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

Polyelectrolyte complexes between (cross-linked) N-carboxyethylchitosan and (quaternized) poly[2-(dimethylamino)ethyl methacrylate]: preparation, characterization, and antibacterial properties.

PubMed

Yancheva, Elena; Paneva, Dilyana; Maximova, Vera; Mespouille, Laetitia; Dubois, Philippe; Manolova, Nevena; Rashkov, Iliya

2007-03-01

Novel polyelectrolyte complexes (PECs) between N-carboxyethylchitosan (CECh) and well-defined (quaternized) poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) have been obtained. The modification of chitosan into CECh allows the preparation of PECs in a pH range in which chitosan cannot form complexes. The CECh/PDMAEMA complex is formed in a narrow pH range around 7. The quaternization of the tertiary amino groups of PDMAEMA enables complex formation with CECh both in neutral and in alkaline medium. Cross-linked CECh is also capable of forming complexes with (quaternized) PDMAEMA. The antibacterial activity of (cross-linked) CECh, (quaternized) PDMAEMA, and their complexes against Escherichia coli has been evaluated. In contrast to (quaternized) PDMAEMA, (cross-linked) CECh exhibits no antibacterial activity. The complex formation between cross-linked CECh and (quaternized) PDMAEMA results in a loss of the inherent antibacterial activity of the latter in neutral medium. In acidic medium, the complexes exhibit strong antibacterial activity due to complex disintegration and release of (quaternized) PDMAEMA.

In vivo bioactivity of rhBMP-2 delivered with novel polyelectrolyte complexation shells assembled on an alginate microbead core template.

PubMed

Abbah, Sunny-Akogwu; Liu, Jing; Lam, Raymond W M; Goh, James C H; Wong, Hee-Kit

2012-09-10

Electrostatic interactions between polycations and polyanions are being explored to fabricate polyelectrolyte complexes (PEC) that could entrap and regulate the release of a wide range of biomolecules. Here, we report the in vivo application of PEC shells fabricated from three different polycations: poly-l-ornithine (PLO), poly-l-arginine (PLA) and DEAE-dextran (DEAE-D) to condense heparin on the surface of alginate microbeads and further control the delivery of recombinant human bone morphogenetic protein 2 (rhBMP-2) in spinal fusion application. We observed large differences in the behavior of PEC shells fabricated from the cationic polyamino acids (PLO and PLA) when compared to the cationic polysaccharide, DEAE-D. Whereas DEAE-D-based PEC shells eroded and released rhBMP-2 over 2 days in vitro, PLO- and PLA-based shells retained at least 60% of loaded rhBMP-2 after 3 weeks of incubation in phosphate-buffered saline. In vivo implantation in a rat model of posterolateral spinal fusion revealed robust bone formation in the PLO- and PLA-based PEC shell groups. This resulted in a significantly enhanced mechanical stability of the fused segments. However, bone induction and biomechanical stability of spine segments implanted with DEAE-D-based carriers were significantly inferior to both PLO- and PLA-based PEC shell groups (p<0.01). From these results, we conclude that PEC shells incorporating native heparin could be used for growth factor delivery in functional bone tissue engineering application and that PLA- and PLO-based complexes could represent superior options to DEAE-D for loading and in vivo delivery of bioactive BMP-2 in this approach. Copyright © 2012 Elsevier B.V. All rights reserved.

Directing the phase behavior of polyelectrolyte complexes using chiral patterned peptides

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

Pacalin, Naomi M.; Leon, Lorraine; Tirrell, Matthew

Polyelectrolyte complexes (PECs) have a broad range of promising applications as soft materials due to their self-assembly and diversity of structure and chemical composition. Peptide polymer PECs are highly biocompatible and biodegradable, making them particularly useful for encapsulation of food additives and flavors, micellar drug delivery, medical and underwater adhesives, fetal membrane patches, and scaffolds for cell growth in tissue engineering. While parameters affecting PEC formation and stability in regards to charge effects are well researched, little is known about the effects of van der Waals interactions, hydrogen bonding, and secondary structure in these materials. Peptide chirality provides a uniquemore » opportunity to manipulate PEC phase to modulate the amount of solid-like (precipitate) or liquid-like (coacervate) character by influencing hydrogen bonding interactions among peptide chains. In previous work, we showed that chiral peptides form solid complexes, while complexes with even one racemic peptide were fluid. This raised the interesting question of how long a homochiral sequence must be to result in solid phase formation. In this work, we designed chiral patterned peptides of polyglutamic acid and polylysine ranging from 50 to 90% L-chiral residues with increasing numbers of sequential L-chiral residues before a chirality change. These polymers were mixed together to form PECs. We observed that 8 or more sequential L-chiral residues are necessary to achieve both the appearance of a precipitate phase and sustained beta-sheets in the complex, as determined by optical imaging and FTIR Spectroscopy. Less homochiral content results in formation of a coacervate phase. Thus, we show that chiral sequence can be used to control the phase transition of PECs. Understanding how to manipulate PEC phase using chiral sequence as presented here may enable tuning of the material properties to achieve the desired mechanical strength for coatings and polymer brushes, or the most effective molecular release kinetics for drug delivery applications, for example.« less

Directing the phase behavior of polyelectrolyte complexes using chiral patterned peptides

NASA Astrophysics Data System (ADS)

Pacalin, Naomi M.; Leon, Lorraine; Tirrell, Matthew

2016-10-01

Polyelectrolyte complexes (PECs) have a broad range of promising applications as soft materials due to their self-assembly and diversity of structure and chemical composition. Peptide polymer PECs are highly biocompatible and biodegradable, making them particularly useful for encapsulation of food additives and flavors, micellar drug delivery, medical and underwater adhesives, fetal membrane patches, and scaffolds for cell growth in tissue engineering. While parameters affecting PEC formation and stability in regards to charge effects are well researched, little is known about the effects of van der Waals interactions, hydrogen bonding, and secondary structure in these materials. Peptide chirality provides a unique opportunity to manipulate PEC phase to modulate the amount of solid-like (precipitate) or liquid-like (coacervate) character by influencing hydrogen bonding interactions among peptide chains. In previous work, we showed that chiral peptides form solid complexes, while complexes with even one racemic peptide were fluid. This raised the interesting question of how long a homochiral sequence must be to result in solid phase formation. In this work, we designed chiral patterned peptides of polyglutamic acid and polylysine ranging from 50 to 90% L-chiral residues with increasing numbers of sequential L-chiral residues before a chirality change. These polymers were mixed together to form PECs. We observed that 8 or more sequential L-chiral residues are necessary to achieve both the appearance of a precipitate phase and sustained β-sheets in the complex, as determined by optical imaging and FTIR Spectroscopy. Less homochiral content results in formation of a coacervate phase. Thus, we show that chiral sequence can be used to control the phase transition of PECs. Understanding how to manipulate PEC phase using chiral sequence as presented here may enable tuning of the material properties to achieve the desired mechanical strength for coatings and polymer brushes, or the most effective molecular release kinetics for drug delivery applications, for example.

Preparation and evaluation of periodontal films based on polyelectrolyte complex formation.

PubMed

Kassem, Abeer Ahmed; Ismail, Fatma Ahmed; Naggar, Viviane Fahim; Aboulmagd, Elsayed

2015-05-01

Local intra-pocket drug delivery devices can provide an effective concentration of the antimicrobial agent at the site of action with avoidance of undesirable side effects. This study explored the application of chitosan-alginate and chitosan-pectin polyelectrolyte complex (PEC) films as drug release regulators for tetracycline HCl (Tc) to treat periodontal pockets. Periodontal films with 1:1 Tc:PEC ratio were prepared using 1:1 chitosan (Ch) to sodium alginate (A) or 1:3 Ch to pectin (P). The scanning electron microscope showed acceptable film appearance and differential scanning calorimetry analysis confirmed complex formation. The in vitro release studies for both films showed a burst drug release, followed by prolonged release for 70 h. A prolonged antibacterial activity of both films against Staphylococcus aureus ATCC 6538 was observed over a period of 21 days. Aging studies indicated that the five months storage period in freezer did not significantly influence the drug release profile or the antibacterial activity of both films. Clinical evaluation showed a significant reduction in pocket depth (p < 0.0001) to their normal values (≤3 mm). PEC films could be exploited as a prolonged drug release devices for treatment of periodontal pockets.

Formation of Polyelectrolyte Complex Colloid Particles between Chitosan and Pectin with Different Degree of Esterification

NASA Astrophysics Data System (ADS)

Wang, Hui; Sun, Hongyuan; He, Jieyu

2017-12-01

The effects of degree of esterification, pectin/chitosan ratio and pH on the formation of polyelectrolyte complex colloid particles between chitosan (CS) and pectin (PE) were investigated. Low methoxyl pectin (LPE) was achieved by de-esterifying high methoxyl pectin (HPE) with pectin methyl esterase. Turbidity titration and colorimetric method was used to determine the stability of complex colloid particles. The structure and morphology of complex particles were characterized by FTIR and TEM. When pectin solution was dropped into chitosan solution, complex colloidal dispersion was stable as PE/CS mass ratio was no more than 3:2. Colloidal particles of HPE-CS complex coagulated at larger ratio of PE/CS than LPE-CS. The maximum complex occurred at pH 6.1 for HPE-CS and pH 5.7 for LPE-CS, and decreasing pH leaded to the dissociation of complex particles. Electrostatic interactions between carboxyl groups on pectin and amino groups on chitosan were confirmed by FTIR. Colloidal particle sizes ranged from about 100 nm to 400 nm with spherical shape.

Preparation of the chitosan/poly(glutamic acid)/alginate polyelectrolyte complexing hydrogel and study on its drug releasing property.

PubMed

Chen, Yu; Yan, Xiaoting; Zhao, Jian; Feng, Huaiyu; Li, Puwang; Tong, Zongrui; Yang, Ziming; Li, Sidong; Yang, Jueying; Jin, Shaohua

2018-07-01

In the current study, a novel semi-dissolution/acidification/sol-gel transition (SD-A-SGT) method was explored for the preparation of polyelectrolyte complexing (PEC) composite hydrogels with natural polymers only. A chitosan (CS) powder was uniformly dispersed in a solution of poly(glutamic acid) (PGA) and alginate (SA) to form a semi-dissolved slurry mixture that was then exposed to an gaseous acidic atmosphere. CS was gradually dissolved and interacted with PGA and SA to form a CS/PGA/SA PEC composite hydrogel with a homogeneous structure. The SD-A-SGT procedure was able to overcome the shortcomings of direct mixing method via the PEC interaction. The effects of the hydrogel composition on its structure and properties were investigated by FTIR, XRD, rheology study, XPS, SEM, and swelling kinetics. The drug delivery performance of the CS/PGA/SA hydrogel was explored using piroxicam (PXC) as a model drug. PXC was in situ embedded in the hydrogel by the SD-A-SGT method. The hydrogel exhibited pH responsive drug release behaviors that were affected by the hydrogel composition. In all, the SD-A-SGT method for preparing PEC composite hydrogels has a great application potential in constructing the CS based hydrogels as medical materials. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of the cross-linking agent on performances of NaCS-CS/WSC microcapsules.

PubMed

Wu, Qing-Xi; Xu, Xin; Wang, Zu-Li; Yao, Shan-Jing; Tong, Wang-Yu; Chen, Yan

2016-11-01

Based on the properties of oppositely charged natural polysaccharides, the polyelectrolyte complexes (PECs) prepared with chitosan-related polycationic polyelectrolytes and cellulose-related polyanionic polyelectrolytes have been widely concerned for their potential applications as micro-drug-carriers for colon. However, the poor mechanical property of the PECs becomes the obstacle encountered in practical applications. This study investigated the effect of the cross-linking agent (sodium polyphosphate, PPS) on the performances of sodium cellulose sulfate -chitosan/water soluble chitosan (NaCS-CS/WSC) microcapsules. The results revealed that PPS could penetrate through the PEC film and form tighter interior structures compared with the microcapsules without the addition of cross-linking agent. The NaCS-CS microcapsules and NaCS-WSC microcapsules with or without PPS had distinct microstructures, which could be ascribed to the different physicochemical properties of CS and WSC. During the formation process, CS can be dissolved in water under acidic conditions, while WSC can be directly dissolved and protonated in acid-free aqueous providing NH3(+) groups quickly, which resulted in the microstructure's difference. Further analysis showed the NaCS-CS-PPS microcapsules and NaCS-WSC-PPS microcapsules had lower swelling ratios due to their tighter interior microstructures that formed. The cross-linking agent had important effect on the total mass of PECs that produced; moreover, the decline of zeta potential of NaCS-CS-PPS microcapsules was lower than that of NaCS-CS microcapsules, similar trend was found in the NaCS-WSC-PPS microcapsules compared with NaCS-WSC microcapsules, indicating the PPS participated in the interactions and played a role in the microcapsules' formation process. Copyright © 2016 Elsevier B.V. All rights reserved.

Polyelectrolyte complexes of hTERT siRNA and polyethyleneimine: Effect of degree of PEG grafting on biological and cellular activity.

PubMed

Safari, Fatemeh; Tamaddon, Ali M; Zarghami, Nosratollah; Abolmali, S; Akbarzadeh, Abolfazl

2016-09-01

Gene silencing by siRNA (short interfering RNA)-targeted human telomerase reverse transcriptase (hTERT) is considered a successful strategy for cancer gene therapy. Polyelectrolyte complexes (PEC) of siRNA and cationic polymers such as polyethyleneimine (PEI) have been widely used for cellular transfection; however, they demonstrate some disadvantages such as cytotoxicity and extracellular matrix restrictions. PEG grafting technology was used in an attempt to improve the biocompatibility of PECs. Considering that this technology may compromise the cellular uptake of PECs, we aimed to study the effect of degree of PEI PEGylation on the carrier cytotoxicity, cellular association, and transfection efficiency of hTERT siRNA in the lung cancer cell line A549. Activated NHS ester of methoxy PEG-COOH 5 KDa was grafted to hyperbranched PEI 25 KDa in the molar ratios of 0.2 and 1. The copolymers were characterized by (1)H-NMR spectroscopy. PECs of PEI or PEG-g-PEI with siRNA, alone or co-incubated with heparin sulfate, were studied by the ethidium bromide exclusion assay. Cytotoxicity of the polymers (PEG-g-PEI vs PEI), alone and upon formation of PEC nanoparticles with hTERT siRNA, was determined by a validated MTT assay, in comparison to a scrambled control sequence, in A549 human lung carcinoma cells. The cellular uptake of the PECs of FITC-labeled siRNA was investigated by flow cytometry at different N/P ratios, and the silencing effect of the transfected siRNA was compared to that of the control sequence for different PECs by real time RT-PCR. The cytotoxicity of PEI decreased significantly by PEG grafting, even at a low degree of PEGylation. Moreover, the nonspecific cytotoxicity of PECs decreased by PEG grafting. PECs of PEG-g-PEI showed more biologic stability on incubation with heparin sulfate. Average particle size and zeta potential of PEC nanoparticles were diminished for those of PEG-g-PEI. The cellular association was more pronounced at an N/P ratio of 2.5 for PECs of PEI and PEG-g-PEI alike. The level of silencing of hTERT mRNA by PEC of PEG-g-PEI was sequence-dependent, and determined non-inferior when compared to the native PEI. Conclusively, the biocompatibility of PEI was improved by a low degree of PEGylation, with no adverse effect on the cellular uptake and the transfection activity. PEC nanoparticles of hTERT siRNA and PEG-g-PEI could act as a promising weapon against A549 cells, which has to be considered for an in vivo evaluation.

A novel pH-responsive hydrogel-based on calcium alginate engineered by the previous formation of polyelectrolyte complexes (PECs) intended to vaginal administration.

PubMed

Ferreira, Natália Noronha; Perez, Taciane Alvarenga; Pedreiro, Liliane Neves; Prezotti, Fabíola Garavello; Boni, Fernanda Isadora; Cardoso, Valéria Maria de Oliveira; Venâncio, Tiago; Gremião, Maria Palmira Daflon

2017-10-01

This work aimed to develop a calcium alginate hydrogel as a pH responsive delivery system for polymyxin B (PMX) sustained-release through the vaginal route. Two samples of sodium alginate from different suppliers were characterized. The molecular weight and M/G ratio determined were, approximately, 107 KDa and 1.93 for alginate_S and 32 KDa and 1.36 for alginate_V. Polymer rheological investigations were further performed through the preparation of hydrogels. Alginate_V was selected for subsequent incorporation of PMX due to the acquisition of pseudoplastic viscous system able to acquiring a differential structure in simulated vaginal microenvironment (pH 4.5). The PMX-loaded hydrogel (hydrogel_PMX) was engineered based on polyelectrolyte complexes (PECs) formation between alginate and PMX followed by crosslinking with calcium chloride. This system exhibited a morphology with variable pore sizes, ranging from 100 to 200 μm and adequate syringeability. The hydrogel liquid uptake ability in an acid environment was minimized by the previous PECs formation. In vitro tests evidenced the hydrogels mucoadhesiveness. PMX release was pH-dependent and the system was able to sustain the release up to 6 days. A burst release was observed at pH 7.4 and drug release was driven by an anomalous transport, as determined by the Korsmeyer-Peppas model. At pH 4.5, drug release correlated with Weibull model and drug transport was driven by Fickian diffusion. The calcium alginate hydrogels engineered by the previous formation of PECs showed to be a promising platform for sustained release of cationic drugs through vaginal administration.

Formulation and evaluation of polyelectrolyte complex-based matrix tablet of Isosorbide Mononitrate

PubMed Central

Syed, Iizhar Ahmed; Niveditha, P.; Ahmad, Ismail

2014-01-01

Introduction: The polyelectrolyte Complexes (PECs) are based on ionic cross-linking. They have been employed to prepare a sustained release matrix tablets. These systems are based upon the fact that their structure can entrap the drug within them. Isosorbide Mononitrate (ISMN) is an anti-anginal organic nitrate vasodilator used in the treatment of various cardiovascular disorders and prophylaxis of angina Pectoris, which is poorly absorbed from the upper GIT, hence CR formulation is desirable. Materials and Methods: Chitosan (CH)/Sodium alginate (SA), Guar gum (GG), and Xanthan gum (XG) were used as PECs, and were prepared using different proportions i.e., in 1:1 and 1:2 ratio. The optimum ratio of CH: SA, CH: GG and CH: XG was in the ratio was 1:2; these are formed due to electrostatic interaction between oppositely charged poly ions. These normally employ a hydrophilic matrix system. Matrix tablet of ISMN was formulated by using PECs as matrix forming agent by wet granulation technique. Results: The tablets were evaluated for hardness, wt variation, drug content, and in-vitro dissolution studies and found to be within limits. Release kinetics data indicated that ISMN released from the PECs-based matrix tablets of CH-SA, CH-GG and CH-XG CP in 1:1 and 1:2 ratio, followed Fickian and non-Fickian diffusion mechanism respectively. Thus, the drug release rate was extended for over a period of more than 12 h stability studies. There is no significant difference in the mean % drug released from formulation CH-X2 after storing for 3 months at 40°C/75% RH. The FT-IR spectra revealed that there was no interaction between polymers and drug, Statistical analysis showed a significant differences (P < 0.05) for the amount of ISMN released from the formulations (MXG) and formulations (CH-X2). Conclusion: Formulation CH-XG2 (1:2) showed better sustained release of highly water-soluble ISMN with the desired release rate. Thus, the formulated PECs-based matrix tablets seems to be a potential candidate for sustained drug delivery of highly soluble drug ISMN in the symptomatic therapy of angina pectoris. PMID:24678461

Durable pectin/chitosan membranes with self-assembling, water resistance and enhanced mechanical properties.

PubMed

Martins, Jéssica G; de Oliveira, Ariel C; Garcia, Patrícia S; Kipper, Matt J; Martins, Alessandro F

2018-05-15

Processing water-soluble polysaccharides, like pectin (PT), into materials with desirable stability and mechanical properties has been challenging. Here we report a new method to create water stable and mechanical resistant polyelectrolyte complex (PEC) membranes from PT and chitosan (CS) assemblies, without covalent crosslinking. This new method overcomes challenges of obtaining stable and durable complexes, by performing the complexation at low pH, enabling complex formation even when using an excess of PT, and when using PT with high degree of O-methoxylation. By performing the complexation at low pH, the complexes form with a high degree of intermolecular association, instead of forming by electrostatic complexation. This method avoids precipitation, and overcomes the aqueous instability typical of PT/CS complexes. After neutralization, the PEC membranes display features characteristic of a high degree of intermolecular association because of the self-assembling of polymer chains. The PT/CS ratio can be tuned to enhance the mechanical strength (σ = 39 MPa) of the membranes. These polysaccharide-based materials can demonstrate advantages over synthetic materials for technological applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Towards biocompatible vaccine delivery systems: interactions of colloidal PECs based on polysaccharides with HIV-1 p24 antigen.

PubMed

Drogoz, Alexandre; Munier, Séverine; Verrier, Bernard; David, Laurent; Domard, Alain; Delair, Thierry

2008-02-01

This work reports on the interactions of a model protein (p24, the capside protein of HIV-1 virus) with colloids obtained from polyelectrolyte complexes (PECs) involving two polysaccharides: chitosan and dextran sulfate (DS). The PECs were elaborated by a one-shot addition of default amounts of one counterpart to the polymer in excess. Depending on the nature of the excess polyelectrolyte, the submicrometric colloid was either positively or negatively charged. HIV-1 capsid p24 protein was chosen as antigen, the ultrapure form, lipopolysaccharide-free (endotoxin-, vaccine grade) was used in most experiments, as the level of purity of the protein had a great impact on the immobilization process. p24 sorption kinetics, isotherms, and loading capacities were investigated for positively and negatively charged particles of chitosans and dextran sulfates differing in degrees of polymerization (DP) or acetylation (DA). Compared with the positive particles, negatively charged colloids had higher binding capacities, faster kinetics, and a better stability of the adsorbed p24. Capacities up to 600 mg x g(-1) (protein-colloid) were obtained, suggesting that the protein interacted within the shell of the particles. Small-angle X-rays scattering experiments confirmed this hypothesis. Finally, the immunogenicity of the p24-covered particles was assessed for vaccine purposes in mice. The antibody titers obtained with immobilized p24 was dose dependent and in the same range as for Freund's adjuvant, a gold standard for humoral responses.

Formation of redispersible polyelectrolyte complex nanoparticles from gallic acid-chitosan conjugate and gum arabic.

PubMed

Hu, Qiaobin; Wang, Taoran; Zhou, Mingyong; Xue, Jingyi; Luo, Yangchao

2016-11-01

Polyelectrolyte complex (PEC) nanoparticles between chitosan (CS) and biomacromolecules offer better physicochemical properties as delivery vehicles for nutrients than other CS-based nanoparticles. Our major objective was to fabricate PEC nanoparticles between water soluble gallic acid-chitosan conjugate (GA-CS) and gum arabic. The optimal fabrication method, physicochemical characteristics and stability were investigated. Furthermore, we also evaluated the effects of nano spray drying technology on the morphology and redispersibility of nanoparticle powders using Buchi B-90 Nano Spray Dryer. Results showed that the mass ratio between GA-CS and gum arabic and the preparation pH had significant contributions in determining the particle size and count rate of the nanoparticles, with the ratio of 3:1 and pH 5.0 being the optimal conditions that resulted in 112.2nm and 122.9kcps. The polyethylene glycol (PEG) played a vital role in forming the well-separated spray dried nanoparticles. The most homogeneous nanoparticles with the smoothest surface were obtained when the mass ratio of GA-CS and PEG was 1:0.5. In addition, the GA-CS/gum arabic spray dried nanoparticles exhibited excellent water-redispersibiliy compared to native CS/gum arabic nanoparticles. Our results demonstrated GA-CS/gum arabic nanoparticles were successfully fabricated with promising physicochemical properties and great potential for their applications in food and pharmaceutical industries. Copyright © 2016 Elsevier B.V. All rights reserved.

Systematic study of alginate-based microcapsules by micropipette aspiration and confocal fluorescence microscopy.

PubMed

Kleinberger, Rachelle M; Burke, Nicholas A D; Dalnoki-Veress, Kari; Stöver, Harald D H

2013-10-01

Micropipette aspiration and confocal fluorescence microscopy were used to study the structure and mechanical properties of calcium alginate hydrogel beads (A beads), as well as A beads that were additionally coated with poly-L-lysine (P) and sodium alginate (A) to form, respectively, AP and APA hydrogels. A beads were found to continue curing for up to 500 h during storage in saline, due to residual calcium chloride carried over from the gelling bath. In subsequent saline washes, micropipette aspiration proved to be a sensitive indicator of gel weakening and calcium loss. Aspiration tests were used to compare capsule stiffness before and after citrate extraction of calcium. They showed that the initial gel strength is largely due to the calcium alginate gel cores, while the long term strength is solely due to the poly-L-lysine-alginate polyelectrolyte complex (PEC) shells. Confocal fluorescence microscopy showed that calcium chloride exposure after PLL deposition led to PLL redistribution into the hydrogel bead, resulting in thicker but more diffuse and weaker PEC shells. Adding a final alginate coating to form APA capsules did not significantly change the PEC membrane thickness and stiffness, but did speed the loss of calcium from the bead core. © 2013.

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.

Colloid, adhesive and release properties of nanoparticular ternary complexes between cationic and anionic polysaccharides and basic proteins like bone morphogenetic protein BMP-2.

PubMed

Petzold, R; Vehlow, D; Urban, B; Grab, A L; Cavalcanti-Adam, E A; Alt, V; Müller, M

2017-03-01

Herein we describe an interfacial local drug delivery system for bone morphogenetic protein 2 (BMP-2) based on coatings of polyelectrolyte complex (PEC) nanoparticles (NP). The application horizon is the functionalization of bone substituting materials (BSM) used for the therapy of systemic bone diseases. Nanoparticular ternary complexes of cationic and anionic polysaccharides and BMP-2 or two further model proteins, respectively, were prepared in dependence of the molar mixing ratio, pH value and of the cationic polysaccharide. As further proteins chymotrypsin (CHY) and papain (PAP) were selected, which served as model proteins for BMP-2 due to similar isoelectric points and molecular weights. As charged polysaccharides ethylenediamine modified cellulose (EDAC) and trimethylammonium modified cellulose (PQ10) were combined with cellulose sulphatesulfate (CS). Mixing diluted cationic and anionic polysaccharide and protein solutions according to a slight either anionic or cationic excess charge colloidal ternary dispersions formed, which were cast onto germanium model substrates by water evaporation. Dynamic light scattering (DLS) demonstrated, that these dispersions were colloidally stable for at least one week. Fourier Transform Infrared (FTIR) showed, that the cast protein loaded PEC NP coatings were irreversibly adhesive at the model substrate in contact to HEPES buffer and solely CHY, PAP and BMP-2 were released within long-term time scale. Advantageously, out of the three proteins BMP-2 showed the smallest initial burst and the slowest release kinetics and around 25% of the initial BMP-2 content were released within 14days. Released BMP-2 showed significant activity in the myoblast cells indicating the ability to regulate the formation of new bone. Therefore, BMP-2 loaded PEC NP are suggested as novel promising tool for the functionalization of BSM used for the therapy of systemic bone diseases. Copyright © 2016 Elsevier B.V. All rights reserved.

Kinetics of Corrosion Inhibition of Aluminum in Acidic Media by Water-Soluble Natural Polymeric Pectates as Anionic Polyelectrolyte Inhibitors.

PubMed

Hassan, Refat M; Zaafarany, Ishaq A

2013-06-17

Corrosion inhibition of aluminum (Al) in hydrochloric acid by anionic polyeletrolyte pectates (PEC) as a water-soluble natural polymer polysaccharide has been studied using both gasometric and weight loss techniques. The results drawn from these two techniques are comparable and exhibit negligible differences. The inhibition efficiency was found to increase with increasing inhibitor concentration and decrease with increasing temperature. The inhibition action of PEC on Al metal surface was found to obey the Freundlich isotherm. Factors such as the concentration and geometrical structure of the inhibitor, concentration of the corrosive medium, and temperature affecting the corrosion rates were examined. The kinetic parameters were evaluated and a suitable corrosion mechanism consistent with the kinetic results is discussed in the paper.

Kinetics of Corrosion Inhibition of Aluminum in Acidic Media by Water-Soluble Natural Polymeric Pectates as Anionic Polyelectrolyte Inhibitors

PubMed Central

Hassan, Refat M.; Zaafarany, Ishaq A.

2013-01-01

Corrosion inhibition of aluminum (Al) in hydrochloric acid by anionic polyeletrolyte pectates (PEC) as a water-soluble natural polymer polysaccharide has been studied using both gasometric and weight loss techniques. The results drawn from these two techniques are comparable and exhibit negligible differences. The inhibition efficiency was found to increase with increasing inhibitor concentration and decrease with increasing temperature. The inhibition action of PEC on Al metal surface was found to obey the Freundlich isotherm. Factors such as the concentration and geometrical structure of the inhibitor, concentration of the corrosive medium, and temperature affecting the corrosion rates were examined. The kinetic parameters were evaluated and a suitable corrosion mechanism consistent with the kinetic results is discussed in the paper. PMID:28809282

Strategies for Improving siRNA-Induced Gene Silencing Efficiency

PubMed Central

Safari, Fatemeh; Rahmani Barouji, Solmaz; Tamaddon, Ali Mohammad

2017-01-01

Purpose: Human telomerase reverse transcriptase (hTERT) plays a crucial role in tumorigenesis and progression of cancers. Gene silencing of hTERT by short interfering RNA (siRNA) is considered as a promising strategy for cancer gene therapy. Various algorithms have been devised for designing a high efficient siRNA which is a significant issue in the clinical usage. Thereby, in the present study, the relation of siRNA designing criteria and the gene silencing efficiency was evaluated. Methods: The siRNA sequences were designed and characterized by using on line soft wares. Cationic co-polymer (polyethylene glycol-g-polyethylene imine (PEG-g-PEI)) was used for the construction of polyelectrolyte complexes (PECs) containing siRNAs. The cellular uptake of the PECs was evaluated. The gene silencing efficiency of different siRNA sequences was investigated and the effect of observing the rational designing on the functionality of siRNAs was assessed. Results: The size of PEG-g-PEI siRNA with N/P (Nitrogen/Phosphate) ratio of 2.5 was 114 ± 0.645 nm. The transfection efficiency of PECs was desirable (95.5% ± 2.4%.). The results of Real-Time PCR showed that main sequence (MS) reduced the hTERT expression up to 90% and control positive sequence (CPS) up to 63%. These findings demonstrated that the accessibility to the target site has priority than the other criteria such as sequence preferences and thermodynamic features. Conclusion: siRNA opens a hopeful window in cancer therapy which provides a convenient and tolerable therapeutic approach. Thereby, using the set of criteria and rational algorithms in the designing of siRNA remarkably affect the gene silencing efficiency. PMID:29399550

Strategies for Improving siRNA-Induced Gene Silencing Efficiency.

PubMed

Safari, Fatemeh; Rahmani Barouji, Solmaz; Tamaddon, Ali Mohammad

2017-12-01

Purpose: Human telomerase reverse transcriptase (hTERT) plays a crucial role in tumorigenesis and progression of cancers. Gene silencing of hTERT by short interfering RNA (siRNA) is considered as a promising strategy for cancer gene therapy. Various algorithms have been devised for designing a high efficient siRNA which is a significant issue in the clinical usage. Thereby, in the present study, the relation of siRNA designing criteria and the gene silencing efficiency was evaluated. Methods: The siRNA sequences were designed and characterized by using on line soft wares. Cationic co-polymer (polyethylene glycol-g-polyethylene imine (PEG-g-PEI)) was used for the construction of polyelectrolyte complexes (PECs) containing siRNAs. The cellular uptake of the PECs was evaluated. The gene silencing efficiency of different siRNA sequences was investigated and the effect of observing the rational designing on the functionality of siRNAs was assessed. Results: The size of PEG-g-PEI siRNA with N/P (Nitrogen/Phosphate) ratio of 2.5 was 114 ± 0.645 nm. The transfection efficiency of PECs was desirable (95.5% ± 2.4%.). The results of Real-Time PCR showed that main sequence (MS) reduced the hTERT expression up to 90% and control positive sequence (CPS) up to 63%. These findings demonstrated that the accessibility to the target site has priority than the other criteria such as sequence preferences and thermodynamic features. Conclusion: siRNA opens a hopeful window in cancer therapy which provides a convenient and tolerable therapeutic approach. Thereby, using the set of criteria and rational algorithms in the designing of siRNA remarkably affect the gene silencing efficiency.

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.

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.

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

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.

Influence of Hydrophobicity on Polyelectrolyte Complexation

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

Sadman, Kazi; Wang, Qifeng; Chen, Yaoyao

Polyelectrolyte complexes are a fascinating class of soft materials that can span the full spectrum of mechanical properties from low viscosity fluids to glassy solids. This spectrum can be accessed by modulating the extent of electrostatic association in these complexes. However, to realize the full potential of polyelectrolyte complexes as functional materials their molecular level details need to be clearly correlated with their mechanical response. The present work demonstrates that by making simple amendments to the chain architecture it is possible to affect the salt responsiveness of polyelectrolyte complexes in a systematic manner. This is achieved by quaternizing poly(4-vinylpyridine) (QVP)more » with methyl, ethyl and propyl substituents– thereby increasing the hydrophobicity with increasing side chain length– and complexing them with a common anionic polyelectrolyte, poly(styrene sulfonate). The mechanical 1 ACS Paragon Plus Environment behavior of these complexes is compared to the more hydrophilic system of poly(styrene sulfonate) and poly(diallyldimethylammonium) by quantifying the swelling behavior in response to salt stimuli. More hydrophobic complexes are found to be more resistant to doping by salt, yet the mechanical properties of the complex remain contingent on the overall swelling ratio of the complex itself, following near universal swelling-modulus master curves that are quantified in this work. The rheological behavior of QVP complex coacervates are found to be approximately the same, only requiring higher salt concentrations to overcome strong hydrophobic interactions, demonstrating that hydrophobicity can be used as an important parameter for tuning the stability of polyelectrolyte complexes in general, while still preserving the ability to be processed “saloplastically”.« less

Influence of Hydrophobicity on Polyelectrolyte Complexation

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

Sadman, Kazi; Wang, Qifeng; Chen, Yaoyao

Polyelectrolyte complexes are a fascinating class of soft materials that can span the full spectrum of mechanical properties from low-viscosity fluids to glassy solids. This spectrum can be accessed by modulating the extent of electrostatic association in these complexes. However, to realize the full potential of polyelectrolyte complexes as functional materials, their molecular level details need to be clearly correlated with their mechanical response. The present work demonstrates that by making simple amendments to the chain architecture, it is possible to affect the salt responsiveness of polyelectrolyte complexes in a systematic manner. This is achieved by quaternizing poly(4-vinylpyridine) (QVP) withmore » methyl, ethyl, and propyl substituents—thereby increasing the hydrophobicity with increasing side chain length—and complexing them with a common anionic polyelectrolyte, poly(styrenesulfonate). The mechanical behavior of these complexes is compared to the more hydrophilic system of poly(styrenesulfonate) and poly(diallyldimethylammonium) by quantifying the swelling behavior in response to salt stimuli. More hydrophobic complexes are found to be more resistant to doping by salt, yet the mechanical properties of the complex remain contingent on the overall swelling ratio of the complex itself, following near universal swelling–modulus master curves that are quantified in this work. Furthermore, the rheological behaviors of QVP complex coacervates are found to be approximately the same, only requiring higher salt concentrations to overcome strong hydrophobic interactions, demonstrating that hydrophobicity can be used as an important parameter for tuning the stability of polyelectrolyte complexes in general, while still preserving the ability to be processed “saloplastically”.« less

Influence of Hydrophobicity on Polyelectrolyte Complexation

DOE PAGES

Sadman, Kazi; Wang, Qifeng; Chen, Yaoyao; ...

2017-11-16

Polyelectrolyte complexes are a fascinating class of soft materials that can span the full spectrum of mechanical properties from low-viscosity fluids to glassy solids. This spectrum can be accessed by modulating the extent of electrostatic association in these complexes. However, to realize the full potential of polyelectrolyte complexes as functional materials, their molecular level details need to be clearly correlated with their mechanical response. The present work demonstrates that by making simple amendments to the chain architecture, it is possible to affect the salt responsiveness of polyelectrolyte complexes in a systematic manner. This is achieved by quaternizing poly(4-vinylpyridine) (QVP) withmore » methyl, ethyl, and propyl substituents—thereby increasing the hydrophobicity with increasing side chain length—and complexing them with a common anionic polyelectrolyte, poly(styrenesulfonate). The mechanical behavior of these complexes is compared to the more hydrophilic system of poly(styrenesulfonate) and poly(diallyldimethylammonium) by quantifying the swelling behavior in response to salt stimuli. More hydrophobic complexes are found to be more resistant to doping by salt, yet the mechanical properties of the complex remain contingent on the overall swelling ratio of the complex itself, following near universal swelling–modulus master curves that are quantified in this work. Furthermore, the rheological behaviors of QVP complex coacervates are found to be approximately the same, only requiring higher salt concentrations to overcome strong hydrophobic interactions, demonstrating that hydrophobicity can be used as an important parameter for tuning the stability of polyelectrolyte complexes in general, while still preserving the ability to be processed “saloplastically”.« less

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.

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.

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

Design of chitosan and its water soluble derivatives-based drug carriers with polyelectrolyte complexes.

PubMed

Wu, Qing-Xi; Lin, Dong-Qiang; Yao, Shan-Jing

2014-12-19

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.

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

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.

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.

Inhibition of atherosclerosis-promoting microRNAs via targeted polyelectrolyte complex micelles

PubMed Central

Kuo, Cheng-Hsiang; Leon, Lorraine; Chung, Eun Ji; Huang, Ru-Ting; Sontag, Timothy J.; Reardon, Catherine A.; Getz, Godfrey S.; Tirrell, Matthew; Fang, Yun

2015-01-01

Polyelectrolyte complex micelles have great potential as gene delivery vehicles because of their ability to encapsulate charged nucleic acids forming a core by neutralizing their charge, while simultaneously protecting the nucleic acids from non-specific interactions and enzymatic degradation. Furthermore, to enhance specificity and transfection efficiency, polyelectrolyte complex micelles can be modified to include targeting capabilities. Here, we describe the design of targeted polyelectrolyte complex micelles containing inhibitors against dys-regulated microRNAs (miRNAs) that promote atherosclerosis, a leading cause of human mortality and morbidity. Inhibition of dys-regulated miRNAs in diseased cells associated with atherosclerosis has resulted in therapeutic efficacy in animal models and has been proposed to treat human diseases. However, the non-specific targeting of microRNA inhibitors via systemic delivery has remained an issue that may cause unwanted side effects. For this reason, we incorporated two different peptide sequences to our miRNA inhibitor containing polyelectrolyte complex micelles. One of the peptides (Arginine-Glutamic Acid-Lysine-Alanine or REKA) was used in another micellar system that demonstrated lesion-specific targeting in a mouse model of atherosclerosis. The other peptide (Valine-Histidine-Proline-Lysine-Glutamine-Histidine-Arginine or VHPKQHR) was identified via phage display and targets vascular endothelial cells through the vascular cell adhesion molecule-1 (VCAM-1). In this study we have tested the in vitro efficacy and efficiency of lesion- and cell-specific delivery of microRNA inhibitors to the cells associated with atherosclerotic lesions via peptide-targeted polyelectrolyte complex micelles. Our results show that REKA-containing micelles (fibrin-targeting) and VHPKQHR-containing micelles (VCAM-1 targeting) can be used to carry and deliver microRNA inhibitors into macrophages and human endothelial cells, respectively. Additionally, the functionality of miRNA inhibitors in cells was demonstrated by analyzing miRNA expression as well as the expression or the biological function of its downstream target protein. Our study provides the first demonstration of targeting dys-regulated miRNAs in atherosclerosis using targeted polyelectrolyte complex micelles and holds promising potential for translational applications. PMID:25685357

Chirality-selected phase behaviour in ionic polypeptide complexes

DOE PAGES

Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; ...

2015-01-14

In this study, polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with amore » β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation.« less

Interaction between like-charged polyelectrolyte-colloid complexes in electrolyte solutions: a Monte Carlo simulation study in the Debye-Hückel approximation.

PubMed

Truzzolillo, D; Bordi, F; Sciortino, F; Sennato, S

2010-07-14

We study the effective interaction between differently charged polyelectrolyte-colloid complexes in electrolyte solutions via Monte Carlo simulations. These complexes are formed when short and flexible polyelectrolyte chains adsorb onto oppositely charged colloidal spheres, dispersed in an electrolyte solution. In our simulations the bending energy between adjacent monomers is small compared to the electrostatic energy, and the chains, once adsorbed, do not exchange with the solution, although they rearrange on the particles surface to accommodate further adsorbing chains or due to the electrostatic interaction with neighbor complexes. Rather unexpectedly, when two interacting particles approach each other, the rearrangement of the surface charge distribution invariably produces antiparallel dipolar doublets that invert their orientation at the isoelectric point. These findings clearly rule out a contribution of dipole-dipole interactions to the observed attractive interaction between the complexes, pointing out that such suspensions cannot be considered dipolar fluids. On varying the ionic strength of the electrolyte, we find that a screening length kappa(-1), short compared with the size of the colloidal particles, is required in order to observe the attraction between like-charged complexes due to the nonuniform distribution of the electric charge on their surface ("patch attraction"). On the other hand, by changing the polyelectrolyte/particle charge ratio xi(s), the interaction between like-charged polyelectrolyte-decorated particles, at short separations, evolves from purely repulsive to strongly attractive. Hence, the effective interaction between the complexes is characterized by a potential barrier, whose height depends on the net charge and on the nonuniformity of their surface charge distribution.

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

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.

Definition of a consensus DNA-binding site for PecS, a global regulator of virulence gene expression in Erwinia chrysanthemi and identification of new members of the PecS regulon.

PubMed

Rouanet, Carine; Reverchon, Sylvie; Rodionov, Dmitry A; Nasser, William

2004-07-16

In Erwinia chrysanthemi, production of pectic enzymes is modulated by a complex network involving several regulators. One of them, PecS, which belongs to the MarR family, also controls the synthesis of various other virulence factors, such as cellulases and indigoidine. Here, the PecS consensus-binding site is defined by combining a systematic evolution of ligands by an exponential enrichment approach and mutational analyses. The consensus consists of a 23-base pair palindromic-like sequence (C(-11)G(-10)A(-9)N(-8)W(-7)T(-6)C(-5)G(-4)T(-3)A(-2))T(-1)A(0)T(1)(T(2)A(3)C(4)G(5)A(6)N(7)N(8)N(9)C(10)G(11)). Mutational experiments revealed that (i) the palindromic organization is required for the binding of PecS, (ii) the very conserved part of the consensus (-6 to 6) allows for a specific interaction with PecS, but the presence of the relatively degenerated bases located apart significantly increases PecS affinity, (iii) the four bases G, A, T, and C are required for efficient binding of PecS, and (iv) the presence of several binding sites on the same promoter increases the affinity of PecS. This consensus is detected in the regions involved in PecS binding on the previously characterized target genes. This variable consensus is in agreement with the observation that the members of the MarR family are able to bind various DNA targets as dimers by means of a winged helix DNA-binding motif. Binding of PecS on a promoter region containing the defined consensus results in a repression of gene transcription in vitro. Preliminary scanning of the E. chrysanthemi genome sequence with the consensus revealed the presence of strong PecS-binding sites in the intergenic region between fliE and fliFGHIJKLMNOPQR which encode proteins involved in the biogenesis of flagellum. Accordingly, PecS directly represses fliE expression. Thus, PecS seems to control the synthesis of virulence factors required for the key steps of plant infection.

PecS is a global regulator of the symptomatic phase in the phytopathogenic bacterium Erwinia chrysanthemi 3937.

PubMed

Hommais, Florence; Oger-Desfeux, Christine; Van Gijsegem, Frédérique; Castang, Sandra; Ligori, Sandrine; Expert, Dominique; Nasser, William; Reverchon, Sylvie

2008-11-01

Pathogenicity of the enterobacterium Erwinia chrysanthemi (Dickeya dadantii), the causative agent of soft-rot disease in many plants, is a complex process involving several factors whose production is subject to temporal regulation during infection. PecS is a transcriptional regulator that controls production of various virulence factors. Here, we used microarray analysis to define the PecS regulon and demonstrated that PecS notably regulates a wide range of genes that could be linked to pathogenicity and to a group of genes concerned with evading host defenses. Among the targets are the genes encoding plant cell wall-degrading enzymes and secretion systems and the genes involved in flagellar biosynthesis, biosurfactant production, and the oxidative stress response, as well as genes encoding toxin-like factors such as NipE and hemolysin-coregulated proteins. In vitro experiments demonstrated that PecS interacts with the regulatory regions of five new targets: an oxidative stress response gene (ahpC), a biosurfactant synthesis gene (rhlA), and genes encoding exported proteins related to other plant-associated bacterial proteins (nipE, virK, and avrL). The pecS mutant provokes symptoms more rapidly and with more efficiency than the wild-type strain, indicating that PecS plays a critical role in the switch from the asymptomatic phase to the symptomatic phase. Based on this, we propose that the temporal regulation of the different groups of genes required for the asymptomatic phase and the symptomatic phase is, in part, the result of a gradual modulation of PecS activity triggered during infection in response to changes in environmental conditions emerging from the interaction between both partners.

PecS Is a Global Regulator of the Symptomatic Phase in the Phytopathogenic Bacterium Erwinia chrysanthemi 3937▿ †

PubMed Central

Hommais, Florence; Oger-Desfeux, Christine; Van Gijsegem, Frédérique; Castang, Sandra; Ligori, Sandrine; Expert, Dominique; Nasser, William; Reverchon, Sylvie

2008-01-01

Pathogenicity of the enterobacterium Erwinia chrysanthemi (Dickeya dadantii), the causative agent of soft-rot disease in many plants, is a complex process involving several factors whose production is subject to temporal regulation during infection. PecS is a transcriptional regulator that controls production of various virulence factors. Here, we used microarray analysis to define the PecS regulon and demonstrated that PecS notably regulates a wide range of genes that could be linked to pathogenicity and to a group of genes concerned with evading host defenses. Among the targets are the genes encoding plant cell wall-degrading enzymes and secretion systems and the genes involved in flagellar biosynthesis, biosurfactant production, and the oxidative stress response, as well as genes encoding toxin-like factors such as NipE and hemolysin-coregulated proteins. In vitro experiments demonstrated that PecS interacts with the regulatory regions of five new targets: an oxidative stress response gene (ahpC), a biosurfactant synthesis gene (rhlA), and genes encoding exported proteins related to other plant-associated bacterial proteins (nipE, virK, and avrL). The pecS mutant provokes symptoms more rapidly and with more efficiency than the wild-type strain, indicating that PecS plays a critical role in the switch from the asymptomatic phase to the symptomatic phase. Based on this, we propose that the temporal regulation of the different groups of genes required for the asymptomatic phase and the symptomatic phase is, in part, the result of a gradual modulation of PecS activity triggered during infection in response to changes in environmental conditions emerging from the interaction between both partners. PMID:18790868

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.

