches, partially occluded, and difficult to recognize on tinted lenses or with antireflection or scratch-resistant coatings. The aim of this article is to present a new generation of portable marking reader based on an extremely simplified concept for visualization and identification of PEMs in PALs. Permanent engraved marks on different PALs are visualized using classical Gabor holography as underlying principle. Gabor holography allows phase sample visualization with adjustable magnification and can be implemented in either classical or digital versions. Here, visual Gabor holography is used to provide a magnified defocused image of the PEMs onto a translucent visualization screen where the PEM is clearly identified. Different types of PALs (conventional, personalized, old and scratched, sunglasses, etc.) have been tested to visualize PEMs with the proposed marking reader. The PEMs are visible in every case, and variable magnification factor can be achieved simply moving up and down the PAL in the instrument. In addition, a second illumination wavelength is also tested, showing the applicability of this novel marking reader for different illuminations. A new concept of marking reader ophthalmic instrument has been presented and validated in the laboratory. The configuration involves only a commercial-grade laser diode and a visualization screen for PEM identification. The instrument is portable, economic, and easy to use, and it can be used for identifying patient's current PAL model and for marking removable PALs again or finding test points regardless of the age of the PAL, its scratches, tints, or coatings.

Predictive NO x emission monitoring on board a passenger ferry

NASA Astrophysics Data System (ADS)

Cooper, D. A.; Andreasson, K.

NO x emissions from a medium speed diesel engine on board a servicing passenger ferry have been indirectly measured using a predictive emission monitoring system (PEMS) over a 1-yr period. Conventional NO x measurements were carried out with a continuous emission monitoring system (CEMS) at the start of the study to provide historical data for the empirical PEMS function. On three other occasions during the year the CEMS was also used to verify the PEMS and follow any changes in emission signature of the engine. The PEMS consisted of monitoring exhaust O 2 concentrations (in situ electrochemical probe), engine load, combustion air temperature and humidity, and barometric pressure. Practical experiences with the PEMS equipment were positive and measurement data were transferred to a land-based office by using a modem data communication system. The initial PEMS function (PEMS1) gave systematic differences of 1.1-6.9% of the calibration domain (0-1725 ppm) and a relative accuracy of 6.7% when compared with CEMS for whole journeys and varying load situations. Further improvements on the performance could be obtained by updating this function. The calculated yearly emission for a total engine running time of 4618 h was 316 t NO x±38 t and the average NO x emission corrected for ambient conditions 14.3 g kWh corr-1. The exhaust profile of the engine in terms of NO x, CO and CO 2 emissions as determined by CEMS was similar for most of the year. Towards the end of the study period, a significantly lower NO x emission was detected which was probably caused by replacement of fuel injector nozzles. The study suggests that PEMS can be a viable option for continuous, long-term NO x measurements on board ships.

Characterization of Polyester Cloth as an Alternative Separator to Nafion Membrane in Microbial Fuel Cells for Bioelectricity Generation Using Swine Wastewater.

PubMed

Kim, Taeyoung; Kang, Sukwon; Sung, Je Hoon; Kang, Youn Koo; Kim, Young Hwa; Jang, Jae Kyung

2016-12-28

Polyester cloth (PC) was selected as a prospective inexpensive substitute separator material for microbial fuel cells (MFCs). PC was compared with a traditional Nafion proton exchange membrane (PEM) as an MFC separator by analyzing its physical and electrochemical properties. A single layer of PC showed higher mass transfer ( e.g ., for O₂/H⁺/ions) than the Nafion PEM; in the case of oxygen mass transfer coefficient (k o ), a rate of 50.0 × 10⁻⁵ cm·s⁻¹ was observed compared with a rate of 20.8 × 10⁻⁵ cm/s in the Nafion PEM. Increased numbers of PC layers were found to reduce the oxygen mass transfer coefficient. In addition, the diffusion coefficient of oxygen (D O ) for PC (2.0-3.3 × 10⁻⁶ cm²/s) was lower than that of the Nafion PEM (3.8 × 10⁻⁶ cm²/s). The PC was found to have a low ohmic resistance (0.29-0.38 Ω) in the MFC, which was similar to that of Nafion PEM (0.31 Ω); this resulted in comparable maximum power density and maximum current density in MFCs with PC and those with Nafion PEMs. Moreover, a higher average current generation was observed in MFCs with PC (104.3 ± 15.3 A/m³) compared with MFCs with Nafion PEM (100.4 ± 17.7 A/m³), as well as showing insignificant degradation of the PC surface, during 177 days of use in swine wastewater. These results suggest that PC separators could serve as a low-cost alternative to Nafion PEMs for construction of cost-effective MFCs.

Readability assessment of Internet-based patient education materials related to endoscopic sinus surgery.

PubMed

Cherla, Deepa V; Sanghvi, Saurin; Choudhry, Osamah J; Liu, James K; Eloy, Jean Anderson

2012-08-01

Numerous professional societies, clinical practices, and hospitals provide Internet-based patient education materials (PEMs) to the general public, but not all of this information is written at a reading level appropriate for the average patient. The National Institutes of Health and the US Department of Health and Human Services recommend that PEMs be written at or below the sixth-grade level. Our purpose was to assess the readability of endoscopic sinus surgery (ESS)-related PEMs available on the Internet and compare readability levels of PEMs provided by three sources: professional societies, clinical practices, and hospitals. A descriptive and correlational design was used for this study. The readability of 31 ESS-related PEMs was assessed with four different readability indices: Flesch-Kincaid Grade Level (FKGL), Flesch Reading Ease Score (FRES), Simple Measure of Gobbledygook (SMOG), and Gunning Frequency of Gobbledygook (Gunning FOG). Averages were evaluated against national recommendations and between each source using analysis of variance and t tests. The majority of PEMs (96.8%) were written above the recommended sixth-grade reading level, based on FKGL (P < .001). Only one article (3.2%) had an FKGL at or below the sixth-grade level. The mean readability values were: FRES 47.1 ± 13.4, FKGL 10.7 ± 2.4, SMOG 13.7 ± 1.6, and Gunning FOG 12.4 ± 2.7. Current Internet-based PEMs related to ESS, regardless of source type, were written well above the recommended sixth-grade level. Materials from the hospitals/university-affiliated websites had lower readability scores, but were still above recommended levels. Web-based PEMs pertaining to ESS should be written with the average patient in mind. Copyright © 2012 The American Laryngological, Rhinological, and Otological Society, Inc.

Novel polyelectrolyte complex based carbon nanotube composite architectures

NASA Astrophysics Data System (ADS)

Razdan, Sandeep

This study focuses on creating novel architectures of carbon nanotubes using polyelectrolytes. Polyelectrolytes are unique polymers possessing resident charges on the macromolecular chains. This property, along with their biocompatibility (true for most polymers used in this study) makes them ideal candidates for a variety of applications such as membranes, drug delivery systems, scaffold materials etc. Carbon nanotubes are also unique one-dimensional nanoscale materials that possess excellent electrical, mechanical and thermal properties owing to their small size, high aspect ratio, graphitic structure and strength arising from purely covalent bonds in the molecular structure. The present study tries to investigate the synthesis processes and material properties of carbon nanotube composites comprising of polyelectrolyte complexes. Carbon nanotubes are dispersed in a polyelectrolyte and are induced into taking part in a complexation process with two oppositely charged polyelectrolytes. The resulting stoichiometric precipitate is then drawn into fiber form and dried as such. The material properties of the carbon nanotube fibers were characterized and related to synthesis parameters and material interactions. Also, an effort was made to understand and predict fiber morphology resulting from the complexation and drawing process. The study helps to delineate the synthesis and properties of the said polyelectrolyte complex-carbon nanotube architectures and highlights useful properties, such as electrical conductivity and mechanical strength, which could make these structures promising candidates for a variety of applications.

Differences in ME and CFS Symptomology in Patients with Normal and Abnormal Exercise Test Results.

PubMed

McManimen, Stephanie L; Jason, Leonard A

2017-01-01

Post-exertional malaise (PEM) is a cardinal symptom of myalgic encephalomyelitis (ME) and chronic fatigue syndrome (CFS), which often distinguishes patients with this illness from healthy controls or individuals with exclusionary illnesses such as depression. However, occurrence rates for PEM fluctuate from subject to how the symptom is operationalized. One commonly utilized method is exercise testing, maximal or submaximal. Many patients with ME and CFS experience PEM after participating in these tests, and often show abnormal results. However, some patients still exhibit normal results after participating in the exercise testing. This study examined the differences between two patient groups with ME and CFS, those with normal results and those with abnormal results, on several PEM-related symptoms and illness characteristics. The results suggest those that displayed abnormal results following testing have more frequent and severe PEM, worse overall functioning, and are more likely to be bedbound than those that displayed normal results.

New membranes based on ionic liquids for PEM fuel cells at elevated temperatures

NASA Astrophysics Data System (ADS)

Ye, H.; Huang, J.; Xu, J. J.; Kodiweera, N. K. A. C.; Jayakody, J. R. P.; Greenbaum, S. G.

Proton exchange membrane (PEM) fuel cells operating at elevated temperature, above 120 °C, will yield significant benefits but face big challenges for the development of suitable PEMs. The objectives of this research are to demonstrate the feasibility of the concept and realize [acid/ionic liquid/polymer] composite gel-type membranes as such PEMs. Novel membranes consisting of anhydrous proton solvent H 3PO 4, the protic ionic liquid PMIH 2PO 4, and polybenzimidazole (PBI) as a matrix have been prepared and characterized for PEM fuel cells intended for operation at elevated temperature (120-150 °C). Physical and electrochemical analyses have demonstrated promising characteristics of these H 3PO 4/PMIH 2PO 4/PBI membranes at elevated temperature. The proton transport mechanism in these new membranes has been investigated by Fourier transform infrared and nuclear magnetic resonance spectroscopic methods.

Application of Thermo-Mechanical Measurements of Plastic Packages for Reliability Evaluation of PEMS

NASA Technical Reports Server (NTRS)

Sharma, Ashok K.; Teverovsky, Alexander

2004-01-01

Thermo-mechanical analysis (TMA) is typically employed for measurements of the glass transition temperature (Tg) and coefficients of thermal expansion (CTE) in molding compounds used in plastic encapsulated microcircuits (PEMs). Application of TMA measurements directly to PEMs allows anomalies to be revealed in deformation of packages with temperature, and thus indicates possible reliability concerns related to thermo-mechanical integrity and stability of the devices. In this work, temperature dependencies of package deformation were measured in several types of PEMs that failed environmental stress testing including temperature cycling, highly accelerated stress testing (HAST) in humid environments, and bum-in (BI) testing. Comparison of thermo-mechanical characteristics of packages and molding compounds in the failed parts allowed for explanation of the observed failures. The results indicate that TMA of plastic packages might be used for quality evaluation of PEMs intended for high-reliability applications.

QCM-D Investigation of Swelling Behavior of Layer-by-Layer Thin Films upon Exposure to Monovalent Ions.

PubMed

O'Neal, Joshua T; Dai, Ethan Y; Zhang, Yanpu; Clark, Kyle B; Wilcox, Kathryn G; George, Ian M; Ramasamy, Nandha E; Enriquez, Daisy; Batys, Piotr; Sammalkorpi, Maria; Lutkenhaus, Jodie L

2018-01-23

Polyelectrolyte multilayers and layer-by-layer assemblies are susceptible to structural changes in response to ionic environment. By altering the salt type and ionic strength, structural changes can be induced by disruption of intrinsically bound ion pairs within the multilayer network via electrostatic screening. Notably, high salt concentrations have been used for the purposes of salt-annealing and self-healing of LbL assemblies with KBr, in particular, yielding a remarkably rapid response. However, to date, the structural and swelling effects of various monovalent ion species on the behavior of LbL assemblies remain unclear, including a quantitative view of ion content in the LbL assembly and thickness changes over a wide concentration window. Here, we investigate the effects of various concentrations of KBr (0 to 1.6 M) on the swelling and de-swelling of LbL assemblies formed from poly(diallyldimethylammonium) polycation (PDADMA) and poly(styrene sulfonate) polyanion (PSS) in 0.5 M NaCl using quartz-crystal microbalance with dissipation (QCM-D) monitoring as compared to KCl, NaBr, and NaCl. The ion content after salt exchange is quantified using neutron activation analysis (NAA). Our results demonstrate that Br - ions have a much greater effect on the structure of as-prepared thin films than Cl - at ionic strengths above assembly conditions, which is possibly caused by the more chaotropic nature of Br - . It is also found that the anion in general dominates the swelling response as compared to the cation because of the excess PDADMA in the multilayer. Four response regimes are identified that delineate swelling due to electrostatic repulsion, slight contraction, swelling due to doping, and film destruction as ionic strength increases. This understanding is critical if such materials are to be used in applications requiring submersion in chemically dynamic environments such as sensors, coatings on biomedical implants, and filtration membranes.

Non-Kinetic Losses Caused by Electrochemical Carbon Corrosion in PEM Fuel Cells

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

Park, Seh Kyu; Shao, Yuyan; Viswanathan, Vilayanur V.

2012-05-01

This paper presented non-kinetic losses in PEM fuel cells under an accelerated stress test of catalyst support. The cathode with carbon-supported Pt catalyst was prepared and characterized with potential hold at 1.2 V vs. SHE in PEM fuel cells. Irreversible losses caused by carbon corrosion were evaluated using a variety of electrochemical characterizations including cyclic voltammetry, linear sweep voltammetry, electrochemical impedance spectroscopy, and polarization technique. Ohmic losses at the cathode with potential hold were determined using its capacitive responses. Concentration losses in PEM fuel cells were analyzed in terms of Tafel behavior and thin film/flooded-agglomerate dynamics.

Endogenous Nod-Factor-Like Signal Molecules Promote Early Somatic Embryo Development in Norway Spruce1

PubMed Central

Dyachok, Julia V.; Wiweger, Malgorzata; Kenne, Lennart; von Arnold, Sara

2002-01-01

Embryogenic cultures of Norway spruce (Picea abies) are composed of pro-embryogenic masses (PEMs) and somatic embryos of various developmental stages. Auxin is important for PEM formation and proliferation. In this report we show that depletion of auxin blocks PEM development and causes large-scale cell death. Extracts of the media conditioned by embryogenic cultures stimulate development of PEM aggregates in auxin-deficient cultures. Partial characterization of the conditioning factor shows that it is a lipophilic, low-molecular-weight molecule, which is sensitive to chitinase and contains GlcNAc residues. On the basis of this information, we propose that the factor is a lipophilic chitin oligosaccharide (LCO). The amount of LCO correlates to the developmental stages of PEMs and embryos, with the highest level in the media conditioned by developmentally blocked cultures. LCO is not present in nonembryogenic cultures. Cell death, induced by withdrawal of auxin, is suppressed by extra supply of endogenous LCO or Nod factor from Rhizobium sp. NGR234. The effect can be mimicked by a chitotetraose or chitinase from Streptomyces griseus. Taken together, our data suggest that endogenous LCO acts as a signal molecule stimulating PEM and early embryo development in Norway spruce. PMID:11842156

Instructions for Plastic Encapsulated Microcircuit(PEM) Selection, Screening and Qualification.

NASA Technical Reports Server (NTRS)

King, Terry; Teverovsky, Alexander; Leidecker, Henning

2002-01-01

The use of Plastic Encapsulated Microcircuits (PEMs) is permitted on NASA Goddard Space Flight Center (GSFC) spaceflight applications, provided each use is thoroughly evaluated for thermal, mechanical, and radiation implications of the specific application and found to meet mission requirements. PEMs shall be selected for their functional advantage and availability, not for cost saving; the steps necessary to ensure reliability usually negate any initial apparent cost advantage. A PEM shall not be substituted for a form, fit and functional equivalent, high reliability, hermetic device in spaceflight applications. Due to the rapid change in wafer-level designs typical of commercial parts and the unknown traceability between packaging lots and wafer lots, lot specific testing is required for PEMs, unless specifically excepted by the Mission Assurance Requirements (MAR) for the project. Lot specific qualification, screening, radiation hardness assurance analysis and/or testing, shall be consistent with the required reliability level as defined in the MAR. Developers proposing to use PEMs shall address the following items in their Performance Assurance Implementation Plan: source selection (manufacturers and distributors), storage conditions for all stages of use, packing, shipping and handling, electrostatic discharge (ESD), screening and qualification testing, derating, radiation hardness assurance, test house selection and control, data collection and retention.

50th Anniversary Perspective: A Perspective on Polyelectrolyte Solutions

PubMed Central

2017-01-01

From the beginning of life with the information-containing polymers until the present era of a plethora of water-based materials in health care industry and biotechnology, polyelectrolytes are ubiquitous with a broad range of structural and functional properties. The main attribute of polyelectrolyte solutions is that all molecules are strongly correlated both topologically and electrostatically in their neutralizing background of charged ions in highly polarizable solvent. These strong correlations and the necessary use of numerous variables in experiments on polyelectrolytes have presented immense challenges toward fundamental understanding of the various behaviors of charged polymeric systems. This Perspective presents the author’s subjective summary of several conceptual advances and the remaining persistent challenges in the contexts of charge and size of polymers, structures in homogeneous solutions, thermodynamic instability and phase transitions, structural evolution with oppositely charged polymers, dynamics in polyelectrolyte solutions, kinetics of phase separation, mobility of charged macromolecules between compartments, and implications to biological systems. PMID:29296029

Molecular dynamics study of linear and comb-like polyelectrolytes in aqueous solution: effect of Ca2+ ions

NASA Astrophysics Data System (ADS)

Tong, Kefeng; Song, Xingfu; Sun, Shuying; Xu, Yanxia; Yu, Jianguo

2014-08-01

All-atom molecular dynamics simulations were employed to provide microscopic mechanism for the salt tolerance of polyelectrolytes dispersants. The conformational variation of polyelectrolytes and interactions between COO- groups and counterions/water molecules were also studied via radius of gyration and pair correlations functions. Sodium polyacrylate (NaPA) and sodium salts of poly(acrylic acid)-poly(ethylene oxide) (NaPA-PEO) were selected as the representative linear and comb-like polyelectrolyte, respectively. The results show that Ca2+ ions interact with COO- groups much stronger than Na+ ions and can bring ion-bridging interaction between intermolecular COO- groups in the NaPA systems. While in the NaPA-PEO systems, the introduced PEO side chains can prevent backbone chains from ion-bridging interactions and weaken the conformational changes. The present results can help in selecting and designing new-type efficient polyelectrolyte dispersants with good salt tolerance.

Fabrication of Thickness-Controllable Micropatterned Polyelectrolyte-Film/Nanoparticle Surfaces by Using the Plasma Oxidation Method.

PubMed

Zhu, Chun-Tao; Ma, Sheng-Hua; Zhang, Ying; Wang, Xue-Jing; Lv, Peng; Han, Xiao-Jun

2016-04-05

We have demonstrated a novel way to form thickness-controllable polyelectrolyte-film/nanoparticle patterns by using a plasma etching technique to form, first, a patterned self-assembled monolayer surface, followed by layer-by-layer assembly of polyelectrolyte-films/nanoparticles. Octadecyltrimethoxysilane (ODS) and (3-aminopropyl)triethoxysilane (APTES) self-assembled monolayers (SAMs) were used for polyelectrolyte-film and nanoparticle patterning, respectively. The resolution of the proposed patterning method can easily reach approximately 2.5 μm. The height of the groove structure was tunable from approximately 2.5 to 150 nm. The suspended lipid membrane across the grooves was fabricated by incubating the patterned polyelectrolyte groove arrays in solutions of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) giant unilamellar vesicles (GUVs). The method demonstrated here reveals a new path to create patterned 2D or 3D structures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Periodic nanoscale patterning of polyelectrolytes over square centimeter areas using block copolymer templates

DOE PAGES

Oded, Meirav; Kelly, Stephen T.; Gilles, Mary K.; ...