The excited states of a porphine-quinone complex under an external electrostatic field calculated by TDDFT

NASA Astrophysics Data System (ADS)

Aittala, Pekka J.; Cramariuc, Oana; Hukka, Terttu I.

2011-01-01

The potential energy curves (PECs) of the Q, B, and the lowest charge transfer (CT) states of a porphine-2,5-dimethyl-1,4-benzoquinone (PQ) complex have been studied by using the time-dependent density functional theory (TDDFT) with the CAM-B3LYP functional without and with the presence of an external electrostatic field. The PECs calculated using CAM-B3LYP with the original parameters α = 0.19, β = 0.65, and μ = 0.33 a0-1 are practically identical with those obtained using BH&HLYP. Applying of CAM-B3LYP with parameters α = 0.19, β = 0.81, and μ = 0.25 a0-1 yields PECs of the excited states that agree well with the PECs calculated previously using the CC2 method.

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

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.

Self-assembly of polyelectrolyte surfactant complexes using large scale MD simulation

NASA Astrophysics Data System (ADS)

Goswami, Monojoy; Sumpter, Bobby

2014-03-01

Polyelectrolytes (PE) and surfactants are known to form interesting structures with varied properties in aqueous solutions. The morphological details of the PE-surfactant complexes depend on a combination of polymer backbone, electrostatic interactions and hydrophobic interactions. We study the self-assembly of cationic PE and anionic surfactants complexes in dilute condition. The importance of such complexes of PE with oppositely charged surfactants can be found in biological systems, such as immobilization of enzymes in polyelectrolyte complexes or nonspecific association of DNA with protein. Many useful properties of PE surfactant complexes come from the highly ordered structures of surfactant self-assembly inside the PE aggregate which has applications in industry. We do large scale molecular dynamics simulation using LAMMPS to understand the structure and dynamics of PE-surfactant systems. Our investigation shows highly ordered pearl-necklace structures that have been observed experimentally in biological systems. We investigate many different properties of PE-surfactant complexation for different parameter ranges that are useful for pharmaceutical, engineering and biological applications.

Effects on communicative requesting and speech development of the Picture Exchange Communication System in children with characteristics of autism.

PubMed

Ganz, Jennifer B; Simpson, Richard L

2004-08-01

Few studies on augmentative and alternative communication (AAC) systems have addressed the potential for such systems to impact word utterances in children with autism spectrum disorders (ASD). The Picture Exchange Communication System (PECS) is an AAC system designed specifically to minimize difficulties with communication skills experienced by individuals with ASD. The current study examined the role of PECS in improving the number of words spoken, increasing the complexity and length of phrases, and decreasing the non-word vocalizations of three young children with ASD and developmental delays (DD) with related characteristics. Participants were taught Phases 1-4 of PECS (i.e., picture exchange, increased distance, picture discrimination, and sentence construction). The results indicated that PECS was mastered rapidly by the participants and word utterances increased in number of words and complexity of grammar.

Complex coacervation in charge complementary biopolymers: Electrostatic versus surface patch binding.

PubMed

Pathak, Jyotsana; Priyadarshini, Eepsita; Rawat, Kamla; Bohidar, H B

2017-12-01

In this review, a number of systems are described to demonstrate the effect of polyelectrolyte chain stiffness (persistence length) on the coacervation phenomena, after we briefly review the field. We consider two specific types of complexation/coacervation: in the first type, DNA is used as a fixed substrate binding to flexible polyions such as gelatin A, bovine serum albumin and chitosan (large persistence length polyelectrolyte binding to low persistence length biopolymer), and in the second case, different substrates such as gelatin A, bovine serum albumin, and chitosan were made to bind to a polyion gelatin B (low persistence length substrate binding to comparable persistence length polyion). Polyelectrolyte chain flexibility was found to have remarkable effect on the polyelectrolyte-protein complex coacervation. The competitive interplay of electrostatic versus surface patch binding (SPB) leading to associative interaction followed by complex coacervation between these biopolymers is elucidated. We modelled the SPB interaction in terms of linear combination of attractive and repulsive Coulombic forces with respect to the solution ionic strength. The aforesaid interactions were established via a universal phase diagram, considering the persistence length of polyion as the sole independent variable. Copyright © 2017 Elsevier B.V. All rights reserved.

LETTER TO THE EDITOR: Iteratively-coupled propagating exterior complex scaling method for electron hydrogen collisions

NASA Astrophysics Data System (ADS)

Bartlett, Philip L.; Stelbovics, Andris T.; Bray, Igor

2004-02-01

A newly-derived iterative coupling procedure for the propagating exterior complex scaling (PECS) method is used to efficiently calculate the electron-impact wavefunctions for atomic hydrogen. An overview of this method is given along with methods for extracting scattering cross sections. Differential scattering cross sections at 30 eV are presented for the electron-impact excitation to the n = 1, 2, 3 and 4 final states, for both PECS and convergent close coupling (CCC), which are in excellent agreement with each other and with experiment. PECS results are presented at 27.2 eV and 30 eV for symmetric and asymmetric energy-sharing triple differential cross sections, which are in excellent agreement with CCC and exterior complex scaling calculations, and with experimental data. At these intermediate energies, the efficiency of the PECS method with iterative coupling has allowed highly accurate partial-wave solutions of the full Schrödinger equation, for L les 50 and a large number of coupled angular momentum states, to be obtained with minimal computing resources.

Effect of complexing agent on the photoelectrochemical properties of bath deposited CdS thin films

NASA Astrophysics Data System (ADS)

Patil, S. B.; Singh, A. K.

2010-02-01

In the present paper photoelectrochemical (PEC) performance of bath deposited CdS thin films based on complexing agents i.e. ammonia and triethanolamine (TEA) has been discussed. Effect of annealing has also been analyzed. The as-deposited and annealed (at 523 K for 1 h in air) films were characterized by X-ray diffraction (XRD), ultraviolet-visible (UV-vis) absorption spectroscopy, SEM, electrochemical impedance spectroscopy (EIS), and PEC properties. XRD studies revealed that the films were nanocrystalline in nature with mixed hexagonal and cubic phases. TEA complex resulted in better crystallinity. Further improvement in the crystallinity of the films was observed after air annealing. The marigold flower-like structure, in addition to flakes morphology, was observed with TEA complex, whereas for ammonia complex only flakes morphology was observed. The UV-vis absorption studies revealed that the optical absorption edge for the films with ammonia and TEA complex was around 475 nm and 500 nm, respectively. Annealing of the films resulted in red shift in the UV-vis absorption. The PEC cell performance of CdS films was found to be strongly affected by crystallinity and morphology of the films resulted due to complexing agent and annealing. The air annealed film deposited using TEA complex showed maximum short circuit current density ( Jsc) and open circuit voltage ( Voc) i.e. 99 μA/cm 2 and 376 mV respectively, under 10 mW/cm 2 of illumination. The films deposited using TEA complex showed good stability under PEC cell conditions.

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.

Macrophage Migration Inhibitory Factor Mediates Proliferative GN via CD74

PubMed Central

Djudjaj, Sonja; Lue, Hongqi; Rong, Song; Papasotiriou, Marios; Klinkhammer, Barbara M.; Zok, Stephanie; Klaener, Ole; Braun, Gerald S.; Lindenmeyer, Maja T.; Cohen, Clemens D.; Bucala, Richard; Tittel, Andre P.; Kurts, Christian; Moeller, Marcus J.; Floege, Juergen; Ostendorf, Tammo

2016-01-01

Pathologic proliferation of mesangial and parietal epithelial cells (PECs) is a hallmark of various glomerulonephritides. Macrophage migration inhibitory factor (MIF) is a pleiotropic cytokine that mediates inflammation by engagement of a receptor complex involving the components CD74, CD44, CXCR2, and CXCR4. The proliferative effects of MIF may involve CD74 together with the coreceptor and PEC activation marker CD44. Herein, we analyzed the effects of local glomerular MIF/CD74/CD44 signaling in proliferative glomerulonephritides. MIF, CD74, and CD44 were upregulated in the glomeruli of patients and mice with proliferative glomerulonephritides. During disease, CD74 and CD44 were expressed de novo in PECs and colocalized in both PECs and mesangial cells. Stress stimuli induced MIF secretion from glomerular cells in vitro and in vivo, in particular from podocytes, and MIF stimulation induced proliferation of PECs and mesangial cells via CD74. In murine crescentic GN, Mif-deficient mice were almost completely protected from glomerular injury, the development of cellular crescents, and the activation and proliferation of PECs and mesangial cells, whereas wild-type mice were not. Bone marrow reconstitution studies showed that deficiency of both nonmyeloid and bone marrow–derived Mif reduced glomerular cell proliferation and injury. In contrast to wild-type mice, Cd74-deficient mice also were protected from glomerular injury and ensuing activation and proliferation of PECs and mesangial cells. Our data suggest a novel molecular mechanism and glomerular cell crosstalk by which local upregulation of MIF and its receptor complex CD74/CD44 mediate glomerular injury and pathologic proliferation in GN. PMID:26453615

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.

One-Step Generation of Multifunctional Polyelectrolyte Microcapsules via Nanoscale Interfacial Complexation in Emulsion (NICE)

DOE PAGES

Kim, Miju; Yeo, Seon Ju; Highley, Christopher B.; ...

2015-07-14

Polyelectrolyte microcapsules represent versatile stimuli-responsive structures that enable the encapsulation, protection, and release of active agents. Their conventional preparation methods, however, tend to be time-consuming, yield low encapsulation efficiency, and seldom allow for the dual incorporation of hydrophilic and hydrophobic materials, limiting their widespread utilization. In this work, we present a method to fabricate stimuli-responsive polyelectrolyte microcapsules in one step based on nanoscale interfacial complexation in emulsions (NICE) followed by spontaneous droplet hatching. NICE microcapsules can incorporate both hydrophilic and hydrophobic materials and also can be induced to trigger the release of encapsulated materials by changes in the solution pHmore » or ionic strength. We also show that NICE microcapsules can be functionalized with nanomaterials to exhibit useful functionality, such as response to a magnetic field and disassembly in response to light. NICE represents a potentially transformative method to prepare multifunctional nanoengineered polyelectrolyte microcapsules for various applications such as drug delivery and cell mimicry.« less

One-Step Generation of Multifunctional Polyelectrolyte Microcapsules via Nanoscale Interfacial Complexation in Emulsion (NICE).

PubMed

Kim, Miju; Yeo, Seon Ju; Highley, Christopher B; Burdick, Jason A; Yoo, Pil J; Doh, Junsang; Lee, Daeyeon

2015-08-25

Polyelectrolyte microcapsules represent versatile stimuli-responsive structures that enable the encapsulation, protection, and release of active agents. Their conventional preparation methods, however, tend to be time-consuming, yield low encapsulation efficiency, and seldom allow for the dual incorporation of hydrophilic and hydrophobic materials, limiting their widespread utilization. In this work, we present a method to fabricate stimuli-responsive polyelectrolyte microcapsules in one step based on nanoscale interfacial complexation in emulsions (NICE) followed by spontaneous droplet hatching. NICE microcapsules can incorporate both hydrophilic and hydrophobic materials and also can be induced to trigger the release of encapsulated materials by changes in the solution pH or ionic strength. We also show that NICE microcapsules can be functionalized with nanomaterials to exhibit useful functionality, such as response to a magnetic field and disassembly in response to light. NICE represents a potentially transformative method to prepare multifunctional nanoengineered polyelectrolyte microcapsules for various applications such as drug delivery and cell mimicry.

One-Step Generation of Multifunctional Polyelectrolyte Microcapsules via Nanoscale Interfacial Complexation in Emulsion (NICE)

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

Kim, Miju; Yeo, Seon Ju; Highley, Christopher B.

Polyelectrolyte microcapsules represent versatile stimuli-responsive structures that enable the encapsulation, protection, and release of active agents. Their conventional preparation methods, however, tend to be time-consuming, yield low encapsulation efficiency, and seldom allow for the dual incorporation of hydrophilic and hydrophobic materials, limiting their widespread utilization. In this work, we present a method to fabricate stimuli-responsive polyelectrolyte microcapsules in one step based on nanoscale interfacial complexation in emulsions (NICE) followed by spontaneous droplet hatching. NICE microcapsules can incorporate both hydrophilic and hydrophobic materials and also can be induced to trigger the release of encapsulated materials by changes in the solution pHmore » or ionic strength. We also show that NICE microcapsules can be functionalized with nanomaterials to exhibit useful functionality, such as response to a magnetic field and disassembly in response to light. NICE represents a potentially transformative method to prepare multifunctional nanoengineered polyelectrolyte microcapsules for various applications such as drug delivery and cell mimicry.« less

Complexation behavior of oppositely charged polyelectrolytes: Effect of charge distribution

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

Zhao, Mingtian; Li, Baohui, E-mail: dliang@pku.edu.cn, E-mail: baohui@nankai.edu.cn; Zhou, Jihan

Complexation behavior of oppositely charged polyelectrolytes in a solution is investigated using a combination of computer simulations and experiments, focusing on the influence of polyelectrolyte charge distributions along the chains on the structure of the polyelectrolyte complexes. The simulations are performed using Monte Carlo with the replica-exchange algorithm for three model systems where each system is composed of a mixture of two types of oppositely charged model polyelectrolyte chains (EGEG){sub 5}/(KGKG){sub 5}, (EEGG){sub 5}/(KKGG){sub 5}, and (EEGG){sub 5}/(KGKG){sub 5}, in a solution including explicit solvent molecules. Among the three model systems, only the charge distributions along the chains are notmore » identical. Thermodynamic quantities are calculated as a function of temperature (or ionic strength), and the microscopic structures of complexes are examined. It is found that the three systems have different transition temperatures, and form complexes with different sizes, structures, and densities at a given temperature. Complex microscopic structures with an alternating arrangement of one monolayer of E/K monomers and one monolayer of G monomers, with one bilayer of E and K monomers and one bilayer of G monomers, and with a mixture of monolayer and bilayer of E/K monomers in a box shape and a trilayer of G monomers inside the box are obtained for the three mixture systems, respectively. The experiments are carried out for three systems where each is composed of a mixture of two types of oppositely charged peptide chains. Each peptide chain is composed of Lysine (K) and glycine (G) or glutamate (E) and G, in solution, and the chain length and amino acid sequences, and hence the charge distribution, are precisely controlled, and all of them are identical with those for the corresponding model chain. The complexation behavior and complex structures are characterized through laser light scattering and atomic force microscopy measurements. The order of the apparent weight-averaged molar mass and the order of density of complexes observed from the three experimental systems are qualitatively in agreement with those predicted from the simulations.« less

Phase behaviour and structure of stable complexes of oppositely charged polyelectrolytes

NASA Astrophysics Data System (ADS)

Mengarelli, V.; Auvray, L.; Zeghal, M.

2009-03-01

We study the formation and structure of stable electrostatic complexes between oppositely charged polyelectrolytes, a long polymethacrylic acid and a shorter polyethylenimine, at low pH, where the polyacid is weakly charged. We explore the phase diagram as a function of the charge and concentration ratio of the constituents. In agreement with theory, turbidity and ζ potential measurements show two distinct regimes of weak and strong complexation, which appear successively as the pH is increased and are separated by a well-defined limit. Weak complexes observed by neutron scattering and contrast matching have an open, non-compact structure, while strong complexes are condensed.

Molecular Structure and Sequence in Complex Coacervates

NASA Astrophysics Data System (ADS)

Sing, Charles; Lytle, Tyler; Madinya, Jason; Radhakrishna, Mithun

Oppositely-charged polyelectrolytes in aqueous solution can undergo associative phase separation, in a process known as complex coacervation. This results in a polyelectrolyte-dense phase (coacervate) and polyelectrolyte-dilute phase (supernatant). There remain challenges in understanding this process, despite a long history in polymer physics. We use Monte Carlo simulation to demonstrate that molecular features (charge spacing, size) play a crucial role in governing the equilibrium in coacervates. We show how these molecular features give rise to strong monomer sequence effects, due to a combination of counterion condensation and correlation effects. We distinguish between structural and sequence-based correlations, which can be designed to tune the phase diagram of coacervation. Sequence effects further inform the physical understanding of coacervation, and provide the basis for new coacervation models that take monomer-level features into account.

Effects of conformational ordering on protein/polyelectrolyte electrostatic complexation: ionic binding and chain stiffening

PubMed Central

Cao, Yiping; Fang, Yapeng; Nishinari, Katsuyoshi; Phillips, Glyn O.

2016-01-01

Coupling of electrostatic complexation with conformational transition is rather general in protein/polyelectrolyte interaction and has important implications in many biological processes and practical applications. This work studied the electrostatic complexation between κ-carrageenan (κ-car) and type B gelatin, and analyzed the effects of the conformational ordering of κ-car induced upon cooling in the presence of potassium chloride (KCl) or tetramethylammonium iodide (Me4NI). Experimental results showed that the effects of conformational ordering on protein/polyelectrolyte electrostatic complexation can be decomposed into ionic binding and chain stiffening. At the initial stage of conformational ordering, electrostatic complexation can be either suppressed or enhanced due to the ionic bindings of K+ and I− ions, which significantly alter the charge density of κ-car or occupy the binding sites of gelatin. Beyond a certain stage of conformational ordering, i.e., helix content θ > 0.30, the effect of chain stiffening, accompanied with a rapid increase in helix length ζ, becomes dominant and tends to dissociate the electrostatic complexation. The effect of chain stiffening can be theoretically interpreted in terms of double helix association. PMID:27030165

Electron- and positron-impact atomic scattering calculations using propagating exterior complex scaling

NASA Astrophysics Data System (ADS)

Bartlett, P. L.; Stelbovics, A. T.; Rescigno, T. N.; McCurdy, C. W.

2007-11-01

Calculations are reported for four-body electron-helium collisions and positron-hydrogen collisions, in the S-wave model, using the time-independent propagating exterior complex scaling (PECS) method. The PECS S-wave calculations for three-body processes in electron-helium collisions compare favourably with previous convergent close-coupling (CCC) and time-dependent exterior complex scaling (ECS) calculations, and exhibit smooth cross section profiles. The PECS four-body double-excitation cross sections are significantly different from CCC calculations and highlight the need for an accurate representation of the resonant helium final-state wave functions when undertaking these calculations. Results are also presented for positron-hydrogen collisions in an S-wave model using an electron-positron potential of V12 = - (8 + (r1 - r2)2)-1/2. This model is representative of the full problem, and the results demonstrate that ECS-based methods can accurately calculate scattering, ionization and positronium formation cross sections in this three-body rearrangement collision.

Evidence of a two-step process and pathway dependency in the thermodynamics of poly(diallyldimethylammonium chloride)/poly(sodium acrylate) complexation.

PubMed

Vitorazi, L; Ould-Moussa, N; Sekar, S; Fresnais, J; Loh, W; Chapel, J-P; Berret, J-F

2014-12-21

Recent studies have pointed out the importance of polyelectrolyte assembly in the elaboration of innovative nanomaterials. Beyond their structures, many important questions on the thermodynamics of association remain unanswered. Here, we investigate the complexation between poly(diallyldimethylammonium chloride) (PDADMAC) and poly(sodium acrylate) (PANa) chains using a combination of three techniques: isothermal titration calorimetry (ITC), static and dynamic light scattering and electrophoresis. Upon addition of PDADMAC to PANa or vice-versa, the results obtained by the different techniques agree well with each other, and reveal a two-step process. The primary process is the formation of highly charged polyelectrolyte complexes of size 100 nm. The secondary process is the transition towards a coacervate phase made of rich and poor polymer droplets. The binding isotherms measured are accounted for using a phenomenological model that provides the thermodynamic parameters for each reaction. Small positive enthalpies and large positive entropies consistent with a counterion release scenario are found throughout this study. Furthermore, this work stresses the importance of the underestimated formulation pathway or mixing order in polyelectrolyte complexation.

Polyelectrolyte-Surfactant Complexes: A New Class of Organogelators

NASA Astrophysics Data System (ADS)

Cavicchi, Kevin; Liu, Yuqing; Guzman, Gustavo

2011-03-01

Polyelectrolyte-surfactant complexes (PE-SURFs) are a class of polymers generated by neutralizing a polyelectrolyte with an oppositely charged surfactant. It has been found that PE-SURFs composed of polystyrene sulfonate and long chain alkyl dimethyl amines act as good organogelators for a range of hydrophobic, organic solvents. Thermo-reversible organogels are formed by heating and cooling PE-SURF/solvent solutions. The gel transition temperature is influenced by the degree of polymerization, the length of the alkyl side-chain, the solubility parameter of the solvent, and the concentration of the gelator. Freeze-drying and scanning electron microscopy characterization of the resultant xerogels shows the formation of rod- and plate-like network morphologies depending on the system parameters. This behavior is consistent with gelation driven by the self-assembly of the amphiphilic PE-SURFs into micellar networks.

Effect of nanodimensional polyethylenimine layer on surface potential barriers of hybrid structures based on silicon single crystal

NASA Astrophysics Data System (ADS)

Malyar, Ivan V.; Gorin, Dmitry A.; Stetsyura, Svetlana V.

2013-01-01

In this report we present the analysis of I-V curves for MIS-structures like silicon substrate / nanodimensional polyelectrolyte layer / metal probe (contact) which is promising for biosensors, microfluidic chips, different devices of molecular electronics, such as OLEDs, solar cells, where polyelectrolyte layers can be used to modify semiconductor surface. The research is directed to investigate the contact phenomena which influence the resulting signal of devices mentioned above. The comparison of I-V characteristics of such structures measured by scanning tunnel microscopy (contactless technique) and using contact areas deposited by thermal evaporation onto the organic layer (the contact one) was carried out. The photoassisted I-V measurements and complex analysis based on Simmons and Schottky models allow one to extract the potential barriers and to observe the changes of charge transport in MIS-structures under illumination and after polyelectrolyte adsorption. The direct correlation between the thickness of the deposited polyelectrolyte layer and both equilibrium tunnel barrier and Schottky barrier height was observed for hybrid structures with polyethylenimine. The possibility of control over the I-V curves of hybrid structure and the height of the potential barriers (for different charge transports) by illumination was confirmed. Based on experimental data and complex analysis the band diagrams were plotted which illustrate the changes of potential barriers for MIS-structures due to the polyelectrolyte adsorption and under the illumination.

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.

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

Sources, distribution and export coefficient of phosphorus in lowland polders of Lake Taihu Basin, China.

PubMed

Huang, Jiacong; Gao, Junfeng; Jiang, Yong; Yin, Hongbin; Amiri, Bahman Jabbarian

2017-12-01

Identifying phosphorus (P) sources, distribution and export from lowland polders is important for P pollution management, however, is challenging due to the high complexity of hydrological and P transport processes in lowland areas. In this study, the spatial pattern and temporal dynamics of P export coefficient (PEC) from all the 2539 polders in Lake Taihu Basin, China were estimated using a coupled P model for describing P dynamics in a polder system. The estimated amount of P export from polders in Lake Taihu Basin during 2013 was 1916.2 t/yr, with a spatially-averaged PEC of 1.8 kg/ha/yr. PEC had peak values (more than 4.0 kg/ha/yr) in the polders near/within the large cities, and was high during the rice-cropping season. Sensitivity analysis based on the coupled P model revealed that the sensitive factors controlling the PEC varied spatially and changed through time. Precipitation and air temperature were the most sensitive factors controlling PEC. Culvert controlling and fertilization were sensitive factors controlling PEC during some periods. This study demonstrated an estimation of PEC from 2539 polders in Lake Taihu Basin, and an identification of sensitive environmental factors affecting PEC. The investigation of polder P export in a watershed scale is helpful for water managers to learn the distribution of P sources, to identify key P sources, and thus to achieve best management practice in controlling P export from lowland areas. Copyright © 2017 Elsevier Ltd. All rights reserved.

Enhanced Photoelectrocatalytic Decomplexation of Cu-EDTA and Cu Recovery by Persulfate Activated by UV and Cathodic Reduction.

PubMed

Zeng, Huabin; Liu, Shanshan; Chai, Buyu; Cao, Di; Wang, Yan; Zhao, Xu

2016-06-21

In order to enhance Cu-EDTA decomplexation and copper cathodic recovery via the photoelectrocatalytic (PEC) process, S2O8(2-) was introduced into the PEC system with a TiO2/Ti photoanode. At a current density of 0.2 mA/cm(2) and initial solution pH of 3.0, the decomplexation ratio of Cu complexes was increased from 47.5% in the PEC process to 98.4% with 5 mM S2O8(2-) addition into the PEC process (PEC/S2O8(2-)). Correspondently, recovery percentage of Cu was increased to 98.3% from 47.4% within 60 min. It was observed that nearly no copper recovery occurred within the initial reaction period of 10 min. Combined with the analysis of ESR and electrochemical LSV curves, it was concluded that activation of S2O8(2-) into SO4(·-) radicals by cathodic reduction occurred, which was prior to the reduction of liberated Cu(2+) ions. UV irradiation of S2O8(2-) also led to the production of SO4(·-). The generated SO4(·-) radicals enhanced the oxidation of Cu-EDTA. After the consumption of S2O8(2-), the Cu recovery via cathodic reduction proceeded quickly. Acidification induced by the transformation of SO4(·-) to OH· favored the copper cathodic recovery. The combined PEC/S2O8(2-) process was also efficient for the TOC removal from a real electroplating wastewater with the Cu recovery efficiency higher than 80%.

Enhancing gelation ability of a dendritic gelator through complexation with a polyelectrolyte.

PubMed

Zhang, Zijian; Yang, Miao; Zhang, Xinjun; Zhang, Lichu; Liu, Bo; Zheng, Ping; Wang, Wei

2009-01-01

A poly(urethane amide) (PUA) dendron with long alkyl chains on its periphery was synthesized and then attached to the backbone of a polyelectrolyte, in which each unit contained a positive charge, by ionizing the carboxyl groups on the apexes of the dendrons to form a dendronized polymer. We found that both the PUA dendron and the dendronized polymer could form organogels in toluene. Interestingly, both the minimum gelation concentration and the gelation time of the dendronized polymer gelator were greatly reduced compared with the dendron alone. Our investigations showed that in the gel phase the intermolecular hydrogen bonding between adjacent dendrons creates similar supramolecular structures in both the dendron and the dendronized polymer gelator, which immobilize solvent molecules by means of interactions between dendrons and solvent molecules. Further studies on the gelation kinetics indicated that the polyelectrolyte backbone plays an important role in prearranging the attached dendritic gelators orderly and quickly into the supramolecular structures through a nucleation-elongation mechanism. Therefore, the gel-forming ability of the dendritic PUA gelator is enhanced by being complexed with the polyelectrolyte. In this work, this positive macromolecular effect is discussed in detail.

Porcine endothelium induces DNA-histone complex formation in human whole blood: a harmful effect of histone on coagulation and endothelial activation.

PubMed

Yoo, Hyun Ju; Kim, Ji-Eun; Gu, Ja Yoon; Lee, Sae Bom; Lee, Hyun Joo; Hwang, Ho Young; Hwang, Yoohwa; Kim, Young Tae; Kim, Hyun Kyung

2016-11-01

Neutrophils play a role in xenograft rejection. When neutrophils are stimulated, they eject the DNA-histone complex into the extracellular space, called neutrophil extracellular traps (NET). We investigated whether NET formation actively occurs in the xenograft and contributes to coagulation and endothelial activation. Human whole blood was incubated with porcine aortic endothelial cells (pEC) from wild-type or α1,3-galactosyltransferase gene-knockout (GTKO) pigs. In the supernatant plasma from human blood, the level of the DNA-histone complex was measured by ELISA, and thrombin generation was measured using a calibrated automated thrombogram. Histone-induced tissue factor and adhesion molecule expression were measured by flow cytometry. pEC from both wild-type and GTKO pigs significantly induced DNA-histone complex formation in human whole blood. The DNA-histone complex produced shortened the thrombin generation time and clotting time. Histone alone dose-dependently induced tissue factor and adhesion molecule expression in pEC. Aurintricarboxylic acid pretreatment partially inhibited pEC-induced DNA-histone complex formation. DNA-histone complex actively generated upon xenotransplantation is a novel target to inhibit coagulation and endothelial activation. To prevent tissue factor and adhesion molecule expression, a strategy to block soluble histone may be required in xenotransplantation. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Comparative genomic analysis shows that avian pathogenic Escherichia coli isolate IMT5155 (O2:K1:H5; ST complex 95, ST140) shares close relationship with ST95 APEC O1:K1 and human ExPEC O18:K1 strains.

PubMed

Zhu Ge, Xiangkai; Jiang, Jingwei; Pan, Zihao; Hu, Lin; Wang, Shaohui; Wang, Haojin; Leung, Frederick C; Dai, Jianjun; Fan, Hongjie

2014-01-01

Avian pathogenic E. coli and human extraintestinal pathogenic E. coli serotypes O1, O2 and O18 strains isolated from different hosts are generally located in phylogroup B2 and ST complex 95, and they share similar genetic characteristics and pathogenicity, with no or minimal host specificity. They are popular objects for the study of ExPEC genetic characteristics and pathogenesis in recent years. Here, we investigated the evolution and genetic blueprint of APEC pathotype by performing phylogenetic and comparative genome analysis of avian pathogenic E. coli strain IMT5155 (O2:K1:H5; ST complex 95, ST140) with other E. coli pathotypes. Phylogeny analyses indicated that IMT5155 has closest evolutionary relationship with APEC O1, IHE3034, and UTI89. Comparative genomic analysis showed that IMT5155 and APEC O1 shared significant genetic overlap/similarities with human ExPEC dominant O18:K1 strains (IHE3034 and UTI89). Furthermore, the unique PAI I5155 (GI-12) was identified and found to be conserved in APEC O2 serotype isolates. GI-7 and GI-16 encoding two typical T6SSs in IMT5155 might be useful markers for the identification of ExPEC dominant serotypes (O1, O2, and O18) strains. IMT5155 contained a ColV plasmid p1ColV5155, which defined the APEC pathotype. The distribution analysis of 10 sequenced ExPEC pan-genome virulence factors among 47 sequenced E. coli strains provided meaningful information for B2 APEC/ExPEC-specific virulence factors, including several adhesins, invasins, toxins, iron acquisition systems, and so on. The pathogenicity tests of IMT5155 and other APEC O1:K1 and O2:K1 serotypes strains (isolated in China) through four animal models showed that they were highly virulent for avian colisepticemia and able to cause septicemia and meningitis in neonatal rats, suggesting zoonotic potential of these APEC O1:K1 and O2:K1 isolates.

Signature-tagged mutagenesis in a chicken infection model leads to the identification of a novel avian pathogenic Escherichia coli fimbrial adhesin.

PubMed

Antão, Esther-Maria; Ewers, Christa; Gürlebeck, Doreen; Preisinger, Rudolf; Homeier, Timo; Li, Ganwu; Wieler, Lothar H

2009-11-12

The extraintestinal pathogen, avian pathogenic E. coli (APEC), known to cause systemic infections in chickens, is responsible for large economic losses in the poultry industry worldwide. In order to identify genes involved in the early essential stages of pathogenesis, namely adhesion and colonization, Signature-tagged mutagenesis (STM) was applied to a previously established lung colonization model of infection by generating and screening a total of 1,800 mutants of an APEC strain IMT5155 (O2:K1:H5; Sequence type complex 95). The study led to the identification of new genes of interest, including two adhesins, one of which coded for a novel APEC fimbrial adhesin (Yqi) not described for its role in APEC pathogenesis to date. Its gene product has been temporarily designated ExPEC Adhesin I (EA/I) until the adhesin-specific receptor is identified. Deletion of the ExPEC adhesin I gene resulted in reduced colonization ability by APEC strain IMT5155 both in vitro and in vivo. Furthermore, complementation of the adhesin gene restored its ability to colonize epithelial cells in vitro. The ExPEC adhesin I protein was successfully expressed in vitro. Electron microscopy of an afimbriate strain E. coli AAEC189 over-expressed with the putative EA/I gene cluster revealed short fimbrial-like appendages protruding out of the bacterial outer membrane. We observed that this adhesin coding gene yqi is prevalent among extraintestinal pathogenic E. coli (ExPEC) isolates, including APEC (54.4%), uropathogenic E. coli (UPEC) (65.9%) and newborn meningitic E. coli (NMEC) (60.0%), and absent in all of the 153 intestinal pathogenic E. coli strains tested, thereby validating the designation of the adhesin as ExPEC Adhesin I. In addition, prevalence of EA/I was most frequently associated with the B2 group of the EcoR classification and ST95 complex of the multi locus sequence typing (MLST) scheme, with evidence of a positive selection within this highly pathogenic complex. This is the first report of the newly identified and functionally characterized ExPEC adhesin I and its significant role during APEC infection in chickens.

Rheology of polyelectrolyte complex materials

NASA Astrophysics Data System (ADS)

Tirrell, Matthew

Fluid polyelectrolyte complexes, sometimes known as complex coacervates, have rheological properties that are very sensitive to structure and salt concentration. Dynamic moduli of such viscoelastic materials very many orders of magnitude between solutions of no added salt to of order tenth molar salt, typical, for example of physiological saline. Indeed, salt plays a role in the rheology of complex coacervates analogous to that which temperature plays on polymer melts, leading to an empirical observation of what may be termed time-salt or frequency salt superposition. Block copolymers containing complexing ionic blocks also exhibit strong salt sensitivity of their rheological properties. Data representing these phenomena will be presented and discussed. Support from NIST, Department of Commerce, via the Center for Hierarchical Materials Design at Northwestern University and the University of Chicago is gratefully acknowledged.

Molecular organization and dynamics of micellar phase of polyelectrolyte-surfactant complexes: ESR spin probe study

NASA Astrophysics Data System (ADS)

Wasserman, A. M.; Kasaikin, V. A.; Zakharova, Yu. A.; Aliev, I. I.; Baranovsky, V. Yu.; Doseva, V.; Yasina, L. L.

2002-04-01

Molecular dynamics and organization of the micellar phase of complexes of linear polyelectrolytes with ionogenic and non-ionogenic surfactants was studied by the ESR spin probe method. Complexes of polyacrylic acid (PAA) and sodium polystyrenesulfonate (PSS) with alkyltrimethylammonium bromides (ATAB), as well as complexes of poly- N, N'-dimethyldiallylammonium chloride (PDACL) with sodium dodecylsulfate (SDS) were studied. The micellar phase of such complexes is highly organized molecular system, molecular ordering of which near the polymeric chain is much higher than in the 'center' of the micelle, it depends on the polymer-detergent interaction, flexibility of polymeric chain and length of carbonic part of the detergent molecule. Complexes of polymethacrylic acid (PMAA) with non-ionic detergent (dodecyl-substituted polyethyleneglycol), show that the local mobility of surfactant in such complexes is significantly lower than in 'free' micelles and depends on the number of micellar particles participating in formation of complexes.

Nanohybrid conjugated polyelectrolytes: highly photostable and ultrabright nanoparticles.

PubMed

Darwish, Ghinwa H; Karam, Pierre

2015-10-07

We present a general and straightforward one-step approach to enhance the photophysical properties of conjugated polyelectrolytes. Upon complexation with an amphiphilic polymer (polyvinylpyrrolidone), an anionic conjugated polyelectrolyte (poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene]) was prepared into small nanoparticles with exceptional photostability and brightness. The polymer fluorescence intensity was enhanced by 23 -fold and could be easily tuned by changing the order of addition. Single molecule experiments revealed a complete suppression of blinking. In addition, after only losing 18% of the original intensity, a remarkable amount of photons were emitted per particle (∼10(9), on average). This number is many folds greater than popular organic fluorescent dyes. We believe that an intimate contact between the two polymers is shielding the conjugated polyelectrolyte from the destructive photooxidation. The prepared nanohybrid particles will prove instrumental in single particle based fluorescent assays and can serve as a probe for the current state-of-the-art bioimaging fluorescence techniques.

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.

Electron-Atom Ionization Calculations using Propagating Exterior Complex Scaling

NASA Astrophysics Data System (ADS)

Bartlett, Philip

2007-10-01

The exterior complex scaling method (Science 286 (1999) 2474), pioneered by Rescigno, McCurdy and coworkers, provided highly accurate ab initio solutions for electron-hydrogen collisions by directly solving the time-independent Schr"odinger equation in coordinate space. An extension of this method, propagating exterior complex scaling (PECS), was developed by Bartlett and Stelbovics (J. Phys. B 37 (2004) L69, J. Phys. B 39 (2006) R379) and has been demonstrated to provide computationally efficient and accurate calculations of ionization and scattering cross sections over a large range of energies below, above and near the ionization threshold. An overview of the PECS method for three-body collisions and the computational advantages of its propagation and iterative coupling techniques will be presented along with results of: (1) near-threshold ionization of electron-hydrogen collisions and the Wannier threshold laws, (2) scattering cross section resonances below the ionization threshold, and (3) total and differential cross sections for electron collisions with excited targets and hydrogenic ions from low through to high energies. Recently, the PECS method has been extended to solve four-body collisions using time-independent methods in coordinate space and has initially been applied to the s-wave model for electron-helium collisions. A description of the extensions made to the PECS method to facilitate these significantly more computationally demanding calculations will be given, and results will be presented for elastic, single-excitation, double-excitation, single-ionization and double-ionization collisions.

Modeling the formation of ordered nano-assemblies comprised by dendrimers and linear polyelectrolytes: The role of Coulombic interactions

NASA Astrophysics Data System (ADS)

Eleftheriou, E.; Karatasos, K.

2012-10-01

Models of mixtures of peripherally charged dendrimers with oppositely charged linear polyelectrolytes in the presence of explicit solvent are studied by means of molecular dynamics simulations. Under the influence of varying strength of electrostatic interactions, these systems appear to form dynamically arrested film-like interconnected structures in the polymer-rich phase. Acting like a pseudo-thermodynamic inverse temperature, the increase of the strength of the Coulombic interactions drive the polymeric constituents of the mixture to a gradual dynamic freezing-in. The timescale of the average density fluctuations of the formed complexes initially increases in the weak electrostatic regime reaching a finite limit as the strength of electrostatic interactions grow. Although the models are overall electrically neutral, during this process the dendrimer/linear complexes develop a polar character with an excess charge mainly close to the periphery of the dendrimers. The morphological characteristics of the resulted pattern are found to depend on the size of the polymer chains on account of the distinct conformational features assumed by the complexed linear polyelectrolytes of different length. In addition, the length of the polymer chain appears to affect the dynamics of the counterions, thus affecting the ionic transport properties of the system. It appears, therefore, that the strength of electrostatic interactions together with the length of the linear polyelectrolytes are parameters to which these systems are particularly responsive, offering thus the possibility for a better control of the resulted structure and the electric properties of these soft-colloidal systems.

Nanohybrid conjugated polyelectrolytes: highly photostable and ultrabright nanoparticles

NASA Astrophysics Data System (ADS)

Darwish, Ghinwa H.; Karam, Pierre

2015-09-01

We present a general and straightforward one-step approach to enhance the photophysical properties of conjugated polyelectrolytes. Upon complexation with an amphiphilic polymer (polyvinylpyrrolidone), an anionic conjugated polyelectrolyte (poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene]) was prepared into small nanoparticles with exceptional photostability and brightness. The polymer fluorescence intensity was enhanced by 23 -fold and could be easily tuned by changing the order of addition. Single molecule experiments revealed a complete suppression of blinking. In addition, after only losing 18% of the original intensity, a remarkable amount of photons were emitted per particle (~109, on average). This number is many folds greater than popular organic fluorescent dyes. We believe that an intimate contact between the two polymers is shielding the conjugated polyelectrolyte from the destructive photooxidation. The prepared nanohybrid particles will prove instrumental in single particle based fluorescent assays and can serve as a probe for the current state-of-the-art bioimaging fluorescence techniques.We present a general and straightforward one-step approach to enhance the photophysical properties of conjugated polyelectrolytes. Upon complexation with an amphiphilic polymer (polyvinylpyrrolidone), an anionic conjugated polyelectrolyte (poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene]) was prepared into small nanoparticles with exceptional photostability and brightness. The polymer fluorescence intensity was enhanced by 23 -fold and could be easily tuned by changing the order of addition. Single molecule experiments revealed a complete suppression of blinking. In addition, after only losing 18% of the original intensity, a remarkable amount of photons were emitted per particle (~109, on average). This number is many folds greater than popular organic fluorescent dyes. We believe that an intimate contact between the two polymers is shielding the conjugated polyelectrolyte from the destructive photooxidation. The prepared nanohybrid particles will prove instrumental in single particle based fluorescent assays and can serve as a probe for the current state-of-the-art bioimaging fluorescence techniques. Electronic supplementary information (ESI) available: Dynamic light scattering, photostability of different nanohybrids, and emission and absorption spectra. See DOI: 10.1039/c5nr03299g

Development of a robust pH-sensitive polyelectrolyte ionomer complex for anticancer nanocarriers

PubMed Central

Lim, Chaemin; Youn, Yu Seok; Lee, Kyung Soo; Hoang, Ngoc Ha; Sim, Taehoon; Lee, Eun Seong; Oh, Kyung Taek

2016-01-01

A polyelectrolyte ionomer complex (PIC) composed of cationic and anionic polymers was developed for nanomedical applications. Here, a poly(ethylene glycol)–poly(lactic acid)–poly(ethylene imine) triblock copolymer (PEG–PLA–PEI) and a poly(aspartic acid) (P[Asp]) homopolymer were synthesized. These polyelectrolytes formed stable aggregates through electrostatic interactions between the cationic PEI and the anionic P(Asp) blocks. In particular, the addition of a hydrophobic PLA and a hydrophilic PEG to triblock copolyelectrolytes provided colloidal aggregation stability by forming a tight hydrophobic core and steric hindrance on the surface of PIC, respectively. The PIC showed different particle sizes and zeta potentials depending on the ratio of cationic PEI and anionic P(Asp) blocks (C/A ratio). The doxorubicin (dox)-loaded PIC, prepared with a C/A ratio of 8, demonstrated pH-dependent behavior by the deprotonation/protonation of polyelectrolyte blocks. The drug release and the cytotoxicity of the dox-loaded PIC (C/A ratio: 8) increased under acidic conditions compared with physiological pH, due to the destabilization of the formation of the electrostatic core. In vivo animal imaging revealed that the prepared PIC accumulated at the targeted tumor site for 24 hours. Therefore, the prepared pH-sensitive PIC could have considerable potential as a nanomedicinal platform for anticancer therapy. PMID:26955270

Weak polyelectrolyte complexation driven by associative charging.

PubMed

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

2018-03-21

Weak polyelectrolytes are relevant for a wide range of fields; in particular, they have been investigated as "smart" materials for chemical separations and drug delivery. The charges on weak polyelectrolytes are dynamic, causing polymer chains to adopt different equilibrium conformations even with relatively small changes to the surrounding environment. Currently, there exists no comprehensive picture of this behavior, particularly where polymer-polymer interactions have the potential to affect charging properties significantly. In this study, we elucidate the novel interplay between weak polyelectrolyte charging and complexation behavior through coupled molecular dynamics and Monte Carlo simulations. Specifically, we investigate a model of two equal-length and oppositely charging polymer chains in an implicit salt solution represented through Debye-Hückel interactions. The charging tendency of each chain, along with the salt concentration, is varied to determine the existence and extent of cooperativity in charging and complexation. Strong cooperation in the charging of these chains is observed at large Debye lengths, corresponding to low salt concentrations, while at lower Debye lengths (higher salt concentrations), the chains behave in apparent isolation. When the electrostatic coupling is long-ranged, we find that a highly charged chain strongly promotes the charging of its partner chain, even if the environment is unfavorable for an isolated version of that partner chain. Evidence of this phenomenon is supported by a drop in the potential energy of the system, which does not occur at the lower Debye lengths where both potential energies and charge fractions converge for all partner chain charging tendencies. The discovery of this cooperation will be helpful in developing "smart" drug delivery mechanisms by allowing for better predictions for the dissociation point of delivery complexes.

Weak polyelectrolyte complexation driven by associative charging

NASA Astrophysics Data System (ADS)

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

2018-03-01

Weak polyelectrolytes are relevant for a wide range of fields; in particular, they have been investigated as "smart" materials for chemical separations and drug delivery. The charges on weak polyelectrolytes are dynamic, causing polymer chains to adopt different equilibrium conformations even with relatively small changes to the surrounding environment. Currently, there exists no comprehensive picture of this behavior, particularly where polymer-polymer interactions have the potential to affect charging properties significantly. In this study, we elucidate the novel interplay between weak polyelectrolyte charging and complexation behavior through coupled molecular dynamics and Monte Carlo simulations. Specifically, we investigate a model of two equal-length and oppositely charging polymer chains in an implicit salt solution represented through Debye-Hückel interactions. The charging tendency of each chain, along with the salt concentration, is varied to determine the existence and extent of cooperativity in charging and complexation. Strong cooperation in the charging of these chains is observed at large Debye lengths, corresponding to low salt concentrations, while at lower Debye lengths (higher salt concentrations), the chains behave in apparent isolation. When the electrostatic coupling is long-ranged, we find that a highly charged chain strongly promotes the charging of its partner chain, even if the environment is unfavorable for an isolated version of that partner chain. Evidence of this phenomenon is supported by a drop in the potential energy of the system, which does not occur at the lower Debye lengths where both potential energies and charge fractions converge for all partner chain charging tendencies. The discovery of this cooperation will be helpful in developing "smart" drug delivery mechanisms by allowing for better predictions for the dissociation point of delivery complexes.

Bathroom greywater recycling using polyelectrolyte-complex bilayer membrane: Advanced study of membrane structure and treatment efficiency.

PubMed

Oh, K S; Poh, P E; Chong, M N; Chan, E S; Lau, E V; Saint, C P

2016-09-05

Polyelectrolyte-complex bilayer membrane (PCBM) was fabricated using biodegradable chitosan and alginate polymers for subsequent application in the treatment of bathroom greywater. In this study, the properties of PCBMs were studied and it was found that the formation of polyelectrolyte network reduced the molecular weight cut-off (MWCO) from 242kDa in chitosan membrane to 2.71kDa in PCBM. The decrease in MWCO of PCBM results in better greywater treatment efficiency, subsequently demonstrated in a greywater filtration study where treated greywater effluent met the household reclaimed water standard of <2 NTU turbidity and <30ppm total suspended solids (TSS). In addition, a further 20% improvement in chemical oxygen demand (COD) removal was achieved as compared to a single layer chitosan membrane. Results from this study show that the biodegradable PCBM is a potential membrane material in producing clean treated greywater for non-potable applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

Modeling competitive substitution in a polyelectrolyte complex

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

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

2015-12-28

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

PecS regulates the urate-responsive expression of type 1 fimbriae in Klebsiella pneumoniae CG43.

PubMed

Wang, Zhe-Chong; Liu, Chia-Jui; Huang, Ying-Jung; Wang, Yu-Seng; Peng, Hwei-Ling

2015-12-01

In the Klebsiella pneumoniae CG43 genome, the divergently transcribed genes coding for PecS, the MarR-type transcription factor, and PecM, the drug metabolite transporter, are located between the type 1 and type 3 fimbrial gene clusters. The intergenic sequence pecO between pecS and pecM contains three putative PecS binding sites and a CpxR box. Electrophoretic mobility shift assay revealed that the recombinant PecS and CpxR could specifically bind to the pecO sequence, and the specific interaction of PecS and pecO could be attenuated by urate. The expression of pecS and pecM was negatively regulated by CpxAR and PecS, and was inducible by exogenous urate in the absence of cpxAR. Compared with CG43S3ΔcpxAR, the derived mutants CG43S3ΔcpxARΔpecS and CG43S3ΔcpxARΔpecSΔpecM exerted similar levels of sensitivity to H2O2 or paraquat, but higher levels of mannose-sensitive yeast agglutination activity and FimA production. The promoter activity and transcript levels of fimA in CG43S3ΔcpxAR were also increased by deleting pecS. However, no binding activity between PecS and the fimA promoter could be observed. Nevertheless, PecS deletion could reduce the expression of the global regulator HNS and release the negative effect of HNS on FimA expression. In CG43S3ΔcpxAR, the expression of FimA as well as PecS was inducible by urate, whilst urate-induced FimA expression was inhibited by the deletion of pecS. Taken together, we propose that K. pneumoniae PecS indirectly and negatively regulates the expression of type 1 fimbriae, and the regulation is urate-inducible in the absence of CpxAR.

Polyelectrolyte Complexes of Low Molecular Weight PEI and Citric Acid as Efficient and Nontoxic Vectors for in Vitro and in Vivo Gene Delivery.

PubMed

Giron-Gonzalez, M Dolores; Salto-Gonzalez, Rafael; Lopez-Jaramillo, F Javier; Salinas-Castillo, Alfonso; Jodar-Reyes, Ana Belen; Ortega-Muñoz, Mariano; Hernandez-Mateo, Fernando; Santoyo-Gonzalez, Francisco

2016-03-16

Gene transfection mediated by the cationic polymer polyethylenimine (PEI) is considered a standard methodology. However, while highly branched PEIs form smaller polyplexes with DNA that exhibit high transfection efficiencies, they have significant cell toxicity. Conversely, low molecular weight PEIs (LMW-PEIs) with favorable cytotoxicity profiles display minimum transfection activities as a result of inadequate DNA complexation and protection. To solve this paradox, a novel polyelectrolyte complex was prepared by the ionic cross-linking of branched 1.8 kDa PEI with citric acid (CA). This system synergistically exploits the good cytotoxicity profile exhibited by LMW-PEI with the high transfection efficiencies shown by highly branched and high molecular weight PEIs. The polyectrolyte complex (1.8 kDa-PEI@CA) was obtained by a simple synthetic protocol based on the microwave irradiation of a solution of 1.8 kDa PEI and CA. Upon complexation with DNA, intrinsic properties of the resulting particles (size and surface charge) were measured and their ability to form stable polyplexes was determined. Compared with unmodified PEIs the new complexes behave as efficient gene vectors and showed enhanced DNA binding capability associated with facilitated intracellular DNA release and enhanced DNA protection from endonuclease degradation. In addition, while transfection values for LMW-PEIs are almost null, transfection efficiencies of the new reagent range from 2.5- to 3.8-fold to those of Lipofectamine 2000 and 25 kDa PEI in several cell lines in culture such as CHO-k1, FTO2B hepatomas, L6 myoblasts, or NRK cells, simultaneously showing a negligible toxicity. Furthermore, the 1.8 kDa-PEI@CA polyelectrolyte complexes retained the capability to transfect eukaryotic cells in the presence of serum and exhibited the capability to promote in vivo transfection in mouse (as an animal model) with an enhanced efficiency compared to 25 kDa PEI. Results support the polyelectrolyte complex of LMW-PEI and CA as promising generic nonviral gene carriers.

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.

Electron-helium S-wave model benchmark calculations. II. Double ionization, single ionization with excitation, and double excitation

NASA Astrophysics Data System (ADS)

Bartlett, Philip L.; Stelbovics, Andris T.

2010-02-01

The propagating exterior complex scaling (PECS) method is extended to all four-body processes in electron impact on helium in an S-wave model. Total and energy-differential cross sections are presented with benchmark accuracy for double ionization, single ionization with excitation, and double excitation (to autoionizing states) for incident-electron energies from threshold to 500 eV. While the PECS three-body cross sections for this model given in the preceding article [Phys. Rev. A 81, 022715 (2010)] are in good agreement with other methods, there are considerable discrepancies for these four-body processes. With this model we demonstrate the suitability of the PECS method for the complete solution of the electron-helium system.

Assessment of DNA complexation onto polyelectrolyte-coated magnetic silica nanoparticles.

PubMed

Dávila-Ibáñez, Ana B; Buurma, Niklaas J; Salgueiriño, Verónica

2013-06-07

The polyelectrolyte-DNA complexation method to form magnetoplexes using silica-coated iron oxide magnetic nanoparticles as inorganic substrates is an attractive and promising process in view of the potential applications including magnetofection, DNA extraction and purification, and directed assembly of nanostructures. Herein, we present a systematic physico-chemical study that provides clear evidence of the type of interactions established, reflects the importance of the DNA length, the nanoparticle size and the ionic strength, and permits the identification of the parameters controlling both the stability and the type of magnetoplexes formed. This information can be used to develop targeted systems with properties optimized for the various proposed applications of magnetoplexes.

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.

Comparative Genomic Analysis Shows That Avian Pathogenic Escherichia coli Isolate IMT5155 (O2:K1:H5; ST Complex 95, ST140) Shares Close Relationship with ST95 APEC O1:K1 and Human ExPEC O18:K1 Strains

PubMed Central

Pan, Zihao; Hu, Lin; Wang, Shaohui; Wang, Haojin; Leung, Frederick C.; Dai, Jianjun; Fan, Hongjie

2014-01-01

Avian pathogenic E. coli and human extraintestinal pathogenic E. coli serotypes O1, O2 and O18 strains isolated from different hosts are generally located in phylogroup B2 and ST complex 95, and they share similar genetic characteristics and pathogenicity, with no or minimal host specificity. They are popular objects for the study of ExPEC genetic characteristics and pathogenesis in recent years. Here, we investigated the evolution and genetic blueprint of APEC pathotype by performing phylogenetic and comparative genome analysis of avian pathogenic E. coli strain IMT5155 (O2:K1:H5; ST complex 95, ST140) with other E. coli pathotypes. Phylogeny analyses indicated that IMT5155 has closest evolutionary relationship with APEC O1, IHE3034, and UTI89. Comparative genomic analysis showed that IMT5155 and APEC O1 shared significant genetic overlap/similarities with human ExPEC dominant O18:K1 strains (IHE3034 and UTI89). Furthermore, the unique PAI I5155 (GI-12) was identified and found to be conserved in APEC O2 serotype isolates. GI-7 and GI-16 encoding two typical T6SSs in IMT5155 might be useful markers for the identification of ExPEC dominant serotypes (O1, O2, and O18) strains. IMT5155 contained a ColV plasmid p1ColV5155, which defined the APEC pathotype. The distribution analysis of 10 sequenced ExPEC pan-genome virulence factors among 47 sequenced E. coli strains provided meaningful information for B2 APEC/ExPEC-specific virulence factors, including several adhesins, invasins, toxins, iron acquisition systems, and so on. The pathogenicity tests of IMT5155 and other APEC O1:K1 and O2:K1 serotypes strains (isolated in China) through four animal models showed that they were highly virulent for avian colisepticemia and able to cause septicemia and meningitis in neonatal rats, suggesting zoonotic potential of these APEC O1:K1 and O2:K1 isolates. PMID:25397580

Improving Photocatalytic Activity through Electrostatic Self-Assembly: Polyelectrolytes as Tool for Solar Energy Conversion?

NASA Astrophysics Data System (ADS)

Groehn, Franziska

2015-03-01

With regard to the world's decreasing energy resources, developing strategies to exploit solar energy become more and more important. One approach is to take advantage of photocatalysis. Inspired by natural systems such as assemblies performing photosynthesis, it is highly promising to self-assemble synthetic functional species to form more effective or tailored supramolecular units. In this contribution, a new type of photocatalytically active self-assembled nanostructures in aqueous solution will be presented: supramolecular nano-objects obtained through self-assembly of macroions and multivalent organic or inorganic counterions. Polyelectrolyte-porphyrin nanoscale assemblies exhibit up to 10-fold higher photocatalytic activity than the corresponding porphyrins without polymeric template. Other self-assembled catalysts based on polyelectrolytes can exhibit expressed selectivity in a photocatalytic model reaction or even allow catalytic reactions in solution that are not possible with the building blocks only. Further, current results on combining different functional units at the polyelectrolyte template represent a next step towards more complex supramolecular structures for solar energy conversion.

Streptomyces coelicolor encodes a urate-responsive transcriptional regulator with homology to PecS from plant pathogens.

PubMed

Huang, Hao; Mackel, Brian J; Grove, Anne

2013-11-01

Many transcriptional regulators control gene activity by responding to specific ligands. Members of the multiple-antibiotic resistance regulator (MarR) family of transcriptional regulators feature prominently in this regard, and they frequently function as repressors in the absence of their cognate ligands. Plant pathogens such as Dickeya dadantii encode a MarR homolog named PecS that controls expression of a gene encoding the efflux pump PecM in addition to other virulence genes. We report here that the soil bacterium Streptomyces coelicolor also encodes a PecS homolog (SCO2647) that regulates a pecM gene (SCO2646). S. coelicolor PecS, which exists as a homodimer, binds the intergenic region between pecS and pecM genes with high affinity. Several potential PecS binding sites were found in this intergenic region. The binding of PecS to its target DNA can be efficiently attenuated by the ligand urate, which also quenches the intrinsic fluorescence of PecS, indicating a direct interaction between urate and PecS. In vivo measurement of gene expression showed that activity of pecS and pecM genes is significantly elevated after exposure of S. coelicolor cultures to urate. These results indicate that S. coelicolor PecS responds to the ligand urate by attenuated DNA binding in vitro and upregulation of gene activity in vivo. Since production of urate is associated with generation of reactive oxygen species by xanthine dehydrogenase, we propose that PecS functions under conditions of oxidative stress.

Streptomyces coelicolor Encodes a Urate-Responsive Transcriptional Regulator with Homology to PecS from Plant Pathogens

PubMed Central

Huang, Hao; Mackel, Brian J.

2013-01-01

Many transcriptional regulators control gene activity by responding to specific ligands. Members of the multiple-antibiotic resistance regulator (MarR) family of transcriptional regulators feature prominently in this regard, and they frequently function as repressors in the absence of their cognate ligands. Plant pathogens such as Dickeya dadantii encode a MarR homolog named PecS that controls expression of a gene encoding the efflux pump PecM in addition to other virulence genes. We report here that the soil bacterium Streptomyces coelicolor also encodes a PecS homolog (SCO2647) that regulates a pecM gene (SCO2646). S. coelicolor PecS, which exists as a homodimer, binds the intergenic region between pecS and pecM genes with high affinity. Several potential PecS binding sites were found in this intergenic region. The binding of PecS to its target DNA can be efficiently attenuated by the ligand urate, which also quenches the intrinsic fluorescence of PecS, indicating a direct interaction between urate and PecS. In vivo measurement of gene expression showed that activity of pecS and pecM genes is significantly elevated after exposure of S. coelicolor cultures to urate. These results indicate that S. coelicolor PecS responds to the ligand urate by attenuated DNA binding in vitro and upregulation of gene activity in vivo. Since production of urate is associated with generation of reactive oxygen species by xanthine dehydrogenase, we propose that PecS functions under conditions of oxidative stress. PMID:23995633

Urate is a ligand for the transcriptional regulator PecS.

PubMed

Perera, Inoka C; Grove, Anne

2010-09-24

PecS is a member of the MarR (multiple antibiotic resistance regulator) family, which has been shown in Erwinia to regulate the expression of virulence genes. MarR homologs typically bind a small molecule ligand, resulting in attenuated DNA binding. For PecS, the natural ligand has not been identified. We have previously shown that urate is a ligand for the Deinococcus radiodurans-encoded MarR homolog HucR (hypothetical uricase regulator) and identified residues responsible for ligand binding. We show here that all four residues involved in urate binding and propagation of conformational changes to DNA recognition helices are conserved in PecS homologs, suggesting that urate is the ligand for PecS. Consistent with this prediction, Agrobacterium tumefaciens PecS specifically binds urate, and urate attenuates DNA binding in vitro. PecS binds two operator sites in the intergenic region between the divergent pecS gene and pecM genes, one of which features two partially overlapping repeats to which PecS binds as a dimer on opposite faces of the duplex. Notably, urate dissociates PecS from cognate DNA, allowing transcription of both genes in vivo. Taken together, our data show that urate is a ligand for PecS and suggest that urate serves a novel function in signaling the colonization of a host plant. Copyright © 2010 Elsevier Ltd. All rights reserved.

Criticality and Connectivity in Macromolecular Charge Complexation

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

Qin, Jian; de Pablo, Juan J.

We examine the role of molecular connectivity and architecture on the complexation of ionic macromolecules (polyelectrolytes) of finite size. A unified framework is developed and applied to evaluate the electrostatic correlation free energy for point-like, rod-like, and coil-like molecules. That framework is generalized to molecules of variable fractal dimensions, including dendrimers. Analytical expressions for the free energy, correlation length, and osmotic pressure are derived, thereby enabling consideration of the effects of charge connectivity, fractal dimension, and backbone stiffness on the complexation behavior of a wide range of polyelectrolytes. Results are presented for regions in the immediate vicinity of the criticalmore » region and far from it. A transparent and explicit expression for the coexistence curve is derived in order to facilitate analysis of experimentally observed phase diagrams.« less

Effect of pectin charge density on formation of multilayer films with chitosan.

PubMed

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

2008-04-01

The effect of pectin charge density on the formation of multilayer films with chitosan (PEC/CHI) is studied by means of electro-optics. Pectins of low (21%) and high (71%) degrees of esterification, which are inversely proportional to the pectin charge density, are used to form films on colloidal beta-FeOOH particles at pH 4.0 when the CHI is fully ionized. We find that, after deposition of the first 3-4 layers, the film thickness increases linearly with the number of adsorbed layers. However, the increase in the film thickness is larger when the film is terminated with CHI. Irregular increase of the film thickness is more marked for the PEC with higher density of charge. Oscillation in the electrical polarizability of the film-coated particles with the number of deposited layers is also registered in the PEC/CHI films. The charge balance of the multilayers, calculated from electrical polarizability of the film-coated particles, is positive, with larger excess of positive charge within the film constructed from CHI and less charged PEC. This is attributed to the ability of CHI to diffuse into the film at each deposition step. Despite the CHI diffusion, the film thickness increases linearly due to the dissolution of unstable PEC/CHI complexes from the film surface.

Supramolecular Systems Behavior at the Air-Water Interface. Molecular Dynamic Simulation Study.

NASA Astrophysics Data System (ADS)

Sandoval, C.; Saavedra, M.; Gargallo, L.; Radić, D.

2008-08-01

Atomistic molecular dynamics simulation (MDS) was development to investigate the structural and dynamic properties of a monolayer of supramolecular systems. The simulations were performed at room temperature, on inclusion complexes (ICs) of α-cyclodextrin (CD) with poly(ethylene-oxide)(PEO), poly(ɛ-caprolactone)(PEC) and poly(tetrahydrofuran)(PTHF). The simulations were carried out for a surface area of 30Å. The trajectories of the MDS show that the system more stable was IC-PEC, being the less stable IC-PEO. The disordered monolayer for the systems was proved by the orientation correlation function and the radial distribution function between the polar groups of ICs and the water molecules. We found that the system IC-PEC was more stable that the systems IC-PTHF and IC-PEO.

Electrochemical determination of the glass transition temperature of thin polyelectrolyte brushes at solid-liquid interfaces by impedance spectroscopy.

PubMed

Alonso-García, Teodoro; Rodríguez-Presa, María José; Gervasi, Claudio; Moya, Sergio; Azzaroni, Omar

2013-07-16

Devising strategies to assess the glass transition temperature (Tg) of polyelectrolyte assemblies at solid-electrolyte interfaces is very important to understand and rationalize the temperature-dependent behavior of polyelectrolyte films in a wide range of settings. Despite the evolving perception of the importance of measuring Tg under aqueous conditions in thin film configurations, its straightforward measurement poses a challenging situation that still remains elusive in polymer and materials science. Here, we describe a new method based on electrochemical impedance spectroscopy (EIS) to estimate the glass transition temperature of planar polyelectrolyte brushes at solid-liquid interfaces. To measure Tg, the charge transfer resistance (Rct) of a redox probe diffusing through the polyelectrolyte brush was measured, and the temperature corresponding to the discontinuous change in Rct was identified as Tg. Furthermore, we demonstrate that impedance measurements not only facilitate the estimation of Tg but also enable a reliable evaluation of the transport properties of the polymeric interface, i.e., determination of diffusion coefficients, close to the thermal transition. We consider that this approach bridges the gap between electrochemistry and the traditional tools used in polymer science and offers new opportunities to characterize the thermal behavior of complex polymeric interfaces and macromolecular assemblies.

Chitosan/lecithin liposomal nanovesicles as an oral insulin delivery system.

PubMed

Al-Remawi, Mayyas; Elsayed, Amani; Maghrabi, Ibrahim; Hamaidi, Mohammad; Jaber, Nisrein

2017-05-01

In the present work, insulin-chitosan polyelectrolyte complexes associated to lecithin liposomes were investigated as a new carrier for oral delivery of insulin. The preparation was characterized in terms of particle size, zeta potential and encapsulation efficiency. Surface tension measurements revealed that insulin-chitosan polyelectrolyte complexes have some degree of hydrophobicity and should be added to lecithin liposomal dispersion and not the vice versa to prevent their adsorption on the surface. Stability of insulin was enhanced when it was associated to liposomes. Significant reduction of blood glucose levels was noticed after oral administration of liposomal preparation to streptozotocin diabetic rats compared to control. The hypoglycemic activity was more prolonged compared to subcutaneously administered insulin.

The Effect of Salt on the Complex Coacervation of Vinyl Polyelectrolytes

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

Perry, Sarah; Li, Yue; Priftis, Dimitrios

2014-06-01

Complex coacervation is an electrostatically-driven phase separation phenomenon that is utilized in a wide range of everyday applications and is of great interest for the creation of self-assembled materials. Here, we utilized turbidity to characterize the effect of salt type on coacervate formation using two vinyl polyelectrolytes, poly(acrylic acid sodium salt) (pAA) and poly(allylamine hydrochloride) (pAH), as simple models for industrial and biological coacervates. We confirmed the dominant role of salt valence on the extent of coacervate formation, while demonstrating the presence of significant secondary effects, which can be described by Hofmeister-like behavior. These results revealed the importance of ion-specificmore » interactions, which are crucial for the informed design of coacervate-based materials for use in complex ionic environments, and can enable more detailed theoretical investigations on the role of subtle electrostatic and thermodynamic effects in complex coacervation.« less

Transcriptome analysis of the Dickeya dadantii PecS regulon during the early stages of interaction with Arabidopsis thaliana.

PubMed

Pédron, Jacques; Chapelle, Emilie; Alunni, Benoît; Van Gijsegem, Frédérique

2018-03-01

PecS is one of the major global regulators controlling the virulence of Dickeya dadantii, a broad-host-range phytopathogenic bacterium causing soft rot on several plant families. To define the PecS regulon during plant colonization, we analysed the global transcriptome profiles in wild-type and pecS mutant strains during the early colonization of the leaf surfaces and in leaf tissue just before the onset of symptoms, and found that the PecS regulon consists of more than 600 genes. About one-half of these genes are down-regulated in the pecS mutant; therefore, PecS has both positive and negative regulatory roles that may be direct or indirect. Indeed, PecS also controls the regulation of a few dozen regulatory genes, demonstrating that this global regulator is at or near the top of a major regulatory cascade governing adaptation to growth in planta. Notably, PecS acts mainly at the very beginning of infection, not only to prevent virulence gene induction, but also playing an active role in the adaptation of the bacterium to the epiphytic habitat. Comparison of the patterns of gene expression inside leaf tissues and during early colonization of leaf surfaces in the wild-type bacterium revealed 637 genes modulated between these two environments. More than 40% of these modulated genes are part of the PecS regulon, emphasizing the prominent role of PecS during plant colonization. © 2017 BSPP AND JOHN WILEY & SONS LTD.

Polyelectrolyte Structure and Interactions in Model Cystic Fibrosis Sputum

NASA Astrophysics Data System (ADS)

Slimmer, Scott; Angelini, Thomas; Liang, Hongjun; Butler, John; Wong, Gerard C. L.

2002-03-01

Cystic fibrosis sputum is a complex fluid consisting of a number of components, including mucin (a glycoprotein), lysozyme (a cationic polypeptide), water, salt, as well as a high concentration of a number of anionic biological polyelectrolytes such as DNA and F-actin. The interactions governing these components are poorly understood, but may have important clinical consequences. For example, the formation of these biological polyelectrolytes into ordered gel phases may contribute significantly to the observed high viscosity of CF sputum. In this work, a number of model systems were created to simulate CF sputum in vitro, in order to elucidate the contributions of the different components. Preliminary results will be presented. This work was supported by NSF DMR-0071761, DOE DEFG02-91ER45439, the Beckman Young Investigator Program, and the Cystic Fibrosis Foundation.

[Evaluation of the sanitary-and-epidemiological safety of flocculating agents used for portable water purification].

PubMed

Zholdakova, Z I; Sinitsyna, O O; Tul'skaia, E A

2006-01-01

Polyelectrolytes used in the practice of water supply to the population were comparatively hygienically studied, by using a complex of hazard indices and a new approach to sanitary-and-epidemiological evaluation of the safety of water-soluble polymers is substantiated. The anionic and cationic flocculating agents from different chemical classes, such as Superflok A-100, Fennopol A 321E, Fennopol K 221E, Praestol 2530 TR, VPK-402, Superflok C-577, Saipan, KF-91, Ecosol-401, a low molecular-weight sodium polyacrylate were tested as model compounds. Moreover, the information already available in the scientific literature on the toxicity of synthetic polyelectrolytes was analyzed. The generalized maximum permissible concentrations were substantiated for individual chemical classes of synthetic polyelectrolytes: polyacrylamides, polyamines, polydiallyldimethylammonium chloride.

pH-Dependent DNA Distortion and Repression of Gene Expression by Pectobacterium atrosepticum PecS.

PubMed

Deochand, Dinesh K; Meariman, Jacob K; Grove, Anne

2016-07-15

Transcriptional activity is exquisitely sensitive to changes in promoter DNA topology. Transcription factors may therefore control gene activity by modulating the relative positioning of -10 and -35 promoter elements. The plant pathogen Pectobacterium atrosepticum, which causes soft rot in potatoes, must alter gene expression patterns to ensure growth in planta. In the related soft-rot enterobacterium Dickeya dadantii, PecS functions as a master regulator of virulence gene expression. Here, we report that P. atrosepticum PecS controls gene activity by altering promoter DNA topology in response to pH. While PecS binds the pecS promoter with high affinity regardless of pH, it induces significant DNA distortion only at neutral pH, the pH at which the pecS promoter is repressed in vivo. At pH ∼8, DNA distortions are attenuated, and PecS no longer represses the pecS promoter. A specific histidine (H142) located in a crevice between the dimerization- and DNA-binding regions is required for pH-dependent changes in DNA distortion and repression of gene activity, and mutation of this histidine renders the mutant protein incapable of repressing the pecS promoter. We propose that protonated PecS induces a DNA conformation at neutral pH in which -10 and -35 promoter elements are suboptimally positioned for RNA polymerase binding; on deprotonation of PecS, binding is no longer associated with significant changes in DNA conformation, allowing gene expression. We suggest that this mode of gene regulation leads to differential expression of the PecS regulon in response to alkalinization of the plant apoplast.

Alcohol--Induced Polyelectrolyte-Surfactant Complex Coacervate Systems: Characterization and Applications in Enzyme and Protein Extraction

NASA Astrophysics Data System (ADS)

Nejati Moshtaghin, Mahboubeh

The focus of this thesis is to achieve a better understanding of the newly discovered surfactant-polyelectrolyte complex coacervate (SPCC) systems induced by fluoroalcohol/acid as well as short chain aliphatic alcohol; and to elucidate their applications in extraction and enrichment of proteins and enzyme. We have discovered that fluoroalcohols and --acids induce complex coacervation and phase separation in the aqueous mixtures of oppositely charged anionic polyelectrolytes; specifically, sodium salts of polyacrylic acid and polymethacrylic acid and cationic surfactant (cetyltrimethylammonium bromide, CTAB) over a broad range of concentrations of mole fractions of the oppositely charged amphiphiles. Accordingly, these new classes of coacervators will significantly broaden the scope and facilitate engineering of new coacervate phases. Toward these goals, we have inspected the formation of surfactant-polyelectrolyte complex coacervates in the presence of fluoroalcohols namely hexafluoroisopropanol (HFIP) and Trifluoroethanol (TFE). Furthermore, the extent of coacervation as a function of concentrations the system components, and charge ratios of the oppositely charged amphiphiles has been investigated. Polyelectrolytes are considered to be milder reagents, as compared to surfactants, regarding proteins denaturation. This highlights the importance of a detailed investigation of the efficiency of our coacervate systems for extraction and preconcentration of proteins and enzymes, especially, when the biological activity of the extracted proteins needs to be maintained based on the objectives mentioned above, the results of the investigations have been organized in four chapters. In Chapter II, the phase behavior of the FA-SPCC will be investigated. The objective is to examine the phase behavior and phase properties with respect to the extent of coacervation in different solution conditions. In particular, the effects of different solution variables such as concentration of FA, oppositely charged amphiphiles (surfactant-polyelectrolyte), and the charge ratio of the surfactant-polyelectrolyte on the extent of coacervation have been investigated. Furthermore, the chemical composition of each phase formed in the coacervate system was determined as a function of HFIP percentage. Phase diagrams of HFIP-PMA-CTAB and 2-propanol-PMA-CTAB were studied. The phase separation occurs over a wide range of polyelectrolyte, surfactant and alcohol concentration. In addition, a study of the dependence of coacervate volume on phase composition in different system (as defined by concentrations and mole charge ratio of amphihiles and alcohols) provided useful insight about possible underlying interactions and mechanisms. It has been concluded that neutralization favors coacervation in both systems. However, according to the compositional analysis of both HFIP and 2-propanol SPCC system, it seems that coacervation mechanisms are different. In Chapter III the properties of 2-propanol--SPCC, with analogous surfactant (CTAB) and polyelectrolyte (PMA) used in Chapter II, will be investigated. In particular, we are interested in examining the difference between the phase separation characteristics of the coacervates induced by 2-propanol and HFIP as coacervator. For this purpose, the phase behavior and the chemical composition of the phases will be analyzed as a function of 2-propanol and constituents concentrations. Chapter IV contains results of our investigations on the activity of a model enzyme (Trypsin) in 2-propanol- and FA-induced SPCC system. These investigations will facilitate understanding whether the aliphatic alcohol, AA- and FA-induced SPCC system denature the model enzymes. Such investigations also help in evaluation of the applicability of the coacervate systems developed in this work in proteomics where the proteolytic activity of enzymes is used for protein digestion. Finally, in Chapter V, the efficiency of the coacervate system (2-propanol-induced-PMA-CTAB) for extraction of cytochrome c, as a model protein, will be investigated.

Folding Behaviors of Protein (Lysozyme) Confined in Polyelectrolyte Complex Micelle.

PubMed

Wu, Fu-Gen; Jiang, Yao-Wen; Chen, Zhan; Yu, Zhi-Wu

2016-04-19

The folding/unfolding behavior of proteins (enzymes) in confined space is important for their properties and functions, but such a behavior remains largely unexplored. In this article, we reported our finding that lysozyme and a double hydrophilic block copolymer, methoxypoly(ethylene glycol)5K-block-poly(l-aspartic acid sodium salt)10 (mPEG(5K)-b-PLD10), can form a polyelectrolyte complex micelle with a particle size of ∼30 nm, as verified by dynamic light scattering and transmission electron microscopy. The unfolding and refolding behaviors of lysozyme molecules in the presence of the copolymer were studied by microcalorimetry and circular dichroism spectroscopy. Upon complex formation with mPEG(5K)-b-PLD10, lysozyme changed from its initial native state to a new partially unfolded state. Compared with its native state, this copolymer-complexed new folding state of lysozyme has different secondary and tertiary structures, a decreased thermostability, and significantly altered unfolding/refolding behaviors. It was found that the native lysozyme exhibited reversible unfolding and refolding upon heating and subsequent cooling, while lysozyme in the new folding state (complexed with the oppositely charged PLD segments of the polymer) could unfold upon heating but could not refold upon subsequent cooling. By employing the heating-cooling-reheating procedure, the prevention of complex formation between lysozyme and polymer due to the salt screening effect was observed, and the resulting uncomplexed lysozyme regained its proper unfolding and refolding abilities upon heating and subsequent cooling. Besides, we also pointed out the important role the length of the PLD segment played during the formation of micelles and the monodispersity of the formed micelles. Furthermore, the lysozyme-mPEG(5K)-b-PLD10 mixtures prepared in this work were all transparent, without the formation of large aggregates or precipitates in solution as frequently observed in other protein-polyelectrolyte systems. Hence, the present protein-PEGylated poly(amino acid) mixture provides an ideal water-soluble model system to study the important role of electrostatic interaction in the complexation between proteins and polymers, leading to important new knowledge on the protein-polymer interactions. Moreover, the polyelectrolyte complex micelle formed between protein and PEGylated polymer may provide a good drug delivery vehicle for therapeutic proteins.

Design and specification of a centralized manufacturing data management and scheduling system

NASA Technical Reports Server (NTRS)

Farrington, Phillip A.

1993-01-01

As was revealed in a previous study, the Materials and Processes Laboratory's Productivity Enhancement Complex (PEC) has a number of automated production areas/cells that are not effectively integrated, limiting the ability of users to readily share data. The recent decision to utilize the PEC for the fabrication of flight hardware has focused new attention on the problem and brought to light the need for an integrated data management and scheduling system. This report addresses this need by developing preliminary designs specifications for a centralized manufacturing data management and scheduling system for managing flight hardware fabrication in the PEC. This prototype system will be developed under the auspices of the Integrated Engineering Environment (IEE) Oversight team and the IEE Committee. At their recommendation the system specifications were based on the fabrication requirements of the AXAF-S Optical Bench.

Polyelectrolyte Complex Optimization for Macrophage Delivery of Redox Enzyme Nanoparticles

PubMed Central

Zhao, Yuling; Haney, Matthew J.; Klyachko, Natalia L.; Li, Shu; Booth, Stephanie L.; Higginbotham, Sheila M.; Jones, Jocelyn; Zimmerman, Matthew C.; Mosley, R. Lee; Kabanov, Alexander V.; Gendelman, Howard E.; Batrakova, Elena V.

2011-01-01

Background We posit that cell-mediated drug delivery can improve transport of therapeutic enzymes to the brain and decrease inflammation and neurodegeneration induced during Parkinson’s disease. Our prior work demonstrated that macrophages loaded with nanoformulated catalase (“nanozyme”) protect the nigrostriatum in a murine model of Parkinson’s disease. Packaging of catalase into block ionomer complex with a synthetic polyelectrolyte block copolymers protects the enzyme degradation in macrophages. Methods We examined relationships between the composition and structure of block ionomer complexes, their physicochemical characteristics, and loadings, release rates, and catalase activity in bone marrow-derived macrophages. Results Formation of block-ionomer complexes resulted in improved aggregation stability. Block ionomer complexes with ε-polylisine, and poly-L-glutamic acid -poly(ethylene glycol) demonstrated the least cytotoxicity and high loading and release rates, however, did not efficiently protect catalase inside macrophages. Conclusion nanozymes with polyethyleneimine- and poly(L-lysine)10-poly(ethylene glycol) provided the best protection of enzymatic activity for cell-mediated drug delivery. PMID:21182416

The PEcAn Project: Model-Data Ecoinformatics for the Observatory Era

NASA Astrophysics Data System (ADS)

Dietze, M. C.; LeBauer, D. S.; Davidson, C. D.; Desai, A. R.; Kooper, R.; McHenry, K.; Mulrooney, P.

2011-12-01

The fundamental questions about how terrestrial ecosystems will respond to climate change are straightforward and well known, yet a small number of important gaps separate the information we have gathered from the understanding required to inform policy and management. A critical gap is that no one data source provides a complete picture of the terrestrial biosphere, and therefore multiple data sources must be integrated in a sensible manner. Process-based models represent an ideal framework for this synthesis, but to date model-data synthesize has only made use of a subset of the available data types, and remains inaccessible to much of the scientific community, largely due to the daunting ecoinformatics challenges. The Predictive Ecosystem Analyzer (PEcAn) is an open-source scientific workflow system and ecoinformatics toolbox that manages the flow of information in and out of regional-scale terrestrial biosphere models, facilitates formal data assimilation, and enables more effective feedbacks between models and field research. PEcAn makes complex analyses transparent, repeatable, and accessible to a diverse array of researchers. PEcAn is not model specific, but rather encapsulates any ecosystem model within a set of standardized input and output modules. Herein we demonstrate PEcAn's ability to automate many of the tasks involved in modeling by gathering and processing a diverse arrays of data sets, initiating ensembles of model runs, visualizing output, and comparing models to observations. PEcAn employs a fully Bayesian approach to model parameterization and the estimation of ecosystem pools and fluxes that allows a straightforward propagation of uncertainties into analyses and forecasts. This approach also makes possible the synthesis of a diverse array of data types operating at different spatial and temporal scales and to easily update predictions as new information becomes available. We also demonstrate PEcAn's ability to iteratively synthesize information for literature trait databases, ground observations, eddy-covariance towers and quantify the reductions in overall uncertainty as each new dataset is added. PEcAn also automates a number of model analyses, such as sensitivity analyses, ensemble prediction, and variance decomposition which collectively allow the system to partition and ascribe uncertainties to different model parameters and processes. PEcAn provides a direct feedback to field research by further automating the estimation of sample sizes and sampling distributions required to reduce model uncertainties, enabling further measurements to be targeted and optimized. Finally, we will present the PEcAn development plan and timeline, including new features such as the synthesis of remotely sensed data, regional-scale data assimilation, and real-time forecasting. Ultimately, PEcAn aims to make ecosystem modeling and data assimilation routine tools for answering scientific questions and informing policy and management.

Coagulation-flocculation mechanisms in wastewater treatment plants through zeta potential measurements.

PubMed

López-Maldonado, E A; Oropeza-Guzman, M T; Jurado-Baizaval, J L; Ochoa-Terán, A

2014-08-30

Based on the polyelectrolyte-contaminant physical and chemical interactions at the molecular level, this article analyzed and discussed the coagulation-flocculation and chemical precipitation processes in order to improve their efficiency. Bench experiments indicate that water pH, polyelectrolyte (PE) dosing strategy and cationic polyelectrolyte addition are key parameters for the stability of metal-PE complexes. The coagulation-flocculation mechanism is proposed based on zeta potential (ζ) measurement as the criteria to define the electrostatic interaction between pollutants and coagulant-flocculant agents. Polyelectrolyte and wastewater dispersions are exposed to an electrophoretic effect to determine ζ. Finally, zeta potential values are compared at pH 9, suggesting the optimum coagulant dose at 162mg/L polydadmac and 67mg/L of flocculant, since a complete removal of TSS and turbidity is achieved. Based on the concentration of heavy metals (0.931mg/L Sn, 0.7mg/L Fe and 0.63mg/L Pb), treated water met the Mexican maximum permissible limits. In addition, the treated water has 45mg O2/L chemical oxygen demand (COD) and 45mg C/L total organic carbon (TOC). The coagulation-flocculation mechanism is proposed taking into account both: zeta potential (ζ)-pH measurement and chemical affinity, as the criteria to define the electrostatic and chemical interaction between pollutants and polyelectrolytes. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Efficacy of pectoral nerve block versus thoracic paravertebral block for postoperative analgesia after radical mastectomy: a randomized controlled trial.

PubMed

Kulhari, S; Bharti, N; Bala, I; Arora, S; Singh, G

2016-09-01

Pectoral nerve (PecS) block is a recently introduced technique for providing surgical anaesthesia and postoperative analgesia during breast surgery. The present study was planned to compare the efficacy and safety of ultrasound-guided PecS II block with thoracic paravertebral block (TPVB) for postoperative analgesia after modified radical mastectomy. Forty adult female patients undergoing radical mastectomy were randomly allocated into two groups. Group 1 patients received a TPVB with ropivacaine 0.5%, 25 ml, whereas Group 2 patents received a PecS II block using same volume of ropivacaine 0.5% before induction of anaesthesia. Patient-controlled morphine analgesia was used for postoperative pain relief. The duration of analgesia was significantly prolonged in patients receiving the PecS II block compared with TPVB [mean (sd), 294.5 (52.76) vs 197.5 (31.35) min in the PecS II and TPVB group, respectively; P<0.0001]. The 24 h morphine consumption was also less in the PecS II block group [mean (sd), 3.90 (0.79) vs 5.30 (0.98) mg in PecS II and TPVB group, respectively; P<0.0001]. Postoperative pain scores were lower in the PecS II group compared with the TVPB group in the initial 2 h after surgery [median (IQR), 2 (2-2.5) vs 4 (3-4) in the Pecs II and TPVB group, respectively; P<0.0001]. Seventeen patients in the PecS II block group had T2 dermatomal spread compared with four patients in the TPVB group (P<0.001). No block-related complication was recorded. We found that the PecS II block provided superior postoperative analgesia than the TPVB in patients undergoing modified radical mastectomy without causing any adverse effect. CTRI/2014/06/004692. © The Author 2016. Published by Oxford University Press on behalf of the British Journal of Anaesthesia. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Chitosan-phosphotungstic acid complex as membranes for low temperature H2-O2 fuel cell

NASA Astrophysics Data System (ADS)

Santamaria, M.; Pecoraro, C. M.; Di Quarto, F.; Bocchetta, P.

2015-02-01

Free-standing Chitosan/phosphotungstic acid polyelectrolyte membranes were prepared by an easy and fast in-situ ionotropic gelation process performed at room temperature. Scanning electron microscopy was employed to study their morphological features and their thickness as a function of the chitosan concentration. The membrane was tested as proton conductor in low temperature H2-O2 fuel cell allowing to get peak power densities up to 350 mW cm-2. Electrochemical impedance measurements allowed to estimate a polyelectrolyte conductivity of 18 mS cm-1.

Interactions Between DNA and Actin in Model Cystic Fibrosis Sputum

NASA Astrophysics Data System (ADS)

Kyung, Hee; Sanders, Lori; Angelini, Thomas; Butler, John; Wong, Gerard

2003-03-01

Cystic fibrosis sputum is a complex fluid which has a high concentration of DNA and F-actin, two anionic biological polyelectrolytes. In this work, we study the interactions between DNA and actin in an aqueous environment over a wide range of polyelectrolyte lengths and salt levels, using synchrotron Small Angle X-ray Scattering(SAXS) and confocal microscopy. Perliminary results indicate the existence of a compressed phase of nematic F-actin in the presence of DNA. This work was supported by NSF DMR-0071761, the Beckman Young Investigator Program, and the Cystic Fibrosis Foundation.

Linear Titration Curves of Acids and Bases.

PubMed

Joseph, N R

1959-05-29

The Henderson-Hasselbalch equation, by a simple transformation, becomes pH - pK = pA - pB, where pA and pB are the negative logarithms of acid and base concentrations. Sigmoid titration curves then reduce to straight lines; titration curves of polyelectrolytes, to families of straight lines. The method is applied to the titration of the dipeptide glycyl aminotricarballylic acid, with four titrable groups. Results are expressed as Cartesian and d'Ocagne nomograms. The latter is of a general form applicable to polyelectrolytes of any degree of complexity.

Layer-by-Layer Assembly of Fluorine-Free Polyelectrolyte-Surfactant Complexes for the Fabrication of Self-Healing Superhydrophobic Films.

PubMed

Wu, Mengchun; An, Ni; Li, Yang; Sun, Junqi

2016-11-29

Fluorine-free self-healing superhydrophobic films are of significance for practical applications because of their extended service life and cost-effective and eco-friendly preparation process. In this study, we report the fabrication of fluorine-free self-healing superhydrophobic films by layer-by-layer (LbL) assembly of poly(sodium 4-styrenesulfonate) (PSS)-1-octadecylamine (ODA) complexes (PSS-ODA) and poly(allylamine hydrochloride) (PAH)-sodium dodecyl sulfonate (SDS) (PAH-SDS) complexes. The wettability of the LbL-assembled PSS-ODA/PAH-SDS films depends on the film structure and can be tailored by changing the NaCl concentration in aqueous dispersions of PSS-ODA complexes and the number of film deposition cycles. The freshly prepared PSS-ODA/PAH-SDS film with micro- and nanoscaled hierarchical structures is hydrophilic and gradually changes to superhydrophobic in air because the polyelectrolyte-complexed ODA and SDS surfactants tend to migrate to the film surface to cover the film with hydrophobic alkyl chains to lower its surface energy. The large amount of ODA and SDS surfactants loaded in the superhydrophobic PSS-ODA/PAH-SDS films and the autonomic migration of these surfactants to the film surface endow the resultant superhydrophobic films with an excellent self-healing ability to restore the damaged superhydrophobicity. The self-healing superhydrophobic PSS-ODA/PAH-SDS films are mechanically robust and can be deposited on various flat and nonflat substrates. The LbL assembly of oppositely charged polyelectrolyte-surfactant complexes provides a new way for the fabrication of fluorine-free self-healing superhydrophobic films with satisfactory mechanical stability, enhanced reliability, and extended service life.

Computer simulations of dendrimer-polyelectrolyte complexes.

PubMed

Pandav, Gunja; Ganesan, Venkat

2014-08-28

We carry out a systematic analysis of static properties of the clusters formed by complexation between charged dendrimers and linear polyelectrolyte (LPE) chains in a dilute solution under good solvent conditions. We use single chain in mean-field simulations and analyze the structure of the clusters through radial distribution functions of the dendrimer, cluster size, and charge distributions. The effects of LPE length, charge ratio between LPE and dendrimer, the influence of salt concentration, and the dendrimer generation number are examined. Systems with short LPEs showed a reduced propensity for aggregation with dendrimers, leading to formation of smaller clusters. In contrast, larger dendrimers and longer LPEs lead to larger clusters with significant bridging. Increasing salt concentration was seen to reduce aggregation between dendrimers as a result of screening of electrostatic interactions. Generally, maximum complexation was observed in systems with an equal amount of net dendrimer and LPE charges, whereas either excess LPE or dendrimer concentrations resulted in reduced clustering between dendrimers.

Surfactant mediated polyelectrolyte self-assembly

DOE PAGES

Goswami, Monojoy; Borreguero Calvo, Jose M.; Pincus, Phillip A.; ...

2015-11-25

Self-assembly and dynamics of polyelectrolyte (PE) surfactant complex (PES) is investigated using molecular dynamics simulations. The complexation is systematically studied for five different PE backbone charge densities. At a fixed surfactant concentration the PES complexation exhibits pearl-necklace to agglomerated double spherical structures with a PE chain decorating the surfactant micelles. The counterions do not condense on the complex, but are released in the medium with a random distribution. The relaxation dynamics for three different length scales, polymer chain, segmental and monomer, show distinct features of the charge and neutral species; the counterions are fastest followed by the PE chain andmore » surfactants. The surfactant heads and tails have the slowest relaxation due to their restricted movement inside the agglomerated structure. At the shortest length scale, all the charge and neutral species show similar relaxation dynamics confirming Rouse behavior at monomer length scales. Overall, the present study highlights the structure-property relationship for polymer-surfactant complexation. These results will help improve the understanding of PES complex and should aid in the design of better materials for future applications.« less

Semiconductor-Based Photoelectrochemical Conversion of Carbon Dioxide: Stepping Towards Artificial Photosynthesis.

PubMed

Pang, Hong; Masuda, Takuya; Ye, Jinhua

2018-01-18

The photoelectrochemical (PEC) carbon dioxide reduction process stands out as a promising avenue for the conversion of solar energy into chemical feedstocks, among various methods available for carbon dioxide mitigation. Semiconductors derived from cheap and abundant elements are interesting candidates for catalysis. Whether employed as intrinsic semiconductors or hybridized with metallic cocatalysts, biocatalysts, and metal molecular complexes, semiconductor photocathodes exhibit good performance and low overpotential during carbon dioxide reduction. Apart from focusing on carbon dioxide reduction materials and chemistry, PEC cells towards standalone devices that use photohybrid electrodes or solar cells have also been a hot topic in recent research. An overview of the state-of-the-art progress in PEC carbon dioxide reduction is presented and a deep understanding of the catalysts of carbon dioxide reduction is also given. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The PECS II block as a major analgesic component for clavicle operations: A description of 7 case reports.

PubMed

Schuitemaker R, J B; Sala-Blanch, X; Rodriguez-Pérez, C L; Mayoral R, J T; López-Pantaleon, L A; Sánchez-Cohen, A P

2018-01-01

Clavicle fractures correspond to 35% of traumatic fractures of the shoulder girdle. Regional anaesthesia has shown better analgesic results than systemic treatment for perioperative management. Innervation of the clavicle is complex, at present its knowledge raises controversy. The lateral pectoral nerve through the innervating musculature predominantly participates in the lateral and anterior part of the clavicle. The following report of 7 cases describes the effective postoperative analgesia of modified PEC II block in patients with middle third clavicle fracture or acromioclavicular dislocation who underwent a modified PEC II block for postoperative pain management, in the context of a multimodal analgesia. The potential advantage of this management over other analgesic procedures should be evaluated in specific clinical trials. Copyright © 2017 Sociedad Española de Anestesiología, Reanimación y Terapéutica del Dolor. Publicado por Elsevier España, S.L.U. All rights reserved.

Interaction of participant characteristics and type of AAC with individuals with ASD: a meta-analysis.