2016-04-07

Nano-patterned materials are beneficial for applications such as solar cells, opto-electronics, and sensing owing to their periodic structure and high interfacial area. We present a non-lithographic approach for assembling polyelectrolytes into periodic nanoscale patterns over cm 2 -scale areas. We used chemically modified block copolymer thin films featuring alternating charged and neutral domains as patterned substrates for electrostatic self-assembly. In-depth characterization of the deposition process using spectroscopy and microscopy techniques, including the state-of-the-art scanning transmission X-ray microscopy (STXM), reveals both the selective deposition of the polyelectrolyte on the charged copolymer domains as well as gradual changes in the film topographymore » that arise from further penetration of the solvent molecules and possibly also the polyelectrolyte into these domains. Our results demonstrate the feasibility of creating nano-patterned polyelectrolyte layers, which opens up new opportunities for structured functional coating fabrication.« less

Concentration and Purification of Influenza Virus on Insoluble Polyelectrolytes

PubMed Central

Wallis, Craig; Homma, Akira; Melnick, Joseph L.

1972-01-01

A method for rapid concentration and purification of influenza virus by adsorption on and elution from an insoluble polyelectrolyte is described. To accomplish this task, influenza virus had to be rendered stable at pH 4 to 5, since viruses adsorb to the polyelectrolyte more efficiently at this pH range. A precipitate which forms in influenza harvests under acid conditions in the cold can be removed by ammonium sulfate at a concentration which traps the precipitate but not the virus. Thus, ammonium sulfate-treated influenza virus in allantoic fluid could be readily concentrated on the polyelectrolyte. Elution yielded a virus concentrate essentially free of nonviral proteins. PMID:4553141

Biosensors from conjugated polyelectrolyte complexes

PubMed Central

Wang, Deli; Gong, Xiong; Heeger, Peter S.; Rininsland, Frauke; Bazan, Guillermo C.; Heeger, Alan J.

2002-01-01

A charge neutral complex (CNC) was formed in aqueous solution by combining an orange light emitting anionic conjugated polyelectrolyte and a saturated cationic polyelectrolyte at a 1:1 ratio (per repeat unit). Photoluminescence (PL) from the CNC can be quenched by both the negatively charged dinitrophenol (DNP) derivative, (DNP-BS−), and positively charged methyl viologen (MV2+). Use of the CNC minimizes nonspecific interactions (which modify the PL) between conjugated polyelectrolytes and biopolymers. Quenching of the PL from the CNC by the DNP derivative and specific unquenching on addition of anti-DNP antibody (anti-DNP IgG) were observed. Thus, biosensing of the anti-DNP IgG was demonstrated. PMID:11756675

Stability of polyelectrolyte-coated iron nanoparticles for T2-weighted magnetic resonance imaging

NASA Astrophysics Data System (ADS)

McGrath, Andrew J.; Dolan, Ciaran; Cheong, Soshan; Herman, David A. J.; Naysmith, Briar; Zong, Fangrong; Galvosas, Petrik; Farrand, Kathryn J.; Hermans, Ian F.; Brimble, Margaret; Williams, David E.; Jin, Jianyong; Tilley, Richard D.

2017-10-01

Iron nanoparticles are highly-effective magnetic nanoparticles for T2 magnetic resonance imaging (MRI). However, the stability of their magnetic properties is dependent on good protection of the iron core from oxidation in aqueous media. Here we report the synthesis of custom-synthesized phosphonate-grafted polyelectrolytes (PolyM3) of various chain lengths, for efficient coating of iron nanoparticles with a native iron oxide shell. The size of the nanoparticle-polyelectrolyte assemblies was investigated by transmission electron microscopy and dynamic light scattering, while surface attachment was confirmed by Fourier transform infrared spectroscopy. Low cytotoxicity was observed for each of the nanoparticle-polyelectrolyte ("Fe-PolyM3") assemblies, with good cell viability (>80%) remaining up to 100 μg mL-1 Fe in HeLa cells. When applied in T2-weighted MRI, corresponding T2 relaxivities (r2) of the Fe-PolyM3 assemblies were found to be dependent on the chain length of the polyelectrolyte. A significant increase in contrast was observed when polyelectrolyte chain length was increased from 6 to 65 repeating units, implying a critical chain length required for stabilization of the α-Fe nanoparticle core.

Teledyne Energy Systems, Inc., Proton Exchange Member (PEM) Fuel Cell Engineering Model Powerplant. Test Report: Initial Benchmark Tests in the Original Orientation

NASA Technical Reports Server (NTRS)

Loyselle, Patricia; Prokopius, Kevin

2011-01-01

Proton Exchange Membrane (PEM) fuel cell technology is the leading candidate to replace the alkaline fuel cell technology, currently used on the Shuttle, for future space missions. During a 5-yr development program, a PEM fuel cell powerplant was developed. This report details the initial performance evaluation test results of the powerplant.

Improved Round Trip Efficiency for Regenerative Fuel Cell Systems

DTIC Science & Technology

2012-05-11

advanced components that enable closed-loop, zero emission, low signature energy storage. The system utilizes proton exchange membrane ( PEM ) fuel cell ...regenerative fuel cell (RFC) systems based on proton exchange membrane ( PEM ) technology. An RFC consists of a fuel cell powerplant, an electrolysis...based on an air independent, hydrogen-oxygen, PEM RFC is feasible within the near term if development efforts proceed forward. Fuel Cell

Evaluation of Ventricle Size Measurements in Infants by Pediatric Emergency Medicine Physicians.

PubMed

Halm, Brunhild M; Leone, Tina A; Chaudoin, Lindsey T; McKinley, Kenneth W; Ruzal-Shapiro, Carrie; Franke, Adrian A; Tsze, Daniel S

2018-06-05

The identification of hydrocephalus in infants by pediatric emergency medicine (PEM) physicians using cranial point-of-care ultrasound (POCUS) has not been evaluated. We aimed to conduct a pilot/proof-of-concept study to evaluate whether PEM physicians can identify hydrocephalus (anterior horn width >5 mm) in 15 infants (mean 69 ± 42 days old) from the neonatal intensive care unit using POCUS. Our exploratory aims were to determine the test characteristics of cranial POCUS performed by PEM physicians for diagnosing hydrocephalus and the interrater reliability between measurements made by the PEM physicians and the radiologist. Depending on the availability, 1 or 2 PEM physicians performed a cranial POCUS through the open anterior fontanel for each infant after a 30-minute didactic lecture to determine the size of the left and right ventricles by measuring the anterior horn width at the foramen of Monroe in coronal view. Within 1 week, an ultrasound (US) technologist performed a cranial US and a radiologist determined the ventricle sizes from the US images; these measurements were the criterion standard. A radiologist determined 12 of the 30 ventricles as hydrocephalic. The sensitivity and specificity of the PEM physicians performed cranial POCUS was 66.7% (95% confidence interval [CI], 34.9%-90.1%) and 94.4% (95% CI, 72.7%-99.9%), whereas the positive and negative predictive values were 88.9% (95% CI, 53.3%-98.2%) and 81.0% (95% CI, 65.5%-90.5%), respectively. The interrater reliability between the PEM physician's and radiologist's measurements was r = 0.91. The entire POCUS examinations performed by the PEM physicians took an average of 1.5 minutes. The time between the cranial POCUS and the radiology US was, on average, 4 days. While the PEM physicians in our study were able to determine the absence of hydrocephalus in infants with high specificity using cranial POCUS, there was insufficient evidence to support the use of this modality for identifying hydrocephalus. Future studies with more participants are warranted to accurately determine test characteristics.

Synthesis and characterization of ion containing polymers

NASA Astrophysics Data System (ADS)

Dou, Shichen

Two types of ion-containing polymers are included in this dissertation. The first was focused on the rheology, solvation, and correlation length of polyelectrolyte solutions in terms of charge density, solvent dielectric constant, and solvent quality. The second was focused on the PEO-based polyester ionomers as single ion conductors. A series of polyelectrolytes with varied charge density (0.03 < alpha < 0.6) and counterions (Cl- and I-) were investigated in good solvent (EG, NMF, and GC) and poor solvent (DW and F). The concentration dependence of the specific viscosity and relaxation time of polyelectrolytes in solution agrees with Dobrynin's theoretical predictions at c < c**. Effective charge density greatly impacts the viscosity of polyelectrolyte semidilute solutions, while residual salt significantly reduces the viscosity of polyelectrolyte solutions at concentrations c < 2cs/f. For polyelectrolyte solutions with less condensed counterions, the correlation length obtained from SAXS and rheology perfectly matches and agrees with de Gennes prediction. Dobrynin scaling model successfully predicts the rheology of polyelectrolyte solutions in all cases: without salt, with low residual salt, and with high residual salt concentration. PEO-based polyester ionomers were synthesized by melt polycondensation. Mn was determined using the 1H NMR of ionomers. No ion-cluster was observed from the DSC, SAXS, and rheology measurements. Ionic conductivity greatly depends on the Tg, T-T g and ion content of the ionomers. PEG600-PTMO650 (z)-Li copolyester ionomers show microphase separation and much lower ionic conductivity, compared to that of PE600-Li. PTMO650-Li shows nonconductor behavior.

Positron emission mammography in breast cancer presurgical planning: comparisons with magnetic resonance imaging

PubMed Central

Narayanan, Deepa; Kalinyak, Judith E.; The, Juliette; Velasquez, Maria Victoria; Kahn, Simone; Saady, Matthew; Mahal, Ravinder; Chrystal, Larraine

2010-01-01

Purpose The objective of this study was to compare the performance characteristics of 18F-fluorodeoxyglucose (FDG) positron emission mammography (PEM) with breast magnetic resonance imaging (MRI) as a presurgical imaging and planning option for index and ipsilateral lesions in patients with newly diagnosed, biopsy-proven breast cancer. Methods Two hundred and eight women >25 years of age (median age = 59.7 ± 14.1 years) with biopsy-proven primary breast cancer enrolled in this prospective, single-site study. MRI, PEM, and whole-body positron emission tomography (WBPET) were conducted on each patient within 7 business days. PEM and WBPET images were acquired on the same day after intravenous administration of 370 MBq of FDG (median = 432.9 MBq). PEM and MRI images were blindly evaluated, compared with final surgical histopathology, and the sensitivity determined. Substudy analysis compared the sensitivity of PEM versus MRI in patients with different menopausal status, breast density, and use of hormone replacement therapy (HRT) as well as determination of performance characteristics for additional ipsilateral lesion detection. Results Two hundred and eight patients enrolled in the study of which 87% (182/208) were analyzable. Of these analyzable patients, 26.4% (48/182), 7.1% (13/182), and 64.2% (120/182) were pre-, peri-, and postmenopausal, respectively, and 48.4% (88/182) had extremely or heterogeneously dense breast tissue, while 33.5% (61/182) had a history of HRT use. Ninety-two percent (167/182) underwent core biopsy for index lesion diagnosis. Invasive cancer was found in 77.5% (141/182), while ductal carcinoma in situ (DCIS) and/or Paget’s disease were found in 22.5% (41/182) of patients. Both PEM and MRI had index lesion depiction sensitivity of 92.8% and both were significantly better than WBPET (67.9%, p < 0.001, McNemar’s test). For index lesions, PEM and MRI had equivalent sensitivity of various tumors, categorized by tumor stage as well as similar invasive tumor size predictions with Spearman's correlation coefficient of 0.61 for both PEM and MRI compared to surgical pathology. Menopausal status, breast density, and HRT did not influence the sensitivity of PEM or MRI. For 67 additional unsuspected ipsilateral lesions or multifocal lesions, PEM had sensitivity of 85% (34/40) and specificity of 74%, (20/27) compared to MRI's sensitivity of 98% (39/40) and specificity of 48% (13/27) [p = 0.074, for sensitivity; p = 0.096 for specificity] Conclusion PEM is a good alternative to MRI as a presurgical breast imaging option and its performance characteristics are not affected by patient menopausal/hormonal status or breast density. PMID:20871992

Positron emission mammography in breast cancer presurgical planning: comparisons with magnetic resonance imaging.

PubMed

Schilling, Kathy; Narayanan, Deepa; Kalinyak, Judith E; The, Juliette; Velasquez, Maria Victoria; Kahn, Simone; Saady, Matthew; Mahal, Ravinder; Chrystal, Larraine

2011-01-01

The objective of this study was to compare the performance characteristics of (18)F-fluorodeoxyglucose (FDG) positron emission mammography (PEM) with breast magnetic resonance imaging (MRI) as a presurgical imaging and planning option for index and ipsilateral lesions in patients with newly diagnosed, biopsy-proven breast cancer. Two hundred and eight women >25 years of age (median age = 59.7 ± 14.1 years) with biopsy-proven primary breast cancer enrolled in this prospective, single-site study. MRI, PEM, and whole-body positron emission tomography (WBPET) were conducted on each patient within 7 business days. PEM and WBPET images were acquired on the same day after intravenous administration of 370 MBq of FDG (median = 432.9 MBq). PEM and MRI images were blindly evaluated, compared with final surgical histopathology, and the sensitivity determined. Substudy analysis compared the sensitivity of PEM versus MRI in patients with different menopausal status, breast density, and use of hormone replacement therapy (HRT) as well as determination of performance characteristics for additional ipsilateral lesion detection. Two hundred and eight patients enrolled in the study of which 87% (182/208) were analyzable. Of these analyzable patients, 26.4% (48/182), 7.1% (13/182), and 64.2% (120/182) were pre-, peri-, and postmenopausal, respectively, and 48.4% (88/182) had extremely or heterogeneously dense breast tissue, while 33.5% (61/182) had a history of HRT use. Ninety-two percent (167/182) underwent core biopsy for index lesion diagnosis. Invasive cancer was found in 77.5% (141/182), while ductal carcinoma in situ (DCIS) and/or Paget's disease were found in 22.5% (41/182) of patients. Both PEM and MRI had index lesion depiction sensitivity of 92.8% and both were significantly better than WBPET (67.9%, p < 0.001, McNemar's test). For index lesions, PEM and MRI had equivalent sensitivity of various tumors, categorized by tumor stage as well as similar invasive tumor size predictions with Spearman's correlation coefficient of 0.61 for both PEM and MRI compared to surgical pathology. Menopausal status, breast density, and HRT did not influence the sensitivity of PEM or MRI. For 67 additional unsuspected ipsilateral lesions or multifocal lesions, PEM had sensitivity of 85% (34/40) and specificity of 74%, (20/27) compared to MRI's sensitivity of 98% (39/40) and specificity of 48% (13/27) [p = 0.074, for sensitivity; p = 0.096 for specificity] PEM is a good alternative to MRI as a presurgical breast imaging option and its performance characteristics are not affected by patient menopausal/hormonal status or breast density.

Fuel cell and membrane therefore

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

Aindow, Tai-Tsui

A fuel cell includes first and second flow field plates, and an anode electrode and a cathode electrode between the flow field plates. A polymer electrolyte membrane (PEM) is arranged between the electrodes. At least one of the flow field plates influences, at least in part, an in-plane anisotropic physical condition of the PEM that varies in magnitude between a high value direction and a low value direction. The PEM has an in-plane physical property that varies in magnitude between a high value direction and a low value direction. The PEM is oriented with its high value direction substantially alignedmore » with the high value direction of the flow field plate.« less

Hydrocarbon-Based Polymer Electrolyte Membranes: Importance of Morphology on Ion Transport and Membrane Stability.

PubMed

Shin, Dong Won; Guiver, Michael D; Lee, Young Moo

2017-03-22

A fundamental understanding of polymer microstructure is important in order to design novel polymer electrolyte membranes (PEMs) with excellent electrochemical performance and stabilities. Hydrocarbon-based polymers have distinct microstructure according to their chemical structure. The ionic clusters and/or channels play a critical role in PEMs, affecting ion conductivity and water transport, especially at medium temperature and low relative humidity (RH). In addition, physical properties such as water uptake and dimensional swelling behavior depend strongly on polymer morphology. Over the past few decades, much research has focused on the synthetic development and microstructural characterization of hydrocarbon-based PEM materials. Furthermore, blends, composites, pressing, shear field, electrical field, surface modification, and cross-linking have also been shown to be effective approaches to obtain/maintain well-defined PEM microstructure. This review summarizes recent work on developments in advanced PEMs with various chemical structures and architecture and the resulting polymer microstructures and morphologies that arise for potential application in fuel cell, lithium ion battery, redox flow battery, actuators, and electrodialysis.

Modeling and simulation of Positron Emission Mammography (PEM) based on double-sided CdTe strip detectors

NASA Astrophysics Data System (ADS)

Ozsahin, I.; Unlu, M. Z.

2014-03-01

Breast cancer is the most common leading cause of cancer death among women. Positron Emission Tomography (PET) Mammography, also known as Positron Emission Mammography (PEM), is a method for imaging primary breast cancer. Over the past few years, PEMs based on scintillation crystals dramatically increased their importance in diagnosis and treatment of early stage breast cancer. However, these detectors have significant limitations like poor energy resolution resulting with false-negative result (missed cancer), and false-positive result which leads to suspecting cancer and suggests an unnecessary biopsy. In this work, a PEM scanner based on CdTe strip detectors is simulated via the Monte Carlo method and evaluated in terms of its spatial resolution, sensitivity, and image quality. The spatial resolution is found to be ~ 1 mm in all three directions. The results also show that CdTe strip detectors based PEM scanner can produce high resolution images for early diagnosis of breast cancer.

H3PO4 imbibed polyacrylamide-graft-chitosan frameworks for high-temperature proton exchange membranes

NASA Astrophysics Data System (ADS)

Yuan, Shuangshuang; Tang, Qunwei; He, Benlin; Chen, Haiyan; Li, Qinghua; Ma, Chunqing; Jin, Suyue; Liu, Zhichao

2014-03-01

Proton exchange membrane (PEM), transferring protons from anode to cathode, is a key component in a PEM fuel cell. In the current work, a new class of PEMs are synthesized benefiting from the imbibition behavior of three-dimensional (3D) polyacrylamide-graft-chitosan (PAAm-graft-chitosan) frameworks to H3PO4 aqueous solution. Interconnected 3D framework of PAAm-graft-chitosan provides tremendous space for holding proton-conducting H3PO4. The highest anhydrous proton conductivity of 0.13 S cm-1 at 165 °C is obtained. A fuel cell using a thick membrane as a PEM showed a peak power density of 405 mW cm-2 with O2 and H2 as the oxidant and fuel, respectively. Results indicate that the interconnected 3D framework provides superhighway for proton conduction. The valued merits on anhydrous proton conductivity, huge H3PO4 loading, and easy synthesis promise the new membranes to be good alternatives as high-temperature PEMs.

Psychometric Evaluation of the Young Children's Participation and Environment Measure (YC-PEM) for use in Singapore.

PubMed

Lim, Chun Yi; Law, Mary; Khetani, Mary; Rosenbaum, Peter; Pollock, Nancy

2018-08-01

To estimate the psychometric properties of a culturally adapted version of the Young Children's Participation and Environment Measure (YC-PEM) for use among Singaporean families. This is a prospective cohort study. Caregivers of 151 Singaporean children with (n = 83) and without (n = 68) developmental disabilities, between 0 and 7 years, completed the YC-PEM (Singapore) questionnaire with 3 participation scales (frequency, involvement, and change desired) and 1 environment scale for three settings: home, childcare/preschool, and community. Setting-specific estimates of internal consistency, test-retest reliability, and construct validity were obtained. Internal consistency estimates varied from .59 to .92 for the participation scales and .73 to .79 for the environment scale. Test-retest reliability estimates from the YC-PEM conducted on two occasions, 2-3 weeks apart, varied from .39 to .89 for the participation scales and from .65 to .80 for the environment scale. Moderate to large differences were found in participation and perceived environmental support between children with and without a disability. YC-PEM (Singapore) scales have adequate psychometric properties except for low internal consistency for the childcare/preschool participation frequency scale and low test-retest reliability for home participation frequency scale. The YC-PEM (Singapore) may be used for population-level studies involving young children with and without developmental disabilities.