PubMed

Ganz, Jennifer B; Mason, Rose A; Goodwyn, Fara D; Boles, Margot B; Heath, Amy K; Davis, John L

2014-11-01

Individuals with autism spectrum disorders (ASD) and complex communication needs often rely on augmentative and alternative communication (AAC) as a means of functional communication. This meta-analysis investigated how individual characteristics moderate effectiveness of three types of aided AAC: the Picture Exchange Communication System (PECS), speech-generating devices (SGDs), and other picture-based AAC. Effectiveness was measured via the Improvement Rate Difference. Results indicated that AAC has small to moderate effects on speech outcomes, and that SGDs appear to be most effective when considering any outcome measure with individuals with ASD without comorbid intellectual/developmental disorders (IDD). PECS appears to be most effective when considering any outcome measure with individuals with ASD and IDD. SGDs and PECS were the most effective type of AAC for preschoolers, when aggregating across outcome measures. No difference was found between systems for elementary-aged and older individuals.

Composite carbohydrate interpenetrating polyelectrolyte nano-complexes (IPNC) as a controlled oral delivery system of citalopram HCl for pediatric use: in-vitro/in-vivo evaluation and histopathological examination.

PubMed

Kamel, Rabab; Abbas, Haidy; El-Naa, Mona

2018-06-01

Citalopram HCl (CH) is one of the few drugs which can be used safely in childhood psychiatric disorders. This study was focused on the preparation of interpenetrating polyelectrolytes nano-complexes (IPNC) to transform the hydrophilic carbohydrate polymers into an insoluble form. The IPNCs were loaded with CH to sustain its effect. The IPNC2 (composed of chitosan:pectin in a 3:1 ratio) showed the most extended drug release pattern (P < 0.05) and followed a Higuchi-order kinetics model. It was characterized using SEM, X-rays diffractometry, and FTIR. In-vivo studies were performed using immature rats with induced depression, and were based on the investigation of behavioral, biochemical, and histopathological changes at different time intervals up to 24 h. Rats treated with IPNC2 showed a significant more rapid onset of action and more extended effect in the behavioral tests, in addition to a significantly higher serotonin brain level up to 24 h, compared to rats treated with the market product (P < 0.05). The histopathological examination showed a profound amelioration of the cerebral cortex features of the depressed rats after IPNC2 administration. This study proves the higher efficacy and more extended effect of the new polyelectrolytes nano-complexes compared to the market product.

Cyborg cells: functionalisation of living cells with polymers and nanomaterials.

PubMed

Fakhrullin, Rawil F; Zamaleeva, Alsu I; Minullina, Renata T; Konnova, Svetlana A; Paunov, Vesselin N

2012-06-07

Living cells interfaced with a range of polyelectrolyte coatings, magnetic and noble metal nanoparticles, hard mineral shells and other complex nanomaterials can perform functions often completely different from their original specialisation. Such "cyborg cells" are already finding a range of novel applications in areas like whole cell biosensors, bioelectronics, toxicity microscreening, tissue engineering, cell implant protection and bioanalytical chemistry. In this tutorial review, we describe the development of novel methods for functionalisation of cells with polymers and nanoparticles and comment on future advances in this technology in the light of other literature approaches. We review recent studies on the cell viability and function upon direct deposition of nanoparticles, coating with polyelectrolytes, polymer assisted assembly of nanomaterials and hard shells on the cell surface. The cell toxicity issues are considered for many practical applications in terms of possible adverse effects of the deposited polymers, polyelectrolytes and nanoparticles on the cell surface.

Fibrillar films obtained from sodium soap fibers and polyelectrolyte multilayers.

PubMed

Zawko, Scott A; Schmidt, Christine E

2011-08-01

An objective of tissue engineering is to create synthetic polymer scaffolds with a fibrillar microstructure similar to the extracellular matrix. Here, we present a novel method for creating polymer fibers using the layer-by-layer method and sacrificial templates composed of sodium soap fibers. Soap fibers were prepared from neutralized fatty acids using a sodium chloride crystal dissolution method. Polyelectrolyte multilayers (PEMs) of polystyrene sulfonate and polyallylamine hydrochloride were deposited onto the soap fibers, crosslinked with glutaraldehyde, and then the soap fibers were leached with warm water and ethanol. The morphology of the resulting PEM structures was a dense network of fibers surrounded by a nonfibrillar matrix. Microscopy revealed that the PEM fibers were solid structures, presumably composed of polyelectrolytes complexed with residual fatty acids. These fibrillar PEM films were found to support the attachment of human dermal fibroblasts. Copyright © 2011 Wiley Periodicals, Inc.

Mechanical properties of bulk graphene oxide/poly(acrylic acid)/poly(ethylenimine) ternary polyelectrolyte complex.

PubMed

Duan, Yipin; Wang, Chao; Zhao, Mengmeng; Vogt, Bryan D; Zacharia, Nicole S

2018-05-30

Ternary complexes formed in a single pot process through the mixing of cationic (branched polyethylenimine, BPEI) and anionic (graphene oxide, GO, and poly(acrylic acid), PAA) aqueous solutions exhibit superior mechanical performance in comparison to their binary analogs. The composition of the ternary complex can be simply tuned through the composition of the anionic solution, which influences the water content and mechanical properties of the complex. Increasing the PAA content in the complex decreases the overall water content due to improved charge compensation with the BPEI, but this change also significantly improves the toughness of the complex. Ternary complexes containing ≤32 wt% PAA were too brittle to generate samples for tensile measurements, while extension in excess of 250% could be reached with 57 wt% PAA. From this work, the influence of GO and PAA on the mechanical properties of GO/PAA/BPEI complexes were elucidated with GO sheets acting to restrain the viscous flow and improve the mechanical strength at low loading (<12.6 wt%) and PAA more efficiently complexes with BPEI than GO to generate a less swollen and stronger network. This combination overcomes the brittle nature of GO-BPEI complexes and viscous creep of PAA-BPEI complexes. Ternary nanocomposite complexes appear to provide an effective route to toughen and strengthen bulk polyelectrolyte complexes.

Automated Geometry assisted PEC for electron beam direct write nanolithography

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

Ocola, Leonidas E.; Gosztola, David J.; Rosenmann, Daniel

Nanoscale geometry assisted proximity effect correction (NanoPEC) is demonstrated to improve PEC for nanoscale structures over standard PEC, in terms of feature sharpness for sub-100 nm structures. The method was implemented onto an existing commercially available PEC software. Plasmonic arrays of crosses were fabricated using regular PEC and NanoPEC, and optical absorbance was measured. Results confirm that the improved sharpness of the structures leads to increased sharpness in the optical absorbance spectrum features. We also demonstrated that this method of PEC is applicable to arbitrary shaped structures beyond crosses.

Inactivation of pecS restores the virulence of mutants devoid of osmoregulated periplasmic glucans in the phytopathogenic bacterium Dickeya dadantii.

PubMed

Bontemps-Gallo, Sébastien; Madec, Edwige; Lacroix, Jean-Marie

2014-04-01

Dickeya dadantii is a phytopathogenic enterobacterium that causes soft rot disease in a wide range of plant species. Maceration, an apparent symptom of the disease, is the result of the synthesis and secretion of a set of plant cell wall-degrading enzymes (PCWDEs), but many additional factors are required for full virulence. Among these, osmoregulated periplasmic glucans (OPGs) and the PecS transcriptional regulator are essential virulence factors. Several cellular functions are controlled by both OPGs and PecS. Strains devoid of OPGs display a pleiotropic phenotype including total loss of virulence, loss of motility and severe reduction in the synthesis of PCWDEs. PecS is one of the major regulators of virulence in D. dadantii, acting mainly as a repressor of various cellular functions including virulence, motility and synthesis of PCWDEs. The present study shows that inactivation of the pecS gene restored virulence in a D. dadantii strain devoid of OPGs, indicating that PecS cannot be de-repressed in strains devoid of OPGs.

Stability of foam films of oppositely charged polyelectrolyte/surfactant mixtures: effect of isoelectric point.

PubMed

Kristen-Hochrein, Nora; Laschewsky, André; Miller, Reinhard; von Klitzing, Regine

2011-12-15

In the present paper, the influence of the surfactant concentration and the degree of charge of a polymer on foam film properties of oppositely charged polyelectrolyte/surfactant mixtures has been investigated. To verify the assumption that the position of the isoelectric point (IEP) does not change the character of the foam film stabilities, the position of the IEP of the polyelectrolyte/surfactant mixtures has been shifted in two different ways. Within the first series of experiments, the foam film properties were studied using a fixed surfactant concentration of 3 × 10(-5) M in the mixture. Due to the low surfactant concentration, this is a rather dilute system. In the second approach, a copolymer of nonionic and ionic monomer units was used to lower the charge density of the polymer. This gave rise to additional interactions between the polyelectrolyte and the surfactant, which makes the description of the foam film behavior more complex. In both systems, the same characteristics of the foam film stabilities were found: The foam film stability is reduced toward the IEP of the system, followed by a destabilization around the IEP. At polyelectrolyte concentrations above the IEP, foam films are very stable. However, the concentration range where unstable films were formed was rather broad, and the mechanisms leading to the destabilization had different origins. The results were compared with former findings on PAMPS/C(14)TAB mixtures with an IEP of 10(-4) M.

[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 PEG-PDMAEMA Block Copolymer Architecture on Polyelectrolyte Complex Formation with Heparin.

PubMed

Välimäki, Salla; Khakalo, Alexey; Ora, Ari; Johansson, Leena-Sisko; Rojas, Orlando J; Kostiainen, Mauri A

2016-09-12

Heparin is a naturally occurring polyelectrolyte consisting of a sulfated polysaccharide backbone. It is widely used as an anticoagulant during major surgical operations. However, the associated bleeding risks require rapid neutralization after the operation. The only clinically approved antidote for heparin is protamine sulfate, which is, however, ineffective against low molecular weight heparin and can cause severe adverse reactions in patients. In this study, the facile synthesis of cationic-neutral diblock copolymers and their effective heparin binding is presented. Poly(ethylene glycol)-poly(2-(dimethylamino)ethyl methacrylate) (PEG-PDMAEMA) block copolymers were synthesized in two steps via atom-transfer radical polymerization (ATRP) using PEG as a macroinitiator. Solution state binding between heparin and a range of PEG-PDMAEMA block copolymers and one homopolymer was studied with dynamic light scattering and methylene blue displacement assay. Also in vitro binding in plasma was studied by utilizing a chromogenic heparin anti-Xa assay. Additionally, quartz crystal microbalance and multiparametric surface plasmon resonance were used to study the surface adsorption kinetics of the polymers on a heparin layer. It was shown that the block copolymers and heparin form electrostatically bound complexes with varying colloidal properties, where the block lengths play a key role in controlling the heparin binding affinity, polyelectrolyte complex size and surface charge. With the optimized polymers (PEG114PDMAEMA52 and PEG114PDMAEMA100), heparin could be neutralized in a dose-dependent manner, and bound efficiently into small neutral complexes, with a hydrodynamic radius less than 100 nm. These complexes had only a limited effect on cell viability. Based on these studies, our approach paves the way for the development of new polymeric heparin binding agents.

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

USGS Publications Warehouse

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

1984-01-01

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

Percutaneous endoscopic colostomy for adults with chronic constipation: Retrospective case series of 12 patients.

PubMed

Strijbos, D; Keszthelyi, D; Masclee, A A M; Gilissen, L P L

2018-05-01

Percutaneous endoscopic colostomy (PEC) is a technique derived from percutaneous endoscopic gastrostomy. When conservative treatment of chronic obstipation fails, colon irrigation via PEC seems less invasive than surgical interventions. However, previous studies have noted high complication rates of PEC, mostly related to infections. Our aim was to report our experiences with PEC in patients with chronic refractory constipation. Retrospective analysis of all patients who underwent PEC for refractory constipation in our secondary referral hospital between 2009 and 2016. Twelve patients received a PEC for chronic, refractory constipation. Short-term efficacy for relief of constipation symptoms was good in 8 patients and moderate in 4 patients. Two patients had the PEC removed because of spontaneous improvement of constipation. Three patients, who initially noticed a positive effect, preferred an ileostomy over PEC after 1-5 years. One PEC was removed because of an abscess. Long-term efficacy is 50%: 6 patients still use their PEC after 3.3 years of follow-up. No mortality occurred. PEC offers a technically easily feasible and safe treatment option for patients with chronic constipation not responding to conventional therapy. Long-term efficacy of PEC in our patients is 50%. © 2017 John Wiley & Sons Ltd.

Recognition unit-free and self-cleaning photoelectrochemical sensing platform on TiO2 nanotube photonic crystals for sensitive and selective detection of dopamine release from mouse brain.

PubMed

Xin, Yanmei; Li, Zhenzhen; Wu, Wenlong; Fu, Baihe; Wu, Hongjun; Zhang, Zhonghai

2017-01-15

For implementing sensitive and selective detection of biological molecules, the biosensors are been designed more and more complicated. The exploration of detection platform in a simple way without loss their sensitivity and selectivity is always a big challenge. Herein, a prototype of recognition biomolecule unit-free photoelectrochemical (PEC) sensing platform with self-cleaning activity is proposed with TiO 2 nanotube photonic crystal (TiO 2 NTPCs) materials as photoelectrode, and dopamine (DA) molecule as both sensitizer and target analyte. The unique adsorption between DA and TiO 2 NTPCs induces the formation of charge transfer complex, which not only expends the optical absorption of TiO 2 into visible light region, thus significantly boosts the PEC performance under illumination of visible light, but also implements the selective detection of DA on TiO 2 photoelectrode. This simple but efficient PEC analysis platform presents a low detection limit of 0.15nm for detection of DA, which allows to realize the sensitive and selective determination of DA release from the mouse brain for its practical application after coupled with a microdialysis probe. The DA functionalized TiO 2 NTPCs PEC sensing platform opens up a new PEC detection model, without using extra-biomolecule auxiliary, just with target molecule naturally adsorbed on the electrode for sensitive and selective detection, and paves a new avenue for biosensors design with minimalism idea. Copyright © 2016 Elsevier B.V. All rights reserved.

Evaluation of Escherichia coli isolates from healthy chickens to determine their potential risk to poultry and human health.

PubMed

Stromberg, Zachary R; Johnson, James R; Fairbrother, John M; Kilbourne, Jacquelyn; Van Goor, Angelica; Curtiss, Roy; Mellata, Melha

2017-01-01

Extraintestinal pathogenic Escherichia coli (ExPEC) strains are important pathogens that cause diverse diseases in humans and poultry. Some E. coli isolates from chicken feces contain ExPEC-associated virulence genes, so appear potentially pathogenic; they conceivably could be transmitted to humans through handling and/or consumption of contaminated meat. However, the actual extraintestinal virulence potential of chicken-source fecal E. coli is poorly understood. Here, we assessed whether fecal E. coli isolates from healthy production chickens could cause diseases in a chicken model of avian colibacillosis and three rodent models of ExPEC-associated human infections. From 304 E. coli isolates from chicken fecal samples, 175 E. coli isolates were screened by PCR for virulence genes associated with human-source ExPEC or avian pathogenic E. coli (APEC), an ExPEC subset that causes extraintestinal infections in poultry. Selected isolates genetically identified as ExPEC and non-ExPEC isolates were assessed in vitro for virulence-associated phenotypes, and in vivo for disease-causing ability in animal models of colibacillosis, sepsis, meningitis, and urinary tract infection. Among the study isolates, 13% (40/304) were identified as ExPEC; the majority of these were classified as APEC and uropathogenic E. coli, but none as neonatal meningitis E. coli. Multiple chicken-source fecal ExPEC isolates resembled avian and human clinical ExPEC isolates in causing one or more ExPEC-associated illnesses in experimental animal infection models. Additionally, some isolates that were classified as non-ExPEC were able to cause ExPEC-associated illnesses in animal models, and thus future studies are needed to elucidate their mechanisms of virulence. These findings show that E. coli isolates from chicken feces contain ExPEC-associated genes, exhibit ExPEC-associated in vitro phenotypes, and can cause ExPEC-associated infections in animal models, and thus may pose a health threat to poultry and consumers.

Evaluation of Escherichia coli isolates from healthy chickens to determine their potential risk to poultry and human health

PubMed Central

Johnson, James R.; Fairbrother, John M.; Kilbourne, Jacquelyn; Van Goor, Angelica; Curtiss, Roy; Mellata, Melha

2017-01-01

Extraintestinal pathogenic Escherichia coli (ExPEC) strains are important pathogens that cause diverse diseases in humans and poultry. Some E. coli isolates from chicken feces contain ExPEC-associated virulence genes, so appear potentially pathogenic; they conceivably could be transmitted to humans through handling and/or consumption of contaminated meat. However, the actual extraintestinal virulence potential of chicken-source fecal E. coli is poorly understood. Here, we assessed whether fecal E. coli isolates from healthy production chickens could cause diseases in a chicken model of avian colibacillosis and three rodent models of ExPEC-associated human infections. From 304 E. coli isolates from chicken fecal samples, 175 E. coli isolates were screened by PCR for virulence genes associated with human-source ExPEC or avian pathogenic E. coli (APEC), an ExPEC subset that causes extraintestinal infections in poultry. Selected isolates genetically identified as ExPEC and non-ExPEC isolates were assessed in vitro for virulence-associated phenotypes, and in vivo for disease-causing ability in animal models of colibacillosis, sepsis, meningitis, and urinary tract infection. Among the study isolates, 13% (40/304) were identified as ExPEC; the majority of these were classified as APEC and uropathogenic E. coli, but none as neonatal meningitis E. coli. Multiple chicken-source fecal ExPEC isolates resembled avian and human clinical ExPEC isolates in causing one or more ExPEC-associated illnesses in experimental animal infection models. Additionally, some isolates that were classified as non-ExPEC were able to cause ExPEC-associated illnesses in animal models, and thus future studies are needed to elucidate their mechanisms of virulence. These findings show that E. coli isolates from chicken feces contain ExPEC-associated genes, exhibit ExPEC-associated in vitro phenotypes, and can cause ExPEC-associated infections in animal models, and thus may pose a health threat to poultry and consumers. PMID:28671990

Complexation of lysozyme with adsorbed PtBS-b-SCPI block polyelectrolyte micelles on silver surface.

PubMed

Papagiannopoulos, Aristeidis; Christoulaki, Anastasia; Spiliopoulos, Nikolaos; Vradis, Alexandros; Toprakcioglu, Chris; Pispas, Stergios

2015-01-20

We present a study of the interaction of the positively charged model protein lysozyme with the negatively charged amphiphilic diblock polyelectrolyte micelles of poly(tert-butylstyrene-b-sodium (sulfamate/carboxylate)isoprene) (PtBS-b-SCPI) on the silver/water interface. The adsorption kinetics are monitored by surface plasmon resonance, and the surface morphology is probed by atomic force microscopy. The micellar adsorption is described by stretched-exponential kinetics, and the micellar layer morphology shows that the micelles do not lose their integrity upon adsorption. The complexation of lysozyme with the adsorbed micellar layers depends on the micelles arrangement and density in the underlying layer, and lysozyme follows the local morphology of the underlying roughness. When the micellar adsorbed amount is small, the layers show low capacity in protein complexation and low resistance in loading. When the micellar adsorbed amount is high, the situation is reversed. The adsorbed layers both with or without added protein are found to be irreversibly adsorbed on the Ag surface.

Equilibration of a polycation - anionic surfactant mixture at the water/vapor interface.

PubMed

Akanno, Andrew; Guzmán, Eduardo; Fernández-Peña, Laura; Llamas, Sara; Ortega, Francisco; Rubio, Ramon Gonzalez

2018-06-01

The adsorption of concentrated poly(diallyldimethylammonium chloride) (PDADMAC) - sodium lauryl ether sulfate (SLES) mixtures at the water / vapor interface has been studied by different surface tension techniques and dilational visco-elasticity measurements. This work tries to shed light on the way in which the formation of polyelectrolyte - surfactant complexes in the bulk affects to the interfacial properties of mixtures formed by a polycation and an oppositely charged surfactant. The results are discussed in terms of a two-step adsorption-equilibration of PDADMAC - SLES complexes at the interface, with the initial stages involving the diffusion of kinetically trapped aggregates formed in the bulk to the interface followed by the dissociation and spreading of such aggregates at the interface. This latter process becomes the main contribution to the surface tension decrease. This work helps on the understanding of the most fundamental bases of the physico-chemical behavior of concentrated polyelectrolyte - surfactant mixtures which present complex bulk and interfacial interactions with interest in both basic and applied sciences.

PecS and PecT coregulate the synthesis of HrpN and pectate lyases, two virulence determinants in Erwinia chrysanthemi 3937.

PubMed

Nasser, William; Reverchon, Sylvie; Vedel, Regine; Boccara, Martine

2005-11-01

Erwinia chrysanthemi strain 3937 is a necrotrophic bacterial plant pathogen. Pectinolytic enzymes and, in particular, pectate lyases play a key role in soft rot symptoms; however, the efficient colonization of plants by E. chrysanthemi requires additional factors. These factors include HrpN (harpin), a heat-stable, glycine-rich hydrophilic protein, which is secreted by the type III secretion system. We investigated the expression of hrpN in E. chrysanthemi 3937 in various environmental conditions and different regulatory backgrounds. Using lacZ fusions, hrpN expression was markedly influenced by the carbon source, osmolarity, growth phase, and growth substrate. hrpN was repressed when pectinolysis started and negatively regulated by the repressors of pectate lyase synthesis, PecS and PecT. Primer extension data and in vitro DNA-protein interaction experiments support a model whereby PecS represses hrpN expression by binding to the hrpN regulatory region and inhibiting transcript elongation. The results suggest coordinated regulation of HrpN and pectate lyases by PecS and PecT. A putative model of the synthesis of these two virulence factors in E. chrysanthemi during pathogenesis is presented.

DNA - peptide polyelectrolyte complexes: Phase control by hybridization

NASA Astrophysics Data System (ADS)

Vieregg, Jeffrey; Lueckheide, Michael; Marciel, Amanda; Leon, Lorraine; Tirrell, Matthew

DNA is one of the most highly-charged molecules known, and interacts strongly with charged molecules in the cell. Condensation of long double-stranded DNA is one of the classic problems of biophysics, but the polyelectrolyte behavior of short and/or single-stranded nucleic acids has attracted far less study despite its importance for both biological and engineered systems. We report here studies of DNA oligonucleotides complexed with cationic peptides and polyamines. As seen previously for longer sequences, double-stranded oligonucleotides form solid precipitates, but single-stranded oligonucleotides instead undergo liquid-liquid phase separation to form coacervate droplets. Complexed oligonucleotides remain competent for hybridization, and display sequence-dependent environmental response. We observe similar behavior for RNA oligonucleotides, and methylphosphonate substitution of the DNA backbone indicates that nucleic acid charge density controls whether liquid or solid complexes are formed. Liquid-liquid phase separations of this type have been implicated in formation of membraneless organelles in vivo, and have been suggested as protocells in early life scenarios; oligonucleotides offer an excellent method to probe the physics controlling these phenomena.

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

Ductile polyelectrolyte macromolecule-complexed zinc phosphate conversion crystal pre-coatings and topcoatings embodying a laminate

DOEpatents

Sugama, Toshifumi; Kukacka, Lawrence E.; Carciello, Neal R.

1987-01-01

This invention relates to a precoat, laminate, and method for ductile coatings on steel and non-ferrous metals which comprises applying a zinc phosphating coating solution modified by a solid polyelectrolyte selected from polyacrylic acid (PAA), polymethacrylic acid (PMA), polyitaconic acid (PIA), and poly-L-glutamic acid. The contacting of the resin with the phosphating solution is made for a period of up to 20 hours at about 80.degree. C. The polyelectrolyte or the precoat is present in about 0.5-5.0% by weight of the total precoat composition and after application, the precoat base is dried for up to 5 hours at about 150.degree. C. to desiccate. Also, a laminate may be formed where polyurethane (PU) is applied as an elastomeric topcoating or polyfuran resin is applied as a glassy topcoating. It has been found that the use of PAA at a molecular weight of about 2.times.10.sup.5 gave improved ductility modulus effect.

Ductile polyelectrolyte macromolecule-complexed zinc phosphate conversion crystal pre-coatings and topcoatings embodying a laminate

DOEpatents

Sugama, T.; Kukacka, L.E.; Carciello, N.R.

1987-04-21

This invention relates to a precoat, laminate, and method for ductile coatings on steel and non-ferrous metals which comprises applying a zinc phosphating coating solution modified by a solid polyelectrolyte selected from polyacrylic acid (PAA), polymethacrylic acid (PMA), polyitaconic acid (PIA), and poly-L-glutamic acid. The contacting of the resin with the phosphating solution is made for a period of up to 20 hours at about 80 C. The polyelectrolyte or the precoat is present in about 0.5--5.0% by weight of the total precoat composition and after application, the precoat base is dried for up to 5 hours at about 150 C to desiccate. Also, a laminate may be formed where polyurethane (PU) is applied as an elastomeric topcoating or polyfuran resin is applied as a glassy topcoating. It has been found that the use of PAA at a molecular weight of about 2 [times] 10[sup 5] gave improved ductility modulus effect. 5 figs.

Ductile polyelectrolyte macromolecule-complexed zinc phosphate conversion crystal pre-coatings and topcoatings embodying a laminate

DOEpatents

Sugama, Toshifumi; Kukacka, L.E.; Carciello, N.R.

1985-11-05

This invention relates to a precoat, laminate, and method for ductile coatings on steel and non-ferrous metals which comprises applying a zinc phosphating coating solution modified by a solid polyelectrolyte selected from polyacrylic acid (PAA), polymethacrylic acid (PMA), polyitaconic acid (PIA), and poly-L-glutamic acid. The contacting of the resin with the phosphating solution is made for a period of up to 20 hours at about 80/sup 0/C. The polyelectrolyte or the precoat is present in about 0.5 to 5.0% by weight of the total precoat composition and after application, the precoat base is dried for up to 5 hours at about 150/sup 0/C to desiccate. Also, a laminate may be formed where polyurethane (PU) is applied as an elastomeric topcoating or polyfuran resin is applied as a glassy topcoating. It has been found that the use of PAA at a molecular weight of about 2 x 10/sup 5/ gave improved ductility modulus effect.

Integrated photoelectrochemical cell and system having a liquid electrolyte

DOEpatents

Deng, Xunming; Xu, Liwei

2010-07-06

An integrated photoelectrochemical (PEC) cell generates hydrogen and oxygen from water while being illuminated with radiation. The PEC cell employs a liquid electrolyte, a multi-junction photovoltaic electrode, and a thin ion-exchange membrane. A PEC system and a method of making such PEC cell and PEC system are also disclosed.

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.

A pilot evaluation study of the Picture Exchange Communication System (PECS) for children with autistic spectrum disorders.

PubMed

Magiati, Iliana; Howlin, Patricia

2003-09-01

A pilot study was conducted to evaluate the effects of training teachers of children with autistic spectrum disorders (ASDs) in the use of the Picture Exchange Communication System (PECS). Thirty-four children with ASDs (29 boys and 5 girls) were selected from eight specialist schools. Teaching staff attended a 2 day PECS workshop and received six half-day visits from PECS consultants. Data on the children's use of PECS, spontaneous communication, and adaptive behaviour were collected before the study and at set times following the workshop. Significant, rapid increases were recorded in the level of PECS attained by the children, in their PECS vocabulary, and in their frequency of PECS use over time. Improvements in children's general level of communication were slower to occur. The majority of participants showed improvements in their ability to use PECS. The results are discussed in relation to the methodological and practical difficulties that arose during the project.

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.

Interfacial complexation in microfluidic droplets for single-step fabrication of microcapsule

NASA Astrophysics Data System (ADS)

Kaufman, Gilad; Nejati, Siamak; Sarfati, Raphael; Boltyanskiy, Rostislav; Williams, Danielle; Liu, Wei; Schloss, Ashley; Regan, Lynn; Yan, Elsa; Dufrense, Eric; Loewenberg, Michael; Osuji, Chinedum

We present microfluidic interfacial complexation in emulsion droplets as a simple single-step approach for fabricating a large variety of stable monodisperse microcapsules with tailored mechanical properties, protein binding and controlled release behavior. We rely on electrostatic interactions and hydrogen bonding to direct the assembly of complementary species at oil-water droplet interfaces to form microcapsules with polyelectrolyte shells, composite polyelectrolyte-nanoparticle shells, and copolymer-nanofiber shells. Additionally, we demonstrate the formation of microcapsules by adsorption of an amphiphilic bacterial hydrophobin, BslA, at oil-in-water and water-in-oil droplets, and protein capture on these capsules using engineered variants of the hydrophobin. We discuss the composition dependence of mechanical properties, shell thickness and release behavior, and regimes of stability for microcapsule fabrication. Nanoparticle based microcapsules display an intriguing plastic deformation response which enables the formation of large aspect ratio asperities by pipette aspiration of the shell.

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

A Pilot Evaluation Study of the Picture Exchange Communication System (PECS) for Children with Autistic Spectrum Disorders.

ERIC Educational Resources Information Center

Magiati, Iliana; Howlin, Patricia

2003-01-01

A study evaluated the effects of training 47 teachers of children with autism in the use of the Picture Exchange Communication System (PECS). Following training, significant, rapid increases were recorded in the level of PECS attained by the students (n=34), in students' PECS vocabulary, and in students' use of PECS. (Contains references.) (CR)

Subtotal Ablation of Parietal Epithelial Cells Induces Crescent Formation

PubMed Central

Sicking, Eva-Maria; Fuss, Astrid; Uhlig, Sandra; Jirak, Peggy; Dijkman, Henry; Wetzels, Jack; Engel, Daniel R.; Urzynicok, Torsten; Heidenreich, Stefan; Kriz, Wilhelm; Kurts, Christian; Ostendorf, Tammo; Floege, Jürgen; Smeets, Bart

2012-01-01

Parietal epithelial cells (PECs) of the renal glomerulus contribute to the formation of both cellular crescents in rapidly progressive GN and sclerotic lesions in FSGS. Subtotal transgenic ablation of podocytes induces FSGS but the effect of specific ablation of PECs is unknown. Here, we established an inducible transgenic mouse to allow subtotal ablation of PECs. Proteinuria developed during doxycycline-induced cellular ablation but fully reversed 26 days after termination of doxycycline administration. The ablation of PECs was focal, with only 30% of glomeruli exhibiting histologic changes; however, the number of PECs was reduced up to 90% within affected glomeruli. Ultrastructural analysis revealed disruption of PEC plasma membranes with cytoplasm shedding into Bowman’s space. Podocytes showed focal foot process effacement, which was the most likely cause for transient proteinuria. After >9 days of cellular ablation, the remaining PECs formed cellular extensions to cover the denuded Bowman’s capsule and expressed the activation marker CD44 de novo. The induced proliferation of PECs persisted throughout the observation period, resulting in the formation of typical cellular crescents with periglomerular infiltrate, albeit without accompanying proteinuria. In summary, subtotal ablation of PECs leads the remaining PECs to react with cellular activation and proliferation, which ultimately forms cellular crescents. PMID:22282596

Zoonotic Potential of Escherichia coli Isolates from Retail Chicken Meat Products and Eggs

PubMed Central

Mitchell, Natalie M.; Johnson, James R.; Johnston, Brian; Curtiss, Roy

2014-01-01

Chicken products are suspected as a source of extraintestinal pathogenic Escherichia coli (ExPEC), which causes diseases in humans. The zoonotic risk to humans from chicken-source E. coli is not fully elucidated. To clarify the zoonotic risk posed by ExPEC in chicken products and to fill existing knowledge gaps regarding ExPEC zoonosis, we evaluated the prevalence of ExPEC on shell eggs and compared virulence-associated phenotypes between ExPEC and non-ExPEC isolates from both chicken meat and eggs. The prevalence of ExPEC among egg-source isolates was low, i.e., 5/108 (4.7%). Based on combined genotypic and phenotypic screening results, multiple human and avian pathotypes were represented among the chicken-source ExPEC isolates, including avian-pathogenic E. coli (APEC), uropathogenic E. coli (UPEC), neonatal meningitis E. coli (NMEC), and sepsis-associated E. coli (SEPEC), as well as an undefined ExPEC group, which included isolates with fewer virulence factors than the APEC, UPEC, and NMEC isolates. These findings document a substantial prevalence of human-pathogenic ExPEC-associated genes and phenotypes among E. coli isolates from retail chicken products and identify key virulence traits that could be used for screening. PMID:25480753

Nanoniobia modification of CdS photoanode for an efficient and stable photoelectrochemical cell.

PubMed

Pareek, Alka; Paik, Pradip; Borse, Pramod H

2014-12-30

Herein we report the surface modification of a CdS film by niobia nanoparticles via thioglycerol as an organic linker and thus fabricate an efficient and a stable photoanode for a photoelectrochemical (PEC) cell. We have synthesized three differenly sized (∼3, ∼6 ,and ∼9 nm) niobia nanoparticles by a hydrothermal synthesis approach and have further investigated the particle-size-dependent PEC performance of the nanoparticle-modified CdS photoanode. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) confirm the formation of Nb2O5 nanoparticles that are prepared via decomposition of the niobium peroxo complex during the hydrothermal reaction and reveal the presence of surface OH(-) groups over niobia nanoparticles that impart a high catalytic property to a material. The nano-Nb2O5-modified photoanode displayed a 23-fold higher power conversion efficiency compared to that of CdS. This modified structure increases the open circuit voltage (OCV) from 0.65 to 0.77 V, which is attributed to the nano-Nb2O5-induced surface passivation effect over bare CdS. Linking of nanoparticles on the CdS surface improves the photocorrosion stability of the CdS photoanode for even longer than 4 h in contrast to the tens of minutes for the base CdS surface. The uniform coverage of the CdS photoanode surface by niobia nanoparticles is thus found to be the controlling parameter for achieving a higher PEC performance and stability of the photoanode. This finding directed us to design an improved CdS photoanode for efficient and prolonged PEC hydrogen generation from a PEC cell.

The cytochrome complex SoxXA of Paracoccus pantotrophus is produced in Escherichia coli and functional in the reconstituted sulfur-oxidizing enzyme system.

PubMed

Rother, Dagmar; Friedrich, Cornelius G

2002-07-29

The heterodimeric c-type cytochrome complex SoxXA of Paracoccus pantotrophus was produced in Escherichia coli. The soxX and soxA genes, separated by two genes in the sox gene cluster of P. pantotrophus, were fused with ribosome binding sites optimal for E. coli and combined to give soxXA in pRD133.27. The cytochrome complex SoxXA was produced in E. coli M15 containing pRD133.27, pREP4 encoding the Lac repressor and plasmid pEC86, carrying essential cytochrome c maturation genes. SoxX and SoxA were formed in a ratio of about 2.5:1. SoxA appeared to be unstable when not complexed with SoxX. The cytochrome complex SoxXA, purified to homogeneity from periplasmic extracts of E. coli M15 (pRD133.27, pREP4, pEC86), exhibited identical biochemical and biophysical properties as compared to SoxXA of P. pantotrophus. Moreover, this cytochrome complex was shown to be equally catalytically active with respect to rates and reactivity with different sulfur substrates in the reconstituted sulfur-oxidizing enzyme system using homogeneous Sox-proteins of P. pantotrophus. Homogeneous SoxX was catalytically inactive.

Time Recovery for a Complex Process Using Accelerated Dynamics.

PubMed

Paz, S Alexis; Leiva, Ezequiel P M

2015-04-14

The hyperdynamics method (HD) developed by Voter (J. Chem. Phys. 1996, 106, 4665) sets the theoretical basis to construct an accelerated simulation scheme that holds the time scale information. Since HD is based on transition state theory, pseudoequilibrium conditions (PEC) must be satisfied before any system in a trapped state may be accelerated. As the system evolves, many trapped states may appear, and the PEC must be assumed in each one to accelerate the escape. However, since the system evolution is a priori unknown, the PEC cannot be permanently assumed to be true. Furthermore, the different parameters of the bias function used may need drastic recalibration during this evolution. To overcome these problems, we present a general scheme to switch between HD and conventional molecular dynamics (MD) in an automatic fashion during the simulation. To decide when HD should start and finish, criteria based on the energetic properties of the system are introduced. On the other hand, a very simple bias function is proposed, leading to a straightforward on-the-fly set up of the required parameters. A way to measure the quality of the simulation is suggested. The efficiency of the present hybrid HD-MD method is tested for a two-dimensional model potential and for the coalescence process of two nanoparticles. In spite of the important complexity of the latter system (165 degrees of freedoms), some relevant mechanistic properties were recovered within the present method.

Parietal cells-new perspectives in glomerular disease.

PubMed

Miesen, Laura; Steenbergen, Eric; Smeets, Bart

2017-07-01

In normal glomeruli, parietal epithelial cells (PECs) line the inside of Bowman's capsule and form an inconspicuous sheet of flat epithelial cells in continuity with the proximal tubular epithelial cells (PTECs) at the urinary pole and with the podocytes at the vascular pole. PECs, PTECs and podocytes have a common mesenchymal origin and are the result of divergent differentiation during embryogenesis. Podocytes and PTECs are highly differentiated cells with well-established functions pertaining to the maintenance of the filtration barrier and transport, respectively. For PECs, no specific function other than a structural one has been known until recently. Possible important functions for PECs in the fate of the glomerulus in glomerular disease have now become apparent: (1) PECs may be involved in the replacement of lost podocytes; (2) PECs form the basis of extracapillary proliferative lesions and subsequent sclerosis in glomerular disease. In addition to the acknowledgement that PECs are crucial in glomerular disease, knowledge has been gained regarding the molecular processes driving the phenotypic changes and behavior of PECs. Understanding these molecular processes is important for the development of specific therapeutic approaches aimed at either stimulation of the regenerative function of PECs or inhibition of the pro-sclerotic action of PECs. In this review, we discuss recent advances pertaining to the role of PECs in glomerular regeneration and disease and address the major molecular processes involved.

Measuring patient experience in dialysis: a new paradigm of quality assessment.

PubMed

Rhee, Connie M; Brunelli, Steven M; Subramanian, Lalita; Tentori, Francesca

2018-04-01

Patients' experience of care (PEC) is as an important dimension in quality of care. As a distinct entity from patient satisfaction and patient health-related quality of life, PEC is defined as patients' perceptions of the range of interactions they have with the health care system, including care from providers, facilities, and health plans. While traditionally PEC may be ascertained via informal assessments, in recent years, especially in the United States, there has been a shift towards standardized surveillance of PEC amongst dialysis patients in order to: (1) set a normative expectation regarding the importance of PEC; (2) standardize the components of patients' experience that are assessed to minimize potential "blind spots"; (3) provide a direct "voice" to the patient in communicating perceptions of their care; (4) facilitate comparisons of quality across facilities; and (5) broaden accountability for PEC to the entire multidisciplinary dialysis care team. In this review, we will discuss the significance of PEC as a quality of care metric in dialysis patients; the history of PEC assessment across other health care arenas; the development of the In-Center Hemodialysis Consumer Assessment of Healthcare Provider and Systems survey as a means to standardize PEC assessment among US dialysis patients; experiences in PEC assessment across international dialysis populations; and future areas of research needed to refine the ascertainment of PEC and its impact upon patient outcomes.

Effects of organoclay to miscibility, mechanical and thermal properties of poly(lactic acid) and propylene-ethylene copolymer blends

NASA Astrophysics Data System (ADS)

Wacharawichanant, S.; Ounyai, C.; Rassamee, P.

2017-07-01

The effects of propylene-ethylene copolymer (PEC or PEC3300) and clay surface modified with 25-30 wt% of trimethylstearyl ammonium (Clay-TSA) on morphology, thermal and mechanical properties of poly(lactic acid) (PLA) were investigated. The morphology analysis showed PLA/PEC3300 blends clearly demonstrated a two-phase separation of dispersed phase and the matrix phase and the addition of Clay-TSA could improve the miscibility of PLA and PEC3300 blends due to the decreased of the domain sizes of dispersed PEC3300 phase in the polymer matrix. From X-ray diffraction analysis showed the intercalation of PLA chains inside the Clay-TSA and this result implied that Clay-TSA platelets acted as an effective compatibilizer. The tensile properties showed the strain at break of PLA was improved after adding PEC3300 while Young’s modulus, tensile strength and storage modulus decreased. The addition of Clay-TSA could improve Young’s modulus of PLA/PEC3300 blends. The addition of Clay-TSA 7 phr showed the maximum of Young’s modulus of PLA/PEC3300/Clay-TSA composites. The thermal properties found that the addition of PEC3300 and Clay-TSA did not change significantly on the glass transition temperature and melting point temperature of PLA. The percent of crystallinity of PLA decreased with increasing PEC content. The thermal stability of PLA improved after adding PEC3300.

Photocatalytic and photoelectrochemical performance of Ta{sub 3}N{sub 5} microcolumn films fabricated using facile reactive sputtering

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

Lin, Der-Hwa; Chang, Kao-Shuo, E-mail: kschang@mail.ncku.edu.tw; Promotion Center for Global Materials Research, National Cheng Kung University, No. 1 University Road, Tainan City 70101, Taiwan

2016-08-21

This paper presents the photocatalytic and photoelectrochemical (PEC) properties of Ta{sub 3}N{sub 5} microcolumn films. The highlights include (1) overcoming the fundamental barrier of standard reactive sputtering for fabricating microcolumns; (2) preventing unnecessary complexity from complicating facile sputtering; (3) an alternative but effective approach for fabricating Ta{sub 3}N{sub 5} without using caustic NH{sub 3} gases; (4) investigating morphology tuning for favorable photocatalysis and PEC reactions; and (5) elucidating the relationships of the structures, morphologies, and properties of Ta{sub 3}N{sub 5} microcolumns. High-resolution transmission electron microscopy and selective-area electron diffraction verified the polycrystallinity of Ta{sub 3}N{sub 5} microcolumns, of which themore » elemental compositions and stoichiometry were measured using electron-probe energy dispersive spectroscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy. The corresponding band gap was determined to be approximately 2.1 eV. The sample exhibited a superior photodegradation capability; the photodegradation rate constant k was determined to be approximately 1.4 times higher than that of P25 under UV irradiation. A photocatalytic and PEC cycling test indicated the photodegradation reusability and photostability of the Ta{sub 3}N{sub 5} microcolumns. The incident photon-to-current efficiency performance reached 6%, suggesting that these microcolumns hold potential for application in PEC devices.« less

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.

Coencapsulation of oxygen carriers and glucose oxidase in polyelectrolyte complex capsules for the enhancement of D-gluconic acid and delta-gluconolactone production.

PubMed

Bucko, Marek; Gemeiner, Peter; Vikartovská, Alica; Mislovicová, Danica; Lacík, Igor; Tkác, Ján

2010-04-01

A novel encapsulated oxidative biocatalyst comprising glucose oxidase (GOD) coencapsulated with oxygen carriers within polyelectrolyte complex capsules was developed for the production of D-gluconic acid and delta-gluconolactone. The capsules containing immobilized GOD were produced by polyelectrolyte complexation with sodium alginate (SA) and cellulose sulfate (CS) as polyanions, poly(methylene-co-guanidine) (PMCG) as the polycation, CaCl(2) as the gelling agent and NaCl as the antigelling agent (GOD-SA-CS/PMCG capsules). Poly(dimethylsiloxane) (PDMS) and an emulsion of n-dodecane (DOD) or perfluorodecaline (PFD) with PDMS were used as the oxygen carriers and MnO(2) was used as a hydrogen peroxide decomposition catalyst. Water-soluble PDMS was found to act as both an oxygen carrier and an emulsifier of water-insoluble DOD and PFD. Stable microcapsules could be produced with concentrations of up to 4% (w/w) of PDMS, 10% (w/w) of DOD and PFD, and 25% (w/w) of MnO(2) in the polyanion solution of SA and CS. Roughly a two-fold increase in the GOD activity from 21.0+/-1.1 to 38.4+/-2.0 U*g(-1) and product space-time yields (STY) from 44.3+/-2.0 to 83.4+/-3.4 g*H*day(-1) could be achieved utilizing coencapsulated oxygen carriers compared to GOD encapsulated in the absence of oxygen carriers. This enhanced production does not significantly depend on the selected oxygen carrier under the conditions used in this study.

Isolation and characterization of polygalacturonase genes (pecA and pecB) from Aspergillus flavus.

PubMed Central

Whitehead, M P; Shieh, M T; Cleveland, T E; Cary, J W; Dean, R A

1995-01-01

Two genes, pecA and pecB, encoding endopolyglacturonases were cloned from a highly aggressive strain of Aspergillus flavus. The pecA gene consisted of 1,228 bp encoding a protein of 363 amino acids with a predicted molecular mass of 37.6 kDa, interrupted by two introns of 58 and 81 bp in length. Accumulation of pecA mRNA in both pectin- or glucose-grown mycelia in the highly aggressive strain matched the activity profile of a pectinase previously identified as P2c. Transformants of a weakly aggressive strain containing a functional copy of the pecA gene produced P2c in vitro, confirming that pecA encodes P2c. The coding region of pecB was determined to be 1,217 bp in length interrupted by two introns of 65 and 54 bp in length. The predicted protein of 366 amino acids had an estimated molecular mass of 38 kDa. Transcripts of this gene accumulated in mycelia grown in medium containing pectin alone, never in mycelia grown in glucose-containing medium, for both highly and weakly aggressive strains. Thus, pecB encodes the activity previously identified as P1 or P3. pecA and pecB share a high degree of sequence identity with polygalacturonase genes from Aspergillus parasiticus and Aspergillus oryzae, further establishing the close relationships between members of the A. flavus group. Conservation of intron positions in these genes also indicates that they share a common ancestor with genes encoding endopolyglacturonases of Aspergillus niger. PMID:7574642

NMR imaging of chitosan and carboxymethyl starch tablets: swelling and hydration of the polyelectrolyte complex.

PubMed

Wang, Y J; Assaad, E; Ispas-Szabo, P; Mateescu, M A; Zhu, X X

2011-10-31

The hydration and swelling properties of the tablets made of chitosan, carboxymethyl starch, and a polyelectrolyte complex of these two polysaccharides have been studied by NMR imaging. We studied the effect of pH and ionic strength on the swelling of the tablets and on the diffusion of fluid into the tablets in water and simulated physiological fluids. The pH value of the fluids exerts a more significant effect than their ionic strengths on the swelling of the tablets. The tablets are compared also with those made of cross-linked high amylose starch. The formation of complex helps to keep the integrity of the tablets in various media and render a slow and restricted swelling similar to that of the tablets of the cross-linked high amylase starch, which is significantly lower than the swelling of chitosan and of carboxymethyl starch. The capacities to modulate the release rate of drugs in different media are discussed by comparing the matrices and evaluating the preparation process of the complex. A sustained release of less soluble drugs such as aspirin in gastrointestinal fluids can be provided by the complex, due to the ionic interaction and hydrogen bonding between the drug and the biopolymer complex. Copyright © 2011 Elsevier B.V. All rights reserved.