Reforming options for hydrogen production from fossil fuels for PEM fuel cells

NASA Astrophysics Data System (ADS)

Ersoz, Atilla; Olgun, Hayati; Ozdogan, Sibel

PEM fuel cell systems are considered as a sustainable option for the future transport sector in the future. There is great interest in converting current hydrocarbon based transportation fuels into hydrogen rich gases acceptable by PEM fuel cells on-board of vehicles. In this paper, we compare the results of our simulation studies for 100 kW PEM fuel cell systems utilizing three different major reforming technologies, namely steam reforming (SREF), partial oxidation (POX) and autothermal reforming (ATR). Natural gas, gasoline and diesel are the selected hydrocarbon fuels. It is desired to investigate the effect of the selected fuel reforming options on the overall fuel cell system efficiency, which depends on the fuel processing, PEM fuel cell and auxiliary system efficiencies. The Aspen-HYSYS 3.1 code has been used for simulation purposes. Process parameters of fuel preparation steps have been determined considering the limitations set by the catalysts and hydrocarbons involved. Results indicate that fuel properties, fuel processing system and its operation parameters, and PEM fuel cell characteristics all affect the overall system efficiencies. Steam reforming appears as the most efficient fuel preparation option for all investigated fuels. Natural gas with steam reforming shows the highest fuel cell system efficiency. Good heat integration within the fuel cell system is absolutely necessary to achieve acceptable overall system efficiencies.

The procedure execution manager and its application to Advanced Photon Source operation

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

Borland, M.

1997-06-01

The Procedure Execution Manager (PEM) combines a complete scripting environment for coding accelerator operation procedures with a manager application for executing and monitoring the procedures. PEM is based on Tcl/Tk, a supporting widget library, and the dp-tcl extension for distributed processing. The scripting environment provides support for distributed, parallel execution of procedures along with join and abort operations. Nesting of procedures is supported, permitting the same code to run as a top-level procedure under operator control or as a subroutine under control of another procedure. The manager application allows an operator to execute one or more procedures in automatic, semi-automatic,more » or manual modes. It also provides a standard way for operators to interact with procedures. A number of successful applications of PEM to accelerator operations have been made to date. These include start-up, shutdown, and other control of the positron accumulator ring (PAR), low-energy transport (LET) lines, and the booster rf systems. The PAR/LET procedures make nested use of PEM`s ability to run parallel procedures. There are also a number of procedures to guide and assist tune-up operations, to make accelerator physics measurements, and to diagnose equipment. Because of the success of the existing procedures, expanded use of PEM is planned.« less

Real-Time Microscopic Monitoring of Flow, Voltage and Current in the Proton Exchange Membrane Water Electrolyzer.

PubMed

Lee, Chi-Yuan; Li, Shih-Chun; Chen, Chia-Hung; Huang, Yen-Ting; Wang, Yu-Syuan

2018-03-15

Looking for alternative energy sources has been an inevitable trend since the oil crisis, and close attentioned has been paid to hydrogen energy. The proton exchange membrane (PEM) water electrolyzer is characterized by high energy efficiency, high yield, simple system and low operating temperature. The electrolyzer generates hydrogen from water free of any carbon sources (provided the electrons come from renewable sources such as solar and wind), so it is very clean and completely satisfies the environmental requirement. However, in long-term operation of the PEM water electrolyzer, the membrane material durability, catalyst corrosion and nonuniformity of local flow, voltage and current in the electrolyzer can influence the overall performance. It is difficult to measure the internal physical parameters of the PEM water electrolyzer, and the physical parameters are interrelated. Therefore, this study uses micro-electro-mechanical systems (MEMS) technology to develop a flexible integrated microsensor; internal multiple physical information is extracted to determine the optimal working parameters for the PEM water electrolyzer. The real operational data of local flow, voltage and current in the PEM water electrolyzer are measured simultaneously by the flexible integrated microsensor, so as to enhance the performance of the PEM water electrolyzer and to prolong the service life.

Real-Time Microscopic Monitoring of Flow, Voltage and Current in the Proton Exchange Membrane Water Electrolyzer

PubMed Central

Lee, Chi-Yuan; Li, Shih-Chun; Chen, Chia-Hung; Huang, Yen-Ting; Wang, Yu-Syuan

2018-01-01

Looking for alternative energy sources has been an inevitable trend since the oil crisis, and close attentioned has been paid to hydrogen energy. The proton exchange membrane (PEM) water electrolyzer is characterized by high energy efficiency, high yield, simple system and low operating temperature. The electrolyzer generates hydrogen from water free of any carbon sources (provided the electrons come from renewable sources such as solar and wind), so it is very clean and completely satisfies the environmental requirement. However, in long-term operation of the PEM water electrolyzer, the membrane material durability, catalyst corrosion and nonuniformity of local flow, voltage and current in the electrolyzer can influence the overall performance. It is difficult to measure the internal physical parameters of the PEM water electrolyzer, and the physical parameters are interrelated. Therefore, this study uses micro-electro-mechanical systems (MEMS) technology to develop a flexible integrated microsensor; internal multiple physical information is extracted to determine the optimal working parameters for the PEM water electrolyzer. The real operational data of local flow, voltage and current in the PEM water electrolyzer are measured simultaneously by the flexible integrated microsensor, so as to enhance the performance of the PEM water electrolyzer and to prolong the service life. PMID:29543734

Finite-size polyelectrolyte bundles at thermodynamic equilibrium

NASA Astrophysics Data System (ADS)

Sayar, M.; Holm, C.

2007-01-01

We present the results of extensive computer simulations performed on solutions of monodisperse charged rod-like polyelectrolytes in the presence of trivalent counterions. To overcome energy barriers we used a combination of parallel tempering and hybrid Monte Carlo techniques. Our results show that for small values of the electrostatic interaction the solution mostly consists of dispersed single rods. The potential of mean force between the polyelectrolyte monomers yields an attractive interaction at short distances. For a range of larger values of the Bjerrum length, we find finite-size polyelectrolyte bundles at thermodynamic equilibrium. Further increase of the Bjerrum length eventually leads to phase separation and precipitation. We discuss the origin of the observed thermodynamic stability of the finite-size aggregates.

Graphene oxide based nanohybrid proton exchange membranes for fuel cell applications: An overview.

PubMed

Pandey, Ravi P; Shukla, Geetanjali; Manohar, Murli; Shahi, Vinod K

2017-02-01

In the context of many applications, such as polymer composites, energy-related materials, sensors, 'paper'-like materials, field-effect transistors (FET), and biomedical applications, chemically modified graphene was broadly studied during the last decade, due to its excellent electrical, mechanical, and thermal properties. The presence of reactive oxygen functional groups in the grapheme oxide (GO) responsible for chemical functionalization makes it a good candidate for diversified applications. The main objectives for developing a GO based nanohybrid proton exchange membrane (PEM) include: improved self-humidification (water retention ability), reduced fuel crossover (electro-osmotic drag), improved stabilities (mechanical, thermal, and chemical), enhanced proton conductivity, and processability for the preparation of membrane-electrode assembly. Research carried on this topic may be divided into protocols for covalent grafting of functional groups on GO matrix, preparation of free-standing PEM or choice of suitable polymer matrix, covalent or hydrogen bonding between GO and polymer matrix etc. Herein, we present a brief literature survey on GO based nano-hybrid PEM for fuel cell applications. Different protocols were adopted to produce functionalized GO based materials and prepare their free-standing film or disperse these materials in various polymer matrices with suitable interactions. This review article critically discussed the suitability of these PEMs for fuel cell applications in terms of the dependency of the intrinsic properties of nanohybrid PEMs. Potential applications of these nanohybrid PEMs, and current challenges are also provided along with future guidelines for developing GO based nanohybrid PEMs as promising materials for fuel cell applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Proton Exchange Membrane (PEM) Fuel Cells for Space Applications

NASA Technical Reports Server (NTRS)

Bradley, Karla

2004-01-01

This presentation will provide a summary of the PEM fuel cell development at the National Aeronautics and Space Administration, Johnson Space Center (NASA, JSC) in support of future space applications. Fuel cells have been used for space power generation due to their high energy storage density for multi-day missions. The Shuttle currently utilizes the alkaline fuel cell technology, which has highly safe and reliable performance. However, the alkaline technology has a limited life due to the corrosion inherent to the alkaline technology. PEM fuel cells are under development by industry for transportation, residential and commercial stationary power applications. NASA is trying to incorporate some of this stack technology development in the PEM fuel cells for space. NASA has some unique design and performance parameters which make developing a PEM fuel cell system more challenging. Space fuel cell applications utilize oxygen, rather than air, which yields better performance but increases the hazard level. To reduce the quantity of reactants that need to be flown in space, NASA also utilizes water separation and reactant recirculation. Due to the hazards of utilizing active components for recirculation and water separation, NASA is trying to develop passive recirculation and water separation methods. However, the ability to develop recirculation components and water separators that are gravity-independent and successfully operate over the full range of power levels is one of the greatest challenges to developing a safe and reliable PEM fuel cell system. PEM stack, accessory component, and system tests that have been performed for space power applications will be discussed.

Saccadic Eye Movement Improves Plantar Sensation and Postural Balance in Elderly Women.

PubMed

Bae, Youngsook

2016-06-01

Vision, proprioception and plantar sensation contribute to the control of postural balance (PB). Reduced plantar sensation alters postural response and is at an increased risk of fall, and eye movements reduce the postural sway. Therefore, the aim of this study was to study the improvement of plantar sensation and PB after saccadic eye movement (SEM) and pursuit eye movement (PEM) in community-dwelling elderly women. Participants (104 females; 75.11 ± 6.25 years) were randomly allocated into the SEM group (n = 52) and PEM groups (n = 52). The SEM group performed eye fixation and SEM for 5 minutes, and the PEM group performed eye fixation and PEM for 5 minutes. The plantar sensation was measured according to the plantar surface area of the feet in contact with the floor surface before and after the intervention. Before and after SEM and PEM with the eyes open and closed, PB was measured as the area (mm(2)), length (cm), and velocity (cm/s) of the fluctuation of the center of pressure (COP). The plantar sensation of both feet improved in both groups (p < 0.01). Significant decreases in the area, length, and velocity of the COP were observed in the eye open and close in both groups (p < 0.01). The length and velocity of the COP significantly decreased in the SEM group compared to the PEM group (p < 0.05). In conclusion, SEM and PEM are effective interventions for improving plantar sensation and PB in elderly women, with greater PB improvement after SEM.

Functional characterization of replication and stability factors of an incompatibility group P-1 plasmid from Xylella fastidiosa.

PubMed

Lee, Min Woo; Rogers, Elizabeth E; Stenger, Drake C

2010-12-01

Xylella fastidiosa strain riv11 harbors a 25-kbp plasmid (pXF-RIV11) belonging to the IncP-1 incompatibility group. Replication and stability factors of pXF-RIV11 were identified and used to construct plasmids able to replicate in X. fastidiosa and Escherichia coli. Replication in X. fastidiosa required a 1.4-kbp region from pXF-RIV11 containing a replication initiation gene (trfA) and the adjacent origin of DNA replication (oriV). Constructs containing trfA and oriV from pVEIS01, a related IncP-1 plasmid of the earthworm symbiont Verminephrobacter eiseniae, also were competent for replication in X. fastidiosa. Constructs derived from pXF-RIV11 but not pVEIS01 replicated in Agrobacterium tumefaciens, Xanthomonas campestris, and Pseudomonas syringae. Although plasmids bearing replication elements from pXF-RIV11 or pVEIS01 could be maintained in X. fastidiosa under antibiotic selection, removal of selection resulted in plasmid extinction after 3 weekly passages. Addition of a toxin-antitoxin addiction system (pemI/pemK) from pXF-RIV11 improved plasmid stability such that >80 to 90% of X. fastidiosa cells retained plasmid after 5 weekly passages in the absence of antibiotic selection. Expression of PemK in E. coli was toxic for cell growth, but toxicity was nullified by coexpression of PemI antitoxin. Deletion of N-terminal sequences of PemK containing the conserved motif RGD abolished toxicity. In vitro assays revealed a direct interaction of PemI with PemK, suggesting that antitoxin activity of PemI is mediated by toxin sequestration. IncP-1 plasmid replication and stability factors were added to an E. coli cloning vector to constitute a stable 6.0-kbp shuttle vector (pXF20-PEMIK) suitable for use in X. fastidiosa.

Measurements of nitric acid, carboxylic acids, and selected aerosol species for the NASA/GTE Pacific Mission - West (PEM-WEST)

NASA Technical Reports Server (NTRS)

Talbot, Robert W.; Dibb, Jack E.

1993-01-01

The research investigation funded through this grant to the University of New Hampshire was performed during a major field expedition conducted by the NASA Tropospheric Chemistry Program. The NASA Global Tropospheric Experiment (GTE) executed an airborne science mission (PEM-WEST A) aboard the NASA Ames DC-8 over the Pacific Ocean during Sep./Oct. 1981. The atmosphere over the central Pacific Ocean is the only major region in the Northern Hemisphere that is relatively free from direct anthropogenic influence. Thus, this environment is ideally suited to study the natural biogeochemical cycles of carbon, nitrogen, ozone, sulfur, and aerosols without serious confounding problems related to anthropogenic emissions. Asian sources account for about 17 percent of the global budgets of nitrogen oxides (NO(x)) and sulfur dioxide (SO2). The Pacific Rim region therefore provides the opportunity to study the anthropogenic impact on natural atmospheric chemical cycles. The PEM-WEST A flights were focused on contrasting the chemistry of 'clean' air over the central Pacific with anthropogenically impacted air advected off the Asian continent. The principal objectives of PEM-WEST A were to investigate the atmospheric chemistry of ozone (O3) and its precursors, and to study important aspects of the atmospheric sulfur cycle over the western Pacific Ocean. Measurements conducted by the University of New Hampshire contributed directly to both of these objectives. Subsequent PEM-WEST field missions are planned by GTE in the mid-1990's to contrast atmospheric chemistry documented during PEM-WEST A with other time periods. This report presents preliminary findings from the PEM-WEST A field mission. Data interpretation is currently ongoing with the goal of manuscript submission of scientific results to a special issue of the Journal of Geophysical Research-Atmospheres in Feb. 1994. The reader is strongly encouraged to review this suite of profession articles to appreciate the overall scientific findings and benefits of the PEM-WEST A field mission.

Real-time sampling of reasons for hedonic food consumption: further validation of the Palatable Eating Motives Scale

PubMed Central

Boggiano, Mary M.; Wenger, Lowell E.; Turan, Bulent; Tatum, Mindy M.; Sylvester, Maria D.; Morgan, Phillip R.; Morse, Kathryn E.; Burgess, Emilee E.

2015-01-01

Highly palatable foods play a salient role in obesity and binge-eating, and if habitually eaten to deal with intrinsic and extrinsic factors unrelated to metabolic need, may compromise adaptive coping and interpersonal skills. This study used event sampling methodology (ESM) to examine whether individuals who report eating palatable foods primarily to cope, to enhance reward, to be social, or to conform, as measured by the Palatable Eating Motives Scale (PEMS), actually eat these foods primarily for the motive(s) they report on the PEMS. Secondly this study examined if the previously reported ability of the PEMS Coping motive to predict BMI would replicate if the real-time (ESM-reported) coping motive was used to predict BMI. A total of 1691 palatable eating events were collected from 169 college students over 4 days. Each event included the day, time, and types of tasty foods or drinks consumed followed by a survey that included an abbreviated version of the PEMS, hunger as an additional possible motive, and a question assessing general perceived stress during the eating event. Two-levels mixed modeling confirmed that ESM-reported motives correlated most strongly with their respective PEMS motives and that all were negatively associated with eating for hunger. While stress surrounding the eating event was strongly associated with the ESM-coping motive, its inclusion in the model as a predictor of this motive did not abolish the significant association between ESM and PEMS Coping scores. Regression models confirmed that scores on the ESM-coping motive predicted BMI. These findings provide ecological validity for the PEMS to identify true-to-life motives for consuming palatable foods. This further adds to the utility of the PEMS in individualizing, and hence improving, treatment strategies for obesity, binge-eating, dietary nutrition, coping, reward acquisition, and psychosocial skills. PMID:26082744

Pacific Exploratory Mission in the tropical Pacific: PEM-Tropics A, August-September 1996

NASA Astrophysics Data System (ADS)

Hoell, J. M.; Davis, D. D.; Jacob, D. J.; Rodgers, M. O.; Newell, R. E.; Fuelberg, H. E.; McNeal, R. J.; Raper, J. L.; Bendura, R. J.

1999-03-01

The NASA Pacific Exploratory Mission to the Pacific tropics (PEM-Tropics) is the third major field campaign of NASA's Global Tropospheric Experiment (GTE) to study the impact of human and natural processes on the chemistry of the troposphere over the Pacific basin. The first two campaigns, PEM-West A and B were conducted over the northwestern regions of the Pacific and focused on the impact of emissions from the Asian continent. The broad objectives of PEM-Tropics included improving our understanding of the oxidizing power of the tropical atmosphere as well as investigating oceanic sulfur compounds and their conversion to aerosols. Phase A of the PEM-Tropics program, conducted between August-September 1996, involved the NASA DC-8 and P-3B aircraft. Phase B of this program is scheduled for March/April 1999. During PEM-Tropics A, the flight tracks of the two aircraft extended zonally across the entire Pacific Basin and meridionally from Hawaii to south of New Zealand. Both aircraft were instrumented for airborne measurements of trace gases and aerosols and meteorological parameters. The DC-8, given its long-range and high-altitude capabilities coupled with the lidar instrument in its payload, focused on transport issues and ozone photochemistry, while the P-3B, with its sulfur-oriented instrument payload and more limited range, focused on detailed sulfur process studies. Among its accomplishments, the PEM-Tropics A field campaign has provided a unique set of atmospheric measurements in a heretofore data sparse region; demonstrated the capability of several new or improved instruments for measuring OH, H2SO4, NO, NO2, and actinic fluxes; and conducted experiments which tested our understanding of HOx and NOx photochemistry, as well as sulfur oxidation and aerosol formation processes. In addition, PEM-Tropics A documented for the first time the considerable and widespread influence of biomass burning pollution over the South Pacific, and identified the South Pacific Convergence Zone as a major barrier for atmospheric transport in the southern hemisphere.

Regulation of anionic lipids in binary membrane upon the adsorption of polyelectrolyte: A Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Duan, Xiaozheng; Li, Yunqi; Zhang, Ran; Shi, Tongfei; An, Lijia; Huang, Qingrong

2013-06-01

We employ Monte Carlo simulations to investigate the interaction between an adsorbing linear flexible cationic polyelectrolyte and a binary fluid membrane. The membrane contains neutral phosphatidyl-choline, PC) and multivalent anionic (phosphatidylinositol, PIP2) lipids. We systematically study the influences of the solution ionic strength, the chain length and the bead charge density of the polyelectrolyte on the lateral rearrangement and the restricted mobility of the multivalent anionic lipids in the membrane. Our findings show that, the cooperativity effect and the electrostatic interaction of the polyelectrolyte beads can significantly affect the segregation extent and the concentration gradients of the PIP2 molecules, and further cooperate to induce the complicated hierarchical mobility behaviors of PIP2 molecules. In addition, when the polyelectrolyte brings a large amount of charges, it can form a robust electrostatic well to trap all PIP2 and results in local overcharge of the membrane. This work presents a mechanism to explain the membrane heterogeneity formation induced by the adsorption of charged macromolecule.

Formulation and stabilization of nano-/microdispersion systems using naturally occurring edible polyelectrolytes by electrostatic deposition and complexation.

PubMed

Kuroiwa, Takashi; Kobayashi, Isao; Chuah, Ai Mey; Nakajima, Mitsutoshi; Ichikawa, Sosaku

2015-12-01

This review paper presents an overview of the formulation and functionalization of nano-/microdispersion systems composed of edible materials. We first summarized general aspects on the stability of colloidal systems and the roles of natural polyelectrolytes such as proteins and ionic polysaccharides for the formation and stabilization of colloidal systems. Then we introduced our research topics on (1) stabilization of emulsions by the electrostatic deposition using natural polyelectrolytes and (2) formulation of stable nanodispersion systems by complexation of natural polyelectrolytes. In both cases, the preparation procedures were relatively simple, without high energy input or harmful chemical addition. The properties of the nano-/microdispersion systems, such as particle size, surface charge and dispersion stability were significantly affected by the concerned materials and preparation conditions, including the type and concentration of used natural polyelectrolytes. These dispersion systems would be useful for developing novel foods having high functionality and good stability. Copyright © 2015 Elsevier B.V. All rights reserved.

Dendritic polyelectrolytes as seen by the Poisson-Boltzmann-Flory theory.

PubMed

Kłos, J S; Milewski, J

2018-06-20

G3-G9 dendritic polyelectrolytes accompanied by counterions are investigated using the Poisson-Boltzmann-Flory theory. Within this approach we solve numerically the Poisson-Boltzmann equation for the mean electrostatic potential and minimize the Poisson-Boltzmann-Flory free energy with respect to the size of the molecules. Such a scheme enables us to inspect the conformational and electrostatic properties of the dendrimers in equilibrium based on their response to varying the dendrimer generation. The calculations indicate that the G3-G6 dendrimers exist in the polyelectrolyte regime where absorption of counterions into the volume of the molecules is minor. Trapping of ions in the interior region becomes significant for the G7-G9 dendrimers and signals the emergence of the osmotic regime. We find that the behavior of the dendritic polyelectrolytes corresponds with the degree of ion trapping. In particular, in both regimes the polyelectrolytes are swollen as compared to their neutral counterparts and the expansion factor is maximal at the crossover generation G7.

Self-assembled virus-membrane complexes

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

Yang, Lihua; Liang, Hongjun; Angelini, Thomas

Anionic polyelectrolytes and cationic lipid membranes can self-assemble into lamellar structures ranging from alternating layers of membranes and polyelectrolytes to 'missing layer' superlattice structures. We show that these structural differences can be understood in terms of the surface-charge-density mismatch between the polyelectrolyte and membrane components by examining complexes between cationic membranes and highly charged M13 viruses, a system that allowed us to vary the polyelectrolyte diameter independently of the charge density. Such virus-membrane complexes have pore sizes that are about ten times larger in area than DNA-membrane complexes, and can be used to package and organize large functional molecules; correlatedmore » arrays of Ru(bpy){sub 3}{sup 2+} macroionic dyes have been directly observed within the virus-membrane complexes using an electron-density reconstruction. These observations elucidate fundamental design rules for rational control of self-assembled polyelectrolyte-membrane structures, which have applications ranging from non-viral gene therapy to biomolecular templates for nanofabrication.« less

Monomer volume fraction profiles in pH responsive planar polyelectrolyte brushes

DOE PAGES

Mahalik, Jyoti P.; Yang, Yubo; Deodhar, Chaitra V.; ...

2016-03-06

Spatial dependencies of monomer volume fraction profiles of pH responsive polyelectrolyte brushes were investigated using field theories and neutron reflectivity experiments. In particular, planar polyelectrolyte brushes in good solvent were studied and direct comparisons between predictions of the theories and experimental measurements are presented. The comparisons between the theories and the experimental data reveal that solvent entropy and ion-pairs resulting from adsorption of counterions from the added salt play key roles in affecting the monomer distribution and must be taken into account in modeling polyelectrolyte brushes. Furthermore, the utility of this physics-based approach based on these theories for the predictionmore » and interpretation of neutron reflectivity profiles in the context of pH responsive planar polyelectrolyte brushes such as polybasic poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and polyacidic poly(methacrylic acid) (PMAA) brushes is demonstrated. The approach provides a quantitative way of estimating molecular weights of the polymers polymerized using surface-initiated atom transfer radical polymerization.« less

Preparation and assessment of carboxylate polyelectrolyte as draw solute for forward osmosis.

PubMed

Cui, Hongtao; Zhang, Hanmin; Jiang, Wei; Yang, Fenglin

2018-02-01

Reverse draw solute diffusion not only reduces the water flux in forward osmosis (FO), but also contaminates the feed solution and eventually increases the regeneration cost of draw solution. In the present study, a new polyelectrolyte was synthesized as FO draw solute to address this problem. Acrylic acid and sodium p-styrenesulfonate monomers with hydrophilic group were used to fabricate carboxylate polyelectrolyte through free radical polymerization reaction. Results demonstrated that the osmotic pressure of carboxylate polyelectrolyte solution had a good linear relationship with concentration, and the viscosity of 0.18 g/mL solution was less than 5.4 cP. Active layer facing draw solution produced the initial water flux of 11.77 LMH and active layer facing feed solution yielded the initial water flux of 6.68 LMH when the concentration of draw solution was 0.18 g/mL. The reverse solute flux was around 1 gMH, and specific reverse solute flux of 0.18 g/mL carboxylate polyelectrolyte draw solution was 0.11 g/L which was much lower than that of traditional inorganic salts. Finally, diluted draw solution was regenerated via ultrafiltration, and the recovery efficiency of 94.78% was achieved. So, carboxylate polyelectrolyte can be suitable draw solute for FO.

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.

Molecular Dynamics Simulations of Adsorption of Poly(acrylic acid) and Poly(methacrylic acid) on Dodecyltrimethylammonium Chloride Micelle in Water: Effect of Charge Density.

PubMed

Sulatha, Muralidharan S; Natarajan, Upendra

2015-09-24

We have investigated the interaction of dodecyltrimethylammonium chloride (DoTA) micelle with weak polyelectrolytes, poly(acrylic acid) and poly(methacrylic acid). Anionic as well as un-ionized forms of the polyelectrolytes were studied. Polyelectrolyte-surfactant complexes were formed within 5-11 ns of the simulation time and were found to be stable. Association is driven purely by electrostatic interactions for anionic chains whereas dispersion interactions also play a dominant role in the case of un-ionized chains. Surfactant headgroup nitrogen atoms are in close contact with the carboxylic oxygens of the polyelectrolyte chain at a distance of 0.35 nm. In the complexes, the polyelectrolyte chains are adsorbed on to the hydrophilic micellar surface and do not penetrate into the hydrophobic core of the micelle. Polyacrylate chain shows higher affinity for complex formation with DoTA as compared to polymethacrylate chain. Anionic polyelectrolyte chains show higher interaction strength as compared to corresponding un-ionized chains. Anionic chains act as polymeric counterion in the complexes, resulting in the displacement of counterions (Na(+) and Cl(-)) into the bulk solution. Anionic chains show distinct shrinkage upon adsorption onto the micelle. Detailed information about the microscopic structure and binding characteristics of these complexes is in agreement with available experimental literature.

Direct AFM force measurements between air bubbles in aqueous polydisperse sodium poly(styrene sulfonate) solutions: effect of collision speed, polyelectrolyte concentration and molar mass.

PubMed

Browne, Christine; Tabor, Rico F; Grieser, Franz; Dagastine, Raymond R

2015-07-01

Interactions between colliding air bubbles in aqueous solutions of polydisperse sodium poly(styrene sulfonate) (NaPSS) using direct force measurements were studied. The forces measured with deformable interfaces were shown to be more sensitive to the presence of the polyelectrolytes when compared to similar measurements using rigid interfaces. The experimental factors that were examined were NaPSS concentration, bubble collision velocity and polyelectrolyte molar mass. These measurements were then compared with an analytical model based on polyelectrolyte scaling theory in order to explain the effects of concentration and bubble deformation on the interaction between bubbles. Typically structural forces from the presence of monodisperse polyelectrolyte between interacting surfaces may be expected, however, it was found that the polydispersity in molar mass resulted in the structural forces to be smoothed and only a depletion interaction was able to be measured between interacting bubbles. It was found that an increase in number density of NaPSS molecules resulted in an increase in the magnitude of the depletion interaction. Conversely this interaction was overwhelmed by an increase in the fluid flow in the system at higher bubble collision velocities. Polymer molar mass dispersity plays a significant role in the interactions present between the bubbles and has implications that also affect the polyelectrolyte overlap concentration of the solution. Further understanding of these implications can be expected to play a role in the improvement in operations in such fields as water treatment and mineral processing where polyelectrolytes are used extensively. Copyright © 2015 Elsevier Inc. All rights reserved.

Planar Solid-Oxide Fuel Cell Research and Development

DTIC Science & Technology

2013-03-28

electrolyte membrane ( PEM ) fuel cells ", Applied Surface Sei., 227 (2004) 56-72. [10] Grujicic, M., and Chittajallu, K. M., "Optimization of the...cathode geometry in polymer electrolyte membrane ( PEM ) fuel cells ", Chem. Eng. Sei., 59 (2004) 5883-5895. 36 [11] Anderson, W.K., Newman, J.C., Whitfield...M., Djilali, N, Suleman, A., "Optimization of a planar self-breathing PEM fuel cell cathode", AIAA 2006-6917, 11th AIAA/ISSMO Multidisciplinary

Investigation into the Implications of Fuel Cell Shipboard Integration into the T-AGOS 19 Class

DTIC Science & Technology

2012-02-01

with each defined by its fundamental electrolyte: i. Alkali Fuel Cells (AFC) ii. Polymer Exchange Membrane ( PEM ) iii. Phosphoric Acid Fuel Cells ...of the PEM family (High Temperature – HTPEM and Direct Methanol Fuel Cells – DMFC) were assessed against a range of basic ship requirements...of Stationary PEM Fuel Cell Systems”, DOE hydrogen program 2010 annual report. [11] US Energy Information Administration, “EIA - Weekly Retail

Pediatric Emergency Medicine (PEM) fellowship: essentials of a three-year academic curriculum. Three-Year Academic Subcommittee of the PEM Fellowship Committee of the Section of Emergency Medicine, American Academy of Pediatrics.

PubMed

Shaw, K N; Schunk, J; Ledwith, C; Lockhart, G

1997-02-01

This committee of fellowship directors has proposed guidelines for an academic curriculum for training fellows in PEM. The curriculum should be modified to each unique program, but is based on current expectation of the American Board of Pediatrics and the ACGME for graduate education. This is the first PEM academic curriculum document in publication. Ongoing refinement and adaptation based on feedback from fellows and directors is essential to provide the best fellowship experience to our trainees. The proposed curriculum is also subject to further change as more details are given for ACGME approval of the fellowship programs.

A monolithic integrated micro direct methanol fuel cell based on sulfo functionalized porous silicon

NASA Astrophysics Data System (ADS)

Wang, M.; Lu, Y. X.; Liu, L. T.; Wang, X. H.

2016-11-01

In this paper, we demonstrate a monolithic integrated micro direct methanol fuel cell (μDMFC) for the first time. The monolithic integrated μDMFC combines proton exchange membrane (PEM) and Pt nanocatalysts, in which PEM is achieved by the functionalized porous silicon membrane and 3D Pt nanoflowers being synthesized in situ on it as catalysts. Sulfo groups functionalized porous silicon membrane serves as a PEM and a catalyst support simultaneously. The μDMFC prototype achieves an open circuit voltage of 0.3 V, a maximum power density of 5.5 mW/cm2. The monolithic integrated μDMFC offers several desirable features such as compatibility with micro fabrication techniques, an undeformable solid PEM and the convenience of assembly.

Antibacterial and anti-adherence effects of a plant extract mixture (PEM) and its individual constituent extracts (Psidium sp., Mangifera sp., and Mentha sp.) on single- and dual-species biofilms.

PubMed

Shafiei, Zaleha; Haji Abdul Rahim, Zubaidah; Philip, Koshy; Thurairajah, Nalina

2016-01-01

Plant extracts mixture (PEM) and its individual constituent plant extracts( Psidium sp., Mangifera sp., Mentha sp.) are known to have an anti-adhering effect towards oral bacteria in the single-species biofilm. To date, the adhering ability of the early and late plaque colonisers ( Streptococcus sanguinis and Streptococcus mutans ) to PEM-treated experimental pellicle have not been investigated in dual-species biofilms. Fresh leaves of these plants were used in the preparation of the respective aqueous extract decoctions. The minimum inhibitory concentration (MIC) of the extracts towards S. sanguinis ATCC BAA-1455 and S. mutans ATCC 25175 was determined using a two-fold serial microdilution method. The sum of fractional inhibitory concentration (ΣFIC) index of PEM and its constituent plant extracts was calculated using the MIC values of the plants. The minimum bactericidal concentration (MBC) of the plant extracts was also determined. The anti-adherence effect of the plant extracts (individually and mixed) was carried out by developing simulated S. sanguinis and S. mutans respectively in single- and dual-species of biofilms in the Nordini's Artificial Mouth (NAM) model system in which the experimental pellicle was pretreated with the plant extract before bacterial inoculation. The bacterial population in the respective biofilms was quantified using ten-fold serial dilutions method and expressed as colony forming unit per ml (CFU/ml). The bacterial population was also viewed using Scanning Electron Microscope (SEM). All experiments were done in triplicate. The PEM compared with its respective constituent plants showed the lowest MIC towards S. sanguinis (3.81 mg/ml) and S. mutans (1.91 mg/ml) and exhibited a synergistic effect. The Psidium sp. (15.24 mg/ml) and, PEM and Psidium sp. (30.48 mg/ml) showed the lowest MBC towards S. sanguinis and S. mutans respectively. The anti-adherence effect of the PEM and its respective constituent plants (except Psidium sp.) was different for the two bacteria in the single-species biofilm. In the dual-species biofilms, PEM demonstrated similar anti-adherence effect towards S. sanguinis and S. mutans . The proportions of the bacterial population viewed under SEM appeared to be in agreement with the quantified population. The combination of the active constituents of the individual plant extracts in PEM may contribute to its low MIC giving rise to the synergistic effect. The different anti-adherence effect towards S. sanguinis and S. mutans in both single- and dual-species biofilms could be due to the different proportion of the active constituents of the extracts and the interaction between different bacteria. The better adhering ability of S. sanguinis towards the PEM-treated pellicle when present together with S. mutans in the dual-species biofilms may suggest the potential of PEM in controlling the balance between the early and late colonisers in biofilms.

Antibacterial and anti-adherence effects of a plant extract mixture (PEM) and its individual constituent extracts (Psidium sp., Mangifera sp., and Mentha sp.) on single- and dual-species biofilms

PubMed Central

Shafiei, Zaleha; Haji Abdul Rahim, Zubaidah; Thurairajah, Nalina

2016-01-01

Background Plant extracts mixture (PEM) and its individual constituent plant extracts(Psidium sp., Mangifera sp., Mentha sp.) are known to have an anti-adhering effect towards oral bacteria in the single-species biofilm. To date, the adhering ability of the early and late plaque colonisers (Streptococcus sanguinis and Streptococcus mutans) to PEM-treated experimental pellicle have not been investigated in dual-species biofilms. Methods Fresh leaves of these plants were used in the preparation of the respective aqueous extract decoctions. The minimum inhibitory concentration (MIC) of the extracts towards S. sanguinis ATCC BAA-1455 and S. mutans ATCC 25175 was determined using a two-fold serial microdilution method. The sum of fractional inhibitory concentration (ΣFIC) index of PEM and its constituent plant extracts was calculated using the MIC values of the plants. The minimum bactericidal concentration (MBC) of the plant extracts was also determined. The anti-adherence effect of the plant extracts (individually and mixed) was carried out by developing simulated S. sanguinis and S. mutans respectively in single- and dual-species of biofilms in the Nordini’s Artificial Mouth (NAM) model system in which the experimental pellicle was pretreated with the plant extract before bacterial inoculation. The bacterial population in the respective biofilms was quantified using ten-fold serial dilutions method and expressed as colony forming unit per ml (CFU/ml). The bacterial population was also viewed using Scanning Electron Microscope (SEM). All experiments were done in triplicate. Results The PEM compared with its respective constituent plants showed the lowest MIC towards S. sanguinis (3.81 mg/ml) and S. mutans (1.91 mg/ml) and exhibited a synergistic effect. The Psidium sp. (15.24 mg/ml) and, PEM and Psidium sp. (30.48 mg/ml) showed the lowest MBC towards S. sanguinis and S. mutans respectively. The anti-adherence effect of the PEM and its respective constituent plants (except Psidium sp.) was different for the two bacteria in the single-species biofilm. In the dual-species biofilms, PEM demonstrated similar anti-adherence effect towards S. sanguinis and S. mutans. The proportions of the bacterial population viewed under SEM appeared to be in agreement with the quantified population. Discussion The combination of the active constituents of the individual plant extracts in PEM may contribute to its low MIC giving rise to the synergistic effect. The different anti-adherence effect towards S. sanguinis and S. mutans in both single- and dual-species biofilms could be due to the different proportion of the active constituents of the extracts and the interaction between different bacteria. The better adhering ability of S. sanguinis towards the PEM-treated pellicle when present together with S. mutans in the dual-species biofilms may suggest the potential of PEM in controlling the balance between the early and late colonisers in biofilms. PMID:27761322

pH-Amplified multilayer films based on hyaluronan: influence of HA molecular weight and concentration on film growth and stability.

PubMed

Shen, Liyan; Chaudouet, Patrick; Ji, Jian; Picart, Catherine

2011-04-11

In this study, we investigate the growth and internal properties of polyelectrolyte multilayer films made of poly(l-lysine) and hyaluronan (PLL/HA) under pH-amplified conditions, that is, by alternate deposition of PLL at high pH and HA at low pH. We focus especially on the influence of the molecular weight of HA in this process as well as on its concentration in solution. Film growth was followed by quartz crystal microbalance and by infrared spectroscopy to quantify the deposited mass and to characterize the internal properties of the films, including the presence of hydrogen bonds and the ionization degree of HA in the films. Film growth was significantly faster for HA of high molecular weight (1300 kDa) as compared with 400 and 200 kDa. PLL was found to exhibit a random structure once deposited in the films. Furthermore, we found that PLL-ending films are more stable when they are placed in PBS than their HA counterparts. This was explained on the basis of more cohesive interactions in the films for PLL-ending films. Finally, we quantified PLL(FITC) diffusion into the films and observed that PLL diffusion is enhanced when PLL is paired with the HA of high MW. All together, these results suggest that besides purely physicochemical parameters such as variation in pH, the molecular weight of HA, its concentration in solution, and the possibility to form intermolecular HA association play important roles in film growth, internal cohesion, and stability.

Logical enzyme triggered (LET) layer-by-layer nanocapsules for drug delivery system

NASA Astrophysics Data System (ADS)

Kelley, Marie-Michelle

Breast cancer is the second leading cause of morbidity and mortality among women in the United States. Early detection and treatment methods have resulted in 100% 5-year survival rates for stage 0-I breast cancer. Unfortunately, the 5-year survival rate of metastatic breast cancer (stage IV) is reduced fivefold. The most challenging issues of metastatic breast cancer treatment are the ability to selectively target the adenoma and adenocarcinoma cells both in their location of origin and as they metastasize following initial treatment. Multilayer/Layer-by-Layer (LbL) nanocapsules have garnered vast interest as anticancer drug delivery systems due to their ability to be easily modified, their capacity to encapsulate a wide range of chemicals and proteins, and their improved pharmacokinetics. Multilayer nanocapsule formation requires the layering of opposing charged polyelectrolytic polymers over a removable core nanoparticle. Our goal is to have a programmable nanocapsules degrade only after receiving and validating specific breast cancer biomarkers. The overall objective is to fabricate a novel programmable LbL nanocapsule with a specific logical system that will enhance functions pertinent to drug delivery systems. Our central hypothesis is that LbL technology coupled with extracellular matrix (ECM) protein substrates will result in a logical enzyme triggered LbL nanocapsule drug delivery system. This platform represents a novel approach toward a logically regulated nano-encapsulated cancer therapy that can selectively follow and deliver chemotherapeutics to cancer cells. The rationale for this project is to overcome a crucial limitation of existing drug delivery systems where chemotherapeutic can be erroneously delivered to non-carcinogenic cells.

Polymeric ionic liquid based on magnetic materials fabricated through layer-by-layer assembly as adsorbents for extraction of pesticides.