Characterization of Extraintestinal Pathogenic Escherichia coli isolated from retail poultry meats from Alberta, Canada.

PubMed

Aslam, Mueen; Toufeer, Mehdi; Narvaez Bravo, Claudia; Lai, Vita; Rempel, Heidi; Manges, Amee; Diarra, Moussa Sory

2014-05-02

Extraintestinal Pathogenic Escherichia coli (ExPEC) have the potential to spread through fecal waste resulting in the contamination of both farm workers and retail poultry meat in the processing plants or environment. The objective of this study was to characterize ExPEC from retail poultry meats purchased from Alberta, Canada and to compare them with 12 human ExPEC representatives from major ExPEC lineages. Fifty-four virulence genes were screened by a set of multiplex PCRs in 700 E. coli from retail poultry meat samples. ExPEC was defined as the detection of at least two of the following virulence genes: papA/papC, sfa, kpsMT II and iutA. Genetic relationships between isolates were determined using pulsed field gel electrophoresis (PFGE). Fifty-nine (8.4%) of the 700 poultry meat isolates were identified as ExPEC and were equally distributed among the phylogenetic groups A, B1, B2 and D. Isolates of phylogenetic group A possessed up to 12 virulence genes compared to 24 and 18 genes in phylogenetic groups B2 and D, respectively. E. coli identified as ExPEC and recovered from poultry harbored as many virulence genes as those of human isolates. In addition to the iutA gene, siderophore-related iroN and fyuA were detected in combination with other virulence genes including those genes encoding for adhesion, protectin and toxin while the fimH, ompT, traT, uidA and vat were commonly detected in poultry ExPEC. The hemF, iss and cvaC genes were found in 40% of poultry ExPEC. All human ExPEC isolates harbored concnf (cytotoxic necrotizing factor 1 altering cytoskeleton and causing necrosis) and hlyD (hemolysin transport) genes which were not found in poultry ExPEC. PFGE analysis showed that a few poultry ExPEC isolates clustered with human ExPEC isolates at 55-70% similarity level. Comparing ExPEC isolated from retail poultry meats provides insight into their virulence potential and suggests that poultry associated ExPEC may be important for retail meat safety. Investigations into the ability of our poultry ExPEC to cause human infections are warranted. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

Polyaspartic Acid Concentration Controls the Rate of Calcium Phosphate Nanorod Formation in High Concentration Systems

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

Krogstad, Daniel V.; Wang, Dongbo; Lin-Gibson, Sheng

Polyelectrolytes are known to greatly affect calcium phosphate (CaP) mineralization. The reaction kinetics as well as the CaP phase, morphology and aggregation state depend on the relative concentrations of the polyelectrolyte and the inorganic ions in a complex, nonlinear manner. This study examines the structural evolution and kinetics of polyaspartic acid (pAsp) directed CaP mineralization at high concentrations of polyelectrolytes, calcium, and total phosphate (19–30 mg/mL pAsp, 50–100 mM Ca2+, Ca/P = 2). Using a novel combination of characterization techniques including cryogenic transmission electron microscopy (cryo-TEM), spectrophotometry, X-ray total scattering pair distribution function analysis, and attenuated total reflectance Fourier transformmore » infrared spectroscopy (ATR-FTIR), it was determined that the CaP mineralization occurred over four transition steps. The steps include the formation of aggregates of pAsp stabilized CaP spherical nanoparticles (sNP), crystallization of sNP, oriented attachment of the sNP into nanorods, and further crystallization of the nanorods. The intermediate aggregate sizes and the reaction kinetics were found to be highly polymer concentration dependent while the sizes of the particles were not concentration dependent. This study demonstrates the complex role of pAsp in controlling the mechanism as well as the kinetics of CaP mineralization.« less

A Web Interface for Eco System Modeling

NASA Astrophysics Data System (ADS)

McHenry, K.; Kooper, R.; Serbin, S. P.; LeBauer, D. S.; Desai, A. R.; Dietze, M. C.

2012-12-01

We have developed the Predictive Ecosystem Analyzer (PEcAn) as an open-source scientific workflow system and ecoinformatics toolbox that manages the flow of information in and out of regional-scale terrestrial biosphere models, facilitates heterogeneous data assimilation, tracks data provenance, and enables more effective feedback between models and field research. The over-arching goal of PEcAn is to make otherwise complex analyses transparent, repeatable, and accessible to a diverse array of researchers, allowing both novice and expert users to focus on using the models to examine complex ecosystems rather than having to deal with complex computer system setup and configuration questions in order to run the models. Through the developed web interface we hide much of the data and model details and allow the user to simply select locations, ecosystem models, and desired data sources as inputs to the model. Novice users are guided by the web interface through setting up a model execution and plotting the results. At the same time expert users are given enough freedom to modify specific parameters before the model gets executed. This will become more important as more and more models are added to the PEcAn workflow as well as more and more data that will become available as NEON comes online. On the backend we support the execution of potentially computationally expensive models on different High Performance Computers (HPC) and/or clusters. The system can be configured with a single XML file that gives it the flexibility needed for configuring and running the different models on different systems using a combination of information stored in a database as well as pointers to files on the hard disk. While the web interface usually creates this configuration file, expert users can still directly edit it to fine tune the configuration.. Once a workflow is finished the web interface will allow for the easy creation of plots over result data while also allowing the user to download the results for further processing. The current workflow in the web interface is a simple linear workflow, but will be expanded to allow for more complex workflows. We are working with Kepler and Cyberintegrator to allow for these more complex workflows as well as collecting provenance of the workflow being executed. This provenance regarding model executions is stored in a database along with the derived results. All of this information is then accessible using the BETY database web frontend. The PEcAn interface.

Implementing the picture exchange communication system (PECS).

PubMed

Liddle, K

2001-01-01

PECS was developed in Delaware, USA over 10 years ago by Bondy and Frost (1994a). Over the last two years PECS has been introduced to this country and has raised a great deal of interest in people working in the field of autistic spectrum disorders (ASD). This paper will address some of the issues that arose during the establishment of PECS in one special school. Changes seen in 21 children with severe learning difficulties who have been taught to use PECS are reported and the use of PECS with children who do not have an ASD is discussed.

Zoonotic potential of Escherichia coli isolates from retail chicken meat products and eggs.

PubMed

Mitchell, Natalie M; Johnson, James R; Johnston, Brian; Curtiss, Roy; Mellata, Melha

2015-02-01

Chicken products are suspected as a source of extraintestinal pathogenic Escherichia coli (ExPEC), which causes diseases in humans. The zoonotic risk to humans from chicken-source E. coli is not fully elucidated. To clarify the zoonotic risk posed by ExPEC in chicken products and to fill existing knowledge gaps regarding ExPEC zoonosis, we evaluated the prevalence of ExPEC on shell eggs and compared virulence-associated phenotypes between ExPEC and non-ExPEC isolates from both chicken meat and eggs. The prevalence of ExPEC among egg-source isolates was low, i.e., 5/108 (4.7%). Based on combined genotypic and phenotypic screening results, multiple human and avian pathotypes were represented among the chicken-source ExPEC isolates, including avian-pathogenic E. coli (APEC), uropathogenic E. coli (UPEC), neonatal meningitis E. coli (NMEC), and sepsis-associated E. coli (SEPEC), as well as an undefined ExPEC group, which included isolates with fewer virulence factors than the APEC, UPEC, and NMEC isolates. These findings document a substantial prevalence of human-pathogenic ExPEC-associated genes and phenotypes among E. coli isolates from retail chicken products and identify key virulence traits that could be used for screening. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Enteric viruses of chickens and turkeys

USDA-ARS?s Scientific Manuscript database

Although enteric disease in commercial poultry operations is common, and often unofficially reported and discussed by field veterinarians as “non-specific enteric disease”, three recognized enteric syndromes do exist in poultry: poult enteritis complex (PEC) and poult enteritis mortality syndrome (P...

ACTIVE PEC APPLICATIONS, THE PEC WEBSITE, AND SLUDGE STABILITY RESEARCH

EPA Science Inventory

Since it's creation in 1985, the Pathogen Equivalency Committee (PEC) has been reviewing novel sludge disinfection technologies with regards to their abilities to protect human health and the environment. The PEC is charged to make recommendations on whether these novel technolog...

PecS is an important player in the regulatory network governing the coordinated expression of virulence genes during the interaction between Dickeya dadantii 3937 and plants.

PubMed

Mhedbi-Hajri, Nadia; Malfatti, Pierrette; Pédron, Jacques; Gaubert, Stéphane; Reverchon, Sylvie; Van Gijsegem, Frédérique

2011-11-01

Successful infection of a pathogen relies on the coordinated expression of numerous virulence factor-encoding genes. In plant-bacteria interactions, this control is very often achieved through the integration of several regulatory circuits controlling cell-cell communication or sensing environmental conditions. Dickeya dadantii (formerly Erwinia chrysanthemi), the causal agent of soft rot on many crops and ornamentals, provokes maceration of infected plants mainly by producing and secreting a battery of plant cell wall-degrading enzymes. However, several other virulence factors have also been characterized. During Arabidopsis infection, most D. dadantii virulence gene transcripts accumulated in a coordinated manner during infection. This activation requires a functional GacA-GacS two-component regulatory system but the Gac system is not involved in the growth phase dependence of virulence gene expression. Here we show that, contrary to Pectobacterium, the AHL-mediated ExpIR quorum-sensing system does not play a major role in the growth phase-dependent control of D. dadantii virulence genes. On the other hand, the global regulator PecS participates in this coordinated expression since, in a pecS mutant, an early activation of virulence genes is observed both in vitro and in planta. This correlated with the known hypervirulence phenotype of the pecS mutant. Analysis of the relationship between the regulatory circuits governed by the PecS and GacA global regulators indicates that these two regulators act independently. PecS prevents a premature expression of virulence genes in the first stages of colonization whereas GacA, presumably in conjunction with other regulators, is required for the activation of virulence genes at the onset of symptom occurrence. © 2011 Society for Applied Microbiology and Blackwell Publishing Ltd.

MicroRNA-193a Regulates the Transdifferentiation of Human Parietal Epithelial Cells toward a Podocyte Phenotype

PubMed Central

Kietzmann, Leonie; Guhr, Sebastian S.O.; Meyer, Tobias N.; Ni, Lan; Sachs, Marlies; Panzer, Ulf; Stahl, Rolf A.K.; Saleem, Moin A.; Kerjaschki, Dontscho; Gebeshuber, Christoph A.

2015-01-01

Parietal epithelial cells have been identified as potential progenitor cells in glomerular regeneration, but the molecular mechanisms underlying this process are not fully defined. Here, we established an immortalized polyclonal human parietal epithelial cell (hPEC) line from naive human Bowman’s capsule cells isolated by mechanical microdissection. These hPECs expressed high levels of PEC-specific proteins and microRNA-193a (miR-193a), a suppressor of podocyte differentiation through downregulation of Wilms’ tumor 1 in mice. We then investigated the function of miR-193a in the establishment of podocyte and PEC identity and determined whether inhibition of miR-193a influences the behavior of PECs in glomerular disease. After stable knockdown of miR-193a, hPECs adopted a podocyte-like morphology and marker expression, with decreased expression levels of PEC markers. In mice, inhibition of miR-193a by complementary locked nucleic acids resulted in an upregulation of the podocyte proteins synaptopodin and Wilms’ tumor 1. Conversely, overexpression of miR-193a in vivo resulted in the upregulation of PEC markers and the loss of podocyte markers in isolated glomeruli. Inhibition of miR-193a in a mouse model of nephrotoxic nephritis resulted in reduced crescent formation and decreased proteinuria. Together, these results show the establishment of a human PEC line and suggest that miR-193a functions as a master switch, such that glomerular epithelial cells with high levels of miR-193a adopt a PEC phenotype and cells with low levels of miR-193a adopt a podocyte phenotype. miR-193a–mediated maintenance of PECs in an undifferentiated reactive state might be a prerequisite for PEC proliferation and migration in crescent formation. PMID:25270065

Single-shot pectoral plane (PECs I and PECs II) blocks versus continuous local anaesthetic infusion analgesia or both after non-ambulatory breast-cancer surgery: a prospective, randomised, double-blind trial.

PubMed

O'Scanaill, P; Keane, S; Wall, V; Flood, G; Buggy, D J

2018-04-01

Pectoral plane blocks (PECs) are increasingly used in analgesia for patients undergoing breast surgery, and were recently found to be at least equivalent to single-shot paravertebral anaesthesia. However, there are no data comparing PECs with the popular practice of continuous local anaesthetic wound infusion (LA infusion) analgesia for breast surgery. Therefore, we compared the efficacy and safety of PECs blocks with LA infusion, or a combination of both in patients undergoing non-ambulatory breast-cancer surgery. This single-centre, prospective, randomised, double-blind trial analysed 45 women to receive either PECs blocks [levobupivacaine 0.25%, 10 ml PECs I and levobupivacaine 0.25%, 20 ml PECs II (PECs group); LA infusion catheter (levobupivacaine 0.1% at 10 ml h -1 for 24 h (LA infusion group); or both (PECs and LA infusion)]. The primary outcome measure was area under the curve of the pain verbal rating score whilst moving vs time (AUC) over 24 h. Secondary outcomes included total opioid consumption at 24 h. AUC moving was mean (SD) 71 (34) mm h -1 vs 58 (41) vs 23 (20) in PECs, LA infusion, and both, respectively; P=0.002. AUC at rest was also significantly lower in patients receiving both. The total 24 h opioid consumption [median (25-75%)] was 14 mg (9-26) vs 11 (8-24) vs 9 (5-11); P=0.4. No adverse events were observed. The combination of both pre-incisional PECs blocks and postoperative LA infusion provides better analgesia over 24 h than either technique alone after non-ambulatory breast-cancer surgery. NCT 03024697. Copyright © 2018 British Journal of Anaesthesia. Published by Elsevier Ltd. All rights reserved.

Electron-helium S-wave model benchmark calculations. I. Single ionization and single excitation

NASA Astrophysics Data System (ADS)

Bartlett, Philip L.; Stelbovics, Andris T.

2010-02-01

A full four-body implementation of the propagating exterior complex scaling (PECS) method [J. Phys. B 37, L69 (2004)] is developed and applied to the electron-impact of helium in an S-wave model. Time-independent solutions to the Schrödinger equation are found numerically in coordinate space over a wide range of energies and used to evaluate total and differential cross sections for a complete set of three- and four-body processes with benchmark precision. With this model we demonstrate the suitability of the PECS method for the complete solution of the full electron-helium system. Here we detail the theoretical and computational development of the four-body PECS method and present results for three-body channels: single excitation and single ionization. Four-body cross sections are presented in the sequel to this article [Phys. Rev. A 81, 022716 (2010)]. The calculations reveal structure in the total and energy-differential single-ionization cross sections for excited-state targets that is due to interference from autoionization channels and is evident over a wide range of incident electron energies.

Principles and applications of photoelectrochemical sensing strategies based on biofunctionalized nanostructures.

PubMed

Zang, Yang; Lei, Jianping; Ju, Huangxian

2017-10-15

Photoelectrochemical (PEC) biosensing is a popular research hotspot that has attracted substantial attention from chemists and biologists due to its low cost and desirable sensitivity. The PEC biosensing mainly refers to the influence of the interaction between recognition element and analyte on photocurrent signal, which involves the charge and energy transfer of PEC reaction between electron donor/acceptor and photoactive material upon light irradiation. Understanding the fundamentals of PEC strategy benefits the development of next-generation PEC sensors. However, the research on detection mechanism of PEC sensors is in the initial stage and need to be further exploited. Thus, with a particular focus on the signal transduction formats, this review highlights the novel concept on PEC sensing strategies, and categorizes the recent illustrative examples into three signaling principles: reactant determinant, electron transfer and energy transfer, providing the comprehensive design guidelines for researchers to develop more advanced PEC sensors. The prospects and challenges for future work are also included. Copyright © 2017 Elsevier B.V. All rights reserved.

Using the picture exchange communication system (PECS) with children with autism: assessment of PECS acquisition, speech, social-communicative behavior, and problem behavior.

PubMed Central

Charlop-Christy, Marjorie H; Carpenter, Michael; Le, Loc; LeBlanc, Linda A; Kellet, Kristen

2002-01-01

The picture exchange communication system (PECS) is an augmentative communication system frequently used with children with autism (Bondy & Frost, 1994; Siegel, 2000; Yamall, 2000). Despite its common clinical use, no well-controlled empirical investigations have been conducted to test the effectiveness of PECS. Using a multiple baseline design, the present study examined the acquisition of PECS with 3 children with autism. In addition, the study examined the effects of PECS training on the emergence of speech in play and academic settings. Ancillary measures of social-communicative behaviors and problem behaviors were recorded. Results indicated that all 3 children met the learning criterion for PECS and showed concomitant increases in verbal speech. Ancillary gains were associated with increases in social-communicative behaviors and decreases in problem behaviors. The results are discussed in terms of the provision of empirical support for PECS as well as the concomitant positive side effects of its use. PMID:12365736

Using the picture exchange communication system (PECS) with children with autism: assessment of PECS acquisition, speech, social-communicative behavior, and problem behavior.

PubMed

Charlop-Christy, Marjorie H; Carpenter, Michael; Le, Loc; LeBlanc, Linda A; Kellet, Kristen

2002-01-01

The picture exchange communication system (PECS) is an augmentative communication system frequently used with children with autism (Bondy & Frost, 1994; Siegel, 2000; Yamall, 2000). Despite its common clinical use, no well-controlled empirical investigations have been conducted to test the effectiveness of PECS. Using a multiple baseline design, the present study examined the acquisition of PECS with 3 children with autism. In addition, the study examined the effects of PECS training on the emergence of speech in play and academic settings. Ancillary measures of social-communicative behaviors and problem behaviors were recorded. Results indicated that all 3 children met the learning criterion for PECS and showed concomitant increases in verbal speech. Ancillary gains were associated with increases in social-communicative behaviors and decreases in problem behaviors. The results are discussed in terms of the provision of empirical support for PECS as well as the concomitant positive side effects of its use.

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

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

Like-charged protein-polyelectrolyte complexation driven by charge patches

NASA Astrophysics Data System (ADS)

Yigit, Cemil; Heyda, Jan; Ballauff, Matthias; Dzubiella, Joachim

2015-08-01

We study the pair complexation of a single, highly charged polyelectrolyte (PE) chain (of 25 or 50 monomers) with like-charged patchy protein models (CPPMs) by means of implicit-solvent, explicit-salt Langevin dynamics computer simulations. Our previously introduced set of CPPMs embraces well-defined zero-, one-, and two-patched spherical globules each of the same net charge and (nanometer) size with mono- and multipole moments comparable to those of globular proteins with similar size. We observe large binding affinities between the CPPM and the like-charged PE in the tens of the thermal energy, kBT, that are favored by decreasing salt concentration and increasing charge of the patch(es). Our systematic analysis shows a clear correlation between the distance-resolved potentials of mean force, the number of ions released from the PE, and CPPM orientation effects. In particular, we find a novel two-site binding behavior for PEs in the case of two-patched CPPMs, where intermediate metastable complex structures are formed. In order to describe the salt-dependence of the binding affinity for mainly dipolar (one-patched) CPPMs, we introduce a combined counterion-release/Debye-Hückel model that quantitatively captures the essential physics of electrostatic complexation in our systems.

Conjugated polyelectrolyte based real-time fluorescence assay for phospholipase C.

PubMed

Liu, Yan; Ogawa, Katsu; Schanze, Kirk S

2008-01-01

A fluorescence turnoff assay for phospholipase C (PLC) from Clostridium perfringens is developed based on the reversible interaction between the natural substrate, phosphatidylcholine, and a fluorescent, water-soluble conjugated polyelectrolyte (CPE). The fluorescence intensity of the CPE in water is increased substantially by the addition of the phospholipid due to the formation of a CPE-lipid complex. Incubation of the CPE-lipid complex with the enzyme PLC causes the fluorescence intensity to decrease (turnoff sensor); the response arises due to PLC-catalyzed hydrolysis of the phosphatidylcholine, which effectively disrupts the CPE-lipid complex. The PLC assay operates with phospholipid substrate concentrations in the micromolar range, and the analytical detection limit for PLC is <1 nM. The optimized assay provides a convenient, rapid, and real-time sensor for PLC activity. The real-time fluorescence intensity from the CPE can be converted to substrate concentration by using an ex situ calibration curve, allowing PLC-catalyzed reaction rates and kinetic parameters to be determined. PLC activation by Ca2+ and inhibition by EDTA and fluoride ion are demonstrated using the optimized sensor.

Strong and weak adsorptions of polyelectrolyte chains onto oppositely charged spheres

NASA Astrophysics Data System (ADS)

Cherstvy, A. G.; Winkler, R. G.

2006-08-01

We investigate the complexation of long thin polyelectrolyte (PE) chains with oppositely charged spheres. In the limit of strong adsorption, when strongly charged PE chains adapt a definite wrapped conformation on the sphere surface, we analytically solve the linear Poisson-Boltzmann equation and calculate the electrostatic potential and the energy of the complex. We discuss some biological applications of the obtained results. For weak adsorption, when a flexible weakly charged PE chain is localized next to the sphere in solution, we solve the Edwards equation for PE conformations in the Hulthén potential, which is used as an approximation for the screened Debye-Hückel potential of the sphere. We predict the critical conditions for PE adsorption. We find that the critical sphere charge density exhibits a distinctively different dependence on the Debye screening length than for PE adsorption onto a flat surface. We compare our findings with experimental measurements on complexation of various PEs with oppositely charged colloidal particles. We also present some numerical results of the coupled Poisson-Boltzmann and self-consistent field equation for PE adsorption in an assembly of oppositely charged spheres.

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.

Albumin-induced apoptosis of glomerular parietal epithelial cells is modulated by extracellular signal-regulated kinase 1/2

PubMed Central

Ohse, Takamoto; Krofft, Ron D.; Wu, Jimmy S.; Eddy, Allison A.; Pippin, Jeffrey W.; Shankland, Stuart J.

2012-01-01

Background. The biological role(s) of glomerular parietal epithelial cells (PECs) is not fully understood in health or disease. Given its location, PECs are constantly exposed to low levels of filtered albumin, which is increased in nephrotic states. We tested the hypothesis that PECs internalize albumin and increased uptake results in apoptosis. Methods. Confocal microscopy of immunofluorescent staining and immunohistochemistry were used to demonstrate albumin internalization in PECs and to quantitate albumin uptake in normal mice and rats as well as experimental models of membranous nephropathy, minimal change disease/focal segmental glomerulosclerosis and protein overload nephropathy. Fluorescence-activated cell sorting analysis was performed on immortalized cultured PECs exposed to fluorescein isothiocyanate (FITC)-labeled albumin in the presence of an endosomal inhibitor or vehicle. Apoptosis was measured by Hoechst staining in cultured PECs exposed to bovine serum albumin. Levels of phosphorylated extracellular signal-regulated kinase 1 and 2 (p-ERK1/2) were restored by retroviral infection of mitogen-activated protein kinase (MEK) 1/2 and reduced by U0126 in PECs exposed to high albumin levels in culture and apoptosis measured by Hoechst staining. Results. PECs internalized albumin normally, and this was markedly increased in all of the experimental disease models (P < 0.05 versus controls). Cultured immortalized PECs also internalize FITC-labeled albumin, which was reduced by endosomal inhibition. A consequence of increased albumin internalization was PEC apoptosis in vitro and in vivo. Candidate signaling pathways underlying these events were examined. Data showed markedly reduced levels of phosphorylated extracellular signal-regulated kinase 1 and 2 (ERK1/2) in PECs exposed to high albumin levels in nephropathy and in culture. A role for ERK1/2 in limiting albumin-induced apoptosis was shown by restoring p-ERK1/2 by retroviral infection, which reduced apoptosis in cultured PECs, while a forced decrease of p-ERK1/2 through inhibition of MEK 1/2 significantly increased albumin-induced PEC apoptosis. Conclusions. A normal role of PECs is to take up filtered albumin. However, this is increased in proteinuric glomerular diseases, leading to apoptosis through changes in ERK1/2. PMID:21896500

Expression and Self-Assembly in Baculovirus of Porcine Enteric Calicivirus Capsids into Virus-Like Particles and Their Use in an Enzyme-Linked Immunosorbent Assay for Antibody Detection in Swine

PubMed Central

Guo, Mingzhang; Qian, Yuan; Chang, Kyeong-Ok; Saif, Linda J.

2001-01-01

Porcine enteric calicivirus (PEC) causes diarrhea and intestinal lesions in pigs. PEC strain Cowden grows to low to moderate titers in cell culture but only with the addition of intestinal contents from uninfected gnotobiotic pigs (W. T. Flynn and L. J. Saif, J. Clin. Microbiol. 26:206–212, 1988; A. V. Parwani, W. T. Flynn, K. L. Gadfield, and L. J. Saif, Arch. Virol. 120:115–122, 1991). Cloning and sequence analysis of the PEC Cowden full-length genome revealed that it is most closely related genetically to the human Sapporo-like viruses. In this study, the complete PEC capsid gene was subcloned into the plasmid pBlueBac4.5 and the recombinant baculoviruses were identified by plaque assay and PCR. The PEC capsid protein was expressed in insect (Sf9) cells inoculated with the recombinant baculoviruses, and the recombinant capsid proteins self- assembled into virus-like particles (VLPs) that were released into the cell supernatant and purified by CsCl gradient centrifugation. The PEC VLPs had the same molecular mass (58 kDa) as the native virus capsid and reacted with pig hyperimmune and convalescent-phase sera to PEC Cowden in enzyme-linked immunosorbent assay (ELISA) and Western blotting. The PEC capsid VLPs were morphologically and antigenically similar to the native virus by immune electron microscopy. High titers (1:102,400 to 204,800) of PEC-specific antibodies were induced in guinea pigs inoculated with PEC VLPs, suggesting that the VLPs could be useful for future candidate PEC vaccines. A fixed-cell ELISA and VLP ELISA were developed to detect PEC serum antibodies in pigs. For the fixed-cell ELISA, Sf9 cells were infected with recombinant baculoviruses expressing PEC capsids, followed by cell fixation with formalin. For the VLP ELISA, the VLPs were used for the coating antigen. Our data indicate that both tests were rapid, specific, and reproducible and might be used for large-scale serological investigations of PEC antibodies in swine. PMID:11283075

New Insights into Glomerular Parietal Epithelial Cell Activation and Its Signaling Pathways in Glomerular Diseases

PubMed Central

Su, Hua; Chen, Shan; He, Fang-Fang; Wang, Yu-Mei; Bondzie, Philip; Zhang, Chun

2015-01-01

The glomerular parietal epithelial cells (PECs) have aroused an increasing attention recently. The proliferation of PECs is the main feature of crescentic glomerulonephritis; besides that, in the past decade, PEC activation has been identified in several types of noninflammatory glomerulonephropathies, such as focal segmental glomerulosclerosis, diabetic glomerulopathy, and membranous nephropathy. The pathogenesis of PEC activation is poorly understood; however, a few studies delicately elucidate the potential mechanisms and signaling pathways implicated in these processes. In this review we will focus on the latest observations and concepts about PEC activation in glomerular diseases and the newest identified signaling pathways in PEC activation. PMID:25866774

Glomerular parietal epithelial cells contribute to adult podocyte regeneration in experimental focal segmental glomerulosclerosis

PubMed Central

Eng, Diana G.; Sunseri, Maria W.; Kaverina, Natalya; Roeder, Sebastian S.; Pippin, Jeffrey W.; Shankland, Stuart J.

2015-01-01

Since adult podocytes cannot adequately proliferate following depletion in disease states there has been interest in the potential role of progenitors in podocyte repair and regeneration. To determine if parietal epithelial cells (PECs) can serve as adult podocyte progenitors following disease-induced podocyte depletion, PECs were permanently labeled in adult PECrtTA/LC1/R26 reporter mice. In normal mice, labeled PECs were confined to Bowman's capsule, while in disease (cytotoxic sheep anti-podocyte antibody), labeled PECs were found in the glomerular tuft in progressively higher numbers by days 7, 14 and 28. Early in disease, the majority of PECs in the tuft co-expressed CD44. By day 28, when podocyte numbers were significantly higher and disease severity was significantly lower, the majority of labeled PECs co-expressed podocyte proteins but not CD44. Neither labeled PECs on the tuft, nor podocytes stained for the proliferation marker BrdU. The de novo expression of phospho-ERK colocalized to CD44 expressing PECs, but not to PECs expressing podocyte markers. Thus, in a mouse model of focal segmental glomerulosclerosis typified by abrupt podocyte depletion followed by regeneration, PECs undergo two phenotypic changes once they migrate to the glomerular tuft. Initially these cells are predominantly activated CD44 expressing cells coinciding with glomerulosclerosis, and later they predominantly exhibit a podocyte phenotype which is likely reparative. PMID:25993321

Escherichia coli and urinary tract infections: the role of poultry-meat.

PubMed

Manges, A R

2016-02-01

Extraintestinal pathogenic Escherichia coli (ExPEC) is the most common cause of community-acquired and hospital-acquired extraintestinal infections. The hypothesis that human ExPEC may have a food animal reservoir has been a topic of investigation by multiple groups around the world. Experimental studies showing the shared pathogenic potential of human ExPEC and avian pathogenic E. coli suggest that these extraintestinal E. coli may be derived from the same bacterial lineages or share common evolutionary roots. The consistent observation of specific human ExPEC lineages in poultry or poultry products, and rarely in other meat commodities, supports the hypothesis that there may be a poultry reservoir for human ExPEC. The time lag between human ExPEC acquisition (in the intestine) and infection is the fundamental challenge facing studies attempting to attribute ExPEC transmission to poultry or other environmental sources. Even whole genome sequencing efforts to address attribution will struggle with defining meaningful genetic relationships outside of a discrete food-borne outbreak setting. However, if even a fraction of all human ExPEC infections, especially antimicrobial-resistant ExPEC infections, is attributable to the introduction of multidrug-resistant ExPEC lineages through contaminated food product(s), the relevance to public health, food animal production and food safety will be significant. Copyright © 2016 European Society of Clinical Microbiology and Infectious Diseases. Published by Elsevier Ltd. All rights reserved.

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.

Characterization and virulence clustering analysis of extraintestinal pathogenic Escherichia coli isolated from swine in China.

PubMed

Zhu, Yinchu; Dong, Wenyang; Ma, Jiale; Yuan, Lvfeng; Hejair, Hassan M A; Pan, Zihao; Liu, Guangjin; Yao, Huochun

2017-04-08

Swine extraintestinal pathogenic Escherichia coli (ExPEC) is an important pathogen that leads to economic and welfare costs in the swine industry worldwide, and is occurring with increasing frequency in China. By far, various virulence factors have been recognized in ExPEC. Here, we investigated the virulence genotypes and clonal structure of collected strains to improve the knowledge of phylogenetic traits of porcine ExPECs in China. We isolated 64 Chinese porcine ExPEC strains from 2013 to 14 in China. By multiplex PCR, the distribution of isolates belonging to phylogenetic groups B1, B2, A and D was 9.4%, 10.9%, 57.8% and 21.9%, respectively. Nineteen virulence-related genes were detected by PCR assay; ompA, fimH, vat, traT and iutA were highly prevalent. Virulence-related genes were remarkably more prevalent in group B2 than in groups A, B1 and D; notably, usp, cnf1, hlyD, papA and ibeA were only found in group B2 strains. Genotyping analysis was performed and four clusters of strains (named I to IV) were identified. Cluster IV contained all isolates from group B2 and Cluster IV isolates had the strongest pathogenicity in a mouse infection model. As phylogenetic group B2 and D ExPEC isolates are generally considered virulent, multilocus sequence typing (MLST) analysis was performed for these isolates to further investigate genetic relationships. Two novel sequence types, ST5170 and ST5171, were discovered. Among the nine clonal complexes identified among our group B2 and D isolates, CC12 and CC95 have been indicated to have high zoonotic pathogenicity. The distinction between group B2 and non-B2 isolates in virulence and genotype accorded with MLST analysis. This study reveals significant genetic diversity among ExPEC isolates and helps us to better understand their pathogenesis. Importantly, our data suggest group B2 (Cluster IV) strains have the highest risk of causing animal disease and illustrate the correlation between genotype and virulence.

Predicting progress in Picture Exchange Communication System (PECS) use by children with autism.

PubMed

Pasco, Greg; Tohill, Christina

2011-01-01

The Picture Exchange Communication System (PECS) is a widely used communication intervention for non-verbal children with autism spectrum disorder. Findings for the benefits of PECS have almost universally been positive, although there is very limited information about the characteristics of PECS users that determine the amount of progress that they are likely to make. To explore the utility of using children's developmental age to predict the subsequent degree of progress using PECS. In a retrospective study, 23 non-verbal 5- and 6-year-old children with autism spectrum disorder attending a special school were assessed to determine their highest level of PECS ability. They were then allocated to one of two groups depending on whether or not they had mastered PECS phase III. All participants had been assessed using the Psycho-Educational Profile-Revised (PEP-R) on entry to the school and before being introduced to PECS. Total developmental age scores were examined to determine whether they accurately predicted membership of the two PECS ability groups. All the 16 children who had mastered PECS phase III had total developmental age scores of 16 months or above, whilst six of the seven children who had not progressed beyond phase III scored below 16 months--the other child had a score of 16 months. The assessment of the developmental level of potential PECS users may provide valuable predictive information for speech-and-language therapists and other professionals in relation to the likely degree of progress and in setting realistic and achievable targets. © 2010 Royal College of Speech & Language Therapists.

Training Paraprofessionals to Implement the Picture Exchange Communication System (PECS)

ERIC Educational Resources Information Center

Sloman, Glenn Matthew

2010-01-01

Based on Skinner's "Verbal Behavior" (1957), the picture exchange communication system (PECS) was designed to teach children with autism functional verbal behavior. Much research has demonstrated the effectiveness and efficiency of PECS in building verbal behavior. However, because PECS training is typically presented in a group format and later…

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

Biologically Complex Planar Cell Plasma Membranes Supported on Polyelectrolyte Cushions Enhance Transmembrane Protein Mobility and Retain Native Orientation.

PubMed

Liu, Han-Yuan; Chen, Wei-Liang; Ober, Christopher K; Daniel, Susan

2018-01-23

Reconstituted supported lipid bilayers (SLB) are widely used as in vitro cell-surface models because they are compatible with a variety of surface-based analytical techniques. However, one of the challenges of using SLBs as a model of the cell surface is the limited complexity in membrane composition, including the incorporation of transmembrane proteins and lipid diversity that may impact the activity of those proteins. Additionally, it is challenging to preserve the transmembrane protein native orientation, function, and mobility in SLBs. Here, we leverage the interaction between cell plasma membrane vesicles and polyelectrolyte brushes to create planar bilayers from cell plasma membrane vesicles that have budded from the cell surface. This approach promotes the direct incorporation of membrane proteins and other species into the planar bilayer without using detergent or reconstitution and preserves membrane constituents. Furthermore, the structure of the polyelectrolyte brush serves as a cushion between the planar bilayer and rigid supporting surface, limiting the interaction of the cytosolic domains of membrane proteins with this surface. Single particle tracking was used to analyze the motion of GPI-linked yellow fluorescent proteins (GPI-YFP) and neon-green fused transmembrane P2X2 receptors (P2X2-neon) and shows that this platform retains over 75% mobility of multipass transmembrane proteins in its native membrane environment. An enzyme accessibility assay confirmed that the protein orientation is preserved and results in the extracellular domain facing toward the bulk phase and the cytosolic side facing the support. Because the platform presented here retains the complexity of the cell plasma membrane and preserves protein orientation and mobility, it is a better representative mimic of native cell surfaces, which may find many applications in biological assays aimed at understanding cell membrane phenomena.

Materials International Space Station Experiment (MISSE) 5 Developed to Test Advanced Solar Cell Technology Aboard the ISS

NASA Technical Reports Server (NTRS)

Wilt, David M.

2004-01-01

The testing of new technologies aboard the International Space Station (ISS) is facilitated through the use of a passive experiment container, or PEC, developed at the NASA Langley Research Center. The PEC is an aluminum suitcase approximately 2 ft square and 5 in. thick. Inside the PEC are mounted Materials International Space Station Experiment (MISSE) plates that contain the test articles. The PEC is carried to the ISS aboard the space shuttle or a Russian resupply vehicle, where astronauts attach it to a handrail on the outer surface of the ISS and deploy the PEC, which is to say the suitcase is opened 180 deg. Typically, the PEC is left in this position for approximately 1 year, at which point astronauts close the PEC and it is returned to Earth. In the past, the PECs have contained passive experiments, principally designed to characterize the durability of materials subjected to the ultraviolet radiation and atomic oxygen present at the ISS orbit. The MISSE5 experiment is intended to characterize state-of-art (SOA) and beyond photovoltaic technologies.

Origin of Parietal Podocytes in Atubular Glomeruli Mapped by Lineage Tracing

PubMed Central

Schulte, Kevin; Berger, Katja; Boor, Peter; Jirak, Peggy; Gelman, Irwin H.; Arkill, Kenton P.; Neal, Christopher R.; Kriz, Wilhelm; Floege, Jürgen; Smeets, Bart

2014-01-01

Parietal podocytes are fully differentiated podocytes lining Bowman’s capsule where normally only parietal epithelial cells (PECs) are found. Parietal podocytes form throughout life and are regularly observed in human biopsies, particularly in atubular glomeruli of diseased kidneys; however, the origin of parietal podocytes is unresolved. To assess the capacity of PECs to transdifferentiate into parietal podocytes, we developed and characterized a novel method for creating atubular glomeruli by electrocoagulation of the renal cortex in mice. Electrocoagulation produced multiple atubular glomeruli containing PECs as well as parietal podocytes that projected from the vascular pole and lined Bowman’s capsule. Notably, induction of cell death was evident in some PECs. In contrast, Bowman’s capsules of control animals and normal glomeruli of electrocoagulated kidneys rarely contained podocytes. PECs and podocytes were traced by inducible and irreversible genetic tagging using triple transgenic mice (PEC- or Pod-rtTA/LC1/R26R). Examination of serial cryosections indicated that visceral podocytes migrated onto Bowman’s capsule via the vascular stalk; direct transdifferentiation from PECs to podocytes was not observed. Similar results were obtained in a unilateral ureter obstruction model and in human diseased kidney biopsies, in which overlap of PEC- or podocyte-specific antibody staining indicative of gradual differentiation did not occur. These results suggest that induction of atubular glomeruli leads to ablation of PECs and subsequent migration of visceral podocytes onto Bowman’s capsule, rather than transdifferentiation from PECs to parietal podocytes. PMID:24071005

Electricity generation and pollutant degradation using a novel biocathode coupled photoelectrochemical cell.

PubMed

Du, Yue; Feng, Yujie; Qu, Youpeng; Liu, Jia; Ren, Nanqi; Liu, Hong

2014-07-01

The photoelectrochemical cell (PEC) is a promising tool for the degradation of organic pollutants and simultaneous electricity recovery, however, current cathode catalysts suffer from high costs and short service lives. Herein, we present a novel biocathode coupled PEC (Bio-PEC) integrating the advantages of photocatalytic anode and biocathode. Electrochemical anodized TiO2 nanotube arrays fabricated on Ti substrate were used as Bio-PEC anodes. Field-emission scanning electron microscope images revealed that the well-aligned TiO2 nanotubes had inner diameters of 60-100 nm and wall-thicknesses of about 5 nm. Linear sweep voltammetry presented the pronounced photocurrent output (325 μA/cm(2)) under xenon illumination, compared with that under dark conditions. Comparing studies were carried out between the Bio-PEC and PECs with Pt/C cathodes. The results showed that the performance of Pt/C cathodes was closely related with the structure and Pt/C loading amounts of cathodes, while the Bio-PEC achieved similar methyl orange (MO) decoloration rate (0.0120 min(-1)) and maximum power density (211.32 mW/m(2)) to the brush cathode PEC with 50 mg Pt/C loading (Brush-PEC, 50 mg). The fill factors of Bio-PEC and Brush-PEC (50 mg) were 39.87% and 43.06%, respectively. The charge transfer resistance of biocathode was 13.10 Ω, larger than the brush cathode with 50 mg Pt/C (10.68 Ω), but smaller than the brush cathode with 35 mg Pt/C (18.35 Ω), indicating the comparable catalytic activity with Pt/C catalyst. The biocathode was more dependent on the nutrient diffusion, such as nitrogen and inorganic carbon, thus resulting in relatively higher diffusion resistance compared to the brush cathode with 50 mg Pt/C loading that yielded similar MO removal and power output. Considering the performance and cost of PEC system, the biocathode was a promising alternative for the Pt/C catalyst.

Impact of pectoral nerve block on postoperative pain and quality of recovery in patients undergoing breast cancer surgery: A randomised controlled trial.

PubMed

Kamiya, Yoshinori; Hasegawa, Miki; Yoshida, Takayuki; Takamatsu, Misako; Koyama, Yu

2018-03-01

In recent years, thoracic wall nerve blocks, such as the pectoral nerve (PECS) block and the serratus plane block have become popular for peri-operative pain control in patients undergoing breast cancer surgery. The effect of PECS block on quality of recovery (QoR) after breast cancer surgery has not been evaluated. To evaluate the ability of PECS block to decrease postoperative pain and anaesthesia and analgesia requirements and to improve postoperative QoR in patients undergoing breast cancer surgery. Randomised controlled study. A tertiary hospital. Sixty women undergoing breast cancer surgery between April 2014 and February 2015. The patients were randomised to receive a PECS block consisting of 30 ml of levobupivacaine 0.25% after induction of anaesthesia (PECS group) or a saline mock block (control group). The patients answered a 40-item QoR questionnaire (QoR-40) before and 1 day after breast cancer surgery. Numeric Rating Scale score for postoperative pain, requirement for intra-operative propofol and remifentanil, and QoR-40 score on postoperative day 1. PECS block combined with propofol-remifentanil anaesthesia significantly improved the median [interquartile range] pain score at 6 h postoperatively (PECS group 1 [0 to 2] vs. Control group 1 [0.25 to 2.75]; P = 0.018]. PECS block also reduced propofol mean (± SD) estimated target blood concentration to maintain bispectral index (BIS) between 40 and 50 (PECS group 2.65 (± 0.52) vs. Control group 3.08 (± 0.41) μg ml; P < 0.001) but not remifentanil consumption (PECS group 10.5 (± 4.28) vs. Control group 10.4 (± 4.68) μg kg h; P = 0.95). PECS block did not improve the QoR-40 score on postoperative day 1 (PECS group 182 [176 to 189] vs. Control group 174.5 [157.75 to 175]). In patients undergoing breast cancer surgery, PECS block combined with general anaesthesia reduced the requirement for propofol but not that for remifentanil, due to the inability of the PECS block to reach the internal mammary area. Further, PECS block improved postoperative pain but not the postoperative QoR-40 score due to the factors that cannot be measured by analgesia immediately after surgery, such as rebound pain. This trial is registered with the University Hospital Medical Information Network Clinical Trials Registry (UMIN000013435).

Proton and metal ion binding to natural organic polyelectrolytes-II. Preliminary investigation with a peat and a humic acid

USGS Publications Warehouse

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

1984-01-01

We summarize here experimental studies of proton and metal ion binding to a peat and a humic acid. Data analysis is based on a unified physico-chemical model for reaction of simple ions with polyelectrolytes employing a modified Henderson-Hasselbalch equation. Peat exhibited an apparent intrinsic acid dissociation constant of 10-4.05, and an apparent intrinsic metal ion binding constant of: 400 for cadmium ion; 600 for zinc ion; 4000 for copper ion; 20000 for lead ion. A humic acid was found to have an apparent intrinsic proton binding constant of 10-2.6. Copper ion binding to this humic acid sample occurred at two types of sites. The first site exhibited reaction characteristics which were independent of solution pH and required the interaction of two ligands on the humic acid matrix to simultaneously complex with each copper ion. The second complex species is assumed to be a simple monodentate copper ion-carboxylate species with a stability constant of 18. ?? 1984.

Two-Ply Composite Membranes with Separation Layers from Chitosan and Sulfoethylcellulose on a Microporous Support Based on Poly(diphenylsulfone-N-phenylphthalimide).

PubMed

Kononova, Svetlana V; Kruchinina, Elena V; Petrova, Valentina A; Baklagina, Yulia G; Romashkova, Kira A; Orekhov, Anton S; Klechkovskaya, Vera V; Skorik, Yury A

2017-12-14

Two-ply composite membranes with separation layers from chitosan and sulfoethylcellulose were developed on a microporous support based on poly(diphenylsulfone- N -phenylphthalimide) and investigated by use of X-ray diffraction and scanning electron microscopy methods. The pervaporation properties of the membranes were studied for the separation of aqueous alcohol (ethanol, propan-2-ol) mixtures of different compositions. When the mixtures to be separated consist of less than 15 wt % water in propan-2-ol, the membranes composed of polyelectrolytes with the same molar fraction of ionogenic groups (-NH₃⁺ for chitosan and -SO₃ - for sulfoethylcellulose) show high permselectivity (the water content in the permeate was 100%). Factors affecting the structure of a non-porous layer of the polyelectrolyte complex formed on the substrate surface and the contribution of that complex to changes in the transport properties of membranes are discussed. The results indicate significant prospects for the use of chitosan and sulfoethylcellulose for the formation of highly selective pervaporation membranes.

Social-Communicative Effects of the Picture Exchange Communication System (PECS) in Autism Spectrum Disorders

ERIC Educational Resources Information Center

Lerna, Anna; Esposito, Dalila; Conson, Massimiliano; Russo, Luigi; Massagli, Angelo

2012-01-01

Background: The Picture Exchange Communication System (PECS) is a common treatment choice for non-verbal children with autism. However, little empirical evidence is available on the usefulness of PECS in treating social-communication impairments in autism. Aims: To test the effects of PECS on social-communicative skills in children with autism,…

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

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.

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.

CHARACTERIZATION OF EXTRAINTESTINAL PATHOGENIC ESCHERICHIA COLI FROM MEAT IN SOUTHERN THAILAND.