PubMed

He, Lijun; Cui, Wenhang; Wang, Yali; Zhao, Wenjie; Xiang, Guoqiang; Jiang, Xiuming; Mao, Pu; He, Juan; Zhang, Shusheng

2017-11-03

In this study, layer-by-layer assembly of polyelectrolyte multilayer films on magnetic silica provided a convenient and controllable way to prepare polymeric ionic liquid-based magnetic adsorbents. The resulting particles were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, and magnetic measurements. The data showed that the magnetic particles had more homogeneous spherical shapes with higher saturation magnetization when compared to those obtained by free radical polymerization method. This facilitated the convenient collection of magnetic particles, with higher extraction repeatability. The extraction performance of the multilayer polymeric ionic liquid-based adsorbents was evaluated by magnetic solid-phase extraction of four pesticides including quinalphos, fenthion, phoxim, and chlorpropham. The data suggested that the extraction efficiency depended on the number of layers in the film. The parameters affecting the extraction efficiency were optimized, and good linearity ranging from 2 to 250μgL -1 was obtained with correlation coefficients of 0.9994-0.9998. Moreover, the proposed method presented low limit of detection (0.5μgL -1 , S/N=3) and limit of quantification (1.5μgL -1 , S/N=10), and good repeatability expressed by the relative standard deviation (2.0%-4.6%, n=5). The extraction recoveries of four pesticides were found to range from 58.9% to 85.8%. The reliability of the proposed method was demonstrated by analyzing environmental water samples, and the results revealed satisfactory spiked recovery, relative standard deviation, and selectivity. Copyright © 2017 Elsevier B.V. All rights reserved.

On-body calibration and measurements using personal radiofrequency exposimeters in indoor diffuse and specular environments.

PubMed

Aminzadeh, Reza; Thielens, Arno; Bamba, Aliou; Kone, Lamine; Gaillot, Davy Paul; Lienard, Martine; Martens, Luc; Joseph, Wout

2016-07-01

For the first time, response of personal exposimeters (PEMs) is studied under diffuse field exposure in indoor environments. To this aim, both numerical simulations, using finite-difference time-domain method, and calibration measurements were performed in the range of 880-5875 MHz covering 10 frequency bands in Belgium. Two PEMs were mounted on the body of a human male subject and calibrated on-body in an anechoic chamber (non-diffuse) and a reverberation chamber (RC) (diffuse fields). This was motivated by the fact that electromagnetic waves in indoor environments have both specular and diffuse components. Both calibrations show that PEMs underestimate actual incident electromagnetic fields. This can be compensated by using an on-body response. Moreover, it is shown that these responses are different in anechoic chamber and RC. Therefore, it is advised to use an on-body calibration in an RC in future indoor PEM measurements where diffuse fields are present. Using the response averaged over two PEMs reduced measurement uncertainty compared to single PEMs. Following the calibration, measurements in a realistic indoor environment were done for wireless fidelity (WiFi-5G) band. Measured power density values are maximally 8.9 mW/m(2) and 165.8 μW/m(2) on average. These satisfy reference levels issued by the International Commission on Non-Ionizing Radiation Protection in 1998. Power density values obtained by applying on-body calibration in RC are higher than values obtained from no body calibration (only PEMs) and on-body calibration in anechoic room, by factors of 7.55 and 2.21, respectively. Bioelectromagnetics. 37:298-309, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Development and validity of a method for the evaluation of printed education material

PubMed Central

Castro, Mauro Silveira; Pilger, Diogo; Fuchs, Flávio Danni; Ferreira, Maria Beatriz Cardoso

Objectives To develop and study the validity of an instrument for evaluation of Printed Education Materials (PEM); to evaluate the use of acceptability indices; to identify possible influences of professional aspects. Methods An instrument for PEM evaluation was developed which included tree steps: domain identification, item generation and instrument design. A reading to easy PEM was developed for education of patient with systemic hypertension and its treatment with hydrochlorothiazide. Construct validity was measured based on previously established errors purposively introduced into the PEM, which served as extreme groups. An acceptability index was applied taking into account the rate of professionals who should approve each item. Participants were 10 physicians (9 men) and 5 nurses (all women). Results Many professionals identified intentional errors of crude character. Few participants identified errors that needed more careful evaluation, and no one detected the intentional error that required literature analysis. Physicians considered as acceptable 95.8% of the items of the PEM, and nurses 29.2%. The differences between the scoring were statistically significant in 27% of the items. In the overall evaluation, 66.6% were considered as acceptable. The analysis of each item revealed a behavioral pattern for each professional group. Conclusions The use of instruments for evaluation of printed education materials is required and may improve the quality of the PEM available for the patients. Not always are the acceptability indices totally correct or represent high quality of information. The professional experience, the practice pattern, and perhaps the gendre of the reviewers may influence their evaluation. An analysis of the PEM by professionals in communication, in drug information, and patients should be carried out to improve the quality of the proposed material. PMID:25214924

Quality measurement in physician-staffed emergency medical services: a systematic literature review.

PubMed

Haugland, Helge; Uleberg, Oddvar; Klepstad, Pål; Krüger, Andreas; Rehn, Marius

2018-05-15

Quality measurement of physician-staffed emergency medical services (P-EMS) is necessary to improve service quality. Knowledge and consensus on this topic are scarce, making quality measurement of P-EMS a high-priority research area. The aim of this review was to identify, describe and evaluate studies of quality measurement in P-EMS. The databases of MEDLINE and Embase were searched initially, followed by a search for included article citations in Scopus. The study eligibility criteria were: (1) articles describing the use of one quality indicator (QI) or more in P-EMS, (2) original manuscripts, (3) articles published from 1 January 1968 until 5 October 2016. The literature search identified 4699 records. 4543 were excluded after reviewing title and abstract. An additional 129 were excluded based on a full-text review. The remaining 27 papers were included in the analysis. Methodological quality was assessed using an adapted critical appraisal tool. The description of used QIs and methods of quality measurement was extracted. Variables describing the involved P-EMSs were extracted as well. In the included papers, a common understanding of which QIs to use in P-EMS did not exist. Fifteen papers used only a single QI. The most widely used QIs were 'Adherence to medical protocols', 'Provision of advanced interventions', 'Response time' and 'Adverse events'. The review demonstrated a lack of shared understanding of which QIs to use in P-EMS. Moreover, papers using only one QI dominated the literature, thus increasing the risk of a narrow perspective in quality measurement. Future quality measurement in P-EMS should rely on a set of consensus-based QIs, ensuring a comprehensive approach to quality measurement.

Integrated Chemical Fuel Microprocessor for Power Generation in MEMS Applications

DTIC Science & Technology

2005-07-01

unreacted fuels (ammonia and hydrocarbon) and carbon monoxide that could otherwise adversely affect hydrogen Proton Exchange Membrane ( PEM ) fuel cell ...High hydrogen purity is required in a variety of processes, from the microelectronics industry to PEM fuel cells . For portable-power applications, it...Geff Ffuel Heat Load Complexity Li-Ion Batteries 330 140 1.2 W Low Carnot Engines *7,878 13,750 10% 50% 395 690 10 W Low Fuel Cells : PEM /Hydride #2,382

Investigation into the Implications of Fuel Cell Shipboard Integration into the T-AGOS 19 Class

DTIC Science & Technology

2012-02-01

with each defined by its fundamental electrolyte: i. Alkali Fuel Cells (AFC) ii. Polymer Exchange Membrane ( PEM ) iii. Phosphoric Acid Fuel Cells ...of the PEM family (High Temperature – HTPEM and Direct Methanol Fuel Cells – DMFC) were assessed against a range of basic ship requirements...of fuel cell stacks in 100+kW power range for realistic marine applications, two technologies can be quickly discounted, namely – AFC, DMFC. PEM

Prescription-event monitoring in Japan (J-PEM).

PubMed

Kubota, Kiyoshi

2002-01-01

In prescription-event monitoring in Japan (J-PEM), patients are identified by prescriptions in individual pharmacies where drugs are dispensed. The methodology is somewhat different to that used by the Drug Safety Research Unit in the UK, in that two questionnaires, one to the pharmacist and the other to the doctor are sent for each patient and the method of concurrent control is employed in J-PEM. In the data analysis, the list of events reported as a suspected reaction or a reason for stopping the drug is made to generate a signal. In addition, a signal may be generated for some events with the statistically significant difference of crude rates followed by the regression analysis or a follow-up study. In J-PEM, Medical Dictionary for Regulatory Activities (MedDRA) terminology is used for data entry and data analysis. Lowest level terms (LLTs) in MedDRA are used in data entry while a signal is generated using preferred terms (PTs). However, to generate a signal effectively, some PTs may be grouped as one term. In addition, if two terms are so similar, it may be instructed that one of those two terms is normally selected in data entry to avoid confusion. Many more PEM studies could be undertaken to determine if MedDRA can be used for effective signal generation, but the usefulness of MedDRA in J-PEM is still to be determined.

Proton Exchange Membrane (PEM) Fuel Cell Status and Remaining Challenges for Manned Space-Flight Applications

NASA Technical Reports Server (NTRS)

Reaves, Will F.; Hoberecht, Mark A.

2003-01-01

The Fuel Cell has been used for manned space flight since the Gemini program. Its power output and water production capability over long durations for the mass and volume are critical for manned space-flight requirements. The alkaline fuel cell used on the Shuttle, while very reliable and capable for it s application, has operational sensitivities, limited life, and an expensive recycle cost. The PEM fuel cell offers many potential improvements in those areas. NASA Glenn Research Center is currently leading a PEM fuel cell development and test program intended to move the technology closer to the point required for manned space-flight consideration. This paper will address the advantages of PEM fuel cell technology and its potential for future space flight as compared to existing alkaline fuel cells. It will also cover the technical hurdles that must be overcome. In addition, a description of the NASA PEM fuel cell development program will be presented, and the current status of this effort discussed. The effort is a combination of stack and ancillary component hardware development, culminating in breadboard and engineering model unit assembly and test. Finally, a detailed roadmap for proceeding fiom engineering model hardware to qualification and flight hardware will be proposed. Innovative test engineering and potential payload manifesting may be required to actually validate/certify a PEM fuel cell for manned space flight.

Plasmid Vectors for Xylella fastidiosa Utilizing a Toxin-Antitoxin System for Stability in the Absence of Antibiotic Selection.

PubMed

Burbank, Lindsey P; Stenger, Drake C

2016-08-01

The phytopathogen Xylella fastidiosa causes disease in a variety of important crop and landscape plants. Functional genetic studies have led to a broader understanding of virulence mechanisms used by this pathogen in the grapevine host. Plasmid shuttle vectors are important tools in studies of bacterial genetics but there are only a limited number of plasmid vectors available that replicate in X. fastidiosa, and even fewer that are retained without antibiotic selection. Two plasmids are described here that show stable replication in X. fastidiosa and are effective for gene complementation both in vitro and in planta. Plasmid maintenance is facilitated by incorporation of the PemI/PemK plasmid addiction system, consisting of PemK, an endoribonuclease toxin, and its cognate antitoxin, PemI. Vector pXf20pemIK utilizes a native X. fastidiosa replication origin as well as a high-copy-number pUC origin for propagation in Escherichia coli cloning strains. Broad-host-range vector pBBR5pemIK is a medium- to low-copy-number plasmid based on the pBBR1 backbone. Both plasmids are maintained for extended periods of time in the absence of antibiotic selection, as well as up to 14 weeks in grapevine, without affecting bacterial fitness. These plasmids present an alternative to traditional complementation and expression vectors which rely on antibiotic selection for plasmid retention.

Performance Evaluation of a PEM Scanner Using the NEMA NU 4—2008 Small Animal PET Standards

NASA Astrophysics Data System (ADS)

Luo, Weidong; Anashkin, Edward; Matthews, Christopher G.

2010-02-01

The recently published NEMA NU 4-2008 Standards has been specially designed for evaluating the performance of small animal PET scanners used in preclinical applications. In this paper, we report on the NU 4 performance of a clinical positron emission mammography (PEM) system. Since there are no PEM specific performance test protocols available, and the NU 2 protocol (intended for whole-body PET scanners) cannot be applied without modification due to the compact design of the PEM scanner, we decided to evaluate the NU 4 Standards as an alternative. We obtained the following results: Trans-axial spatial resolution 1.8 mm FWHM for high resolution reconstruction mode and 2.4 mm FWHM for standard resolution reconstruction mode with no significant variation within the field of view. The total system sensitivity was 0.16 cps/Bq. In image quality testing, the uniformity was found to be 3.9% STD at the standard resolution mode and 5.6% at the high resolution mode when measured with a 34 mm paddle separation. The NEMA NU 4-2008 Standards were found to be a practicable tool to evaluate the performance of the PEM scanner after some modifications to address the specifics of its detector configuration. Furthermore, the PEM scanner's in-plane spatial resolution was comparable to other small animal PET scanners with good image quality.

Low-Cost Proton Conducting Membranes for PEM Fuel Cells

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

Hu, Hongxing

Proton exchange membrane (PEM) is the key component in PEM fuel cells that critically determines the system performance and its economic viability. Presently, the state-of-the-art PEMs, such as Nafion membranes, are based on perfluorosulfonic acid (PFSA) ionomers. But these ionomer materials are expensive, particularly at the low volumes that will be needed for initial commercialization. Besides, they are not suitable for fuel cells operated beyond 100°C, because of the limitations connected to the humidification requirement of such membrane materials, limiting the maximum operating temperature to about 90°C. Fuel cells for transportation applications are required to operate in a wide temperaturemore » range from –20°C to 120°C. Low-cost PEMs with capabilities in a range of temperature and humidity conditions are urgently needed to meet the DOE fuel cell targets for transportation applications. Amsen Technologies LLC chooses to address the DOE call with a novel reinforced PEM approach based on new, non-PFSA proton conducting ionomers developed from our previous DOE SBIR projects. Along with this approach is the use of very cheap, ultra thin and highly porous microporous polymer meshes as the support for the membrane. The new PEM is expected to have significant cost advantages over traditional PEMs. The microporous polyolefin support costs $2-3/m 2; and the new ionomers that Amsen has developed are estimated at ~$250/kg at the higher end including material costs and labor costs (which may go down in the future as the processing is optimized and production scaled up). These have led to an estimate of total material cost for the membrane at $11 to $12/m 2, offering high potential of meeting the DOE cost targets (≤$20/m 2) after adding processing cost and profit margin. The Phase I results have successfully demonstrated that it is very promising to develop the intended low-cost, high-performance PEM membrane. Suitable material system has been identified, and suitable process for forming the new PEM has been developed. Uniform membranes have been reproducibly fabricated. These membranes have been extensively characterized and evaluated in terms of microstructural features, and relevant physical and chemical properties including proton conductivity and area specific proton resistance in a range of temperature and humidity conditions, resistance to electronic conduction, water uptake/swelling, dimensional stability, chemical stability, and mechanical durability. Membrane electrode assemblies (MEA) with the new membrane have been successfully prepared and tested for fuel cell operation. The new PEM showed higher proton conductivity than Nafion membranes for all measurement conditions used in Phase I. With high proton conductivity and ultra-thin thickness (~20 /m), the new membrane showed high promise to met DOE targets for the low ASR. The ASR targets have been met for relatively high RH but not yet for RH ≤ 70%. Further optimization in ionomer chemistry and membrane processing is needed in order to meet the ASR targets for a wide range of temperature and humidity conditions. The new membrane showed fairly high electronic resistance at 1373 ohm cm 2, meeting the DOE target for electronic resistance (> 1000 ohm cm 2). The new membrane also has demonstrated promisingly high chemical stability, high mechanical durability, and high dimensional stability. Fuel cell operation using MEAs with the new membrane have shown the same level of fuel cell performance as MEAs with Nafion membranes. Overall, the new membrane has been demonstrated to have high potential of meeting all DOE performance targets for fuel cell applications as well as the cost targets. The manufacturers of PEM fuel cells, PEM electrolyzers, redox flow batteries, and MEA are the end-users and customers of PEMs. For commercialization purpose and potential partnering relations, we have been talking with many such manufacturers. They have responded with extremely high interest in the new PEM being developed in the present technology. Accomplishments so far have laid down a strong base for Amsen to further the development efforts on this new PEM and to pursue commercialization. The near-term future work will be mainly focused on further development and systematical optimization of the material system, processing, and performance of the new membrane; systematical evaluation of the new membrane in terms of all relevant properties including long-term mechanical, chemical, and combined chemical/mechanical durabilities using DOE specified testing protocols; development of production scale-up scheme; and preparation for commercialization.« less

Compendium of NASA Data Base for the Global Tropospheric Experiment's Pacific Exploratory Mission - Tropics B (PEM-Tropics B). Volume 2; P-3B

NASA Technical Reports Server (NTRS)

Scott, A. Donald, Jr.; Kleb, Mary M.; Raper, James L.

2000-01-01

This report provides a compendium of NASA aircraft data that are available from NASA's Global Tropospheric Experiment's (GTE) Pacific Exploratory Mission-Tropics B (PEM-Tropics B) conducted in March and April 1999. PEM-Tropics B was conducted during the southern-tropical wet season when the influence from biomass burning observed in PEM-Tropics A was minimal. Major deployment sites were Hawaii, Kiritimati (Christmas Island), Tahiti, Fiji, and Easter Island. The broad goals of PEM-Tropics B were to improved understanding of the oxidizing power of the atmosphere and the processes controlling sulfur aerosol formation and to establish baseline values for chemical species that are directly coupled to the oxidizing power and aerosol loading of the troposphere. The purpose of this document is to provide a representation of aircraft data that will be available in archived format via NASA Langley's Distributed Active Archive Center (DAAC) or are available through the GTE Project Office archive. The data format is not intended to support original research/analysis, but to assist the reader in identifying data that are of interest.

Compendium of NASA Data Base for the Global Tropospheric Experiment's Pacific Exploratory Mission-Tropics B (PEM-Tropics B). Volume 1; DC-8

NASA Technical Reports Server (NTRS)

Scott, A. Donald, Jr.; Kleb, Mary M.; Raper, James L.

2000-01-01

This report provides a compendium of NASA aircraft data that are available from NASA's Global Tropospheric Experiment's (GTE) Pacific Exploratory Mission-Tropics B (PEM-Tropics B) conducted in March and April 1999. PEM-Tropics B was conducted during the southern-tropical wet season when the influence from biomass burning observed in PEM-Tropics A was minimal. Major deployment sites were Hawaii, Kiritimati (Christmas Island), Tahiti, Fiji, and Easter Island. The broad goals of PEM-Tropics B were to improved understanding of the oxidizing power of the atmosphere and the processes controlling sulfur aerosol formation and to establish baseline values for chemical species that are directly coupled to the oxidizing power and aerosol loading of the troposphere. The purpose of this document is to provide a representation of aircraft data that will be available in archived format via NASA Langley's Distributed Active Archive Center (DAAC) or are available through the GTE Project Office archive. The data format is not intended to support original research/analysis, but to assist the reader in identifying data that are of interest.

Defining Geodetic Reference Frame using Matlab®: PlatEMotion 2.0

NASA Astrophysics Data System (ADS)

Cannavò, Flavio; Palano, Mimmo

2016-03-01

We describe the main features of the developed software tool, namely PlatE-Motion 2.0 (PEM2), which allows inferring the Euler pole parameters by inverting the observed velocities at a set of sites located on a rigid block (inverse problem). PEM2 allows also calculating the expected velocity value for any point located on the Earth providing an Euler pole (direct problem). PEM2 is the updated version of a previous software tool initially developed for easy-to-use file exchange with the GAMIT/GLOBK software package. The software tool is developed in Matlab® framework and, as the previous version, includes a set of MATLAB functions (m-files), GUIs (fig-files), map data files (mat-files) and user's manual as well as some example input files. New changes in PEM2 include (1) some bugs fixed, (2) improvements in the code, (3) improvements in statistical analysis, (4) new input/output file formats. In addition, PEM2 can be now run under the majority of operating systems. The tool is open source and freely available for the scientific community.

Highly Conductive, Stretchable, and Transparent Solid Polymer Electrolyte Membrane

NASA Astrophysics Data System (ADS)

He, Ruixuan; Echeverri, Mauricio; Kyu, Thein

2014-03-01

With the guidance of ternary phase diagrams, completely amorphous polymer electrolyte membranes (PEM) were successfully prepared by melt processing for lithium-ion battery. The PEM under consideration consisted of poly (ethylene glycol diacrylate) (PEGDA), succinonitrile (SCN) and Lithium bis(trifluoro-methane)sulfonamide (LiTFSI). After UV-crosslinking, the PEM is transparent and light-weight. Addition of SCN plastic crystal affords not only dissociation of the lithium salt, but also plasticization to the crosslinked PEGDA network. Of particular importance is the achievement of room-temperature ionic conductivity of ~10-3 S/cm, which is comparable to that of commercial liquid electrolyte. Higher ionic conductivities were achieved at elevated temperatures or with use of a moderately higher molecular weight of PEGDA. In terms of electrochemical and chemical stability, the PEM exhibited oxidative stability up to 5 V against lithium reference electrode. Stable interface behavior between the PEM and lithium electrode is also seen with ageing time. In the tensile tests, samples containing low molecular weight PEGDA are stiffer, whereas the high molecular weight PEGDA is stretchable up to 80% elongation. Supported by NSF-DMR 1161070.