PubMed

Sukkua, Kannika; Pomwised, Rattanaruji; Rattanachuay, Pattamarat; Khianngam, Saowapar; Sukhumungoon, Pharanai

2017-01-01

Extraintestinal pathogenic Escherichia coli (ExPEC) is an E. coli group, which causes diseases in systems outside human intestinal tract. ExPEC isolates were recovered from fresh chicken (25%) and pork (10%) meats, but not beef and shrimp, from markets in southern Thailand. Among the 14 ExPEC strains isolated, all carried iutA and fimH, coding for aerobactin and type 1 fimbriae, respectively. Two ExPEC strains from chicken meat possessed kpsMTK1 coding for K1 capsular antigen, responsible for neonatal meningitis. Antimicrobial susceptibility assay revealed that all ExPEC were resistant to streptomycin and carried blaTEM, but susceptible to imipenem. Phylogenetic group analysis showed that 4, 4, and 6 ExPEC strains belonged to group A, B1 and D, respectively. ExPEC strains were classified into four serotypes, namely, O8 (2 strains), O15 (2 strains), O25 (1 strain), and O127a (1 strain), with the remaining untypeable. DNA profiling analysis by BOX-PCR revealed clonality of strains with the same serotype. The existence of ExPEC in meat products should cause concern regarding food safety and public health not only in southern Thailand but also throughout the country.

Inclusion Complexes Behavior at the Air-Water Interface. Molecular Dynamic Simulation Study.

NASA Astrophysics Data System (ADS)

Gargallo, L.; Vargas, D.; Sandoval, C.; Saavedra, M.; Becerra, N.; Leiva, A.; Radić, D.

2008-08-01

The interfacial properties of the inclusion complexes (ICs), obtained from the threading of α-cyclodextrin (α-CD) onto poly(ethylene-oxide)(PEO), poly(ɛ-caprolactone)(PEC) and poly(tetrahydrofuran)(PTHF) and their precursor homopolymers (PHPoly), were studied at the air-water interface. The free surface energy was determined by wettability measurements. The experimental behavior of these systems was described by an atomistic molecular dynamics simulation (MDS).

General Characterization Methods for Photoelectrochemical Cells for Solar Water Splitting.

PubMed

Shi, Xinjian; Cai, Lili; Ma, Ming; Zheng, Xiaolin; Park, Jong Hyeok

2015-10-12

Photoelectrochemical (PEC) water splitting is a very promising technology that converts water into clean hydrogen fuel and oxygen by using solar light. However, the characterization methods for PEC cells are diverse and a systematic introduction to characterization methods for PEC cells has rarely been attempted. Unlike most other review articles that focus mainly on the material used for the working electrodes of PEC cells, this review introduces general characterization methods for PEC cells, including their basic configurations and methods for characterizing their performance under various conditions, regardless of the materials used. Detailed experimental operation procedures with theoretical information are provided for each characterization method. The PEC research area is rapidly expanding and more researchers are beginning to devote themselves to related work. Therefore, the content of this Minireview can provide entry-level knowledge to beginners in the area of PEC, which might accelerate progress in this area. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies on stability of PEC cells formed with CdS:Al films

NASA Astrophysics Data System (ADS)

Lokhande, C. D.; Pawar, S. H.

1984-02-01

Aluminum doped and undoped CdS films are deposited on stainless steel substrates by chemical bath deposition technique and are employed in PEC cells. The effects of heat treatment to photoanode and addition of salts like KCl and NaCl in an electrolyte on the stability of the PEC cells are studied. It is found that though the PEC cells formed with CdS films are stable in NaOH-Na 2S-S electrolyte, the stability of PEC cells formed with Al doped CdS films is achieved only after the addition of saturated salts in the electrolyte.

Advantages and disadvantages of graduated and inverse graduated compression hosiery in patients with chronic venous insufficiency and healthy volunteers: A prospective, mono-centric, blinded, open randomised, controlled and cross-over trial.

PubMed

Riebe, Helene; Konschake, Wolfgang; Haase, Hermann; Jünger, Michael

2018-02-01

Background The therapeutic effectiveness of compression therapy depends on the selection of compression hosiery. Objectives To assess efficacy and tolerability of graduated elastic compression stockings (GECS) and inverse graduated elastic compression stockings (PECS). Methods Thirty-two healthy volunteers and thirty-two patients with chronic venous insufficiency were analysed; wear period: one week for each stocking type (randomised, blinded). volume reduction of 'Lower leg' (Image3D®) and 'Distal leg and foot' (water plethysmography). clinical symptoms of chronic venous insufficiency assessed by the Venous Clinical Severity Score, side effects and wear comfort in both groups. Results Volume of 'Lower leg': significant reduction in healthy volunteers (mean GECS: -37.5 mL, mean PECS: -37.2 mL) and in patients (mean GECS: -55.6 mL, mean PECS: -41.6 mL). Volume of 'Distal lower leg and foot': significant reduction in healthy volunteers (mean GECS: -27 mL, mean PECS: -16.7 mL), significant reduction in patients by GECS (mean: -43.4 mL), but non-significant reduction by PECS (mean: -22.6 mL). Clinical symptoms of chronic venous insufficiency were improved significantly better with GECS than with PECS, p < 0.001. GECS led to more painful constrictions, p = 0.047, PECS slipped down more often, p < 0.001. Conclusion GECS and PECS reduce volume of the segment 'Lower leg' in patients and healthy volunteers. Patients' volume of the 'Distal lower leg and foot', however, were diminished significantly only by GECS ( p = 0.0001). Patients' complaints were improved by both GECS and PECS, and GECS were superior to PECS.

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.

Some Activities of MISSE 6 Mission

NASA Technical Reports Server (NTRS)

Prasad, Narasimha S.

2009-01-01

The objective of the Materials International Space Station Experiment (MISSE) is to study the performance of novel materials when subjected to the synergistic effects of the harsh space environment for several months. In this paper, a few laser and optical elements from NASA Langley Research Center (LaRC) that have been flown on MISSE 6 mission will be discussed. These items were characterized and packed inside a ruggedized Passive Experiment Container (PEC) that resembles a suitcase. The PEC was tested for survivability due to launch conditions. Subsequently, the MISSE 6 PEC was transported by the STS-123 mission to International Space Station (ISS) on March 11, 2008. The astronauts successfully attached the PEC to external handrails and opened the PEC for long term exposure to the space environment. The plan is to retrieve the MISSE 6 PEC by STS-128 mission in August 2009.

The interaction of pulsed eddy current with metal surface crack for various coils

NASA Astrophysics Data System (ADS)

Yang, Hung-Chi; Tai, Cheng-Chi

2002-05-01

We study the interaction of pulsed eddy current (PEC) with metal surface cracks using various coils that have different geometric sizes. In the previous work, we have showed that the PEC technique can be used to inspect electrical-discharge-machined (EDM) notches with depth from 0.5 mm to 9 mm. The results showed that the relationship between PEC signals and crack depth is obvious. In this work, we further try a series of coils with different radii, heights, turns and shapes. We will discuss the effects of these coil parameters on the PEC signal. Some other critical problems of PEC measurements such as signal drift that caused by heating effect of coil currents will be studied. We also show more experiments on fatigue cracks to demonstrate the capability of PEC technique for cracks inspection.

The effects of PECS teaching to Phase III on the communicative interactions between children with autism and their teachers.

PubMed

Carr, Deborah; Felce, Janet

2007-04-01

The study investigated the impact of mastery of the Picture Exchange Communication System (PECS) to Phase III, on the communications of children with autism. Children aged between 3 and 7 years, formed a PECS intervention group and a non-intervention control group. The intervention group received 15 h of PECS teaching over 5 weeks. Three 2-h classroom observations recorded communications between the children and their teachers. These occurred: 6 weeks before teaching; during the week immediately prior to teaching; during the week immediately following teaching. For the control group, two 2-h observations were separated by a 5-week interval without PECS teaching. Communicative initiations and dyadic interactions increased significantly between the children and teachers in the PECS group but not for the control group.

Evaluation of pharmaceuticals in surface water: reliability of PECs compared to MECs.

PubMed

Celle-Jeanton, Hélène; Schemberg, Dimitri; Mohammed, Nabaz; Huneau, Frédéric; Bertrand, Guillaume; Lavastre, Véronique; Le Coustumer, Philippe

2014-12-01

Due to the current analytical processes that are not able to measure all the pharmaceutical molecules and to the high costs and the consumption of time to sample and analyze PhACs, models to calculate Predicted Environmental Concentrations (PECs) have been developed. However a comparison between MECs and PECs, taking into account the methods of calculations and peculiarly the parameters included in the calculation (consumption data, pharmacokinetic parameters, elimination rate in STPs and in the environment), is necessary to assess the validity of PECs. MEC variations of sixteen target PhACs [acetaminophen (ACE), amlodipine (AML), atenolol (ATE), caffeine (CAF), carbamazepine (CAR), doxycycline (DOX), epoxycarbamazepine (EPO), fluvoxamine (FLU), furosemide (FUR), hydrochlorothiazide (HYD), ifosfamide (IFO), losartan (LOS), pravastatin (PRA), progesterone (PROG), ramipril (RAM), trimetazidine (TRI)] have been evaluated during one hydrological cycle, from October 2011 to October 2012 and compared to PECs calculated by using an adaptation of the models proposed by Heberer and Feldmann (2005) and EMEA (2006). Comparison of PECs and MECS has been achieved for six molecules: ATE, CAR, DOX, FUR, HYD and PRA. DOX, FUR and HYD present differences between PECs and MECs on an annual basis but their temporal evolutions follow the same trends. PEC evaluation for these PhACs could then be possible but need some adjustments of consumption patterns, pharmacokinetic parameters and/or mechanisms of (bio)degradation. ATE, CAR and PRA are well modeled; PECs can then be used as reliable estimation of concentrations without any reserve. Copyright © 2014 Elsevier Ltd. All rights reserved.

Polyelectrolyte properties of single stranded DNA measured using SAXS and single molecule FRET: beyond the wormlike chain model

PubMed Central

Meisburger, Steve P.; Sutton, Julie L.; Chen, Huimin; Pabit, Suzette A.; Kirmizialtin, Serdal; Elber, Ron; Pollack, Lois

2013-01-01

Nucleic acids are highly charged polyelectrolytes that interact strongly with salt ions. Rigid, base-paired regions are successfully described with worm like chain models, but non base-paired single stranded regions have fundamentally different polymer properties because of their greater flexibility. Recently, attention has turned to single stranded nucleic acids due to the growing recognition of their biological importance, as well as the availability of sophisticated experimental techniques sensitive to the conformation of individual molecules. We investigate polyelectrolyte properties of poly(dT), an important and widely studied model system for flexible single stranded nucleic acids, in physiologically important mixed mono- and di-valent salt. We report measurements of the form factor and interparticle interactions using SAXS, end to end distances using smFRET, and number of excess ions using ASAXS. We present a coarse-grained model that accounts for flexibility, excluded volume, and electrostatic interactions in these systems. Predictions of the model are validated against experiment. We also discuss the state of all-atom, explicit solvent Molecular Dynamics simulations of poly(dT), the next step in understanding the complexities of ion interactions with these highly charged and flexible polymers. PMID:23606337

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

PubMed

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

2016-09-01

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

A Study of BMP-2-Loaded Bipotential Electrolytic Complex around a Biphasic Calcium Phosphate-Derived (BCP) Scaffold for Repair of Large Segmental Bone Defect

PubMed Central

Paul, Kallyanashis; Padalhin, Andrew R.; Linh, Nguyen Thuy Ba; Kim, Boram; Sarkar, Swapan Kumar; Lee, Byong Taek

2016-01-01

A bipotential polyelectrolyte complex with biphasic calcium phosphate (BCP) powder dispersion provides an excellent option for protein adsorption and cell attachment and can facilitate enhanced bone regeneration. Application of the bipotential polyelectrolyte complex embedded in a spongy scaffold for faster healing of large segmental bone defects (LSBD) can be a promising endeavor in tissue engineering application. In the present study, a hollow scaffold suitable for segmental long bone replacement was fabricated by the sponge replica method applying the microwave sintering process. The fabricated scaffold was coated with calcium alginate at the shell surface, and genipin-crosslinked chitosan with biphasic calcium phosphate (BCP) dispersion was loaded at the central hollow core. The chitosan core was subsequently loaded with BMP-2. The electrolytic complex was characterized using SEM, porosity measurement, FTIR spectroscopy and BMP-2 release for 30 days. In vitro studies such as MTT, live/dead, cell proliferation and cell differentiation were performed. The scaffold was implanted into a 12 mm critical size defect of a rabbit radius. The efficacy of this complex is evaluated through an in vivo study, one and two month post implantation. BV/TV ratio for BMP-2 loaded sample was (42±1.76) higher compared with hollow BCP scaffold (32±0.225). PMID:27711142

Effects of Natural Organic Matter on Stability, Transport and Deposition of Engineered Nano-particles in Porous Media

EPA Science Inventory

The interaction of nano-particles and organic substances, like natural organic matter, could have significant influence on the fate, transport and bioavailability of toxic substances. Natural organic matter (NOM) is a mixture of chemically complex polyelectrolytes with varying m...

Solar water oxidation using nickel-borate coupled BiVO4 photoelectrodes.

PubMed

Choi, Sung Kyu; Choi, Wonyong; Park, Hyunwoong

2013-05-07

A naturally abundant nickel-borate (Ni-Bi) complex is demonstrated to successfully catalyze the photoelectrochemical (PEC) water oxidation of BiVO4 electrodes at 1.23 VRHE with nearly 100% faradaic efficiency for oxygen evolution. Ni-Bi is electrodeposited (ED) and photodeposited (PD) for varying times on BiVO4 electrodes in the 0.1 M borate electrolyte with 1 mM Ni(2+) at pH 9.2. Surprisingly, optimally deposited Ni-Bi films (ED-10 s and PD-30 min) display the same layer thickness of ca. 40 nm. Both Ni-Bi films enhance the photocurrent generation of BiVO4 at 1.23 VRHE by a factor of 3-4 under AM 1.5-light irradiation (100 mW cm(-2)) along with ca. 250% increase in the incident and absorbed photon-to-current efficiencies. Impedance analysis further reveals that the charge transfer resistance at BiVO4 is markedly decreased by Ni-Bi deposits. The primary role of Ni-Bi has been suggested to be a hole-conductor making photogenerated electrons more mobile and catalyzing a four-hole transfer to water through cyclic changes between the lower and higher Ni oxidation states. However, thick Ni-Bi films (>~40 nm) significantly reduce the PEC performance of BiVO4 due to the kinetic bottleneck and charge recombination. Under identical PEC conditions (0.1 M, pH 9.2), the borate electrolyte (good proton acceptor) is found to be better than nitrate (poor proton acceptor), indicative of a proton-coupled electron transfer pathway in PEC water oxidation.

The Effects of PECS Teaching to Phase III on the Communicative Interactions between Children with Autism and Their Teachers

ERIC Educational Resources Information Center

Carr, Deborah; Felce, Janet

2007-01-01

The study investigated the impact of mastery of the Picture Exchange Communication System (PECS) to Phase III, on the communications of children with autism. Children aged between 3 and 7 years, formed a PECS intervention group and a non-intervention control group. The intervention group received 15 h of PECS teaching over 5 weeks. Three 2-h…

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.

Meta-analysis of PECS with individuals with ASD: investigation of targeted versus non-targeted outcomes, participant characteristics, and implementation phase.

PubMed

Ganz, Jennifer B; Davis, John L; Lund, Emily M; Goodwyn, Fara D; Simpson, Richard L

2012-01-01

The Picture Exchange Communication System (PECS) is a widely used picture/icon aided augmentative communication system designed for learners with autism and other developmental disorders. This meta-analysis analyzes the extant empirical literature for PECS relative to targeted (functional communication) and non-targeted concomitant outcomes (behavior, social skills, and speech) for learners with autism, learners with autism and intellectual disabilities and those with autism and multiple disabilities. Effect size analyses were done using the Improvement Rate Difference method, an advanced metric. Effect sizes were independently analyzed for targeted and non-targeted outcomes, student age, learner disability, and number of phases in the PECS protocol acquired by learners. Results supported the judgment that PECS is a promising intervention method. Analysis also revealed that functional communication outcomes associated with the PECS protocol were most impacted, that preschool children and those with autism generally showed the strongest training effects, and that in general students who advanced through the most PECS protocol phases had the best outcomes. Copyright © 2011 Elsevier Ltd. All rights reserved.

Investigating the Acquisition, Generalization, and Emergence of Untrained Verbal Operants for Mands Acquired Using the Picture Exchange Communication System in Adults With Severe Developmental Disabilities

PubMed Central

Ziomek, Megan M; Rehfeldt, Ruth Anne

2008-01-01

This study compared the total amount of training time and total number of trial blocks for individuals with severe developmental disabilities to acquire mands under control of unconditioned establishing operations and mands under control of transitive conditioned establishing operations for manual sign and for the Picture Exchange Communication System (PECS). Also examined was the generalization of mands across settings and communicative partners, as well as the emergence of untrained tacts and intraverbals for mands acquired using PECS. Mands for preferred items and for items needed to complete a chained task were acquired more rapidly and in fewer training blocks for PECS than for manual sign. Moreover, mands established using PECS generalized across settings and communicative partners. Finally, untrained tacts and intraverbals using PECS were shown to emerge for some of the participants following PECS training. These results suggest that PECS may be a viable alternative communication system for adults with severe developmental disabilities who have little or no history of systematic instruction and limited imitative repertoires. PMID:22477401

Investigating the acquisition, generalization, and emergence of untrained verbal operants for mands acquired using the picture exchange communication system in adults with severe developmental disabilities.

PubMed

Ziomek, Megan M; Rehfeldt, Ruth Anne

2008-01-01

This study compared the total amount of training time and total number of trial blocks for individuals with severe developmental disabilities to acquire mands under control of unconditioned establishing operations and mands under control of transitive conditioned establishing operations for manual sign and for the Picture Exchange Communication System (PECS). Also examined was the generalization of mands across settings and communicative partners, as well as the emergence of untrained tacts and intraverbals for mands acquired using PECS. Mands for preferred items and for items needed to complete a chained task were acquired more rapidly and in fewer training blocks for PECS than for manual sign. Moreover, mands established using PECS generalized across settings and communicative partners. Finally, untrained tacts and intraverbals using PECS were shown to emerge for some of the participants following PECS training. These results suggest that PECS may be a viable alternative communication system for adults with severe developmental disabilities who have little or no history of systematic instruction and limited imitative repertoires.

Effect of screening on the transport of polyelectrolytes through nanopores

NASA Astrophysics Data System (ADS)

Oukhaled, G.; Bacri, L.; Mathé, J.; Pelta, J.; Auvray, L.

2008-05-01

We study the transport of dextran sulfate molecules (Mw=8000 Da) through a bacterial α-hemolysin channel inserted into a bilayer lipid membrane submitted to an external electric field. We detect the current blockades induced by the molecules threading through one pore and vary the ionic strength in an unexplored range starting at 10-3 M. In the conditions of the experiment, the polyelectrolyte molecules enter the pore only if the Debye screening length is smaller than the pore radius in agreement with theory. We also observe that large potentials favour the passage of the molecules. The distribution of blockade durations suggests that a complex process governs the kinetics of the molecules. The dwelling time increases sharply as the Debye length increases and approaches the pore radius.

Actin - Lysozyme Interactions in Model Cystic Fibrosis Sputum

NASA Astrophysics Data System (ADS)

Sanders, Lori; Slimmer, Scott; Angelini, Thomas; Wong, Gerard C. L.

2003-03-01

Cystic fibrosis sputum is a complex fluid consisting of mucin (a glycoprotein), lysozyme (a cationic polypeptide), water, salt, as well as a high concentration of a number of anionic biological polyelectrolytes such as DNA and F-actin. The interactions governing these components are poorly understood, but may have important clinical consequences. For example, the formation of these biological polyelectrolytes into ordered gel phases may contribute significantly to the observed high viscosity of CF sputum. In this work, a number of model systems containing actin, lysozyme, and KCl were created to simulate CF sputum in vitro. These model systems were studied using small angle x-ray scattering and confocal fluorescence microscopy. Preliminary results will be presented. This work was supported by NSF DMR-0071761, the Beckman Young Investigator Program, and the Cystic Fibrosis Foundation.

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.

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.

Photoelectrochemical enzymatic biosensors.

PubMed

Zhao, Wei-Wei; Xu, Jing-Juan; Chen, Hong-Yuan

2017-06-15

Enzymatic biosensors have been valuable bioanalytical devices for analysis of diverse targets in disease diagnosis, biological and biomedical research, etc. Photoelectrochemical (PEC) bioanalysis is a recently emerged method that promptly becoming a subject of new research interests due to its attractive potential for future bioanalysis with high sensitivity and specificity. PEC enzymatic biosensors integrate the inherent sensitivities of PEC bioanalysis and the selectivity of enzymes and thus share their both advantages. Currently, PEC enzymatic biosensors have become a hot topic of significant research and the recent impetus has grown rapidly as demonstrated by increased research papers. Given the pace of advances in this area, this review will make a thorough discussion and survey on the fundamentals, sensing strategies, applications and the state of the art in PEC enzymatic biosensors, followed by future prospects based on our own opinions. We hope this work could provide an accessible introduction to PEC enzymatic biosensors for any scientist. Copyright © 2016 Elsevier B.V. All rights reserved.

Urinary excretion of ciprofloxacin after administration of extended release tablets in healthy volunteers. Swellable drug-polyelectrolyte matrix versus bilayer tablets.

PubMed

Guzmán, M L; Romañuk, C B; Sanchez, M F; Luciani Giacobbe, L C; Alarcón-Ramirez, L P; Battistini, F D; Alovero, F L; Jimenez-Kairuz, A F; Manzo, R H; Olivera, María Eugenia

2018-02-01

This paper builds on a previous paper in which new ciprofloxacin extended-release tablets were developed based on a ciprofloxacin-based swellable drug polyelectrolyte matrix (SDPM-CIP). The matrix contains a molecular dispersion of ciprofloxacin ionically bonded to the acidic groups of carbomer, forming the polyelectrolyte-drug complex CB-CIP. This formulation showed that the release profile of the ciprofloxacin bilayer tablets currently commercialised can be achieved with a simpler strategy. Thus, since ciprofloxacin urine concentrations are associated with the clinical cure of urinary tract infections, the goal of this work was to compare the urinary excretion of SDPM-CIP tablets with those of the CIPRO XR® bilayer tablets. A batch of SDPM-CIP tablets was manufactured by the wet granulation method and the CB-CIP ionic complex was obtained in situ. Fasted healthy volunteers received a single oral dose of 500 mg ciprofloxacin of either formulation in a randomised crossover study. Urinary concentrations were assessed by HPLC at intervals up to 36 h. Pharmacokinetic parameters (rate of urinary excretion, maximum urine excretion rate, t max , area under the curve, amount and percentage of the ciprofloxacin dose excreted in urine) showed no statistical differences between both formulations at any of the time intervals of collection. The processing conditions to obtain SDPM-CIP tablets are easy to scale up since they involve technology currently employed in the pharmaceutical industry and the process is less challenging to implement. In addition, SDPM-CIP tablets met pharmacopoeial quality specifications.

Lipid Layers on Polyelectrolyte Multilayers: Understanding Lipid-Polyelectrolyte Interactions and Applications on the Surface Engineering of Nanomaterials.

PubMed

Diamanti, Eleftheria; Gregurec, Danijela; Gabriela, Romero; Cuellar, J L; Donath, E; Moya, S E

2016-06-01

In this manuscript we review work of our group on the assembly of lipid layers on top of polyelectrolyte multilayers (PEMs). The assembly of lipid layers with zwitterionic and charged lipids on PEMs is studied as a function of lipid and polyelectrolyte composition by the Quartz Crystal Microbalance. Polyelectrolyte lipid interactions are studied by means of Atomic Force Spectroscopy. We also show the coating of lipid layers for engineering different nanomaterials, i.e., carbon nanotubes and poly(lactic-co-glycolic) nanoparticles and how these can be used to decrease in vitro toxicity and to direct the intracellular localization of nanomaterials.

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.

INTRODUCING THE FIRST EVER PEC WEBSITE

EPA Science Inventory

Since it's creation in 1985, the Pathogen Equivalency Committee (PEC) has been reviewing novel sludge disinfection technologies and their ability to protect human health and the environment. The PEC is charged to make recommendations on whether these novel technologies provide eq...

Interaction of Participant Characteristics and Type of AAC with Individuals with ASD: A Meta-Analysis

ERIC Educational Resources Information Center

Ganz, Jennifer B.; Mason, Rose A.; Goodwyn, Fara D.; Boles, Margot B.; Heath, Amy K.; Davis, John L.

2014-01-01

Individuals with autism spectrum disorders (ASD) and complex communication needs often rely on augmentative and alternative communication (AAC) as a means of functional communication. This meta-analysis investigated how individual characteristics moderate effectiveness of three types of aided AAC: the Picture Exchange Communication System (PECS),…

Preschoolers with Autism Spectrum Disorders: Evaluating the Impact of a Home-Based Intervention to Promote Their Communication

ERIC Educational Resources Information Center

McConkey, Roy; Truesdale-Kennedy, Maria; Crawford, Heather; McGreevy, Elaine; Reavey, Michaela; Cassidy, Arlene

2010-01-01

The complexities that practitioners face in evaluating interventions are illustrated in this article. An early intervention programme (known as Keyhole), based mainly around Treatment and Education of Autistic and related Communications handicapped CHildren (TEACCH), Picture Exchange Communication System (PECS) and Hanen approaches, was delivered…

The ABCG transporter PEC1/ABCG32 is required for the formation of the developing leaf cuticle in Arabidopsis.

PubMed

Fabre, Guillaume; Garroum, Imène; Mazurek, Sylwester; Daraspe, Jean; Mucciolo, Antonio; Sankar, Martial; Humbel, Bruno M; Nawrath, Christiane

2016-01-01

The cuticle is an essential diffusion barrier on aerial surfaces of land plants whose structural component is the polyester cutin. The PERMEABLE CUTICLE1/ABCG32 (PEC1) transporter is involved in plant cuticle formation in Arabidopsis. The gpat6 pec1 and gpat4 gapt8 pec1 double and triple mutants are characterized. Their PEC1-specific contributions to aliphatic cutin composition and cuticle formation during plant development are revealed by gas chromatography/mass spectrometry and Fourier-transform infrared spectroscopy. The composition of cutin changes during rosette leaf expansion in Arabidopsis. C16:0 monomers are in higher abundance in expanding than in fully expanded leaves. The atypical cutin monomer C18:2 dicarboxylic acid is more prominent in fully expanded leaves. Findings point to differences in the regulation of several pathways of cutin precursor synthesis. PEC1 plays an essential role during expansion of the rosette leaf cuticle. The reduction of C16 monomers in the pec1 mutant during leaf expansion is unlikely to cause permeability of the leaf cuticle because the gpat6 mutant with even fewer C16:0 monomers forms a functional rosette leaf cuticle at all stages of development. PEC1/ABCG32 transport activity affects cutin composition and cuticle structure in a specific and non-redundant fashion. © 2015 The Authors. New Phytologist © 2015 New Phytologist Trust.

[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.

Thermodynamics of the interaction of the food additive tartrazine with serum albumins: a microcalorimetric investigation.

PubMed

Basu, Anirban; Kumar, Gopinatha Suresh

2015-05-15

The thermodynamics of the interaction of the food colourant tartrazine with two homologous serum proteins, HSA and BSA, were investigated, employing microcalorimetric techniques. At T=298.15K the equilibrium constants for the tartrazine-BSA and HSA complexation process were evaluated to be (1.92 ± 0.05) × 10(5)M(-1) and (1.04 ± 0.05) × 10(5)M(-1), respectively. The binding was driven by a large negative standard molar enthalpic contribution. The binding was dominated essentially by non-polyelectrolytic forces which remained largely invariant at all salt concentrations. The polyelectrolytic contribution was weak at all salt concentrations and accounted for only 6-18% of the total standard molar Gibbs energy change in the salt concentration range 10-50mM. The negative standard molar heat capacity values, in conjunction with the enthalpy-entropy compensation phenomenon observed, established the involvement of dominant hydrophobic forces in the complexation process. Tartrazine enhanced the stability of both serum albumins against thermal denaturation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Salt Effects on Surface Structures of Polyelectrolyte Multilayers (PEMs) Investigated by Vibrational Sum Frequency Generation (SFG) Spectroscopy.

PubMed

Ge, Aimin; Matsusaki, Michiya; Qiao, Lin; Akashi, Mitsuru; Ye, Shen

2016-04-26

Sum frequency generation (SFG) vibrational spectroscopy was employed to investigate the surface structures of polyelectrolyte multilayers (PEMs) constructed by sequentially alternating adsorption of poly(diallyldimethylammonium chloride) (PDDA) and poly(styrenesulfonate) (PSS). It was found that the surface structures and surface charge density of the as-deposited PEMs of PDDA/PSS significantly depend on the concentration of sodium chloride (NaCl) present in the polyelectrolyte solutions. Furthermore, it was found that the surface structure of the as-deposited PEMs is in a metastable state and will reach the equilibrium state by diffusion of the polyelectrolyte chain after an aging process, resulting in a polyelectrolyte mixture on the PEM surfaces.

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.

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.

Characteristics and psychosocial predictors of psychiatric emergency center transport and length of stay in patients with dementia and Alzheimer's disease: a preliminary report.

PubMed

Nejtek, Vicki A; Hardy, Sarah; Hall, James R; Winter, A Scott

2011-07-01

Agitation and aggression are common behaviors that often lead to psychiatric emergency center (PEC) admission of nursing home patients with dementia or Alzheimer's disease. However, few if any data are available that adequately describe characteristics and psychosocial triggers of agitation and aggression leading to transport and admission to a PEC. A preliminary investigation to explore all possible characteristics and psychosocial predictors of PEC transport and length of stay in men and women nursing home patients with dementia or Alzheimer's disease was designed. Frequency distributions, chi-square, analyses of variance, and regression analyses were used to analyze the data. One hundred PEC patient charts were reviewed, of which 58 charts were missing information and 42 charts provided evaluable data. Nursing homes located in impoverished areas transported patients to the PEC significantly more often than those in affluent areas. A disconnect between the agitated/aggressive mental state reported by nursing home staff leading to the PEC transport and the calm/cooperative mental status PEC clinicians observed during the admission process was evident. Data from the charts also showed that 74% of patients received off-label antipsychotics rather than FDA-approved medications to treat dementia or Alzheimer's disease. This is one of the few studies to identify characteristics and psychosocial triggers of PEC use and length of stay in nursing home patients. We also highlight potentially dangerous antipsychotic use in dementia and Alzheimer disease. Thus, our data add to the existing knowledge base regarding PEC utilization, length of stay, and pharmacotherapy in nursing home patients with dementia and Alzheimer's disease. Given the preliminary nature of this study, however, the results should be interpreted with caution.

Opioid-sparing effects of the thoracic interfascial plane blocks: A meta-analysis of randomized controlled trials.

PubMed

Singh, Preet Mohinder; Borle, Anuradha; Kaur, Manpreet; Trikha, Anjan; Sinha, Ashish

2018-01-01

Thoracic interfascial plane blocks and modification (PECS) have recently gained popularity for analgesic potential during breast surgery. We evaluate/consolidate the evidence on opioid-sparing effect of PECS blocks in comparison with conventional intravenous analgesia (IVA) and paravertebral block (PVB). Prospective, randomized controlled trials comparing PECS block to conventional IVA or PVB in patients undergoing breast surgery published till June 2017 were searched in the medical database. Comparisons were made for 24-h postoperative morphine consumption and intraoperative fentanyl-equivalent consumption. Final analysis included nine trials (PECS vs. IVA 4 trials and PECS vs. PVB 5 trials). PECS block showed a decreased intraoperative fentanyl consumption over IVA by 49.20 mcg (95% confidence interval [CI] =42.67-55.74) ( I 2 = 98.47%, P < 0.001) and PVB by 15.88 mcg (95% CI = 12.95-18.81) ( I 2 = 95.51%, P < 0.001). Postoperative, 24-h morphine consumption with PECS block was lower than IVA by 7.66 mg (95% CI being 6.23-9.10) ( I 2 = 63.15, P < 0.001) but was higher than PVB group by 1.26 mg (95% CI being 0.91-1.62) ( I 2 = 99.53%, P < 0.001). Two cases of pneumothorax were reported with PVB, and no complication was reported in any other group. Use of PECS block and its modifications with general anesthesia for breast surgery has significant opioid-sparing effect intraoperatively and during the first 24 h after surgery. It also has higher intraoperative opioid-sparing effect when compared to PVB. During the 1 st postoperative day, PVB has slightly more morphine sparing potential that may however be associated with higher complication rates. The present PECS block techniques show marked interstudy variations and need standardization.

[A monitor for the emergency psychiatric service chain].

PubMed

Salden, M E F H; van Kemenade, J F L M; van Dam, A; Mulder, C L

2014-01-01

Many organisations are involved in the delivery of psychiatric emergency care to patients in crisis. We therefore refer to these organisations as the Psychiatric Emergency Chain (PEC). The quality of the PEC determines the quality of the psychiatric emergency care in a region. In order to measure the quality of this type of care a monitor has been developed in collaboration with the main stakeholders in the region Western North Brabant (WNB). To develop a monitor to measure the quality of a PEC in a region, identify weak spots in the chain and feed back the results to the chain. By searching the literature, studying the primary process in the chain and by having interviews with stakeholders we compiled a questionnaire for monitoring the pec. The monitor was tested in the WNB region and adjusted on the basis of experiences with the respondents. Then the monitor was generalised and tested in another region (Eindhoven and the Kempen) in order to find out whether this instrument might also be applicable to other pecs in the Netherlands. The monitor provided the PEC with a common language for evaluating the chain. The monitor was able to pinpoint particular weak spots and collaboration problems such as the response time required to reach the emergency, communication between and within organisations and domain discussions between different stakeholders. Chain partners used the results of the monitor to negotiate better collaborative agreements and to improve their care. The monitor is able to pinpoint problem areas in the PEC and subsequently to generate feedback to its stakeholders. This creates opportunities for improvement in the PEC. Therefore the monitor is a useful instrument for evaluating a local PEC periodically.

Features of electrocoagulation syndrome after endoscopic submucosal dissection for colorectal neoplasm.

PubMed

Yamashina, Takeshi; Takeuchi, Yoji; Uedo, Noriya; Hamada, Kenta; Aoi, Kenji; Yamasaki, Yasushi; Matsuura, Noriko; Kanesaka, Takashi; Akasaka, Tomofumi; Yamamoto, Sachiko; Hanaoka, Noboru; Higashino, Koji; Ishihara, Ryu; Iishi, Hiroyasu

2016-03-01

Endoscopic submucosal dissection (ESD) is a promising treatment for large gastrointestinal superficial neoplasms, although it is technically difficult, and perforation and delayed bleeding are well-known adverse events. However, there have been no large studies about electrocoagulation syndrome after colorectal ESD. The aim of this study was to evaluate the incidence and clinical significant risk factors of post-ESD coagulation syndrome (PECS). This was a retrospective cohort study conducted in a referral cancer center. A total of 336 patients with colorectal neoplasms (143 adenomas or serrated lesions and 193 carcinomas) underwent ESD from January 2011 to June 2013. Incidence, outcome, and factors associated with occurrence of PECS were investigated. Occurred in 32 patients (9.5%). The median time until PECS was 15.5 h, and the median period of PECS was 32.5 h. Fever (≥37.6 °C) after ESD was found in 41% of the PECS group and 9% of the non-PECS group (P < 0.001). All PECS cases were managed conservatively. On multivariate analysis, female patients (odds ratio [OR] = 3.2, P = 0.002), lesion location at ascending colon and cecum (OR = 3.5, P = 0.001), and resected specimen ≥40 mm (OR = 2.1, P = 0.05) were independent risk factors for PECS. Occurred in 32 patients (9.5%) with colorectal ESD; however, all cases had a good outcome with conservative management. Female sex, tumor location at the ascending colon and cecum, and resected specimen ≥40 mm were independently significant risk factors for PECS. © 2015 Journal of Gastroenterology and Hepatology Foundation and John Wiley & Sons Australia, Ltd.

Effect of insulin-coated trimethyl chitosan nanoparticles on IGF-1, IGF-2, and apoptosis in the hippocampus of diabetic male rats.

PubMed

Kalantarian, Giti; Ziamajidi, Nasrin; Mahjoub, Reza; Goodarzi, Mohammad Taghi; Saidijam, Massoud; Asl, Sara Soleimani; Abbasalipourkabir, Roghayeh

2018-06-06

Subcutaneous injection of insulin can lead to problems such as hypoglycemia and edema. The purpose of this research was to evaluate the effect of oral insulin-coated trimethyl chitosan nanoparticles on control of glycemic status, IGF-1 and IGF-2 levels, and apoptosis in the hippocampus of rats with diabetes mellitus. Insulin-coated trimethyl chitosan nanoparticles were prepared by the complex polyelectrolyte (PEC) method. Insulin loading content, loading efficiency, quantity and quality of particle size were evaluated. In vivo study was performed in different treatment groups of male Wistar rats with diabetes mellitus by insulin-coated trimethyl chitosan nanoparticles or subcutaneous injection of trade insulin. The duration of diabetes was eight weeks and the treatment was started after that time and continued for another two weeks. Body weight, fasting blood glucose (FBS), hippocampal apoptosis, and immunohistochemical (IHC) protein levels of IGF-1 and IGF-2 were assessed at the end of the experiments. The size and polydispersity indexes were 533 nanometers and 0.533, respectively. Insulin coated trimethyl chitosan nanoparticles showed high loading efficiency (97.67% ) and loading content (48.83% ). The spherical shape of nanoparticle was confirmed by transmission electron microscopic (TEM). The amine, amide, ether and aliphatic groups were evaluated using FT-IR spectrophotometer which represented the correctness of the insulin coated trimethyl chitosan nanoparticles. Although the apoptotic index was not changed either by insulin-coated nano-particles or commercial insulin in vivo results showed the efficacy of insulin-coated nanoparticles as well as commercial insulin in compensated weight loss, FBS and protein levels of IGF-1 and IGF-2. The present study showed the efficacy of insulin coated nanoparticle in oral route manner that can be tested in Phase I- III clinical trials. However, a behavioral study could reveal the efficacy of insulin-loaded nanoparticles in the improvement of cognitive changes through the modulation of IGF-1 and IGF-2 levels in the hippocampus.

AN UPDATE ON TECHNOLOGIES SEEKING PFRP EQUIVALENCY

EPA Science Inventory

This presentation will: 1) Review the mandate of the Pathogen Equivalency Committee (PEC), 2) Review the PEC's current membership (of 10), 3) Discuss how a typical application is evaluated, 4) Note where information can be found by those interested in applying to the PEC, 5) List...

"Brief report: increase in production of spoken words in some children with autism after PECS teaching to Phase III".

PubMed

Carr, Deborah; Felce, Janet

2007-04-01

The context for this work was an evaluation study [Carr, D., & Felce, J. A. (in press)] of the early phases of the Picture Exchange Communication System (PECS) [Frost, L. A., & Bondy, A. S. (1994). The picture exchange communication system training manual. Cherry Hill, NJ: Pyramid Educational Consultants, Inc.; Frost, L. A., & Bondy, A. S. (2004). The picture exchange communication system training manual, 2nd edn. Newark, DE: Pyramid Educational Consultants, Inc.]. This paper reports that five of 24 children who received 15 h of PECS teaching towards Phase III over a period of 4-5 weeks, showed concomitant increases in speech production, either in initiating communication with staff or in responding, or both. No children in the PECS group demonstrated a decrease in spoken words after receiving PECS teaching. In the control group, only one of 17 children demonstrated a minimal increase and four of 17 children demonstrated a decrease in use of spoken words after a similar period without PECS teaching.

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.

Enhanced photoelectrocatalytic decomposition of copper cyanide complexes and simultaneous recovery of copper with a Bi2MoO6 electrode under visible light by EDTA/K4P2O7.

PubMed

Zhao, Xu; Zhang, Juanjuan; Qiao, Meng; Liu, Huijuan; Qu, Jiuhui

2015-04-07

Simultaneous photoelectrocatalytic (PEC) oxidation of cyanides and recovery of copper in a PEC reactor with a Bi(2)MoO(6) photoanode was investigated at alkaline conditions under visible light irradiation. The surface variation of the Bi(2)MoO(6) photoanode and titanium cathode was characterized. The Cu mass distribution onto the anode, in the solution, and onto the cathode was fully investigated. In the individual PEC oxidation of copper cyanides, the formation of a black copper oxide on the anode occurred. By keeping the initial cyanide concentration at 0.01 mM, the effect of EDTA/K(4)P(2)O(7) was examined at different molar ratios of EDTA/K(4)P(2)O(7) to cyanide. It was indicated that the oxidation of cyanides increased and simultaneous copper electrodeposition with zero value onto the cathode was feasible at pH 11. Under the optimal conditions, the total cyanide concentration was lowered from 250 to 5.0 mg/L, and the Cu recovery efficiency deposited onto the cathode was higher than 90%. Cyanate was the only product. The role of the photogenerated hole in the oxidation of cyanide ions was confirmed.

Nanomechanics of layer-by-layer polyelectrolyte complexes: a manifestation of ionic cross-links and fixed charges.

PubMed

Han, Biao; Chery, Daphney R; Yin, Jie; Lu, X Lucas; Lee, Daeyeon; Han, Lin

2016-01-28

This study investigates the roles of two distinct features of ionically cross-linked polyelectrolyte networks - ionic cross-links and fixed charges - in determining their nanomechanical properties. The layer-by-layer assembled poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) network is used as the model material. The densities of ionic cross-links and fixed charges are modulated through solution pH and ionic strength (IS), and the swelling ratio, elastic and viscoelastic properties are quantified via an array of atomic force microscopy (AFM)-based nanomechanical tools. The roles of ionic cross-links are underscored by the distinctive elastic and viscoelastic nanomechanical characters observed here. First, as ionic cross-links are highly sensitive to solution conditions, the instantaneous modulus, E0, exhibits orders-of-magnitude changes upon pH- and IS-governed swelling, distinctive from the rubber elasticity prediction based on permanent covalent cross-links. Second, ionic cross-links can break and self-re-form, and this mechanism dominates force relaxation of PAH/PAA under a constant indentation depth. In most states, the degree of relaxation is >90%, independent of ionic cross-link density. The importance of fixed charges is highlighted by the unexpectedly more elastic nature of the network despite low ionic cross-link density at pH 2.0, IS 0.01 M. Here, the complex is a net charged, loosely cross-linked, where the degree of relaxation is attenuated to ≈50% due to increased elastic contribution arising from fixed charge-induced Donnan osmotic pressure. In addition, this study develops a new method for quantifying the thickness of highly swollen polymer hydrogel films. It also underscores important technical considerations when performing nanomechanical tests on highly rate-dependent polymer hydrogel networks. These results provide new insights into the nanomechanical characters of ionic polyelectrolyte complexes, and lay the ground for further investigation of their unique time-dependent properties.

Release mechanism of doxazosin from carrageenan matrix tablets: Effect of ionic strength and addition of sodium dodecyl sulphate.

PubMed

Kos, Petra; Pavli, Matej; Baumgartner, Saša; Kogej, Ksenija

2017-08-30

The polyelectrolyte matrix tablets loaded with an oppositely charged drug exhibit complex drug-release mechanisms. In this study, the release mechanism of a cationic drug doxazosin mesylate (DM) from matrix tablets based on an anionic polyelectrolyte λ-carrageenan (λ-CARR) is investigated. The drug release rates from λ-CARR matrices are correlated with binding results based on potentiometric measurements using the DM ion-sensitive membrane electrode and with molecular characteristics of the DM-λ-CARR-complex particles through hydrodynamic size measurements. Experiments are performed in solutions with different ionic strength and with the addition of an anionic surfactant sodium dodecyl sulphate (SDS). It is demonstrated that in addition to swelling and erosion of tablets, the release rates depend strongly on cooperative interactions between DM and λ-CARR. Addition of SDS at concentrations below its critical micelle concentration (CMC) slows down the DM release through hydrophobic binding of SDS to the DM-λ-CARR complex. On the contrary, at concentrations above the CMC SDS pulls DM from the complex by forming mixed micelles with it and thus accelerates the release. Results involving SDS show that the concentration of surfactants that are naturally present in gastrointestinal environment may have a great impact on the drug release process. Copyright © 2017 Elsevier B.V. All rights reserved.

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

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.

Passive emission colorimetric sensor (PECS) for measuring emission rates of formaldehyde based on an enzymatic reaction and reflectance photometry.

PubMed

Shinohara, Naohide; Kajiwara, Tomohisa; Ohnishi, Masato; Kodama, Kenichi; Yanagisawa, Yukio

2008-06-15

A coin-sized passive emission colorimetric sensor (PECS) based on an enzymatic reaction and a portable reflectance photometry device were developed to determine the emission rates of formaldehyde from building materials and other materials found indoors in only 30 minutes on-site. The color change of the PECS linearly correlated to the concentration of formaldehyde aqueous solutions up to 28 microg/mL. The correlation between the emission rates measured by using the PECS and those measured by using a desiccator method or by using a chamber method was fitted with a linear function and a power function, and the determination coefficients were more than 0.98. The reproducible results indicate that the emission rates could be obtained with the correlation equations from the data measured by using the PECS and the portable reflectance photometry device. Limits of detection (LODs) were 0.051 mg/L for the desiccator method and 3.1 microg/m2/h for the chamber method. Thus, it was confirmed that the emission rates of formaldehyde from the building materials classified as F four-star (< 0.3 mg/L (desiccator method) or < 5.0 microg/m2/h (chamber method)), based on Japanese Industrial Standards (JIS), could be measured with the PECS. The measurement with PECS was confirmed to be precise (RSD < 10%). Other chemicals emitted from indoor materials, such as methanol, ethanol, acetone, toluene, and xylene, interfered little with the measurement of formaldehyde emission rates by using the PECS.

Structural and biochemical characteristics of locomotory muscles of emperor penguins, Aptenodytes forsteri.

PubMed

Ponganis, P J; Costello, M L; Starke, L N; Mathieu-Costello, O; Kooyman, G L

1997-07-01

Structural and biochemical characteristics of the primary muscles used for swimming (pectoralis, PEC and supracoracoideus, SC) were compared to those of leg muscles in emperor penguins (Aptenodytes forsteri). The mass of PEC-SC was four times that of the leg musculature, and mitochondrial volume density in PEC and SC (4%) was two-thirds that in sartorius (S) and gastrocnemius. The differences in muscle mass and mitochondrial density yielded a 2.2-fold greater total mitochondrial content in PEC-SC than leg muscles, which appears to account for the 1.8-fold greater whole-body highest oxygen consumption previously recorded in emperor penguins during swimming compared to walking. Calculation of maximal mitochondrial O2 consumption in PEC-SC and leg muscle yielded value of 5.8-6.9 ml O2 ml-1 min-1, which are similar to those in locomotory muscles of most mammals and birds. A distinct feature of emperor penguin muscle was its myoglobin content, with concentrations in PEC-SC (6.4 g 100 g-1 among the highest measured in any species. This resulted in a PEC-SC O2 store greater than that of the entire blood. In addition, ratios of myoglobin content to mitochondrial volume density and to citrate synthase activity were 4.4 and 2.5 times greater in PEC than in S, indicative of the significant role of myoglobin in the adaptation of muscle to cardiovascular adjustments during diving.

New Polymer Electrolyte Cell Systems

NASA Technical Reports Server (NTRS)

Smyrl, William H.; Owens, Boone B.; Mann, Kent; Pappenfus, T.; Henderson, W.

2004-01-01

PAPERS PUBLISHED: 1. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Complexes of Lithium Imide Salts with Tetraglyme and Their Polyelectrolyte Composite Materials. Journal of the Electrochemical Society (2004), 15 1 (2), A209-A2 15. 2. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Ionic-liquidlpolymer electrolyte composite materials for electrochemical device applications. Polymeric Materials Science and Engineering (2003), 88 302. 3. Pappenfus, Ted R.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; and Smyrl, William H. Ionic Conductivity of a poly(vinylpyridinium)/Silver Iodide Solid Polymer Electrolyte System. Solid State Ionics (in press 2004). 4. Pappenfus Ted M.; Mann, Kent R; Smyrl, William H. Polyelectrolyte Composite Materials with LiPFs and Tetraglyme. Electrochemical and Solid State Letters, (2004), 7(8), A254.

Nucleic acid polymeric properties and electrostatics: Directly comparing theory and simulation with experiment.

PubMed

Sim, Adelene Y L

2016-06-01

Nucleic acids are biopolymers that carry genetic information and are also involved in various gene regulation functions such as gene silencing and protein translation. Because of their negatively charged backbones, nucleic acids are polyelectrolytes. To adequately understand nucleic acid folding and function, we need to properly describe its i) polymer/polyelectrolyte properties and ii) associating ion atmosphere. While various theories and simulation models have been developed to describe nucleic acids and the ions around them, many of these theories/simulations have not been well evaluated due to complexities in comparison with experiment. In this review, I discuss some recent experiments that have been strategically designed for straightforward comparison with theories and simulation models. Such data serve as excellent benchmarks to identify limitations in prevailing theories and simulation parameters. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

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

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.

Continuous Production of Discrete Plasmid DNA-Polycation Nanoparticles Using Flash Nanocomplexation.

PubMed

Santos, Jose Luis; Ren, Yong; Vandermark, John; Archang, Maani M; Williford, John-Michael; Liu, Heng-Wen; Lee, Jason; Wang, Tza-Huei; Mao, Hai-Quan

2016-12-01

Despite successful demonstration of linear polyethyleneimine (lPEI) as an effective carrier for a wide range of gene medicine, including DNA plasmids, small interfering RNAs, mRNAs, etc., and continuous improvement of the physical properties and biological performance of the polyelectrolyte complex nanoparticles prepared from lPEI and nucleic acids, there still exist major challenges to produce these nanocomplexes in a scalable manner, particularly for lPEI/DNA nanoparticles. This has significantly hindered the progress toward clinical translation of these nanoparticle-based gene medicine. Here the authors report a flash nanocomplexation (FNC) method that achieves continuous production of lPEI/plasmid DNA nanoparticles with narrow size distribution using a confined impinging jet device. The method involves the complex coacervation of negatively charged DNA plasmid and positive charged lPEI under rapid, highly dynamic, and homogeneous mixing conditions, producing polyelectrolyte complex nanoparticles with narrow distribution of particle size and shape. The average number of plasmid DNA packaged per nanoparticles and its distribution are similar between the FNC method and the small-scale batch mixing method. In addition, the nanoparticles prepared by these two methods exhibit similar cell transfection efficiency. These results confirm that FNC is an effective and scalable method that can produce well-controlled lPEI/plasmid DNA nanoparticles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Continuous Production of Discrete Plasmid DNA-Polycation Nanoparticles Using Flash Nanocomplexation

PubMed Central

Santos, Jose Luis; Ren, Yong; Vandermark, John; Archang, Maani M.; Williford, John-Michael; Liu, Heng-wen; Lee, Jason; Wang, Tza-Huei; Mao, Hai-Quan

2016-01-01

Despite successful demonstration of linear polyethyleneimine (lPEI) as an effective carrier for a wide range of gene medicine, including DNA plasmids, small interfering RNAs, mRNAs, etc., and continuous improvement of the physical properties and biological performance of the polyelectrolyte complex nanoparticles prepared from lPEI and nucleic acids, there still exist major challenges to produce these nanocomplexes in a scalable manner, particularly for lPEI/DNA nanoparticles. This has significantly hindered the progress towards clinical translation of these nanoparticle-based gene medicine. Here we report a flash nanocomplexation (FNC) method that achieves continuous production of lPEI/plasmid DNA nanoparticles with narrow size distribution using a confined impinging jet device. The method involves the complex coacervation of negatively charged DNA plasmid and positive charged lPEI under rapid, highly dynamic, and homogeneous mixing conditions, producing polyelectrolyte complex nanoparticles with narrow distribution of particle size and shape. The average number of plasmid DNA packaged per nanoparticles and its distribution are similar between the FNC method and the small-scale batch mixing method. In addition, the nanoparticles prepared by these two methods exhibit similar cell transfection efficiency. These results confirm that FNC is an effective and scalable method that can produce well-controlled lPEI/plasmid DNA nanoparticles. PMID:27717227

On the role of methacrylic acid copolymers in the intracellular delivery of antisense oligonucleotides.

PubMed

Yessine, Marie-Andrée; Meier, Christian; Petereit, Hans-Ulrich; Leroux, Jean-Christophe

2006-05-01

The delivery of active biomacromolecules to the cytoplasm is a major challenge as it is generally hindered by the endosomal/lysosomal barrier. Synthetic titratable polyanions can overcome this barrier by destabilizing membrane bilayers at pH values typically found in endosomes. This study investigates how anionic polyelectrolytes can enhance the cytoplasmic delivery of an antisense oligonucleotide (ODN). Novel methacrylic acid (MAA) copolymers were examined for their pH-sensitive properties and ability to destabilize cell membranes in a pH-dependent manner. Ternary complex formulations prepared with the ODN, a cationic lipid and a MAA copolymer were systematically characterized with respect to their size, zeta potential, antisense activity, cytotoxicity and cellular uptake using the A549 human lung carcinoma cell line. The MAA copolymer substantially increased the activity of the antisense ODN in inhibiting the expression of protein kinase C-alpha. Uptake, cytotoxicity and antisense activity were strongly dependent on copolymer concentration. Metabolic inhibitors demonstrated that endocytosis was the major internalization pathway of the complexes, and that endosomal acidification was essential for ODN activity. Confocal microscopy analysis of cells incubated with fluorescently-labeled complexes revealed selective delivery of the ODN, but not of the copolymer, to the cytoplasm/nucleus. This study provides new insight into the mechanisms of intracellular delivery of macromolecular drugs, using synthetic anionic polyelectrolytes.

Large Electro-Optic Kerr Effect in Ionic Liquid Crystals: Connecting Features of Liquid Crystals and Polyelectrolytes.

PubMed

Schlick, M Christian; Kapernaum, Nadia; Neidhardt, Manuel M; Wöhrle, Tobias; Stöckl, Yannick; Laschat, Sabine; Giesselmann, Frank

2018-06-06

The electro-optic Kerr effect in simple dipolar fluids such as nitrobenzene has been widely applied in electro-optical phase modulators and light shutters. In 2005, the discovery of the large Kerr effect in liquid-crystalline blue phases (Y. Hisakado et al., Adv. Mater. 2005, 17, 96-98.) gave new directions to the search for advanced Kerr effect materials. Even though the Kerr effect is present in all transparent and optically isotropic media, it is well known that the effect can be anomalously large in complex fluids, namely in the isotropic phase of liquid crystals or in polyelectrolyte solutions. Herein, it is shown that the Kerr effect in the isotropic phase of ionic liquid crystals combines the effective counterion polarization mechanism found in polyelectrolytes and the unique pretransitional growth of the Kerr constant found in the isotropic phase of nematic liquid crystals. Maximum Kerr constants in the order of several 10 -11  m V -2 (ten times higher than the Kerr constant of the toxic nitrobenzene and less temperature sensitive than Kerr constants of nematic liquid crystals) make ionic liquid crystals attractive as new class of functional materials in low-speed Kerr effect applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Increasing Functional Communication in Non-Speaking Preschool Children: Comparison of PECS and VOCA

ERIC Educational Resources Information Center

Bock, Stacey Jones; Stoner, Julia B.; Beck, Ann R.; Hanley, Laurie; Prochnow, Jessica

2005-01-01

For individuals who have complex communication needs and for the interventionists who work with them, the collection of empirically derived data that support the use of an intervention approach is critical. The purposes of this study were to continue building an empirically derived base of support for, and to compare the relative effectiveness of…

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.

Experimental Evaluation of the Training Structure of the Picture Exchange Communication System (PECS)

ERIC Educational Resources Information Center

Cummings, Anne R.; Carr, James E.; LeBlanc, Linda A.

2012-01-01

The Picture Exchange Communication System (PECS) is a picture-based alternative communication method that is widely accepted and utilized with individuals with disabilities. Although prior studies have examined the clinical efficacy of PECS, none have experimentally evaluated its manualized training structure. We experimentally evaluated the…

Impact of the picture exchange communication system: effects on communication and collateral effects on maladaptive behaviors.

PubMed

Ganz, Jennifer B; Parker, Richard; Benson, Joanne

2009-12-01

Many children with autism require intensive instruction in the use of augmentative or alternative communication systems, such as the Picture Exchange Communication System (PECS). This study investigated the use of PECS with three young boys with autism to determine the impact of PECS training on use of pictures for requesting, use of intelligible words, and maladaptive behaviors. A multiple baseline-probe design with a staggered start was implemented. Results indicated that all of the participants quickly learned to make requests using pictures and that two used intelligible speech following PECS instruction; maladaptive behaviors were variable throughout baseline and intervention phases. Although all of the participants improved in at least one dependent variable, there remain questions regarding who is best suited for PECS and similar interventions.

Effectiveness of the Picture Exchange Communication System (PECS) on communication and speech for children with autism spectrum disorders: a meta-analysis.

PubMed

Flippin, Michelle; Reszka, Stephanie; Watson, Linda R

2010-05-01

The Picture Exchange Communication System (PECS) is a popular communication-training program for young children with autism spectrum disorders (ASD). This meta-analysis reviews the current empirical evidence for PECS in affecting communication and speech outcomes for children with ASD. A systematic review of the literature on PECS written between 1994 and June 2009 was conducted. Quality of scientific rigor was assessed and used as an inclusion criterion in computation of effect sizes. Effect sizes were aggregated separately for single-subject and group studies for communication and speech outcomes. Eight single-subject experiments (18 participants) and 3 group studies (95 PECS participants, 65 in other intervention/control) were included. Results indicated that PECS is a promising but not yet established evidence-based intervention for facilitating communication in children with ASD ages 1-11 years. Small to moderate gains in communication were demonstrated following training. Gains in speech were small to negative. This meta-analysis synthesizes gains in communication and relative lack of gains made in speech across the PECS literature for children with ASD. Concerns about maintenance and generalization are identified. Emerging evidence of potential preintervention child characteristics is discussed. Phase IV was identified as a possibly influential program characteristic for speech outcomes.

Broiler chickens, broiler chicken meat, pigs and pork as sources of ExPEC related virulence genes and resistance in Escherichia coli isolates from community-dwelling humans and UTI patients.

PubMed

Jakobsen, Lotte; Spangholm, Daniel J; Pedersen, Karl; Jensen, Lars B; Emborg, Hanne-Dorthe; Agersø, Yvonne; Aarestrup, Frank M; Hammerum, Anette M; Frimodt-Møller, Niels

2010-08-15

Urinary tract infection (UTI) is one of the most common bacterial infections. UTI is primarily caused by extraintestinal pathogenic Escherichia coli (ExPEC) from the patients' own fecal flora. The ExPEC often belong to phylogroups B2 and D, the groups which include potent human ExPEC isolates causing UTI, bacteremia, and meningitis. The external sources of these ExPEC in the human intestine are unknown. The food supply may transmit ExPEC to humans. However, evidence of this hypothesis is limited. To assess this hypothesis, the objective of our study was to investigate the presence of ExPEC related virulence genes in E. coli isolates from UTI patients, community-dwelling humans, meat, and production animals. Accordingly, we included 964 geographically and temporally matched E. coli isolates from UTI patients (n=102), community-dwelling humans (n=109), fresh Danish (n=197) and imported broiler chicken meat (n=86), broiler chickens (n=138), fresh Danish (n=177) and imported pork (n=10), and pigs (n=145) in the study. All isolates were investigated for the presence of eight ExPEC related genes (kpsM II, papA, papC, iutA, sfaS, focG, afa, hlyD) using PCR. To investigate any similarities between isolates from the different origins, we performed a cluster analysis including antimicrobial resistance data previously published. We detected seven of the eight ExPEC related genes in isolates from broiler chicken meat, broiler chickens, pork and pigs. Our findings suggest that broiler chicken meat, broiler chickens, pork and pigs could be the source of strains with these ExPEC related virulence genes in community-dwelling humans and UTI patients. Especially detection of ExPEC related virulence genes in isolates belonging to phylogroups B2 and D is very concerning and may have a significant medical impact. The cluster analysis of virulence gene and antimicrobial resistance profiles showed strong similarities between UTI patient, community-dwelling human isolates, meat, and production animal isolates. Thus, these strains from meat and production animals may pose a zoonotic risk. Copyright 2010 Elsevier B.V. All rights reserved.

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

Sediment contamination of residential streams in the metropolitan kansas city area, USA: Part II. whole-sediment toxicity to the amphipod hyalella azteca

USGS Publications Warehouse

Tao, J.; Ingersoll, C.G.; Kemble, N.E.; Dias, J.R.; Murowchick, J.B.; Welker, G.; Huggins, D.

2010-01-01

This is the second part of a study that evaluates the influence of nonpoint sources on the sediment quality of five adjacent streams within the metropolitan Kansas City area, central United States. Physical, chemical, and toxicity data (Hyalella azteca 28-day whole-sediment toxicity test) for 29 samples collected in 2003 were used for this evaluation, and the potential causes for the toxic effects were explored. The sediments exhibited a low to moderate toxicity, with five samples identified as toxic to H. azteca. Metals did not likely cause the toxicity based on low concentrations of metals in the pore water and elevated concentrations of acid volatile sulfide in the sediments. Although individual polycyclic aromatic hydrocarbons (PAHs) frequently exceeded effect-based sediment quality guidelines [probable effect concentrations (PECs)], only four of the samples had a PEC quotient (PEC-Q) for total PAHs over 1.0 and only one of these four samples was identified as toxic. For the mean PEC-Q for organochlorine compounds (chlordane, dieldrin, sum DDEs), 4 of the 12 samples with a mean PEC-Q above 1.0 were toxic and 4 of the 8 samples with a mean PEC-Q above 3.0 were toxic. Additionally, four of eight samples were toxic, with a mean PEC-Q above 1.0 based on metals, PAHs, polychlorinated biphenyls (PCBs), and organochlorine pesticides. The increase in the incidence of toxicity with the increase in the mean PEC-Q based on organochlorine pesticides or based on metals, PAHs, PCBs, and organochlorine pesticides suggests that organochlorine pesticides might have contributed to the observed toxicity and that the use of a mean PEC-Q, rather than PEC-Qs for individual compounds, might be more informative in predicting toxic effects. Our study shows that stream sediments subject to predominant nonpoint sources contamination can be toxic and that many factors, including analysis of a full suite of PAHs and pesticides of both past and present urban applications and the origins of these organic compounds, are important to identify the causes of toxicity. ?? 2010 Springer Science+Business Media, LLC.

Enhancement in hydrogen evolution using Au-TiO2 hollow spheres with microbial devices modified with conjugated oligoelectrolytes

PubMed Central

Ngaw, Chee Keong; Wang, Victor Bochuan; Liu, Zhengyi; Zhou, Yi; Kjelleberg, Staffan; Zhang, Qichun; Tan, Timothy Thatt Yang; Loo, Say Chye Joachim

2015-01-01

Objective: Although photoelectrochemical (PEC) water splitting heralds the emergence of the hydrogen economy, the need for external bias and low efficiency stymies the widespread application of this technology. By coupling water splitting (in a PEC cell) to a microbial fuel cell (MFC) using Escherichia coli as the biocatalyst, this work aims to successfully demonstrate a sustainable hybrid PEC–MFC platform functioning solely by biocatalysis and solar energy, at zero bias. Through further chemical modification of the photo-anode (in the PEC cell) and biofilm (in the MFC), the performance of the hybrid system is expected to improve in terms of the photocurrent generated and hydrogen evolved. Methods: The hybrid system constitutes the interconnected PEC cell with the MFC. Both PEC cell and MFC are typical two-chambered systems housing the anode and cathode. Au-TiO2 hollow spheres and conjugated oligoelectrolytes were synthesised chemically and introduced to the PEC cell and MFC, respectively. Hydrogen evolution measurements were performed in triplicates. Results: The hybrid PEC–MFC platform generated a photocurrent density of 0.35 mA/cm2 (~70× enhancement) as compared with the stand-alone P25 standard PEC cell (0.005 mA/cm2) under one-sun illumination (100 mW/cm2) at zero bias (0 V vs. Pt). This increase in photocurrent density was accompanied by continuous H2 production. No H2 was observed in the P25 standard PEC cell whereas H2 evolution rate was ~3.4 μmol/h in the hybrid system. The remarkable performance is attributed to the chemical modification of E. coli through the incorporation of novel conjugated oligoelectrolytes in the MFC as well as the lower recombination rate and higher photoabsorption capabilities in the Au-TiO2 hollow spheres electrode. Conclusions: The combined strategy of photo-anode modification in PEC cells and chemically modified MFCs shows great promise for future exploitation of such synergistic effects between MFCs and semiconductor-based PEC water splitting. PMID:28721235

Reducing mTOR augments parietal epithelial cell density in a model of acute podocyte depletion and in aged kidneys

PubMed Central

McNicholas, Bairbre A.; Eng, Diana G.; Lichtnekert, Julia; Rabinowitz, Peter S.; Pippin, Jeffrey W.

2016-01-01

Parietal epithelial cell (PEC) response to glomerular injury may underlie a common pathway driving fibrogenesis following podocyte loss that typifies several glomerular disorders. Although the mammalian target of rapamycin (mTOR) pathway is important in cell homeostasis, little is known of the biological role or impact of reducing mTOR activity on PEC response following podocyte depletion, nor in the aging kidney. The purpose of these studies was to determine the impact on PECs of reducing mTOR activity following abrupt experimental depletion in podocyte number, as well as in a model of chronic podocyte loss and sclerosis associated with aging. Podocyte depletion was induced by an anti-podocyte antibody and rapamycin started at day 5 until death at day 14. Reducing mTOR did not lead to a greater reduction in podocyte density, despite greater glomerulosclerosis. However, mTOR inhibition lead to an increase in PEC density and PEC-derived crescent formation. Additionally, markers of epithelial-to-mesenchymal transition (platelet-derived growth factor receptor-β, α-smooth muscle actin, Notch-3) and PEC activation (CD44, collagen IV) were further increased by mTOR reduction. Aged mice treated with rapamycin for 1, 2, and 10 wk before death at 26.5 mo (≈75-yr-old human age) had increased the number of glomeruli with a crescentic appearance. mTOR inhibition at either a high or low level lead to changes in PEC phenotype, indicating PEC morphology is sensitive to changes mediated by global mTOR inhibition. PMID:27440779

Risk Factors of Post-Endoscopic Submucosal Dissection Electrocoagulation Syndrome for Colorectal Neoplasm.

PubMed

Ito, Sayo; Hotta, Kinichi; Imai, Kenichiro; Yamaguchi, Yuichiro; Kishida, Yoshihiro; Takizawa, Kohei; Kakushima, Naomi; Tanaka, Masaki; Kawata, Noboru; Yoshida, Masao; Ishiwatari, Hirotoshi; Matsubayashi, Hiroyuki; Ono, Hiroyuki

2018-06-04

Colorectal endoscopic submucosal dissection (ESD) is used for the treatment of large colorectal superficial neoplasms. However, there have been no large studies on electrocoagulation syndrome developing after colorectal ESD. The aim of this study was to clarify the incidence and clinical risk factors of post-ESD electrocoagulation syndrome (PECS). A total of 692 patients (median age, 70 years; 395 men) with 692 lesions, who underwent colorectal ESD at a tertiary cancer center between July 2010 and December 2015 were eligible. PECS was clinically diagnosed based on the presence of localized abdominal tenderness matching the ESD enforcement site, and fever (>37.5°C) or an inflammatory response (C-reactive protein level >0.5 mg/dL or leukocytosis >10000 cells/μL), without obvious findings of perforation, which developed at >6 h post-ESD. Outcomes of the procedure, the incidence of PECS, and risk factors associated with PECS were assessed. The incidence of PECS was 4.8% (33 patients), and all patients improved by conservative treatment. On multivariate analysis, the female sex (odds ratio [OR] 2.6; 95% confidence interval [95% CI], 1.2-5.7), tumor location at the cecum (OR 14.5; 95% CI: 3.7-53.7 vs rectum), and the presence of submucosal fibrosis (OR 2.8; 95% CI: 1.1-7.5) were found to be independent risk factors of PECS. This study identified the risk factors for PECS. Patients with high risk factors of PECS require careful management after colorectal ESD. This article is protected by copyright. All rights reserved.

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).

The Picture Exchange Communication System (PECS): What Do the Data Say?

ERIC Educational Resources Information Center

Sulzer-Azaroff, Beth; Hoffman, Anne O.; Horton, Catherine B.; Bondy, Andrew; Frost, Lori

2009-01-01

Originally designed to enable young children with autism lacking functional communication to initiate requests and to describe what they observed, the Picture Exchange Communication System (PECS) has been the subject of an ever-expanding body of research and development. Thirty-four peer-reviewed published reports on PECS are analyzed in this…

Long-Term Effects of PECS on Social-Communicative Skills of Children with Autism Spectrum Disorders: A Follow-Up Study

ERIC Educational Resources Information Center

Lerna, Anna; Esposito, Dalila; Conson, Massimiliano; Massagli, Angelo

2014-01-01

Background: The Picture Exchange Communication System (PECS) is a popular augmentative communication system frequently used with "nonverbal" children with autism. Several studies suggested that PECS could represent an effective tool for promoting improvement of several social-communicative skills. Only sparse evidence is instead…

The Picture Exchange Communication System: Communicative Outcomes for Young Children with Disabilities.

ERIC Educational Resources Information Center

Schwartz, Ilene S.; Garfinkle, Ann N.; Bauer, Janet

1998-01-01

Presents two studies documenting the use of the Picture Exchange Communication System (PECS) for 31 preschool children with severe disabilities. Initial findings indicated the children could learn to use PECS quickly and efficiently. The second study, which included 18 participants, found that PECS use generalized to untrained settings. (Author/CR)

Understanding the Picture Exchange Communication System and Its Application in Physical Education

ERIC Educational Resources Information Center

Green, Amanda; Sandt, Dawn

2013-01-01

This article presents the Picture Exchange Communication System (PECS) and its applications in physical education. The PECS is an appropriate communication intervention for students with autism who lack functional communication skills. It is often confused with other visual support strategies, so the authors delineate the six phases of PECS and…

Influence of molecular weight of chemically sulfated citrus pectin fractions on their antithrombotic and bleeding effects.

PubMed

Cipriani, Thales R; Gracher, Ana Helena P; de Souza, Lauro M; Fonseca, Roberto J C; Belmiro, Celso L R; Gorin, Philip A J; Sassaki, Guilherme L; Iacomini, Marcello

2009-05-01

Evaluated were the anticoagulant and antithrombotic activities, and bleeding effect of two chemically sulfated polysaccharides, obtained from citric pectin, with different average molar masses. Both low-molecular-weight (Pec-LWS, 3,600 g/mol) and high-molecular-weight sulfated pectins (Pec-HWS, 12,000 g/mol) had essentially the same structure, consisting of a (1-->4)-linked alpha-D-GalpA chain with almost all its HO-2 and HO-3 groups substituted by sulfate. Both polysaccharides had anticoagulant activity in vitro, although Pec-HWS was a more potent antithrombotic agent in vivo, giving rise to total inhibition of venous thrombosis at a dose of 3.5 mg/kg body weight. Surprisingly, in contrast with heparin, Pec-HWS and Pec-LWS are able to directly inhibit alpha-thrombin and factor Xa by a mechanism independent of antithrombin (AT) and/or heparin co-factor II (HCII). Moreover, Pec-HWS provided a lower risk of bleeding than heparin at a dose of 100% effectiveness against venous thrombosis, indicating it to be a promising antithrombotic agent.

Ion-Conductive and Thermal Properties of a Synergistic Poly(ethylene carbonate)/Poly(trimethylene carbonate) Blend Electrolyte.

PubMed

Li, Zhenguang; Mogensen, Ronnie; Mindemark, Jonas; Bowden, Tim; Brandell, Daniel; Tominaga, Yoichi

2018-05-11

Electrolytes comprising poly(ethylene carbonate) (PEC)/poly(trimethylene carbonate) (PTM C) with lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) are prepared by a simple solvent casting method. Although PEC and PTMC have similar chemical structures, they are immiscible and two glass transitions are present in the differential scanning calorimetry (DSC) measurements. Interestingly, these two polymers change to miscible blends with the addition of LiTFSI, and the ionic conductivity increases with increasing lithium salt concentration. The optimum composition of the blend electrolyte is achieved at PEC 6 PTMC 4 , with a conductivity as high as 10 -6 S cm -1 at 50 °C. This value is greater than that for single PEC- and PTMC-based electrolytes. Moreover, the thermal stability of the blend-based electrolytes is improved as compared to PEC-based electrolytes. It is clear that the interaction between CO groups and Li + gives rise to a compatible amorphous phase of PEC and PTMC. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Engineering MoSx/Ti/InP Hybrid Photocathode for Improved Solar Hydrogen Production

NASA Astrophysics Data System (ADS)

Li, Qiang; Zheng, Maojun; Zhong, Miao; Ma, Liguo; Wang, Faze; Ma, Li; Shen, Wenzhong

2016-07-01

Due to its direct band gap of ~1.35 eV, appropriate energy band-edge positions, and low surface-recombination velocity, p-type InP has attracted considerable attention as a promising photocathode material for solar hydrogen generation. However, challenges remain with p-type InP for achieving high and stable photoelectrochemical (PEC) performances. Here, we demonstrate that surface modifications of InP photocathodes with Ti thin layers and amorphous MoSx nanoparticles can remarkably improve their PEC performances. A high photocurrent density with an improved PEC onset potential is obtained. Electrochemical impedance analyses reveal that the largely improved PEC performance of MoSx/Ti/InP is attributed to the reduced charge-transfer resistance and the increased band bending at the MoSx/Ti/InP/electrolyte interface. In addition, the MoSx/Ti/InP photocathodes function stably for PEC water reduction under continuous light illumination over 2 h. Our study demonstrates an effective approach to develop high-PEC-performance InP photocathodes towards stable solar hydrogen production.

Engineering MoSx/Ti/InP Hybrid Photocathode for Improved Solar Hydrogen Production

PubMed Central

Li, Qiang; Zheng, Maojun; Zhong, Miao; Ma, Liguo; Wang, Faze; Ma, Li; Shen, Wenzhong

2016-01-01

Due to its direct band gap of ~1.35 eV, appropriate energy band-edge positions, and low surface-recombination velocity, p-type InP has attracted considerable attention as a promising photocathode material for solar hydrogen generation. However, challenges remain with p-type InP for achieving high and stable photoelectrochemical (PEC) performances. Here, we demonstrate that surface modifications of InP photocathodes with Ti thin layers and amorphous MoSx nanoparticles can remarkably improve their PEC performances. A high photocurrent density with an improved PEC onset potential is obtained. Electrochemical impedance analyses reveal that the largely improved PEC performance of MoSx/Ti/InP is attributed to the reduced charge-transfer resistance and the increased band bending at the MoSx/Ti/InP/electrolyte interface. In addition, the MoSx/Ti/InP photocathodes function stably for PEC water reduction under continuous light illumination over 2 h. Our study demonstrates an effective approach to develop high-PEC-performance InP photocathodes towards stable solar hydrogen production. PMID:27431993

Engineering MoSx/Ti/InP Hybrid Photocathode for Improved Solar Hydrogen Production.

PubMed

Li, Qiang; Zheng, Maojun; Zhong, Miao; Ma, Liguo; Wang, Faze; Ma, Li; Shen, Wenzhong

2016-07-19

Due to its direct band gap of ~1.35 eV, appropriate energy band-edge positions, and low surface-recombination velocity, p-type InP has attracted considerable attention as a promising photocathode material for solar hydrogen generation. However, challenges remain with p-type InP for achieving high and stable photoelectrochemical (PEC) performances. Here, we demonstrate that surface modifications of InP photocathodes with Ti thin layers and amorphous MoSx nanoparticles can remarkably improve their PEC performances. A high photocurrent density with an improved PEC onset potential is obtained. Electrochemical impedance analyses reveal that the largely improved PEC performance of MoSx/Ti/InP is attributed to the reduced charge-transfer resistance and the increased band bending at the MoSx/Ti/InP/electrolyte interface. In addition, the MoSx/Ti/InP photocathodes function stably for PEC water reduction under continuous light illumination over 2 h. Our study demonstrates an effective approach to develop high-PEC-performance InP photocathodes towards stable solar hydrogen production.

MISSE 6-Testing Materials in Space

NASA Technical Reports Server (NTRS)

Prasad, Narasimha S; Kinard, William H.

2008-01-01

The objective of the Materials International Space Station Experiment (MISSE) is to study the performance of novel materials when subjected to the synergistic effects of the harsh space environment by placing them in space environment for several months. In this paper, a few materials and components from NASA Langley Research Center (LaRC) that have been flown on MISSE 6 mission will be discussed. These include laser and optical elements for photonic devices. The pre-characterized MISSE 6 materials were packed inside a ruggedized Passive Experiment Container (PEC) that resembles a suitcase. The PEC was tested for survivability due to launch conditions. Subsequently, the MISSE 6 PEC was transported by the STS-123 mission to International Space Station (ISS) on March 11, 2008. The astronauts successfully attached the PEC to external handrails and opened the PEC for long term exposure to the space environment.

Opioid-sparing effects of the thoracic interfascial plane blocks: A meta-analysis of randomized controlled trials

PubMed Central

Singh, Preet Mohinder; Borle, Anuradha; Kaur, Manpreet; Trikha, Anjan; Sinha, Ashish

2018-01-01

Background: Thoracic interfascial plane blocks and modification (PECS) have recently gained popularity for analgesic potential during breast surgery. We evaluate/consolidate the evidence on opioid-sparing effect of PECS blocks in comparison with conventional intravenous analgesia (IVA) and paravertebral block (PVB). Materials and Methods: Prospective, randomized controlled trials comparing PECS block to conventional IVA or PVB in patients undergoing breast surgery published till June 2017 were searched in the medical database. Comparisons were made for 24-h postoperative morphine consumption and intraoperative fentanyl-equivalent consumption. Results: Final analysis included nine trials (PECS vs. IVA 4 trials and PECS vs. PVB 5 trials). PECS block showed a decreased intraoperative fentanyl consumption over IVA by 49.20 mcg (95% confidence interval [CI] =42.67–55.74) (I2 = 98.47%, P < 0.001) and PVB by 15.88 mcg (95% CI = 12.95–18.81) (I2 = 95.51%, P < 0.001). Postoperative, 24-h morphine consumption with PECS block was lower than IVA by 7.66 mg (95% CI being 6.23–9.10) (I2 = 63.15, P < 0.001) but was higher than PVB group by 1.26 mg (95% CI being 0.91–1.62) (I2 = 99.53%, P < 0.001). Two cases of pneumothorax were reported with PVB, and no complication was reported in any other group. Conclusions: Use of PECS block and its modifications with general anesthesia for breast surgery has significant opioid-sparing effect intraoperatively and during the first 24 h after surgery. It also has higher intraoperative opioid-sparing effect when compared to PVB. During the 1st postoperative day, PVB has slightly more morphine sparing potential that may however be associated with higher complication rates. The present PECS block techniques show marked interstudy variations and need standardization. PMID:29416465

Regular physical education class enhances sociality and physical fitness while reducing psychological problems in children of multicultural families

PubMed Central

Park, Jae-Wan; Park, Seong-Hwan; Koo, Chang-Mo; Eun, Denny; Kim, Kang-Ho; Lee, Chan-Bok; Ham, Joung-Hyun; Jang, Jeong-Hoon; Jee, Yong-Seok

2017-01-01

This study investigated the influence of physical education class (PEC) as an intervention method for aggression, sociality, stress, and physical fitness levels in children from multicultural families. The hypothesis was that participating in PEC would result in reduced aggression and stress and improved sociality and physical fitness in multicultural children. A three-item questionnaire, a body composition test, and physical fitness tests were given three times. Eighty-four subjects were divided into four groups: multicultural children who participated in PEC (multi-PEG, n=12), multicultural children who did not participate in PEC (multi-NPEG, n=13), single-cultural children who participated in PEC (sing-PEG, n=11), and single-cultural children who did not participate in PEC (sing-NPEG, n=12), respectively. Parametric and nonparametric statistical methods were conducted on the collected data with a significance level set a priori at P<0.05. After 8 weeks of PEC, fat mass (F=2.966, P=0.045) and body mass index (F=3.654, P=0.021) had significantly different interaction effects. In the aspect of interaction effects from physical fitness variables, cardiopulmonary endurance (F=21.961, P=0.001), flexibility (F=8.892, P=0.001), muscular endurance (F=31.996, P=0.001), muscular strength (F=4.570, P=0.008), and power (F=24.479, P=0.001) were significantly improved in the multi-PEG compared to those of the other three groups. Moreover, sociality (F=22.144, P=0.001) in the multi-PEG was enhanced, whereas aggression (F=6.745, P=0.001) and stress (F=3.242, P=0.033) levels were reduced. As conclusion, the PEC reduced aggression and stress levels, and improved sociality and physical fitness levels after 8 weeks. This study confirmed that PEC for children from multicultural families can improve psychosocial factors and physical health. PMID:28503529

Inhibitory effects of rosmarinic acid on pterygium epithelial cells through redox imbalance and induction of extrinsic and intrinsic apoptosis.

PubMed

Chen, Ya-Yu; Tsai, Chia-Fang; Tsai, Ming-Chu; Hsu, Yu-Wen; Lu, Fung-Jou

2017-07-01

Pterygium is a common tumor-like ocular disease, which may be related to exposure to chronic ultraviolet (UV) radiation. Although the standard treatment for pterygium is surgical intervention, the recurrence rate of pterygium is high when no effective inhibitory drug is used after surgery. Rosmarinic acid (RA) is a polyphenol antioxidant with many biological activities, including anti-UV and anti-tumor properties. This study aimed to examine the inhibitory effects of RA on pterygium epithelial cells (PECs). Methylthiazolyldiphenyl-tetrazolium bromide (MTT) assay was used to examine the cell cytotoxicity of PECs after RA treatment. A fluorescent probe, DCFH-DA (2',7'-dichlorofluorescin diacetate), was stained with PECs to measure intracellular reactive oxygen species (ROS) levels. Antioxidant activity assays were used to measure the levels of superoxide dismutase (SOD) and catalase (CAT) in PECs. Western blot analysis was used to determine the protein expression of nuclear factor E2-related factor 2 (Nrf2), heme oxygenase 1 (HO-1), quinone acceptor oxidoreductase 1 (NQO1), and apoptosis-associated proteins. RA significantly reduced the cell viability of the PECs. Treatment with RA remarkably increased the Nrf2 protein expression levels in the nucleus, HO-1 and NQO1 protein expression levels, and the activities of SOD and CAT. As a result, intracellular ROS levels in PECs were decreased. Additionally, the induction of extrinsic apoptosis on PECs by RA was associated with increasing expressions levels of Fas, Fas-associated protein with death domain (FADD), tumor necrosis factor-alpha (TNF-α), and caspase 8 protein. Moreover, the induction of intrinsic apoptotic cell death in PECs was confirmed through upregulation of cytochrome c, Bax, caspase 9, and caspase 3 and downregulation of Bcl-2 and pro-caspase 3. Our study demonstrated that RA could inhibit the viability of PECs through regulation of extrinsic and intrinsic apoptosis pathways. Therefore, RA may have potential as a therapeutic medication for pterygium. Copyright © 2017 Elsevier Ltd. All rights reserved.

Regular physical education class enhances sociality and physical fitness while reducing psychological problems in children of multicultural families.

PubMed

Park, Jae-Wan; Park, Seong-Hwan; Koo, Chang-Mo; Eun, Denny; Kim, Kang-Ho; Lee, Chan-Bok; Ham, Joung-Hyun; Jang, Jeong-Hoon; Jee, Yong-Seok

2017-04-01

This study investigated the influence of physical education class (PEC) as an intervention method for aggression, sociality, stress, and physical fitness levels in children from multicultural families. The hypothesis was that participating in PEC would result in reduced aggression and stress and improved sociality and physical fitness in multicultural children. A three-item questionnaire, a body composition test, and physical fitness tests were given three times. Eighty-four subjects were divided into four groups: multicultural children who participated in PEC (multi-PEG, n=12), multicultural children who did not participate in PEC (multi-NPEG, n=13), single-cultural children who participated in PEC (sing-PEG, n=11), and single-cultural children who did not participate in PEC (sing-NPEG, n=12), respectively. Parametric and nonparametric statistical methods were conducted on the collected data with a significance level set a priori at P <0.05. After 8 weeks of PEC, fat mass ( F =2.966, P =0.045) and body mass index ( F =3.654, P =0.021) had significantly different interaction effects. In the aspect of interaction effects from physical fitness variables, cardiopulmonary endurance ( F =21.961, P =0.001), flexibility ( F =8.892, P =0.001), muscular endurance ( F =31.996, P =0.001), muscular strength ( F =4.570, P =0.008), and power ( F =24.479, P =0.001) were significantly improved in the multi-PEG compared to those of the other three groups. Moreover, sociality ( F =22.144, P =0.001) in the multi-PEG was enhanced, whereas aggression ( F =6.745, P =0.001) and stress ( F =3.242, P =0.033) levels were reduced. As conclusion, the PEC reduced aggression and stress levels, and improved sociality and physical fitness levels after 8 weeks. This study confirmed that PEC for children from multicultural families can improve psychosocial factors and physical health.

The Picture Exchange Communication System.

PubMed

Bondy, A; Frost, L

2001-10-01

The Picture Exchange Communication System (PECS) is an alternative/augmentative communication system that was developed to teach functional communication to children with limited speech. The approach is unique in that it teaches children to initiate communicative interactions within a social framework. This article describes the advantages to implementing PECS over traditional approaches. The PECS training protocol is described wherein children are taught to exchange a single picture for a desired item and eventually to construct picture-based sentences and use a variety of attributes in their requests. The relationship of PECS's implementation to the development of speech in previously nonvocal students is reviewed.

Ultrasound description of Pecs II (modified Pecs I): a novel approach to breast surgery.

PubMed

Blanco, R; Fajardo, M; Parras Maldonado, T

2012-11-01

The Pecs block (pectoral nerves block) is an easy and reliable superficial block inspired by the infraclavicular block approach and the transversus abdominis plane blocks. Once the pectoralis muscles are located under the clavicle the space between the two muscles is dissected to reach the lateral pectoral and the medial pectoral nerves. The main indications are breast expanders and subpectoral prosthesis where the distension of these muscles is extremely painful. A second version of the Pecs block is described, called "modified Pecs block" or Pecs block type II. This novel approach aims to block at least the pectoral nerves, the intercostobrachial, intercostals III-IV-V-VI and the long thoracic nerve. These nerves need to be blocked to provide complete analgesia during breast surgery, and it is an alternative or a rescue block if paravertebral blocks and thoracic epidurals failed. This block has been used in our unit in the past year for the Pecs I indications described, and in addition for, tumorectomies, wide excisions, and axillary clearances. The ultrasound sequence to perform this block is shown, together with simple X-ray dye images and gadolinium MRI images to understand the spread and pathways that can explain the benefit of this novel approach. Copyright © 2012 Sociedad Española de Anestesiología, Reanimación y Terapéutica del Dolor. Published by Elsevier España. All rights reserved.

Human Primary Intestinal Epithelial Cells as an Improved In Vitro Model for Cryptosporidium parvum Infection

PubMed Central

Cabada, Miguel M.; Nichols, Joan; Gomez, Guillermo; White, A. Clinton

2013-01-01

The study of human intestinal pathogens has been limited by the lack of methods for the long-term culture of primary human intestinal epithelial cells (PECs). The development of infection models with PECs would allow a better understanding of host-parasite interactions. The objective of this study was to develop a novel method for prolonged in vitro cultivation of PECs that can be used to study Cryptosporidium infection. We isolated intact crypts from human intestines removed during weight loss surgery. The fragments of intestinal layers were cultivated with culture medium supplemented with growth factors and antiapoptotic molecules. After 7 days, the PECs formed self-regenerating cell clusters, forming villi that resemble intestinal epithelium. The PECs proliferated and remained viable for at least 60 days. The cells expressed markers for intestinal stem cells, epithelial cells, and mature enterocytes. The PECs were infected with Cryptosporidium. In contrast to older models in which parasite numbers decay, the burden of parasites increased for >120 h. In summary, we describe here a novel method for the cultivation of self-regenerating human epithelial cells from small intestinal crypts, which contain both intestinal stem cells and mature villus cells. We present data that suggest these cells support Cryptosporidium better than existing cell lines. PECs should provide an improved tool for studying host-parasite interactions involving Cryptosporidium and other intestinal pathogens. PMID:23509153

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.

The PEC Network 1993. Directory of the Peace Education Commission. Peace Education Miniprints, No. 47.

ERIC Educational Resources Information Center

Bjerstedt, Ake, Ed.

This extensive list of the council members of the Peace Education Commission (PEC) from 1992-1994 gives mailing addresses and some telephone and fax numbers to enable direct contact with network members. The Peace Education Commission (PEC) facilitates international cooperation among individuals interested in peace education and research related…

Introducing the PEC Network: Mailing Addresses of the Peace Education Commission. Peace Education Miniprints No. 1.

ERIC Educational Resources Information Center

Bjerstedt, Ake, Ed.

The Peace Education Commission (PEC) was established to facilitate international cooperation among individuals interested in peace education and research related to the field. The major ambition of PEC is to serve as a useful network for transnational information and support in the peace education area. This document gives current mailing…

Meta-Analysis of PECS with Individuals with ASD: Investigation of Targeted versus Non-Targeted Outcomes, Participant Characteristics, and Implementation Phase

ERIC Educational Resources Information Center

Ganz, Jennifer B.; Davis, John L.; Lund, Emily M.; Goodwyn, Fara D.; Simpson, Richard L.

2012-01-01

The Picture Exchange Communication System (PECS) is a widely used picture/icon aided augmentative communication system designed for learners with autism and other developmental disorders. This meta-analysis analyzes the extant empirical literature for PECS relative to targeted (functional communication) and non-targeted concomitant outcomes…

Picture Exchange Communication System with Individuals with Developmental Disabilities: A Meta-Analysis of Single Subject Studies

ERIC Educational Resources Information Center

Hart, Stephanie L.; Banda, Devender R.

2010-01-01

Picture Exchange Communication System (PECS) is a picture-based communication strategy used to teach communication skills to persons with developmental disabilities including autism. This article systematically reviews 13 published single-subject studies to examine the effectiveness of PECS, the effects of PECS on speech and problem behaviors,…

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.

Synthesis and in vitro characterization of entirely S-protected thiolated pectin for drug delivery.

PubMed

Hintzen, Fabian; Hauptstein, Sabine; Perera, Glen; Bernkop-Schnürch, Andreas

2013-11-01

The study was aimed to synthesize a thiolated polymer (thiomer) that is resistant to oxidation in solutions above pH 5. In order to protect a pectin-cysteine conjugate against premature oxidation, the thiomer was S-protected by a disulfide connected leaving group. Therefore, 2-mercaptonicotinic acid was first coupled to L-cysteine by a disulfide exchange reaction and the purified product was subsequently attached to pectin by a carbodiimide mediated amid bond formation. The obtained fully S-protected thiolated pectin was in vitro characterized with respect to co- and mucoadhesive properties and stability toward oxidation. The results indicated a 1.8-fold and 2.3-fold enhanced disintegration time at pH 6.8 of the S-protected thiolated pectin (Pec-Cys-MNA) compared to thiolated pectin (Pec-Cys) and unmodified pectin (Pec). Moreover, rheological measurements of polymer/mucus mixtures showed a 1.6-fold (compared to Pec-Cys) and 6.7-fold (compared to Pec) increased dynamic viscosity of Pec-Cys-MNA. On the other hand, in the presence of a strong oxidizing agent such as H2O2 (0.3% v/v), no increase in viscosity of Pec-Cys-MNA could be observed. A 6-month experiment also demonstrated the long-term stability of a liquid formulation based on Pec-Cys-MNA. Further investigations proved that the first time all thiol groups on a thiolated polymer could be protected owing to the novel synthesis. Accordingly, these features may help to develop thiomer based liquid or gel formulations targeting mucosal surfaces such as nasal, ocular or vaginal drug delivery systems. Copyright © 2013 Elsevier B.V. All rights reserved.

Long-term effects of PECS on social-communicative skills of children with autism spectrum disorders: a follow-up study.

PubMed

Lerna, Anna; Esposito, Dalila; Conson, Massimiliano; Massagli, Angelo

2014-01-01

The Picture Exchange Communication System (PECS) is a popular augmentative communication system frequently used with 'nonverbal' children with autism. Several studies suggested that PECS could represent an effective tool for promoting improvement of several social-communicative skills. Only sparse evidence is instead available on the long-term effectiveness of this treatment system. To test the long-term effects of PECS, for which a follow-up study was conducted by assessing social-communicative skills in nonverbal preschool children with autism after 12 months from treatment completion. Two groups of children (N = 14) were assessed; one group had completed the PECS training and the other conventional language therapy (CLT). At follow-up all children received the same pre- and post-treatment assessment. Outcome measures were the following: Communication and Social domains of Autism Diagnostic Observation Schedule (ADOS); Language and Personal-Social subscales of the Griffiths' Mental Developmental Scales (GMDS); Communication and Social Abilities domains of the Vineland Adaptive Behavior Scales (VABS); and several social-communicative variables coded in an unstructured setting. The PECS group showed significant improvements compared with the CLT group on ADOS severity scores (Communication, Social and Total), on GMDS Social domain and on VABS Communication and Social domains. PECS-related gains on the VABS Social domain and on specific social-communicative measures coded during free-play, i.e. frequency of joint attention and initiation, and duration of cooperative play, were stable after 1-year follow-up. Cooperative play continued to improve on follow-up with respect to both post- and pre-treatment assessment. These findings demonstrated that PECS training can promote long-term enhancement of specific socio-communicative skills in children with autism. © 2014 Royal College of Speech and Language Therapists.