Chemical characterization of solid polymer electrolyte membrane surfaces in LiFePO4 half-cells

NASA Astrophysics Data System (ADS)

Kyu, Thein; He, Ruixuan; Peng, Fang; Dunn, William E.; Kyu's Group Team, Dr.

High temperature (60 °C) capacity retention of succinonitrile plasticized solid polymer electrolyte membrane (PEM) in a LiFePO4 half-cell was investigated with or without lithium bis(oxalato)borate (LiBOB) modification. Various symmetric cells and half-cells were studied under different thermal and electrochemical conditions. At room temperature cycling, the unmodified PEM in the half-cell appeared stable up to 50 cycles tested. Upon cycling at 60 °C, the capacity decays rapidly and concurrently the cell resistance increased. The chemical compositions of the solid PEM surfaces on both cathode and anode sides were analyzed. New IR bands (including those belonged to amide) were discerned on the unmodified PEM surface of the Li electrode side at 60 °C suggestive of side reaction, but no new bands develop during room temperature cycling. To our astonishment, the side reaction was effectively suppressed upon LiBOB addition (0.4 wt%) into the PEM, contributing to increased high temperature capacity retention at 60°C. Plausible mechanisms of capacity fading and improved cycling performance due to LiBOB modification are discussed.

In situ fluorescence spectroscopy correlates ionomer degradation to reactive oxygen species generation in an operating fuel cell.

PubMed

Prabhakaran, Venkateshkumar; Arges, Christopher G; Ramani, Vijay

2013-11-21

The rate of generation of reactive oxygen species (ROS) within the polymer electrolyte membrane (PEM) of an operating proton exchange member fuel cell (PEMFC) was monitored using in situ fluorescence spectroscopy. A modified barrier layer was introduced between the PEM and the electrocatalyst layer to eliminate metal-dye interactions and fluorescence resonance energy transfer (FRET) effects during measurements. Standard fuel cell operating parameters (temperature, relative humidity, and electrode potential) were systematically varied to evaluate their influence on the rate of ROS generation during PEMFC operation. Independently, the macroscopic rate of PEM degradation was measured by monitoring the fluoride ion emission rate (FER) in the effluent stream at each operating condition. The ROS generation reaction rate constant (estimated from the in situ fluorescence experiments) correlated perfectly with the measured FER across all conditions, demonstrating unequivocally for the first time that a direct correlation exists between in situ ROS generation and PEM macroscopic degradation. The activation energy for ROS generation within the PEM was estimated to be 12.5 kJ mol(-1).

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

NASA Astrophysics Data System (ADS)

Farina, Robert M.

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

Genetic Engineering: A Possible Strategy for Protein-Energy Malnutrition Regulation.

PubMed

Guleria, Praveen; Kumar, Vineet; Guleria, Shiwani

2017-12-01

Protein-energy malnutrition (PEM) has adversely affected the generations of developing countries. It is a syndrome that in severity causes death. PEM generally affects infants of 1-5 age group. This manifestation is maintained till adulthood in the form of poor brain and body development. The developing nations are continuously making an effort to curb PEM. However, it is still a prime concern as it was in its early years of occurrence. Transgenic crops with high protein and enhanced nutrient content have been successfully developed. Present article reviews the studies documenting genetic engineering-mediated improvement in the pulses, cereals, legumes, fruits and other crop plants in terms of nutritional value, stress tolerance, longevity and productivity. Such genetically engineered crops can be used as a possible remedial tool to eradicate PEM.

Noncovalent PEGylation through Protein-Polyelectrolyte Interaction: Kinetic Experiment and Molecular Dynamics Simulation.

PubMed

Kurinomaru, Takaaki; Kuwada, Kengo; Tomita, Shunsuke; Kameda, Tomoshi; Shiraki, Kentaro

2017-07-20

Noncovalent binding of polyethylene glycol (PEG) to a protein surface is a unique protein handling technique to control protein function and stability. A diblock copolymer containing PEG and polyelectrolyte chains (PEGylated polyelectrolyte) is a promising candidate for noncovalent attachment of PEG to a protein surface because of the binding through multiple electrostatic interactions without protein denaturation. To obtain a deeper understanding of protein-polyelectrolyte interaction at the molecular level, we investigated the manner in which cationic PEGylated polyelectrolyte binds to anionic α-amylase in enzyme kinetic experiments and molecular dynamics (MD) simulations. Cationic PEG-block-poly(N,N-dimethylaminoethyl) (PEG-b-PAMA) inhibited the enzyme activity of anionic α-amylase due to binding of PAMA chains. Enzyme kinetics revealed that the inhibition of α-amylase activity by PEG-b-PAMA is noncompetitive inhibition manner. In MD simulations, the PEG-b-PAMA molecule was initially located at six different placements of the x-, y-, and z-axis ±20 Å from the center of α-amylase, which showed that the PEG-b-PAMA nonspecifically bound to the α-amylase surface, corresponding to the noncompetitive inhibition manner that stems from the polymer binding to an enzyme surface other than the active site. In addition, the enzyme activity of α-amylase in the presence of PEG-b-PAMA was not inhibited by increasing the ionic strength, consistent with the MD simulation; i.e., PEG-b-PAMA did not interact with α-amylase in high ionic strength conditions. The results reported in this paper suggest that enzyme inhibition by PEGylated polyelectrolyte can be attributed to the random electrostatic interaction between protein and polyelectrolyte.

Novel polyelectrolytes

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Yen, Shiao-Ping Siao (Inventor)

1978-01-01

Cationic polyelectrolytes are formed by the polymerization in absence of oxygen of a monomer of the general formula: ##STR1## where x is 3 or more than 6 and Z is I, Br or Cl to form high charge density linear polymers. Segments of the linear polymer may be attached to or formed in the presence of polyfunctional reactive tertiary amines or halogen polymeric substrates or polyfunctional lower molecular reactive polyfunctional substrates to form branched or star polyelectrolytes by a quaternization polymerization reaction.

Glucose Oxidase Adsorption on Sequential Adsorbed Polyelectrolyte Films Studied by Spectroscopic Techniques

NASA Astrophysics Data System (ADS)

Tristán, Ferdinando; Solís, Araceli; Palestino, Gabriela; Gergely, Csilla; Cuisinier, Frédéric; Pérez, Elías

2005-04-01

The adsorption of Glucose Oxidase (GOX) on layers of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) deposited on Sequentially Adsorbed Polyelectrolyte Films (SAPFs) were studied by three different spectroscopic techniques. These techniques are: Optical Wave Light Spectroscopy (OWLS) to measure surface density; Fluorescence Resonance Energy Transfer (FRET) to verify the adsorption of GOX on the surface; and Fourier Transform Infrared Spectroscopy in Attenuated Total Reflection mode (FTIR-HATR) to inspect local structure of polyelectrolytes and GOX. Two positive and two negative polyelectrolytes are used: Cationic poly(ethyleneimine) (PEI) and poly(allylamine hydrochloride) (PAH) and anionic poly(sodium 4-styrene sulfonate) (PSS) and poly(acrylic acid) (PAA). These spectroscopic techniques do not require any labeling for GOX or SAPFs, specifically GOX and PSS are naturally fluorescent and are used as a couple donor-acceptor for the FRET technique. The SAPFs are formed by a (PEI)-(PSS/PAH)2 film followed by (PAA/PAH)n bilayers. GOX is finally deposited on top of SAPFs at different values of n (n=1..5). Our results show that GOX is adsorbed on positive ended SAPFs forming a monolayer. Contrary, GOX adsorption is not observed on negative ended film polyelectrolyte. GOX stability was tested adding a positive and a negative polyelectrolyte after GOX adsorption. Protein is partially removed by PAH and PAA, with lesser force by PAA.

Counterion adsorption theory of dilute polyelectrolyte solutions: Apparent molecular weight, second virial coefficient, and intermolecular structure factor

PubMed Central

Muthukumar, M.

2012-01-01

Polyelectrolyte chains are well known to be strongly correlated even in extremely dilute solutions in the absence of additional strong electrolytes. Such correlations result in severe difficulties in interpreting light scattering measurements in the determination of the molecular weight, radius of gyration, and the second virial coefficient of charged macromolecules at lower ionic strengths from added strong electrolytes. By accounting for charge-regularization of the polyelectrolyte by the counterions, we present a theory of the apparent molecular weight, second virial coefficient, and the intermolecular structure factor in dilute polyelectrolyte solutions in terms of concentrations of the polymer and the added strong electrolyte. The counterion adsorption of the polyelectrolyte chains to differing levels at different concentrations of the strong electrolyte can lead to even an order of magnitude discrepancy in the molecular weight inferred from light scattering measurements. Based on counterion-mediated charge regularization, the second virial coefficient of the polyelectrolyte and the interchain structure factor are derived self-consistently. The effect of the interchain correlations, dominating at lower salt concentrations, on the inference of the radius of gyration and on molecular weight is derived. Conditions for the onset of nonmonotonic scattering wave vector dependence of scattered intensity upon lowering the electrolyte concentration and interpretation of the apparent radius of gyration are derived in terms of the counterion adsorption mechanism. PMID:22830728

Thermodynamic model for polyelectrolyte hydrogels.

PubMed

Arndt, Markus C; Sadowski, Gabriele

2014-09-04

The composition and swelling behavior of hydrogels may be dramatically influenced by external stimuli. Polyelectrolyte hydrogels consisting of charged polymers are particularly well-known for a high sensitivity to the presence of ionic species. For a thermodynamic description of such systems, the polyelectrolyte Perturbed-Chain Statistical Association Fluid Theory (pePC-SAFT) equation of state was augmented and merged with an extension of the modeling of hydrogels. This combined approach allowed for two effects to be taken into account: first, charges along the polymer chain and their interaction with mobile ions of the same or opposite charge in aqueous solutions and, second, the elastic interactions of swellable networks and their effect on Helmholtz energy and pressure. Thus, predictions of the degree of counterion condensation on the polymer chains could be made both for vapor-liquid equilibria of aqueous polyelectrolyte solutions and for polyelectrolyte hydrogels in aqueous salt solutions. The influence of temperature and molecular weight thereon was predicted successfully, and the impact of the degree of neutralization and the effect of additional salts were examined in comparison to literature data. With the inclusion of the influence of the Donnan potential, our model gave good predictions of swellable polyelectrolyte hydrogel systems in salt solutions. Poly(acrylic acid) and poly(methacrylic acid) gels were studied along with their corresponding sodium salts. Their swelling behavior in aqueous NaCl and NaNO3 solutions was examined.

PEM/SPE fuel cell

DOEpatents

Grot, Stephen Andreas

1998-01-01

A PEM/SPE fuel cell including a membrane-electrode assembly (MEA) having a plurality of oriented filament embedded the face thereof for supporting the MEA and conducting current therefrom to contiguous electrode plates.

Polyelectrolyte brushes in mixed ionic medium studied via intermolecular forces

NASA Astrophysics Data System (ADS)

Farina, Robert; Laugel, Nicolas; Pincus, Philip; Tirrell, Matthew

2011-03-01

The vast uses and applications of polyelectrolyte brushes make them an attractive field of research especially with the growing interest in responsive materials. Polymers which respond via changes in temperature, pH, and ionic strength are increasingly being used for applications in drug delivery, chemical gating, etc. When polyelectrolyte brushes are found in either nature (e.g., surfaces of cartilage and mammalian lung interiors) or commercially (e.g., skin care products, shampoo, and surfaces of medical devices) they are always surrounded by mixed ionic medium. This makes the study of these brushes in varying ionic environments extremely relevant for both current and future potential applications. The polyelectrolyte brushes in this work are diblock co-polymers of poly-styrene sulfonate (N=420) and poly-t-butyl styrene (N=20) which tethers to a hydrophobic surface allowing for a purely thermodynamic study of the polyelectrolyte chains. Intermolecular forces between two brushes are measured using the SFA. As multi-valent concentrations are increased, the brushes collapse internally and form strong adhesion between one another after contact (properties not seen in a purely mono-valent environment).

Alkaline polymer electrolyte membranes for fuel cell applications.

PubMed

Wang, Yan-Jie; Qiao, Jinli; Baker, Ryan; Zhang, Jiujun

2013-07-07

In this review, we examine the most recent progress and research trends in the area of alkaline polymer electrolyte membrane (PEM) development in terms of material selection, synthesis, characterization, and theoretical approach, as well as their fabrication into alkaline PEM-based membrane electrode assemblies (MEAs) and the corresponding performance/durability in alkaline polymer electrolyte membrane fuel cells (PEMFCs). Respective advantages and challenges are also reviewed. To overcome challenges hindering alkaline PEM technology advancement and commercialization, several research directions are then proposed.

Mitigation of CO Poisoning on Functionalized Pt/TiN(001) Surface: A Fundamental Study of the Next-Generation Fuel Cell Technologies

DTIC Science & Technology

2014-05-27

TiN(100) surface (Pt/TiN) could be a promising catalyst for proton exchange membrane fuel cells ( PEM FCs). The adsorption properties of molecules on Pt...under both acidic and basic operation conditions in PEM FCs. 15. SUBJECT TERMS Catalysis, fuel cells , density functional theory, density functional...poisoning on functionalized Pt/TiN surfaces under both acidic and basic operation conditions in PEM FCs. 15. SUBJECT TERMS Catalysis, fuel cells

Motion of Molecular Probes and Viscosity Scaling in Polyelectrolyte Solutions at Physiological Ionic Strength

PubMed Central

Sozanski, Krzysztof; Wisniewska, Agnieszka; Kalwarczyk, Tomasz; Sznajder, Anna; Holyst, Robert

2016-01-01

We investigate transport properties of model polyelectrolyte systems at physiological ionic strength (0.154 M). Covering a broad range of flow length scales—from diffusion of molecular probes to macroscopic viscous flow—we establish a single, continuous function describing the scale dependent viscosity of high-salt polyelectrolyte solutions. The data are consistent with the model developed previously for electrically neutral polymers in a good solvent. The presented approach merges the power-law scaling concepts of de Gennes with the idea of exponential length scale dependence of effective viscosity in complex liquids. The result is a simple and applicable description of transport properties of high-salt polyelectrolyte solutions at all length scales, valid for motion of single molecules as well as macroscopic flow of the complex liquid. PMID:27536866

Thermal Analysis on Cryogenic Liquid Hydrogen Tank on an Unmanned Aerial Vehicle System

NASA Technical Reports Server (NTRS)

Wang, Xiao-Yen; Harpster, George; Hunter, James

2007-01-01

Thermal analyses are performed on the liquid hydrogen (LH2) tank designed for an unmanned aerial vehicle (UAV) powered by solar arrays and a regenerative proton-exchange membrane (PEM) fuel cell. A 14-day cruise mission at a 65,000 ft altitude is considered. Thermal analysis provides the thermal loads on the tank system and the boiling-off rates of LH2. Different approaches are being considered to minimize the boiling-off rates of the LH2. It includes an evacuated multilayer insulation (MLI) versus aerogel insulation on the LH2 tank and aluminum versus stainless steel spacer rings between the inner and outer tank. The resulting boil-off rates of LH2 provided by the one-dimensional model and three-dimensional finite element analysis (FEA) on the tank system are presented and compared to validate the results of the three-dimensional FEA. It concludes that heat flux through penetrations by conduction is as significant as that through insulation around the tank. The tank system with MLI insulation and stainless steel spacer rings result in the lowest boiling-off rate of LH2.

CONJUGATED POLYMERS AND POLYELECTROLYTES IN SOLAR PHOTOCONVERSION, Final Technical Report

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

Schanze, Kirk S

2014-08-05

This DOE-supported program investigated the fundamental properties of conjugated polyelectrolytes, with emphasis placed on studies of excited state energy transport, self-assembly into conjugated polyelectroyte (CPE) based films and colloids, and exciton transport and charge injection in CPE films constructed atop wide bandgap semiconductors. In the most recent grant period we have also extended efforts to examine the properties of low-bandgap donor-acceptor conjugated polyelectrolytes that feature strong visible light absorption and the ability to adsorb to metal-oxide interfaces.

Combined chemo- and photo-thermal therapy delivered by multifunctional theranostic gold nanorod-loaded microcapsules

NASA Astrophysics Data System (ADS)

Chen, Haiyan; di, Yingfeng; Chen, Dan; Madrid, Kyle; Zhang, Min; Tian, Caiping; Tang, Liping; Gu, Yueqing

2015-05-01

A polyelectrolyte microcapsule-based, cancer-targeting, and controlled drug delivery system has been developed as a multifunctional theranostic agent for synergistic cancer treatment. This new system, called FA-MC@GNR, is composed of folic acid (FA)-modified, multi-layered, hollow microcapsules loaded with gold nanorods (GNRs), and undergoes thermal degradation under near infrared (NIR) light. Either an NIR dye (MPA) or anti-cancer drug (doxorubicin, DOX) was loaded into the microcapsules via physical adsorption, yielding FA-MC@GNRs/MPA or FA-MC@GNRs/DOX, both of which exhibit no obvious toxicity, high stability, and remarkably improved tumor-targeting capabilities in vivo. Utilizing the strong NIR absorption of FA-MC@GNRs/DOX, we demonstrate the system's ability to simultaneously elicit photothermal therapy and controlled chemotherapy, achieving synergistic cancer treatment both in vitro cellular and in vivo animal experiments. Our study presents a new type of multifunctional micro-carrier for the delivery of chemotherapeutic drugs and photothermal agents, which has been shown to be an effective therapeutic approach for combined cancer treatment.

PEM/SPE fuel cell

DOEpatents

Grot, S.A.

1998-01-13

A PEM/SPE fuel cell is described including a membrane-electrode assembly (MEA) having a plurality of oriented filament embedded the face thereof for supporting the MEA and conducting current therefrom to contiguous electrode plates. 4 figs.

Injection of polyelectrolytes enhances mobility of zero-valent iron nanoparticles in carbonate-rich porous media

NASA Astrophysics Data System (ADS)

Laumann, Susanne; Micić, Vesna; Schmid, Doris; Hofmann, Thilo

2013-04-01

The application of nanoscale zero-valent iron (nZVI) for in situ groundwater remediation has received increased attention as a beneficial and novel remediation technique. A precondition for effective nZVI field applications is its delivery to the contaminated source zones. This has proved to be difficult due to the limited mobility of nZVI, which remains one major obstacle to widespread utilization of this remediation approach (O'CAROLL ET AL., 2012). One important factor that controls mobility of nZVI is physical and chemical heterogeneity within the subsurface, such as mineralogical variations (KIM ET AL., 2012). In our previous study we showed that the nZVI transport in carbonate-rich porous media is significantly reduced compared to that in quartz porous media (LAUMANN ET AL., 2012). This is caused by favorable nZVI deposition onto carbonate sand and is attributed to the less negative surface charge of carbonate compared to that of quartz sand under the range of water chemical conditions typically encountered in aquifers. New strategies are therefore required to improve nZVI mobility in carbonate-rich porous media. One approach can be the injection of polyelectrolytes in the subsurface, which are expected to adsorb onto aquifer grains and provide greater repulsion between nZVI and the porous media. In this study the effect of co-injected polyelectrolytes on the transport of polyacrylic acid (PAA) coated nZVI in two model porous media, quartz and carbonate sands was evaluated. Column experiments were carried out aiming to evaluate mobility of PAA-nZVI co-injected with four polyelectrolytes, including natural organic matter (NOM), humic acid, carboxymethyl cellulose (CMC), and lignin sulfonate. The results demonstrated that the co-injection of the chosen polyelectrolytes does not influence mobility of PAA-nZVI in quartz sand; the breakthrough with co-injected polyelectrolytes was similar to that of the pure PAA-nZVI dispersion. This observation can be explained by the strong negative surface charge of the quartz sand, which was apparently not changed in the presence of polyelectrolytes. Conversely, the co-injected polyelectrolytes affected the breakthrough in carbonate sand, increasing nZVI mobility for approximately 15%. This can be explained by the attachment of the polyelectrolytes to the less negatively charged carbonate sand, which then promoted the PAA-nZVI mobility. Even though there are structural differences among the polyelectrolytes applied in this study, our results showed no significant variations in the PAA-nZVI mobility when these polyelectrolytes are present at concentration of 50 mg L-1. Lignin sulfonate was furthermore selected to investigate the effect of different polyelectrolyte concentrations (0, 10, 25, 50, 250, and 500 mg L-1) on the PAA-nZVI mobility. The results showed that higher lignin sulfonate concentrations (250 and 500 mg L-1) do not affect the transport of PAA-nZVI in quartz sand. In carbonate sand, on contrary, increasing mobility due to co-injected lignin sulfonate was observed at concentrations above 25 mg L-1, having the highest value with 500 mg L-1 co-injected with the PAA-nZVI dispersion. Overall, the results demonstrated that lignin sulfonate adsorption onto the carbonate sand reduce PAA-nZVI deposition onto aquifer grains and promote its mobility, the effect which is more pronounced at higher polyelectrolyte concentrations co-injected with the PAA-nZVI dispersion. The project is funded by the Federal Ministry of Agriculture, Forestry, Environment and Water Management (BMLFUW). Management by Kommunalkredit Public Consulting GmbH. Literature O'CAROLL, D. ET AL., (2012): Advances in Water Resources, in press. KIM, H.-J. ET AL., (2012): Journal of Colloid and Interface Science 370, 1-10. LAUMANN, S. ET AL., (2012): Environmental Pollution, submitted.

NASA's PEM Fuel Cell Power Plant Development Program for Space Applications

NASA Technical Reports Server (NTRS)

Hoberecht, Mark A.

2008-01-01

A three-center NASA team led by the Glenn Research Center in Cleveland, Ohio is completing a five-year PEM fuel cell power plant development program for future space applications. The focus of the program has been to adapt commercial PEM fuel cell technology for space applications by addressing the key mission requirements of using pure oxygen as an oxidant and operating in a multi-gravity environment. Competing vendors developed breadboard units in the 1 to 5 kW power range during the first phase of the program, and a single vendor developed a nominal 10-kW engineering model power pant during the second phase of the program. Successful performance and environmental tests conducted by NASA established confidence that PEM fuel cell technology will be ready to meet the electrical power needs of future space missions.

Proton Exchange Membrane (PEM) fuel Cell for Space Shuttle

NASA Technical Reports Server (NTRS)

Hoffman, William C., III; Vasquez, Arturo; Lazaroff, Scott M.; Downey, Michael G.

1999-01-01

Development of a PEM fuel cell powerplant (PFCP) for use in the Space Shuttle offers multiple benefits to NASA. A PFCP with a longer design life than is delivered currently from the alkaline fuel will reduce Space Shuttle Program maintenance costs. A PFCP compatible with zero-gravity can be adapted for future NASA transportation and exploration programs. Also, the commercial PEM fuel cell industry ensures a competitive environment for select powerplant components. Conceptual designs of the Space Shuttle PFCP have resulted in identification of key technical areas requiring resolution prior to development of a flight system. Those technical areas include characterization of PEM fuel cell stack durability under operational conditions and water management both within and external to the stack. Resolution of the above issues is necessary to adequately control development, production, and maintenance costs for a PFCP.

Investigation of polymer electrolyte membrane chemical degradation and degradation mitigation using in situ fluorescence spectroscopy

PubMed Central

Prabhakaran, Venkateshkumar; Arges, Christopher G.; Ramani, Vijay

2012-01-01

A fluorescent molecular probe, 6-carboxy fluorescein, was used in conjunction with in situ fluorescence spectroscopy to facilitate real-time monitoring of degradation inducing reactive oxygen species within the polymer electrolyte membrane (PEM) of an operating PEM fuel cell. The key requirements of suitable molecular probes for in situ monitoring of ROS are presented. The utility of using free radical scavengers such as CeO2 nanoparticles to mitigate reactive oxygen species induced PEM degradation was demonstrated. The addition of CeO2 to uncatalyzed membranes resulted in close to 100% capture of ROS generated in situ within the PEM for a period of about 7 h and the incorporation of CeO2 into the catalyzed membrane provided an eightfold reduction in ROS generation rate. PMID:22219367

Protein Energy Malnutrition during Vaccination Has Limited Influence on Vaccine Efficacy but Abolishes Immunity if Administered during Mycobacterium tuberculosis Infection

PubMed Central

Hoang, Truc; Agger, Else Marie; Cassidy, Joseph P.; Christensen, Jan P.

2015-01-01

Protein energy malnutrition (PEM) increases susceptibility to infectious diseases, including tuberculosis (TB), but it is not clear how PEM influences vaccine-promoted immunity to TB. We demonstrate that PEM during low-level steady-state TB infection in a mouse model results in rapid relapse of Mycobacterium tuberculosis, as well as increased pathology, in both Mycobacterium bovis BCG-vaccinated and unvaccinated animals. PEM did not change the overall numbers of CD4 T cells in BCG-vaccinated animals but resulted in an almost complete loss of antigen-specific cytokine production. Furthermore, there was a change in cytokine expression characterized by a gradual loss of multifunctional antigen-specific CD4 T cells and an increased proportion of effector cells expressing gamma interferon and tumor necrosis factor alpha (IFN-γ+ TNF-α+ and IFN-γ+ cells). PEM during M. tuberculosis infection completely blocked the protection afforded by the H56-CAF01 subunit vaccine, and this was associated with a very substantial loss of the interleukin-2-positive memory CD4 T cells promoted by this vaccine. Similarly, PEM during the vaccination phase markedly reduced the H56-CAF01 vaccine response, influencing all cytokine-producing CD4 T cell subsets, with the exception of CD4 T cells positive for TNF-α only. Importantly, this impairment was reversible and resupplementation of protein during infection rescued both the vaccine-promoted T cell response and the protective effect of the vaccine against M. tuberculosis infection. PMID:25754202

Proton exchange membrane fuel cell technology for transportation applications

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

Swathirajan, S.

1996-04-01

Proton Exchange Membrane (PEM) fuel cells are extremely promising as future power plants in the transportation sector to achieve an increase in energy efficiency and eliminate environmental pollution due to vehicles. GM is currently involved in a multiphase program with the US Department of Energy for developing a proof-of-concept hybrid vehicle based on a PEM fuel cell power plant and a methanol fuel processor. Other participants in the program are Los Alamos National Labs, Dow Chemical Co., Ballard Power Systems and DuPont Co., In the just completed phase 1 of the program, a 10 kW PEM fuel cell power plantmore » was built and tested to demonstrate the feasibility of integrating a methanol fuel processor with a PEM fuel cell stack. However, the fuel cell power plant must overcome stiff technical and economic challenges before it can be commercialized for light duty vehicle applications. Progress achieved in phase I on the use of monolithic catalyst reactors in the fuel processor, managing CO impurity in the fuel cell stack, low-cost electrode-membrane assembles, and on the integration of the fuel processor with a Ballard PEM fuel cell stack will be presented.« less

Securing electronic mail: The risks and future of electronic mail

NASA Astrophysics Data System (ADS)

Weeber, S. A.

1993-03-01

The network explosion of the past decade has significantly affected how many of us conduct our day to day work. We increasingly rely on network services such as electronic mail, file transfer, and network newsgroups to collect and distribute information. Unfortunately, few of the network services in use today were designed with the security issues of large heterogeneous networks in mind. In particular, electronic mail, although heavily relied upon, is notoriously insecure. Messages can be forged, snooped, and even altered by users with only a moderate level of system proficiency. The level of trust that can be assigned at present to these services needs to be carefully considered. In the past few years, standards and tools have begun to appear addressing the security concerns of electronic mail. Principal among these are RFC's 1421, 1422, 1423, and 1424, which propose Internet standards in the areas of message encipherment, key management, and algorithms for privacy enhanced mail (PEM). Additionally, three PEM systems, offering varying levels of compliance with the PEM RFC's, have also recently emerged: PGP, RIPEM, and TIS/PEM. This paper addresses the motivations and requirements for more secure electronic mail, and evaluates the suitability of the currently available PEM systems.

Processes in suspensions of nanocomposite microcapsules exposed to external electric fields

NASA Astrophysics Data System (ADS)

Ermakov, A. V.; Lomova, M. V.; Kim, V. P.; Chumakov, A. S.; Gorbachev, I. A.; Gorin, D. A.; Glukhovskoy, E. G.

2016-04-01

Microcapsules with and without magnetite nanoparticles incorporated in the polyelectrolyte shell were prepared. The effect of external electric field on the nanocomposite polyelectrolyte microcapsules containing magnetite nanoparticles in the shell was studied in this work as a function of the electric field strength. Effect of electric fields on polyelectrolyte microcapsules and the control over integrity of polyelectrolyte microcapsules with and without inorganic nanoparticles by constant electric field has been investigated. Beads effect, aggregation and deformations of nanocomposite microcapsule shell in response to electric field were observed by confocal laser scanning microscopy (CLSM). Thus, a new approach for effect on the nanocomposite microcapsule, including opening microcapsule shell by an electric field, was demonstrated. These results can be used for creation of new systems for drug delivery systems with controllable release by external electric field.

Essentials of Pediatric Emergency Medicine Fellowship: Part 6: Program Administration.

PubMed

Kim, In K; Zuckerbraun, Noel; Kou, Maybelle; Vu, Tien; Levasseur, Kelly; Yen, Kenneth; Chapman, Jennifer; Doughty, Cara; McAneney, Constance; Zaveri, Pavan; Hsu, Deborah

2016-10-01

This article is the sixth in a 7-part series that aims to comprehensively describe the current state and future directions of pediatric emergency medicine (PEM) fellowship training from the essential requirements to considerations for successfully administering and managing a program to the careers that may be anticipated upon program completion. This article provides a broad overview of administering and supervising a PEM fellowship program. It explores 3 topics: the principles of program administration, committee management, and recommendations for minimum time allocated for PEM fellowship program directors to administer their programs.

Critical concerns, solutions and guidelines for use of plastic encapsulated microcircuits for space flight applications

NASA Technical Reports Server (NTRS)

Virmani, Nick; Shaw, Jack

1997-01-01

Some of the concerns and risk mitigation procedures for using plastic encapsulated microcircuits (PEMs) for space applications are discussed. Despite their advantages, PEMs cannot be implemented in all space applications by replacing military parts numbers with their commercial counterparts in product designs and part lists. The technical and procurement concerns are summarized, and suggestions for high reliability procurements are given. The ability to withstand deleterious environmental effects and to meet mission critical reliability is the key to the successful use of PEMs for space applications.

Tropospheric Diagnostic Modeling Studies of PEM-Tropics B Field Data: Investigation of the HOx/NOx/O3 Photochemical System and its Coupling to Sulfur Chemistry

NASA Technical Reports Server (NTRS)

Davis, Douglas D.

2001-01-01

Over the time period of this NASA grant the PI has helped plan and execute the PEM-Tropics B field program. He has also helped organize and co-chair two data workshops which have focused on the detailed analysis of PEM-Tropics B data. His direct participation in these analyses has led to his involvement in 13 manuscripts, nine of which are in print, two in press, and two submitted. A complete list of papers is given.

Electro-responsive polyelectrolyte-coated surfaces.

PubMed

Sénéchal, V; Saadaoui, H; Rodriguez-Hernandez, J; Drummond, C

2017-07-01

The anchoring of polymer chains at solid surfaces is an efficient way to modify interfacial properties like the stability and rheology of colloidal dispersions, lubrication and biocompatibility. Polyelectrolytes are good candidates for the building of smart materials, as the polyion chain conformation can often be tuned by manipulation of different physico-chemical variables. However, achieving efficient and reversible control of this process represents an important technological challenge. In this regard, the application of an external electrical stimulus on polyelectrolytes seems to be a convenient control strategy, for several reasons. First, it is relatively easy to apply an electric field to the material with adequate spatiotemporal control. In addition, in contrast to chemically induced changes, the molecular response to a changing electric field occurs relatively quickly. If the system is properly designed, this response can then be used to control the magnitude of surface properties. In this work we discuss the effect of an external electric field on the adhesion and lubrication properties of several polyelectrolyte-coated surfaces. The influence of the applied field is investigated at different pH and salt conditions, as the polyelectrolyte conformation is sensitive to these variables. We show that it is possible to fine tune friction and adhesion using relatively low applied fields.

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

PubMed Central

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

2009-01-01

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

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

PubMed

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

2009-05-01

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

Performance optimization of coagulant/flocculant in the treatment of wastewater from a beverage industry.

PubMed

Amuda, O S; Amoo, I A; Ajayi, O O

2006-02-28

This study investigated the effect of coagulation/flocculation treatment process on wastewater of Fumman Beverage Industry, Ibadan, Nigeria. The study also compared different dosages of coagulant, polyelectrolyte (non-ionic polyacrylamide) and different pH values of the coagulation processes. The effect of different dosages of polyelectrolyte in combination with coagulant was also studied. The results reveal that low pH values (3-8), enhance removal efficiency of the contaminants. Percentage removal of 78, 74 and 75 of COD, TSS and TP, respectively, were achieved by the addition of 500 mg/L Fe2(SO4)3.3H2O and 93, 94 and 96% removal of COD, TSS and TP, respectively, were achieved with the addition of 25 mg/L polyelectrolyte to the coagulation process. The volume of sludge produced, when coagulant was used solely, was higher compared to the use of polyelectrolyte combined with Fe2(SO4)3.3H2O. This may be as a result of non-ionic nature of the polyelectrolyte; hence, it does not chemically react with solids of the wastewater. Coagulation/flocculation may be useful as a pre-treatment process for beverage industrial wastewater prior to biological treatment.

Electrolyte-stimulated biphasic dissolution profile and stability enhancement for tablets containing drug-polyelectrolyte complexes.

PubMed

Kindermann, Christoph; Matthée, Karin; Sievert, Frank; Breitkreutz, Jörg

2012-10-01

Recently introduced drug-polyelectrolyte complexes prepared by hot-melt extrusion should be processed to solid dosage forms with tailor-made release properties. Their potential of stability enhancement should be investigated. Milled hot-melt extruded naproxen-EUDRAGIT® E PO polyelectrolyte complexes were subsequently processed to double-layer tablets with varying complex loadings on a rotary-die press. Physicochemical interactions were studied under ICH guideline conditions and using the Gordon-Taylor equation. Sorption and desorption were determined to investigate the influence of moisture and temperature on the complex and related to stability tests under accelerated conditions. Naproxen release from the drug-polyelectrolyte complex is triggered by electrolyte concentration. Depending on the complex loading, phosphate buffer pH 6.8 stimulated a biphasic dissolution profile of the produced double-layer tablets: immediate release from the first layer with 65% loading and prolonged release from the second layer within 24 h (98.5% loading). XRPD patterns proved pseudopolymorphism for tablets containing the pure drug under common storage conditions whereas the drug-complex was stable in the amorphous state. Drug-polyelectrolyte complexes enable tailor-made dissolution profiles of solid dosage forms by electrolyte stimulation and increase stability under common storage conditions.

The 2015 Academic College of Emergency Experts in India's INDO-US Joint Working Group White Paper on Establishing an Academic Department and Training Pediatric Emergency Medicine Specialists in India

PubMed Central

Mahajan, Prashant; Batra, Prerna; Shah, Binita R; Saha, Abhijeet; Galwankar, Sagar; Aggrawal, Praveen; Hassoun, Ameer; Batra, Bipin; Bhoi, Sanjeev; Kalra, Om Prakash; Shah, Dheeraj

2015-01-01

The concept of pediatric emergency medicine (PEM) is virtually nonexistent in India. Suboptimally, organized prehospital services substantially hinder the evaluation, management, and subsequent transport of the acutely ill and/or injured child to an appropriate facility. Furthermore, the management of the ill child at the hospital level is often provided by overburdened providers who, by virtue of their training, lack experience in the skills required to effectively manage pediatric emergencies. Finally, the care of the traumatized child often requires the involvement of providers trained in different specialities, which further impedes timely access to appropriate care. The recent recognition of Doctor of Medicine (MD) in Emergency Medicine (EM) as an approved discipline of study as per the Indian Medical Council Act provides an unprecedented opportunity to introduce PEM as a formal academic program in India. PEM has to be developed as a 3-year superspeciality course (in PEM) after completion of MD/Diplomate of National Board (DNB) Pediatrics or MD/DNB in EM. The National Board of Examinations (NBE) that accredits and administers postgraduate and postdoctoral programs in India also needs to develop an academic program – DNB in PEM. The goals of such a program would be to impart theoretical knowledge, training in the appropriate skills and procedures, development of communication and counseling techniques, and research. In this paper, the Joint Working Group of the Academic College of Emergency Experts in India (JWG-ACEE-India) gives its recommendations for starting 3-year DM/DNB in PEM, including the curriculum, infrastructure, staffing, and training in India. This is an attempt to provide an uniform framework and a set of guiding principles to start PEM as a structured superspeciality to enhance emergency care for Indian children. PMID:26807394

The Habitat Demonstration Unit Project Overview

NASA Technical Reports Server (NTRS)

Kennedy, Kriss J.; Grill, Tracy R.; Tri, Terry O.; Howe, Alan S.

2010-01-01

This paper will describe an overview of the National Aeronautics and Space Administration (NASA) led multi-center Habitat Demonstration Unit (HDU) Project. The HDU project is a "technology-pull" project that integrates technologies and innovations from numerous NASA centers. This project will be used to investigate and validate surface architectures, operations concepts, and requirements definition of various habitation concepts. The first habitation configuration this project will build and test is the Pressurized Excursion Module (PEM). This habitat configuration - the PEM - is based on the Constellation Architecture Scenario 12.1 concept of a vertically oriented habitat module. The HDU project will be tested as part of the 2010 Desert Research and Technologies Simulations (D-RATS) test objectives. The purpose of this project is to develop, integrate, test, and evaluate a habitat configuration in the context of the mission architectures and surface operation concepts. A multi-center approach will be leveraged to build, integrate, and test the PEM through a shared collaborative effort of multiple NASA centers. The HDU project is part of the strategic plan from the Exploration Systems Mission Directorate (ESMD) Directorate Integration Office (DIO) and the Lunar Surface Systems Project Office (LSSPO) to test surface elements in a surface analog environment. The 2010 analog field test will include two Lunar Electric Rovers (LER) and the PEM among other surface demonstration elements. This paper will describe the overall objectives, its various habitat configurations, strategic plan, and technology integration as it pertains to the 2010 and 2011 field analog tests. To accomplish the development of the PEM from conception in June 2009 to rollout for operations in July 2010, the HDU project team is using a set of design standards to define the interfaces between the various systems of PEM and to the payloads, such as the Geology Lab, that those systems will support. Scheduled activities such as early fit-checks and the utilization of a habitat avionics test bed prior to equipment installation into PEM are planned to facilitate the integration process.

Properties and degradation of the gasket component of a proton exchange membrane fuel cell--a review.

PubMed

Basuli, Utpal; Jose, Jobin; Lee, Ran Hee; Yoo, Yong Hwan; Jeong, Kwang-Un; Ahn, Jou-Hyeon; Nah, Changwoon

2012-10-01

Proton exchange membrane (PEM) fuel cell stack requires gaskets and seals in each cell to keep the reactant gases within their respective regions. Gasket performance is integral to the successful long-term operation of a fuel cell stack. This review focuses on properties, performance and degradation mechanisms of the different polymer gasket materials used in PEM fuel cell under normal operating conditions. The different degradation mechanisms and their corresponding representative mitigation strategies are also presented here. Summary of various properties of elastomers and their advantages and disadvantages in fuel cell'environment are presented. By considering the level of chemical degradation, mechanical properties and cost effectiveness, it can be proposed that EPDM is one of the best choices for gasket material in PEM fuel cell. Finally, the challenges that remain in using rubber component as in PEM fuel cell, as well as the prospects for exploiting them in the future are discussed.

Prescription-event monitoring: methodology and recent progress.

PubMed

Rawson, N S; Pearce, G L; Inman, W H

1990-01-01

Event monitoring was first suggested 25 years ago as a way of detecting adverse reactions to drugs. Prescription-event monitoring (PEM), which has been developed by the Drug Safety Research Unit, is the first large-scale systematic post-marketing surveillance method to use event monitoring in the U.K. PEM identifies patients, who have been prescribed a particular drug, and their doctors from photocopies of National Health Service prescriptions which are processed centrally in England. A personalized follow-up questionnaire ("green form") is mailed to each patient's general practitioner, usually on the first anniversary of the initial prescription, asking for information about the patient, especially any "events" that he or she may have experienced since beginning treatment with the drug. The methodology of PEM is presented, together with examples of analyses that can be performed using results from recent studies. The problems and benefits of PEM are discussed.

Magnetic resonance imaging (MRI) of PEM dehydration and gas manifold flooding during continuous fuel cell operation

NASA Astrophysics Data System (ADS)

Minard, Kevin R.; Viswanathan, Vilayanur V.; Majors, Paul D.; Wang, Li-Qiong; Rieke, Peter C.

Magnetic resonance imaging (MRI) was employed for visualizing water inside a proton exchange membrane (PEM) fuel cell during 11.4 h of continuous operation with a constant load. Two-dimensional images acquired every 128 s revealed the formation of a dehydration front that propagated slowly over the surface of the fuel cell membrane-starting from gas inlets and progressing toward gas outlets. After traversing the entire PEM surface, channels in the gas manifold began to flood on the cathode side. To establish a qualitative understanding of these observations, acquired images were correlated to the current output and the operating characteristics of the fuel cell. Results demonstrate the power of MRI for visualizing changing water distributions during PEM fuel cell operation, and highlight its potential utility for studying the causes of cell failure and/or strategies of water management.

A simple electric circuit model for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Lazarou, Stavros; Pyrgioti, Eleftheria; Alexandridis, Antonio T.

A simple and novel dynamic circuit model for a proton exchange membrane (PEM) fuel cell suitable for the analysis and design of power systems is presented. The model takes into account phenomena like activation polarization, ohmic polarization, and mass transport effect present in a PEM fuel cell. The proposed circuit model includes three resistors to approach adequately these phenomena; however, since for the PEM dynamic performance connection or disconnection of an additional load is of crucial importance, the proposed model uses two saturable inductors accompanied by an ideal transformer to simulate the double layer charging effect during load step changes. To evaluate the effectiveness of the proposed model its dynamic performance under load step changes is simulated. Experimental results coming from a commercial PEM fuel cell module that uses hydrogen from a pressurized cylinder at the anode and atmospheric oxygen at the cathode, clearly verify the simulation results.

Conjugated-polyelectrolyte-grafted cotton fibers act as "micro flypaper" for the removal and destruction of bacteria.

PubMed

Ista, Linnea K; Dascier, Dimitri; Ji, Eunkyung; Parthasarathy, Anand; Corbitt, Thomas S; Schanze, Kirk S; Whitten, David G

2011-08-01

We demonstrate herein a method for chemically modifying cotton fibers and cotton-containing fabric with a light-activated, cationic phenylene-ethynylene (PPE-DABCO) conjugated polyelectrolyte biocide. When challenged with Pseudomonas aeruginosa and Bacillus atropheaus vegetative cells from liquid suspension, light-activated PPE-DABCO effects 1.2 and 8 log, respectively, losses in viability of the exposed bacteria. These results suggest that conjugated polyelectrolytes retain their activity when grafted to fabrics, showing promise for use in settings where antimicrobial textiles are needed.

Ring-opening polymerization of 19-electron [2]cobaltocenophanes: a route to high-molecular-weight, water-soluble polycobaltocenium polyelectrolytes.

PubMed

Mayer, Ulrich F J; Gilroy, Joe B; O'Hare, Dermot; Manners, Ian

2009-08-05

Water-soluble, high-molecular-weight polycobaltocenium polyelectrolytes have been prepared by ring-opening polymerization (ROP) techniques. Anionic polymerization of a strained 19-electron dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium chloride resulted in the formation of oligomers with up to nine repeat units. Thermal ROP of dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium nitrate resulted in the formation of high-molecular-weight polycobaltocenium nitrate, a redox-active cobalt-containing polyelectrolyte.

Effect of dielectric discontinuity on a spherical polyelectrolyte brush

NASA Astrophysics Data System (ADS)

Tergolina, Vinicius B.; dos Santos, Alexandre P.

2017-09-01

In this paper we perform molecular dynamics simulations of a spherical polyelectrolyte brush and counterions in a salt-free medium. The dielectric discontinuity on the grafted nanoparticle surface is taken into account by the method of image charges. Properties of the polyelectrolyte brush are obtained for different parameters, including valency of the counterions, radius of the nanoparticle, and the brush total charge. The monovalent counterions density profiles are obtained and compared with a simple mean-field theoretical approach. The theory allows us to obtain osmotic properties of the system.

Molecular simulation of the swelling of polyelectrolyte gels by monovalent and divalent counterions

PubMed Central

Yin, De-Wei; Horkay, Ferenc; Douglas, Jack F.; de Pablo, Juan J.

2008-01-01

Permanently crosslinked polyelectrolyte gels are known to undergo discontinuous first-order volume phase transitions, the onset of which may be caused by a number of factors. In this study we examine the volumetric properties of such polyelectrolyte gels in relation to the progressive substitution of monovalent counterions by divalent counterions as the gels are equilibrated in solvents of different dielectric qualities. We compare the results of coarse-grained molecular dynamics simulations of polyelectrolyte gels with previous experimental measurements by others on polyacrylate gels. The simulations show that under equilibrium conditions there is an approximate cancellation between the electrostatic contribution and the counterion excluded-volume contribution to the osmotic pressure in the gel-solvent system; these two contributions to the osmotic pressure have, respectively, energetic and entropic origins. The finding of such a cancellation between the two contributions to the osmotic pressure of the gel-solvent system is consistent with experimental observations that the swelling behavior of polyelectrolyte gels can be described by equations of state for neutral gels. Based on these results, we show and explain that a modified form of the Flory–Huggins model for nonionic polymer solutions, which accounts for neither electrostatic effects nor counterion excluded-volume effects, fits both experimental and simulated data for polyelectrolyte gels. The Flory–Huggins interaction parameters obtained from regression to the simulation data are characteristic of ideal polymer solutions, whereas the experimentally obtained interaction parameters, particularly that associated with the third virial coefficient, exhibit a significant departure from ideality, leading us to conclude that further enhancements to the simulation model, such as the inclusion of excess salt, the allowance for size asymmetric electrolytes, or the use of a distance-dependent solvent dielectricity model, may be required. Molecular simulations also reveal that the condensation of divalent counterions onto the polyelectrolyte network backbone occurs preferentially over that of monovalent counterions. PMID:19045224

Molecular simulation of the swelling of polyelectrolyte gels by monovalent and divalent counterions.

PubMed

Yin, De-Wei; Horkay, Ferenc; Douglas, Jack F; de Pablo, Juan J

2008-10-21

Permanently crosslinked polyelectrolyte gels are known to undergo discontinuous first-order volume phase transitions, the onset of which may be caused by a number of factors. In this study we examine the volumetric properties of such polyelectrolyte gels in relation to the progressive substitution of monovalent counterions by divalent counterions as the gels are equilibrated in solvents of different dielectric qualities. We compare the results of coarse-grained molecular dynamics simulations of polyelectrolyte gels with previous experimental measurements by others on polyacrylate gels. The simulations show that under equilibrium conditions there is an approximate cancellation between the electrostatic contribution and the counterion excluded-volume contribution to the osmotic pressure in the gel-solvent system; these two contributions to the osmotic pressure have, respectively, energetic and entropic origins. The finding of such a cancellation between the two contributions to the osmotic pressure of the gel-solvent system is consistent with experimental observations that the swelling behavior of polyelectrolyte gels can be described by equations of state for neutral gels. Based on these results, we show and explain that a modified form of the Flory-Huggins model for nonionic polymer solutions, which accounts for neither electrostatic effects nor counterion excluded-volume effects, fits both experimental and simulated data for polyelectrolyte gels. The Flory-Huggins interaction parameters obtained from regression to the simulation data are characteristic of ideal polymer solutions, whereas the experimentally obtained interaction parameters, particularly that associated with the third virial coefficient, exhibit a significant departure from ideality, leading us to conclude that further enhancements to the simulation model, such as the inclusion of excess salt, the allowance for size asymmetric electrolytes, or the use of a distance-dependent solvent dielectricity model, may be required. Molecular simulations also reveal that the condensation of divalent counterions onto the polyelectrolyte network backbone occurs preferentially over that of monovalent counterions.

Gas/Water and Heat Management of PEM-Based Fuel Cell and Electrolyzer Systems for Space Applications

NASA Astrophysics Data System (ADS)

Guo, Qing; Ye, Fang; Guo, Hang; Ma, Chong Fang

2017-02-01

Hydrogen/oxygen fuel cells were successfully utilized in the field of space applications to provide electric energy and potable water in human-rated space mission since the 1960s. Proton exchange membrane (PEM) based fuel cells, which provide high power/energy densities, were reconsidered as a promising space power equipment for future space exploration. PEM-based water electrolyzers were employed to provide life support for crews or as major components of regenerative fuel cells for energy storage. Gas/water and heat are some of the key challenges in PEM-based fuel cells and electrolytic cells, especially when applied to space scenarios. In the past decades, efforts related to gas/water and thermal control have been reported to effectively improve cell performance, stability lifespan, and reduce mass, volume and costs of those space cell systems. This study aimed to present a primary review of research on gas/water and waste thermal management for PEM-based electrochemical cell systems applied to future space explorations. In the fuel cell system, technologies related to reactant supplement, gas humidification, water removal and active/passive water separation were summarized in detail. Experimental studies were discussed to provide a direct understanding of the effect of the gas-liquid two-phase flow on product removal and mass transfer for PEM-based fuel cell operating in a short-term microgravity environment. In the electrolyzer system, several active and static passive phaseseparation methods based on diverse water supplement approaches were discussed. A summary of two advanced passive thermal management approaches, which are available for various sizes of space cell stacks, was specifically provided

A comparison of a mini-PEMS and a 1065 compliant PEMS for on-road gaseous and particulate emissions from a light duty diesel truck.

PubMed

Yang, Jiacheng; Durbin, Thomas D; Jiang, Yu; Tange, Takeshi; Karavalakis, Georgios; Cocker, David R; Johnson, Kent C

2018-05-31

The primary goal of this study was to compare emissions measurements between a 1065 compliant PEMS, and the NTK Compact Emissions Meter (NCEM) capable of measuring NOx, PM, and solid PN. Both units were equipped on a light-duty diesel truck and tested over local, highway, and downtown driving routes. The results indicate that the NOx measurements for the NCEM were within approximately ±10% of those the 1065 compliant PEMS, which suggests that the NCEM could be used as a screening tool for NOx emissions. The NCEM showed larger differences for PM emissions on an absolute level, but this was at PM levels well below the 1 mg/mi level. The NCEM differences ranged from -2% to +26% if the comparisons are based on a percentage of the 1.0 mg/mi standard. Larger differences were also seen for PN emissions, with the NCEM measuring higher PN emissions, which can primarily be attributed to a zero current offset that we observed for the NCEM, which has been subsequently improved in the latest generation of the NCEM system. The comparisons between the 1065 compliant PEMS and the NCEM suggest that there could be applications for the NCEM or other mini-PEMS for applications such as identification of potential issues by regulatory agencies, manufacturer evaluation and validation of emissions under in-use conditions, and potential use in inspection and maintenance (I/M) programs, especially for heavy-duty vehicles. Copyright © 2017. Published by Elsevier B.V.

Validation of environmental content in the Young Children's Participation and Environment Measure.

PubMed

Khetani, Mary A

2015-02-01

To evaluate the concurrent validity of the environment content in the newly developed Young Children's Participation and Environment Measure (YC-PEM). Cross-sectional study. Data were collected online. Convenience and snowball sampling methods were used to survey caregivers of children (N=381; 85 children with developmental disabilities and delays and 296 children without developmental disabilities and delays) aged 0 and 5 years (mean age, 36.49±20.18 mo). Not applicable. The YC-PEM includes an assessment of the effect of environment on children's participation for 3 settings: home, daycare/preschool, and community. Pearson and Spearman correlational analyses were used to examine the concurrent validity of the YC-PEM environmental content according to a criterion measure, the Craig Hospital Inventory of Environmental Factors-Child and Parent Version (CHIEF-CP). The YC-PEM and the CHIEF-CP items were first mapped to the International Classification of Functioning, Disability, and Health-Children and Youth Version to identify items for pairwise comparison. We found small to moderate negative associations for 51 of 66 pairwise comparisons involving CHIEF-CP and YC-PEM environment items (r=-.13 to -.39; P<.01). Significant associations were found for items in all 5 International Classification of Functioning, Disability and Health-Children and Youth Version environmental domains. Results lend further support for the use of the YC-PEM for valid caregiver assessment of the physical, social, attitudinal, and institutional features of environments in terms of their effect on young children's participation within the home, daycare/preschool, and community settings. Copyright © 2015 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.

Determining content for a simulation-based curriculum in pediatric emergency medicine: results from a national Delphi process.

PubMed

Bank, Ilana; Cheng, Adam; McLeod, Peter; Bhanji, Farhan

2015-11-01

By the end of residency training, pediatric emergency medicine (PEM) residents are expected to have developed the confidence and abilities required to manage acutely ill children. Acquisition of competence requires exposure and/or supplemental formal education for critical and noncritical medical clinical presentations. Simulation can provide experiential learning and can improve trainees' knowledge, skills, and attitudes. The primary objective of this project was to identify the content for a simulation-based national curriculum for PEM training. We recruited participants for the Delphi study by contacting current PEM program directors and immediate past program directors as well as simulation experts at all of the Canadian PEM fellowship sites. We determined the appropriate core content for the Delphi study by combining the PEM core content requirements of the Royal College of Physicians and Surgeons of Canada (RCPSC) and the American Board of Pediatrics (ABP). Using the Delphi method, we achieved consensus amongst the national group of PEM and simulation experts. The participants completed a three-round Delphi (using a four-point Likert scale). Response rates for the Delphi were 85% for the first round and 77% for second and third rounds. From the initial 224 topics, 53 were eliminated (scored <2). Eighty-five topics scored between 2 and 3, and 87 scored between 3 and 4. The 48 topics, which were scored between 3.5 and 4.0, were labeled as "key curriculum topics." We have iteratively identified a consensus for the content of a national simulation-based curriculum.

Emerging Fuel Cell Technology Being Developed: Offers Many Benefits to Air Vehicles

NASA Technical Reports Server (NTRS)

Walker, James F.; Civinskas, Kestutis C.

2004-01-01

Fuel cells, which have recently received considerable attention for terrestrial applications ranging from automobiles to stationary power generation, may enable new aerospace missions as well as offer fuel savings, quiet operations, and reduced emissions for current and future aircraft. NASA has extensive experience with fuel cells, having used them on manned space flight systems over four decades. Consequently, the NASA Glenn Research Center has initiated an effort to investigate and develop fuel cell technologies for multiple aerospace applications. Two promising fuel cell types are the proton exchange membrane (PEM) and solid oxide fuel cell (SOFC). PEM technology, first used on the Gemini spacecraft in the sixties, remained unutilized thereafter until the automotive industry recently recognized the potential. PEM fuel cells are low-temperature devices offering quick startup time but requiring relatively pure hydrogen fuel. In contrast, SOFCs operate at high temperatures and tolerate higher levels of impurities. This flexibility allows SOFCs to use hydrocarbon fuels, which is an important factor considering our current liquid petroleum infrastructure. However, depending on the specific application, either PEM or SOFC can be attractive. As only NASA can, the Agency is pursuing fuel cell technology for civil uninhabited aerial vehicles (UAVs) because it offers enhanced scientific capabilities, including enabling highaltitude, long-endurance missions. The NASA Helios aircraft demonstrated altitudes approaching 100,000 ft using solar power in 2001, and future plans include the development of a regenerative PEM fuel cell to provide nighttime power. Unique to NASA's mission, the high-altitude aircraft application requires the PEM fuel cell to operate on pure oxygen, instead of the air typical of terrestrial applications.

Baseline Testing of Ultracapacitors for the Next Generation Launch Technology (NGLT) Project. Revised

NASA Technical Reports Server (NTRS)

Eichenberg, Dennis J.

2005-01-01

The NASA John H. Glenn Research Center initiated baseline testing of ultracapacitors for the Next Generation Launch Transportation (NGLT) project to obtain empirical data for determining the feasibility of using ultracapacitors for the project. There are large transient loads associated with NGLT that require either a very large primary energy source or an energy storage system. The primary power source used for these tests is a proton exchange membrane (PEM) fuel cell. The energy storage system can consist of devices such as batteries, flywheels, or ultracapacitors. Ultracapacitors were used for these tests. Ultracapacitors are ideal for applications such as NGLT where long life, maintenance-free operation, and excellent low-temperature performance is essential. State-of-the-art symmetric ultracapacitors were used for these tests. The ultracapacitors were interconnected in an innovative configuration to minimize interconnection impedance. PEM fuel cells provide excellent energy density, but not good power density. Ultracapacitors provide excellent power density, but not good energy density. The combination of PEM fuel cells and ultracapacitors provides a power source with excellent energy density and power density. The life of PEM fuel cells is shortened significantly by large transient loads. Ultracapacitors used in conjunction with PEM fuel cells reduce the transient loads applied to the fuel cell, and thus appreciably improves its life. PEM fuel cells were tested with and without ultracapacitors, to determine the benefits of ultracapacitors. The report concludes that the implementation of symmetric ultracapacitors in the NGLT power system can provide significant improvements in power system performance and reliability.

Baseline Testing of Ultracapacitors for the Next Generation Launch Technology (NGLT) Project

NASA Technical Reports Server (NTRS)

Eichenberg, Dennis J.

2004-01-01

The NASA John H. Glenn Research Center initiated baseline testing of ultracapacitors for the Next Generation Launch Transportation (NGLT) project to obtain empirical data for determining the feasibility of using ultracapacitors for the project. There are large transient loads associated with NGLT that require either a very large primary energy source or an energy storage system. The primary power source used for these tests is a proton exchange membrane (PEM) fuel cell. The energy storage system can consist of devices such as batteries, flywheels, or ultracapacitors. Ultracapacitors were used for these tests. Ultracapacitors are ideal for applications such as NGLT where long life, maintenance-free operation, and excellent low-temperature performance is essential. State-of-the-art symmetric ultracapacitors were used for these tests. The ultracapacitors were interconnected in an innovative configuration to minimize interconnection impedance. PEM fuel cells provide excellent energy density, but not good power density. Ultracapacitors provide excellent power density, but not good energy density. The combination of PEM fuel cells and ultracapacitors provides a power source with excellent energy density and power density. The life of PEM fuel cells is shortened significantly by large transient loads. Ultracapacitors used in conjunction with PEM fuel cells reduce the transient loads applied to the fuel cell, and thus appreciably improves its life. PEM fuel cells were tested with and without ultracapacitors, to determine the benefits of ultracapacitors. The report concludes that the implementation of symmetric ultracapacitors in the NGLT power system can provide significant improvements in power system performance and reliability.

Design of Chitosan and Its Water Soluble Derivatives-Based Drug Carriers with Polyelectrolyte Complexes

PubMed Central

Wu, Qing-Xi; Lin, Dong-Qiang; Yao, Shan-Jing

2014-01-01

Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have been considered well-suited as biomaterials for a number of vital drug carriers with targeted/controlled release profiles, e.g., films, capsules, microcapsules. In this work, an overview highlights not only the favorable properties of chitosan and its water soluble derivatives but also the good performance of the polyelectrolyte complexes produced based on chitosan. Their various types of applications as drug carriers are reviewed in detail. PMID:25532565