Social-communicative effects of the Picture Exchange Communication System (PECS) in autism spectrum disorders.

PubMed

Lerna, Anna; Esposito, Dalila; Conson, Massimiliano; Russo, Luigi; Massagli, Angelo

2012-01-01

The Picture Exchange Communication System (PECS) is a common treatment choice for non-verbal children with autism. However, little empirical evidence is available on the usefulness of PECS in treating social-communication impairments in autism. To test the effects of PECS on social-communicative skills in children with autism, concurrently taking into account standardized psychometric data, standardized functional assessment of adaptive behaviour, and information on social-communicative variables coded in an unstructured setting. Eighteen preschool children (mean age = 38.78 months) were assigned to two intervention approaches, i.e. PECS and Conventional Language Therapy (CLT). Both PECS (Phases I-IV) and CLT were delivered three times per week, in 30-min sessions, for 6 months. Outcome measures were the following: Autism Diagnostic Observation Schedule (ADOS) domain scores for Communication and Reciprocal Social Interaction; Language and Personal-Social subscales of the Griffiths' Mental Developmental Scales (GMDS); Communication and Social Abilities domains of the Vineland Adaptive Behavior Scales (VABS); and several social-communicative variables coded in an unstructured setting. Results demonstrated that the two groups did not differ at Time 1 (pre-treatment assessment), whereas at Time 2 (post-test) the PECS group showed a significant improvement with respect to the CLT group on the VABS social domain score and on almost all the social-communicative abilities coded in the unstructured setting (i.e. joint attention, request, initiation, cooperative play, but not eye contact). These findings showed that PECS intervention (Phases I-IV) can improve social-communicative skills in children with autism. This improvement is especially evident in standardized measures of adaptive behaviour and measures derived from the observation of children in an unstructured setting. © 2012 Royal College of Speech and Language Therapists.

Human and Avian Extraintestinal Pathogenic Escherichia coli: Infections, Zoonotic Risks, and Antibiotic Resistance Trends

PubMed Central

2013-01-01

Abstract Extraintestinal pathogenic Escherichia coli (ExPEC) constitutes ongoing health concerns for women, newborns, elderly, and immunocompromised individuals due to increased numbers of urinary tract infections (UTIs), newborn meningitis, abdominal sepsis, and septicemia. E. coli remains the leading cause of UTIs, with recent investigations reporting the emergence of E. coli as the predominant cause of nosocomial and neonatal sepsis infections. This shift from the traditional Gram-positive bacterial causes of nosocomial and neonatal sepsis infections could be attributed to the use of intrapartum chemoprophylaxis against Gram-positive bacteria and the appearance of antibiotic (ATB) resistance in E. coli. While ExPEC strains cause significant healthcare concerns, these bacteria also infect chickens and cause the poultry industry economic losses due to costs of containment, mortality, and disposal of carcasses. To circumvent ExPEC-related costs, ATBs are commonly used in the poultry industry to prevent/treat microbial infections and promote growth and performance. In an unfortunate linkage, chicken products are suspected to be a source of foodborne ExPEC infections and ATB resistance in humans. Therefore, the emergence of multidrug resistance (MDR) (resistance to three or more classes of antimicrobial agents) among avian E. coli has created major economic and health concerns, affecting both human healthcare and poultry industries. Increased numbers of immunocompromised individuals, including the elderly, coupled with MDR among ExPEC strains, will continue to challenge the treatment of ExPEC infections and likely lead to increased treatment costs. With ongoing complications due to emerging ATB resistance, novel treatment strategies are necessary to control ExPEC infections. Recognizing and treating the zoonotic risk posed by ExPEC would greatly enhance food safety and positively impact human health. PMID:23962019

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.

Parietal Epithelial Cells Participate in the Formation of Sclerotic Lesions in Focal Segmental Glomerulosclerosis

PubMed Central

Smeets, Bart; Kuppe, Christoph; Sicking, Eva-Maria; Fuss, Astrid; Jirak, Peggy; van Kuppevelt, Toin H.; Endlich, Karlhans; Wetzels, Jack F.M.; Gröne, Hermann-Josef; Floege, Jürgen

2011-01-01

The pathogenesis of the development of sclerotic lesions in focal segmental glomerulosclerosis (FSGS) remains unknown. Here, we selectively tagged podocytes or parietal epithelial cells (PECs) to determine whether PECs contribute to sclerosis. In three distinct models of FSGS (5/6-nephrectomy + DOCA-salt; the murine transgenic chronic Thy1.1 model; or the MWF rat) and in human biopsies, the primary injury to induce FSGS associated with focal activation of PECs and the formation of cellular adhesions to the capillary tuft. From this entry site, activated PECs invaded the affected segment of the glomerular tuft and deposited extracellular matrix. Within the affected segment, podocytes were lost and mesangial sclerosis developed within the endocapillary compartment. In conclusion, these results demonstrate that PECs contribute to the development and progression of the sclerotic lesions that define FSGS, but this pathogenesis may be relevant to all etiologies of glomerulosclerosis. PMID:21719782

Hierarchical Cu2O foam/g-C3N4 photocathode for photoelectrochemical hydrogen production

NASA Astrophysics Data System (ADS)

Ma, Xinzhou; Zhang, Jingtao; Wang, Biao; Li, Qiuguo; Chu, Sheng

2018-01-01

Solar photoelectrochemical (PEC) hydrogen production is a promising way for solving energy and environment problems. Earth-abundant Cu2O is a potential light absorber for PEC hydrogen production. In this article, hierarchical porous Cu2O foams are prepared by thermal oxidation of the electrochemically deposited Cu foams. PEC performances of the Cu2O foams are systematically studied and discussed. Benefiting from their higher light harvesting and more efficient charge separation, the Cu2O foams demonstrate significantly enhanced photocurrents and photostability compared to their film counterparts. Moreover, by integrating g-C3N4, hierarchical Cu2O foam/g-C3N4 composites are prepared with further improved photocurrent and photostability, appearing to be potential photocathodes for solar PEC hydrogen production. This study may provide a new and useful insight for the development of Cu2O-based photocathodes for PEC hydrogen production.

Parent-implemented picture exchange communication system (PECS) training: an analysis of YouTube videos.

PubMed

Jurgens, Anneke; Anderson, Angelika; Moore, Dennis W

2012-01-01

To investigate the integrity with which parents and carers implement PECS in naturalistic settings, utilizing a sample of videos obtained from YouTube. Twenty-one YouTube videos meeting selection criteria were identified. The videos were reviewed for instances of seven implementer errors and, where appropriate, presence of a physical prompter. Forty-three per cent of videos and 61% of PECS exchanges contained errors in parent implementation of specific teaching strategies of the PECS training protocol. Vocal prompts, incorrect error correction and the absence of timely reinforcement occurred most frequently, while gestural prompts, insistence on speech, incorrect use of the open hand prompt and not waiting for the learner to initiate occurred less frequently. Results suggest that parents engage in vocal prompting and incorrect use of the 4-step error correction strategy when using PECS with their children, errors likely to result in prompt dependence.

Modeling and Simulations in Photoelectrochemical Water Oxidation: From Single Level to Multiscale Modeling.

PubMed

Zhang, Xueqing; Bieberle-Hütter, Anja

2016-06-08

This review summarizes recent developments, challenges, and strategies in the field of modeling and simulations of photoelectrochemical (PEC) water oxidation. We focus on water splitting by metal-oxide semiconductors and discuss topics such as theoretical calculations of light absorption, band gap/band edge, charge transport, and electrochemical reactions at the electrode-electrolyte interface. In particular, we review the mechanisms of the oxygen evolution reaction, strategies to lower overpotential, and computational methods applied to PEC systems with particular focus on multiscale modeling. The current challenges in modeling PEC interfaces and their processes are summarized. At the end, we propose a new multiscale modeling approach to simulate the PEC interface under conditions most similar to those of experiments. This approach will contribute to identifying the limitations at PEC interfaces. Its generic nature allows its application to a number of electrochemical systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Monte Carlo simulations of flexible polyanions complexing with whey proteins at their isoelectric point

NASA Astrophysics Data System (ADS)

de Vries, R.

2004-02-01

Electrostatic complexation of flexible polyanions with the whey proteins α-lactalbumin and β-lactoglobulin is studied using Monte Carlo simulations. The proteins are considered at their respective isoelectric points. Discrete charges on the model polyelectrolytes and proteins interact through Debye-Hückel potentials. Protein excluded volume is taken into account through a coarse-grained model of the protein shape. Consistent with experimental results, it is found that α-lactalbumin complexes much more strongly than β-lactoglobulin. For α-lactalbumin, strong complexation is due to localized binding to a single large positive "charge patch," whereas for β-lactoglobulin, weak complexation is due to diffuse binding to multiple smaller charge patches.

Occurrence and Trends of Selected Chemical Constituents in Bottom Sediment, Grand Lake O' the Cherokees, Northeast Oklahoma, 1940-2008

USGS Publications Warehouse

Juracek, Kyle E.; Becker, Mark F.

2009-01-01

After over 100 years of continuous activity, lead and zinc mining in the Tri-State Mining District (hereafter referred to as the TSMD) in parts of southeast Kansas, southwest Missouri, and northeast Oklahoma ended in the 1970s. The mining activity resulted in substantial historical and ongoing input of cadmium, lead, and zinc to the environment including Grand Lake O' the Cherokees (hereafter referred to as Grand Lake), a large reservoir in northeast Oklahoma. To help determine the extent and magnitude of contamination in Grand Lake, a one-year study was conducted by the U.S. Geological Survey in cooperation with the U.S. Fish and Wildlife Service. Bottom-sediment coring at five sites was used to investigate the occurrence of cadmium, lead, zinc, and other selected constituents in the bottom sediment of Grand Lake. Cadmium concentrations in the bottom sediment of Grand Lake ranged from 2.3 to 3.6 mg/kg (milligrams per kilogram) with a median of 3.5 mg/kg (5 samples). Compared to an estimated local background concentration of 0.6 mg/kg, the historical mining activity increased cadmium concentrations by about 280 to 500 percent. Lead concentrations ranged from 35 to 102 mg/kg with a median of 59 mg/kg (50 samples). Compared to an estimated local background concentration of 20 mg/kg, the historical mining activity increased lead concentrations by about 75 to 410 percent. The range in zinc concentrations was 380 to 986 mg/kg with a median of 765 mg/kg (50 samples). Compared to an estimated local background concentration of 100 mg/kg, the historical mining activity increased zinc concentrations by about 280 to 890 percent. With the exception of the most upstream coring site, the lead and zinc depositional profiles generally were similar in terms of the range in concentrations measured and the temporal pattern observed. Depositional profiles for lead and zinc indicated mid-core peaks followed by concentrations that decreased since about the 1980s. The depositional profiles reflect the complex interaction of several factors including historical mining and related activities, mine drainage, remediation, landscape stabilization, precipitation and associated runoff, and the erosion and transport of contaminated and clean sediments within the basin. Compared to sediment-quality guidelines, the Grand Lake samples had cadmium concentrations that were substantially less than the general probable-effects concentration (PEC) (4.98 mg/kg) and a TSMD-specific PEC (11.1 mg/kg). The PECs represent the concentration above which toxic biological effects are likely to occur. Likewise, all sediment samples had lead concentrations that were substantially less than the general PEC (128 mg/kg) and a TSMD-specific PEC (150 mg/kg). Zinc concentrations typically exceeded the general PEC (459 mg/kg), but were substantially less than a TSMD-specific PEC (2,083 mg/kg). Throughout the history of Grand Lake, lead and zinc concentrations in the deposited sediment did not approach or exceed the TSMD-specific PECs. As of 2008, legacy effects of mining still included the delivery of contaminated sediment to Grand Lake by the Spring and Neosho Rivers. The Neosho River, with its larger flows and less-contaminated sediment, likely dilutes the load of contaminated sediment delivered to Grand Lake by the Spring River. The information contained in this report provides a baseline of Grand Lake conditions with which to compare future conditions that may represent a response to changes in mining-related activity in the Grand Lake Basin.

Complexation of Polyelectrolyte Micelles with Oppositely Charged Linear Chains.

PubMed

Kalogirou, Andreas; Gergidis, Leonidas N; Miliou, Kalliopi; Vlahos, Costas

2017-03-02

The formation of interpolyelectrolyte complexes (IPECs) from linear AB diblock copolymer precursor micelles and oppositely charged linear homopolymers is studied by means of molecular dynamics simulations. All beads of the linear polyelectrolyte (C) are charged with elementary quenched charge +1e, whereas in the diblock copolymer only the solvophilic (A) type beads have quenched charge -1e. For the same Bjerrum length, the ratio of positive to negative charges, Z +/- , of the mixture and the relative length of charged moieties r determine the size of IPECs. We found a nonmonotonic variation of the size of the IPECs with Z +/- . For small Z +/- values, the IPECs retain the size of the precursor micelle, whereas at larger Z +/- values the IPECs decrease in size due to the contraction of the corona and then increase as the aggregation number of the micelle increases. The minimum size of the IPECs is obtained at lower Z +/- values when the length of the hydrophilic block of the linear diblock copolymer decreases. The aforementioned findings are in agreement with experimental results. At a smaller Bjerrum length, we obtain the same trends but at even smaller Z +/- values. The linear homopolymer charged units are distributed throughout the corona.

Distinctive viscoelastic and viscoplastic nanomechanics of ionically cross-linked polyelectrolyte complexes under intermittent relaxation and creep

NASA Astrophysics Data System (ADS)

Han, Biao; Ma, Tianzhu; Lee, Daeyeon; Shenoy, Vivek; Han, Lin

This study aims to reveal unique nanoscale viscoelastic and viscoplastic properties of ionically linked polyelectrolyte networks. Layer-by-layer PAH/PAA complexes were tested by four continuous loading cycles in aqueous solutions. In each cycle, AFM-nanoindentation via a microspherical tip (R =5 μm) was applied up to 1 μN force, followed by a 30-60 sec hold at either a constant indentation depth to measure relaxation, or a constant force to measure creep. At a highly cross-linked, net neutral state (0.01M, pH 5.5), instantaneous modulus increased by 2.7-fold from first to last cycle, while the degree of relaxation (>95%) remain consistent. These results indicate repeated loading increases local cross-link density, while relaxation is consistently dominated by cross-link breaking and re-formation. In contrast, under creep, modulus increased by a similar 3.5-fold, and degree of creep is significantly attenuated from ~50% to 45% from first to last cycle. Results from creep suggest constant viscous flow of polymer chains in the absence of permanent anchorage. As a result, an irreversible deformation (~370nm) was observed after multiple creep cycles, suggesting the presence of viscoplasticity.

Significance of Algal Polymer in Designing Amphotericin B Nanoparticles

PubMed Central

Bhatia, Saurabh; Kumar, Vikash; Sharma, Kiran; Nagpal, Kalpana; Bera, Tanmoy

2014-01-01

Development of oral amphotericin B (AmB) loaded nanoparticles (NPs) demands a novel technique which reduces its toxicity and other associated problems. Packing of AmB in between two oppositely charged ions by polyelectrolyte complexation technique proved to be a successful strategy. We have developed a novel carrier system in form of polyelectrolyte complex of AmB by using chitosan (CS) and porphyran (POR) as two oppositely charged polymers with TPP as a crosslinking agent. Initially POR was isolated from Porphyra vietnamensis followed by the fact that its alkali induced safe reduction in molecular weight was achieved. Formulation was optimized using three-factor three-level (33) central composite design. High concentration of POR in NPs was confirmed by sulfated polysaccharide (SP) assay. Degradation and dissolution studies suggested the stability of NPs over wide pH range. Hemolytic toxicity data suggested the safety of prepared formulation. In vivo and in vitro antifungal activity demonstrated the high antifungal potential of optimized formulation when compared with standard drug and marketed formulations. Throughout the study TPP addition did not cause any significant changes. Therefore, these experimental oral NPs may represent an interesting carrier system for the delivery of AmB. PMID:25478596

Development of antibacterial paper coated with sodium hyaluronate stabilized curcumin-Ag nanohybrid and chitosan via polyelectrolyte complexation for medical applications

NASA Astrophysics Data System (ADS)

Rao Kummara, Madhusudana; Kumar, Anuj; Soo, Han Sung

2017-11-01

Sodium hyaluronate (HA) stabilized curcumin-Ag (Cur-Ag) hybrid nanoparticles were prepared in the water-ethanol mixture under constant mechanical stirring condition. The obtained HA stabilized Cur-Ag hybrid nanoparticles were characterized by fourier transform infrared spectroscopy, UV-visible spectroscopy, and x-ray diffraction to confirm the formation and structural interactions. The obtained Cur-Ag hybrid nanoparticles showed spherical shape with their size range 5-12 nm that was increased with the increasing a amount of silver ions as confirmed by transmission electron microscopic analysis. Further, a fibrous cellulose filter paper was impregnated with these hybrid nanoparticles and chitosan (CS) as biopolymer via polyelectrolyte complexation. The morphological analysis confirmed the uniform distribution of hybrid nanoparticle system onto the cellulose fibers of the fibrous filter paper. As per disc diffusion method, the Cur-Ag hybrid nanoparticles impregnated CS-coated filter paper exhibited excellent antibacterial properties against gram-negative Escherichia coli (E.coli) bacteria compared to HA stabilized Cur only. Moreover, as prepared hybrid nanoparticles impregnated biocomposite system is eco-friendly with efficient antibacterial property and have good potential to be used in medical applications.

Complex coacervation of supercharged proteins with polyelectrolytes.

PubMed

Obermeyer, Allie C; Mills, Carolyn E; Dong, Xue-Hui; Flores, Romeo J; Olsen, Bradley D

2016-04-21

Complexation of proteins with polyelectrolytes or block copolymers can lead to phase separation to generate a coacervate phase or self-assembly of coacervate core micelles. However, many proteins do not coacervate at conditions near neutral pH and physiological ionic strength. Here, protein supercharging is used to systematically explore the effect of protein charge on the complex coacervation with polycations. Four model proteins were anionically supercharged to varying degrees as quantified by mass spectrometry. Proteins phase separated with strong polycations when the ratio of negatively charged residues to positively charged residues on the protein (α) was greater than 1.1-1.2. Efficient partitioning of the protein into the coacervate phase required larger α (1.5-2.0). The preferred charge ratio for coacervation was shifted away from charge symmetry for three of the four model proteins and indicated an excess of positive charge in the coacervate phase. The composition of protein and polymer in the coacervate phase was determined using fluorescently labeled components, revealing that several of the coacervates likely have both induced charging and a macromolecular charge imbalance. The model proteins were also encapsulated in complex coacervate core micelles and micelles formed when the protein charge ratio α was greater than 1.3-1.4. Small angle neutron scattering and transmission electron microscopy showed that the micelles were spherical. The stability of the coacervate phase in both the bulk and micelles improved to increased ionic strength as the net charge on the protein increased. The micelles were also stable to dehydration and elevated temperatures.

Visible light photoelectrochemical aptasensor for adenosine detection based on CdS/PPy/g-C3N4 nanocomposites.

PubMed

Liu, Yixin; Ma, Hongmin; Zhang, Yong; Pang, Xuehui; Fan, Dawei; Wu, Dan; Wei, Qin

2016-12-15

In this work, a label-free photoelectrochemical (PEC) aptasensor was developed for adenosine detection based on CdS/PPy/g-C3N4 nanocomposites. The CdS/g-C3N4 heterojunction effectively prevented the photogenerated charges recombination of g-C3N4 and self-photocorrosion processes of CdS, improving photo-to-current conversion efficiency. The introduced polypyrrole (PPy) nanoparticles could lead to a more effective separation of photogenerated charges, thus resulting in a further increasing of photocurrent. The CdS/PPy/g-C3N4 was firstly employed as the photoactive materials for fabrication of aptasensor, and SH-aptamer was then adsorbed on the CdS/PPy/g-C3N4 modified electrodes through S-Cd bond. With increasing of adenosine concentration, the photocurrent decreased as the formation of SH-aptamer-adenosine bioaffinity complexes. Under optimal conditions, the PEC aptasensor had a sensitive response to adenosine in a linear range of 0.3nmolL(-1) to 200nmolL(-1) with a detection limit of 0.1nmolL(-1). Besides, the as-proposed aptasensor has also been applied in human serum samples analysis. The aptasensor exhibits high sensitivity and good stability, thus opening up a new promising PEC platform for some other small molecules analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

Membership Directory of the PEC Network: Mailing Addresses of the Peace Education Commission. Peace Education Miniprints No. 21.

ERIC Educational Resources Information Center

Bjerstedt, Ake, Ed.

The Peace Education Commission (PEC) was established to facilitate international cooperation among individuals interested in peace education and research related to peace education. The main ambition of PEC is to serve as a useful network for transnational information and support in the peace education area. This document provides current mailing…

Effectiveness of the Picture Exchange Communication System (PECS) on Communication and Speech for Children with Autism Spectrum Disorders: A Meta-Analysis

ERIC Educational Resources Information Center

Flippin, Michelle; Reszka, Stephanie; Watson, Linda R.

2010-01-01

Purpose: The Picture Exchange Communication System (PECS) is a popular communication-training program for young children with autism spectrum disorders (ASD). This meta-analysis reviews the current empirical evidence for PECS in affecting communication and speech outcomes for children with ASD. Method: A systematic review of the literature on PECS…

Acquisition and Generalization of the Picture Exchange Communication System Behaviors across Settings, Persons, and Stimulus Classes with Three Students with Autism

ERIC Educational Resources Information Center

Dogoe, Maud S.; Banda, Devender R.; Lock, Robin H.

2010-01-01

This study examined the acquisition and generalization of requesting behaviors learned through PECS with three children with autism. A single-subject multiple baseline across participants design was used to determine the effects of PECS. Results indicated that all three participants acquired PECS skills for requesting and generalized the skills…

Pectoral nerve block (Pecs block) with sedation for breast conserving surgery without general anesthesia.

PubMed

Moon, Eun-Jin; Kim, Seung-Beom; Chung, Jun-Young; Song, Jeong-Yoon; Yi, Jae-Woo

2017-09-01

Most regional anesthesia in breast surgeries is performed as postoperative pain management under general anesthesia, and not as the primary anesthesia. Regional anesthesia has very few cardiovascular or pulmonary side-effects, as compared with general anesthesia. Pectoral nerve block is a relatively new technique, with fewer complications than other regional anesthesia. We performed Pecs I and Pec II block simultaneously as primary anesthesia under moderate sedation with dexmedetomidine for breast conserving surgery in a 49-year-old female patient with invasive ductal carcinoma. Block was uneventful and showed no complications. Thus, Pecs block with sedation could be an alternative to general anesthesia for breast surgeries.

The expression of xenobiotic-metabolizing enzymes in human prostate and in prostate epithelial cells (PECs) derived from primary cultures.

PubMed

Al-Buheissi, S Z; Cole, K J; Hewer, A; Kumar, V; Bryan, R L; Hudson, D L; Patel, H R; Nathan, S; Miller, R A; Phillips, D H

2006-06-01

Dietary heterocyclic amines (HCAs) are carcinogenic in rodent prostate requiring activation by enzymes such as cytochrome P450 (CYP) and N-acetyltransferase (NAT). We investigated by Western blotting and immunohistochemistry the expression of CYP1A1, CYP1A2, and NAT1 in human prostate and in prostate epithelial cells (PECs) derived from primary cultures and tested their ability to activate the dietary carcinogen 2-amino-3-methylimidazo[4,5-f]quinoline (IQ) and its N-hydroxy metabolite (N-OH-IQ) to DNA-damaging moieties. Western blotting identified CYP1A1, CYP1A2, and NAT1. Immunohistochemistry localized NAT1 to the cytoplasm of PECs. Inter-individual variation was observed in the expression levels of CYP1A1, 1A2, and NAT1 (11, 75, and 35-fold, respectively). PECs expressed CYP1A1 and NAT1 but not CYP1A2. When incubated with IQ or N-OH-IQ, PECs formed DNA adducts indicating their ability to metabolically activate these compounds. Prostate cells possess the capacity to activate dietary carcinogens. PECs may provide a useful model system to study their role in prostate carcinogenesis.

High-aspect ratio micro- and nanostructures enabled by photo-electrochemical etching for sensing and energy harvesting applications

NASA Astrophysics Data System (ADS)

Alhalaili, Badriyah; Dryden, Daniel M.; Vidu, Ruxandra; Ghandiparsi, Soroush; Cansizoglu, Hilal; Gao, Yang; Saif Islam, M.

2018-03-01

Photo-electrochemical (PEC) etching can produce high-aspect ratio features, such as pillars and holes, with high anisotropy and selectivity, while avoiding the surface and sidewall damage caused by traditional deep reactive ion etching (DRIE) or inductively coupled plasma (ICP) RIE. Plasma-based techniques lead to the formation of dangling bonds, surface traps, carrier leakage paths, and recombination centers. In pursuit of effective PEC etching, we demonstrate an optical system using long wavelength (λ = 975 nm) infra-red (IR) illumination from a high-power laser (1-10 W) to control the PEC etching process in n-type silicon. The silicon wafer surface was patterned with notches through a lithography process and KOH etching. Then, PEC etching was introduced by illuminating the backside of the silicon wafer to enhance depth, resulting in high-aspect ratio structures. The effect of the PEC etching process was optimized by varying light intensities and electrolyte concentrations. This work was focused on determining and optimizing this PEC etching technique on silicon, with the goal of expanding the method to a variety of materials including GaN and SiC that are used in designing optoelectronic and electronic devices, sensors and energy harvesting devices.

Chasing the long tail of environmental data: PEcAn is nuts about Brown Dog

NASA Astrophysics Data System (ADS)

Dietze, M.; Cowdery, E.; Desai, A. R.; Gardella, A.; Kelly, R.; Kooper, R.; LeBauer, D.; Mantooth, J.; McHenry, K.; Serbin, S.; Shiklomanov, A. N.; Simkins, J.; Viskari, T.; Raiho, A.

2015-12-01

The Predictive Ecosystem Analyzer (PEcAn) is a ecological modeling informatics system that manages the flows of information in and out of terrestrial biosphere models, provenance tracking, visualization, analysis, and model-data fusion. We are in the process of scaling the PEcAn system from one that currently supports a handful of models and system nodes to one that aims to provide bottom-up connectivity across much of the model-data integration done by the terrestrial biogeochemistry community. This talk reports on the current state of PEcAn, it's data processing workflows, and the near- and long-term challenges faced. Particular emphasis will be given to the tools being developed by the Brown Dog project to make unstructured, un-curated data more accessible: the Data Access Proxy (DAP) and the Data Tilling Service (DTS). The use of the DAP to process meteorological data and the DTS to read vegetation data will be demonstrated and other Brown Dog environmental case studies will be briefly touched on. Beyond data processing, facilitating data discovery and import into PEcAn and distributing analyses across the PEcAn network (i.e. bringing models to data) are key challenges moving forward.

Direct coupled-channels deperturbation analysis of the A{sup 1}Σ{sup +} ∼ b{sup 3}Π complex in LiCs with experimental accuracy

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

Kowalczyk, P., E-mail: Pawel.Kowalczyk@fuw.edu.pl; Jastrzebski, W.; Szczepkowski, J.

2015-06-21

We have carried out the direct deperturbation analysis of about 780 rovibronic term values of the strongly spin-orbit (SO) coupled A{sup 1}Σ{sup +} and b{sup 3}Π states of the {sup 7}Li{sup 133}Cs molecule recorded by polarization labelling spectroscopy technique. The explicit A{sup 1}Σ{sup +} ∼ b{sup 3}Π{sub Ω=0,1,2} coupled-channels treatment allowed us to reproduce 95% experimental term values with a standard deviation of 0.05 cm{sup −1} which is close to the accuracy of the present experiment. The initial potential energy curves (PECs) of the mutually perturbed states and SO matrix elements were ab initio evaluated in the basis of themore » spin-averaged wave functions. The empirically refined PECs and SO functions, along with the theoretical transition dipole moments, were used to predict energy and radiative properties of the A ∼ b complex for low J levels of both {sup 7}Li{sup 133}Cs and {sup 6}Li{sup 133}Cs isotopologues. The reasonable candidates for the stimulated Raman transitions between initial Feshbach resonance states, the mixed levels of the A ∼ b complex, and absolute ground X{sup 1}Σ{sup +} (v = 0 and J = 0) state were identified.« less

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

Development of Solid-State Nanopore Technology for Life Detection

NASA Technical Reports Server (NTRS)

Bywaters, K. B.; Schmidt, H.; Vercoutere, W.; Deamer, D.; Hawkins, A. R.; Quinn, R. C.; Burton, A. S.; Mckay, C. P.

2017-01-01

Biomarkers for life on Earth are an important starting point to guide the search for life elsewhere. However, the search for life beyond Earth should incorporate technologies capable of recognizing an array of potential biomarkers beyond what we see on Earth, in order to minimize the risk of false negatives from life detection missions. With this in mind, charged linear polymers may be a universal signature for life, due to their ability to store information while also inherently reducing the tendency of complex tertiary structure formation that significantly inhibit replication. Thus, these molecules are attractive targets for biosignature detection as potential "self-sustaining chemical signatures." Examples of charged linear polymers, or polyelectrolytes, include deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) as well as synthetic polyelectrolytes that could potentially support life, including threose nucleic acid (TNA) and other xenonucleic acids (XNAs). Nanopore analysis is a novel technology that has been developed for singlemolecule sequencing with exquisite single nucleotide resolution which is also well-suited for analysis of polyelectrolyte molecules. Nanopore analysis has the ability to detect repeating sequences of electrical charges in organic linear polymers, and it is not molecule- specific (i.e. it is not restricted to only DNA or RNA). In this sense, it is a better life detection technique than approaches that are based on specific molecules, such as the polymerase chain reaction (PCR), which requires that the molecule being detected be composed of DNA.

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.

Electrostatic Forces as Dominant Interactions Between Proteins and Polyanions: an ESI MS Study of Fibroblast Growth Factor Binding to Heparin Oligomers

NASA Astrophysics Data System (ADS)

Minsky, Burcu Baykal; Dubin, Paul L.; Kaltashov, Igor A.

2017-04-01

The interactions between fibroblast growth factors (FGFs) and their receptors (FGFRs) are facilitated by heparan sulfate (HS) and heparin (Hp), highly sulfated biological polyelectrolytes. The molecular basis of FGF interactions with these polyelectrolytes is highly complex due to the structural heterogeneity of HS/Hp, and many details still remain elusive, especially the significance of charge density and minimal chain length of HS/Hp in growth factor recognition and multimerization. In this work, we use electrospray ionization mass spectrometry (ESI MS) to investigate the association of relatively homogeneous oligoheparins (octamer, dp8, and decamer, dp10) with acidic fibroblast growth factor (FGF-1). This growth factor forms 1:1, 2:1, and 3:1 protein/heparinoid complexes with both dp8 and dp10, and the fraction of bound protein is highly dependent on protein/heparinoid molar ratio. Multimeric complexes are preferentially formed on the highly sulfated Hp oligomers. Although a variety of oligomers appear to be binding-competent, there is a strong correlation between the affinity and the overall level of sulfation (the highest charge density polyanions binding FGF most strongly via multivalent interactions). These results show that the interactions between FGF-1 and Hp oligomers are primarily directed by electrostatics, and also demonstrate the power of ESI MS as a tool to study multiple binding equilibria between proteins and structurally heterogeneous polyanions.

Enzyme-polyelectrolyte complexes in water-ethanol mixtures: negatively charged groups artificially introduced into alpha-chymotrypsin provide additional activation and stabilization effects.

PubMed

Kudryashova, E V; Gladilin, A K; Vakurov, A V; Heitz, F; Levashov, A V; Mozhaev, V V

1997-07-20

Formation of noncovalent complexes between alpha-chymotrypsin (CT) and a polyelectrolyte, polybrene (PB), has been shown to produce two major effects on enzymatic reactions in binary mixtures of polar organic cosolvents with water. (i) At moderate concentrations of organic cosolvents (10% to 30% v/v), enzymatic activity of CT is higher than in aqueous solutions, and this activation effect is more significant for CT in complex with PB (5- to 7-fold) than for free enzyme (1.5- to 2.5-fold). (ii) The range of cosolvent concentrations that the enzyme tolerates without complete loss of catalytic activity is much broader. For enhancement of enzyme stability in the complex with the polycation, the number of negatively charged groups in the protein has been artificially increased by using chemical modification with pyromellitic and succinic anhydrides. Additional activation effect at moderate concentrations of ethanol and enhanced resistance of the enzyme toward inactivation at high concentrations of the organic solvent have been observed for the modified preparations of CT in the complex with PB as compared with an analogous complex of the native enzyme. Structural changes behind alterations in enzyme activity in water-ethanol mixtures have been studied by the method of circular dichroism (CD). Protein conformation of all CT preparations has not changed significantly up to 30% v/v of ethanol where activation effects in enzymatic catalysis were most pronounced. At higher concentrations of ethanol, structural changes in the protein have been observed for different forms of CT that were well correlated with a decrease in enzymatic activity. (c) 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 55: 267-277, 1997.

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

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.

Reduced-Volume Fracture Toughness Characterization for Transparent Polymers

DTIC Science & Technology

2015-03-21

Caruthers et al. (2004) developed a thermodynamically consistent, nonlinear viscoelastic bulk constitutive model based on a potential energy clock ( PEC ...except that relaxation times change. Because of its formulation, the PEC model predicts mechanical yield as a natural consequence of relaxation...softening type of behavior, but hysteresis effects are not naturally accounted for. Adolf et al. (2009) developed a method of simplifying the PEC model

Effects of Mother-Implemented Picture Exchange Communication System (PECS) Training on Independent Communicative Behaviors of Young Children with Autism Spectrum Disorders

ERIC Educational Resources Information Center

Park, Ju Hee; Alber-Morgan, Sheila R.; Cannella-Malone, Helen

2011-01-01

This study examined the effects of mother-implemented Picture Exchange Communication System (PECS) training on the independent communication of three young children with autism spectrum disorders. Three mothers were trained to teach their child PECS Phases 1 through 3B, which they did with high integrity. Moreover, all three children successfully…

T cell phenotype and intracellular IFN-γ production in peritoneal exudate cells and gut intraepithelial lymphocytes during acute Toxoplasma gondii infection in mice

PubMed Central

Shin, Dae-Whan

2002-01-01

Although there are many reports on the splenic (systemic) T cell response after Toxoplasma gondii infection, little information is available regarding the local T cell responses of peritoneal exudate cells (PEC) and gut intraepithelial lymphocytes (IEL) following peroral infection with bradyzoites. Mice were infected with 40 cysts of the 76K strain of T. gondii, and then sacrificed at days 0, 1, 4, 7 and 10 postinfection (PI). The cellular composition and T cell responses of PEC and IEL were analyzed. The total number of PEC and IEL per mouse increased after infection, but the ratio of increase was higher in IEL. Lymphocytes were the major component of both PEC and IEL. The relative percentages of PEC macrophages and neutrophils/eosinophils increased significantly at day 1 and 4 PI, whereas those of IEL did not change significantly. The percentage of PEC NK1.1 and γδ T cells peaked at day 4 PI (p < 0.0001), and CD4 and CD8α T cells increased continuously after infection. The percentages of IEL CD8α and γδ T cells decreased slightly at first, and then increased. CD4 and NK1.1 T cells of IEL did not change significantly after infection. IFN-γ-producing PEC NK1.1 T cells increased significantly from day 1 PI, but the other T cell subsets produced IFN-γ abundantly thereafter. The proportion of IEL IFN-γ-producing CD8α and γδ T cells increased significantly after infection, while IEL NK1.1 T cells had similar IFN-γ production patterns. Taken together, CD4 T cells were the major phenotype and the important IFN-γ-producing T cell subsets in PEC after oral infection with T. gondii, whereas CD8α T cells had these roles in IEL. These results suggest that PEC and IEL comprise different cell differentials and T cell responses, and according to infection route these factors may contribute to the different cellular immune responses. PMID:12325441

Genomic characterisation of an endometrial pathogenic Escherichia coli strain reveals the acquisition of genetic elements associated with extra-intestinal pathogenicity.

PubMed

Goldstone, Robert J; Popat, Roman; Schuberth, Hans-Joachim; Sandra, Olivier; Sheldon, I Martin; Smith, David G E

2014-12-06

Strains of Escherichia coli cause a wide variety of intestinal and extra-intestinal diseases in both humans and animals, and are also often found in healthy individuals or the environment. Broadly, a strong phylogenetic relationship exists that distinguishes most E. coli causing intestinal disease from those that cause extra-intestinal disease, however, isolates within a recently described subclass of Extra-Intestinal Pathogenic E. coli (ExPEC), termed endometrial pathogenic E. coli, tend to be phylogenetically distant from the vast majority of characterised ExPECs, and more closely related to human intestinal pathogens. In this work, we investigate the genetic basis for ExPEC infection in the prototypic endometrial pathogenic E. coli strain MS499. By investigating the genome of MS499 in comparison with a range of other E. coli sequences, we have discovered that this bacterium has acquired substantial lengths of DNA which encode factors more usually associated with ExPECs and less frequently found in the phylogroup relatives of MS499. Many of these acquired factors, including several iron acquisition systems and a virulence plasmid similar to that found in several ExPECs such as APEC O1 and the neonatal meningitis E. coli S88, play characterised roles in a variety of typical ExPEC infections and appear to have been acquired recently by the evolutionary lineage leading to MS499. Taking advantage of the phylogenetic relationship we describe between MS499 and several other closely related E. coli isolates from across the globe, we propose a step-wise evolution of a novel clade of sequence type 453 ExPECs within phylogroup B1, involving the recruitment of ExPEC virulence factors into the genome of an ancestrally non-extraintestinal E. coli, which has repurposed this lineage with the capacity to cause extraintestinal disease. These data reveal the genetic components which may be involved in this phenotype switching, and argue that horizontal gene exchange may be a key factor in the emergence of novel lineages of ExPECs.

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.

Pectoral nerve block (Pecs block) with sedation for breast conserving surgery without general anesthesia

PubMed Central

Moon, Eun-Jin; Kim, Seung-Beom; Chung, Jun-Young; Song, Jeong-Yoon

2017-01-01

Most regional anesthesia in breast surgeries is performed as postoperative pain management under general anesthesia, and not as the primary anesthesia. Regional anesthesia has very few cardiovascular or pulmonary side-effects, as compared with general anesthesia. Pectoral nerve block is a relatively new technique, with fewer complications than other regional anesthesia. We performed Pecs I and Pec II block simultaneously as primary anesthesia under moderate sedation with dexmedetomidine for breast conserving surgery in a 49-year-old female patient with invasive ductal carcinoma. Block was uneventful and showed no complications. Thus, Pecs block with sedation could be an alternative to general anesthesia for breast surgeries. PMID:28932733

[Adaptation of the picture exchange communication system in a school context].

PubMed

Almeida, Maria Amélia; Piza, Maria Helena Machado; Lamônica, Dionísa Aparecida Cusin

2005-01-01

Alternative communication. To evaluate the efficacy of the adapted Pecs and Picture Communication Symbols (PCS) in the communication of a child with cerebral palsy. The participant of this study was a 9 year and 10 months old girl, with athetoid quadriplegia. All stages of the adapted Pecs were applied (Walter, 2000), using the PCS pictures (Johnson, 1998), associated with the functional curriculum proposed by LeBlanc (1991). An experimental AB Design was used in order to test the procedures. The subject was able to pass through all of the adapted Pecs phases and to use her communication board in school activities. The adapted Pecs proved to be effective in improving the subject's communication abilities.

Feeding associations between Guiana dolphins, Sotalia guianensis (Van Bénèden, 1864) and seabirds in the Lagamar estuary, Brazil.

PubMed

Santos, M C O; Oshima, J E F; Pacífico, E S; Silva, E

2010-02-01

The main objective of the present study was to describe the characteristics regarding interactions between Guiana dolphins, Sotalia guianensis and seabirds in feeding associations in two distinct areas of the Lagamar estuary, Brazil. Boat-based surveys directed towards photo-identification studies of S. guianensis were conducted in the Cananéia Estuary (CE) (25 degrees 01' S and 47 degrees 55' W) from July 2004 to March 2008, as well as in the Paranaguá Estuarine Complex (PEC) (25 degrees 24' S and 48 degrees 24' W) from April 2006 to February 2008. On all occasions when seabirds were observed engaging in multi-species feeding associations with S. guianensis, data on species involved and their numbers were gathered. From 435 observed groups of S. guianensis in the CE, 38 (8.7%) involved interactions with seabirds. In the PEC, from the 286 observed groups, 32 (11.2%) involved the mentioned interactions. The following seabirds were observed in feeding associations with S. guianensis: Fregata magnificens, Sula leucogaster, Phalacrocorax brasilianus, and Sterna sp. In the CE, S. leucogaster was more commonly observed in feeding associations with Guiana dolphins (chi2 = 22.84; d.f. = 3, p < 0.05), while in the PEC no differences were reported when comparing seabird species (chi2 = 5.78; d.f.=3, p = 0.1223). In the CE, feeding associations were significantly more frequent in inner waters (subset A0; chi2 = 9.52; d.f. = 2, p < 0.05), and in winter (chi2 = 12.46; d.f. = 1, p < 0.05). Within these events, 44.7% of the association groups were composed by more than one seabird species. Seasonality in feeding associations was also observed in the PEC (chi2 = 4.76; d.f. = 1, p < 0.05), with same patterns observed in the CE. Interactions were more frequent in inner waters of the Laranjeiras bay, PEC (chi2 = 11.65; d.f. = 2, p < 0.05). Within these events, 74.2% of the association groups were composed by more than one seabird species. Water transparency, prey and seabird abundance and distribution, cetacean group size, and the life cycle of prey and seabirds are listed as the main factors addressing multi-species feeding associations in the Lagamar estuary.

Continuous PECS II block for postoperative analgesia in patients undergoing transapical transcatheter aortic valve implantation.

PubMed

Shakuo, Tomoharu; Kakumoto, Shinichi; Kuribayashi, Junya; Oe, Katsunori; Seo, Katsuhiro

2017-01-01

It has been reported that PECS II block can alleviate postoperative pain following transapical transcatheter aortic valve implantation (TA-TAVI). However, the effectiveness of continuous PECS II block with catheterization has not yet been reported on the postoperative pain in patients undergoing TA-TAVI. We experienced two cases of TA-TAVI who received PECS II block with catheterization to manage postoperative pain. In the first case, a bolus injection for intraoperative pain and subsequent catheterization were performed before the implantation. However, the patient developed severe pain postoperatively in spite of the continuous block due to displacement of the catheter. In the second case, a bolus injection and the catheterization for the continuous block were performed before and after the implantation, respectively, which provided high-quality pain control. Continuous PECS II block may be useful to control perioperative pain associated with TA-TAVI. The insertion of the catheter after the implantation could be useful to avoid its displacement during the surgery.

Reducing PEC uncertainty in coastal zones: a case study on carbamazepine, oxcarbazepine and their metabolites.

PubMed

Fenet, Hélène; Arpin-Pont, Lauren; Vanhoutte-Brunier, Alice; Munaron, Dominique; Fiandrino, Annie; Martínez Bueno, Maria-Jesus; Boillot, Clotilde; Casellas, Claude; Mathieu, Olivier; Gomez, Elena

2014-07-01

Concentrations of the antiepileptic drugs carbamazepine (Cbz), oxcarbazepine (OxCz) and their main metabolites were predicted in a wastewater treatment plant (WTP) and in the vicinity of its submarine outfall located in a Mediterranean coastal zone. Refined predicted environmental concentrations (PECs) were calculated in effluents based on consumption data and human excretion rates. PECs were estimated in the sea using the hydrodynamic MARS 3D model integrating meteorological data, oceanic conditions (wind, tide, atmospheric pressure), freshwater and sewage inputs. Measured environmental concentrations (MECs) were compared to PECs to assess the estimation relevance. In the coastal zone, PEC and MEC were in the same magnitude range. Modeling of Cbz diffusion and advection just above the submarine outfall showed the influence of the thermocline during summer, with low diffusion of Cbz from the bottom to the surface. This work allowed understanding the dispersion of target compounds and deserved further development for a better acknowledgement of vulnerability at local scales. Copyright © 2014 Elsevier Ltd. All rights reserved.

A photoelectrochemical (PEC) study on graphene oxide based hematite thin films heterojunction (R-GO/Fe2O3)

NASA Astrophysics Data System (ADS)

Sharma, Poonam; Zachariah, Michael; Ehrman, Sheryl; Shrivastava, Rohit; Dass, Sahab; Satsangi, Vibha; Michael Zachariah, Sheryl Ehrman Collaboration; Rohit Shrivastava, Sahab Dass Collaboration; Vibha R Satsangi, Poonam Sharma Team

2013-03-01

Graphene has an excellent electronic conductivity, a high theoretical surface area of 2630 m2/g and excellent mechanical properties and, thus, is a promising component for high-performance electrode materials. Following this, GO has been used to modify the PEC response of photoactive material hematite thin films in PEC cell. A reduced graphene oxide/iron oxide (R-GO/Fe2O3) thin film structure has been successfully prepared on ITO by directly growing iron oxide particles on the thermally reduced graphene oxide sheets prepared from suspension of exfoliated graphene oxide. R-GO/Fe2O3 thin films were tested in PEC cell and offered ten times higher photocurrent density than pristine Fe2O3 thin film sample. XRD, SEM, EDS, UV-Vis, Mott-Schottky and Raman studies were carried out to study spectro-electrochemical properties. Enhanced PEC performance of these photoelectrodes was attributed to its porous morphology, improved conductivity upon favorable carrier transfer across the oxides interface.

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

Photocatalytic and Photoelectrochemically Degradation of Chlorsulfuron herbicide

NASA Astrophysics Data System (ADS)

Guo, Xu; Liu, Hongwei; Miao, Jinjie; Ma, Zhen

2017-12-01

Photocatalytic and photo electrochemical (PEC) degradation of chlorsulfuron herbicide were studied. Two novel PEC electrodes Ti/IrO2-Pt-WO3 (TIW) and Ti/IrO2-Pt-Ag3PO4 (TIA) were designed and some important factors were studied. Lower current density showed lower removal efficiency than higher conditions by electrochemical method. Furthermore, PEC showed higher degradation efficiency than the sum of individual EO and photocatalytic methode.

Effect of treated sunflower meal with tannin extracted from pistachio hulls on in vitro gas production and ruminal fermentation

PubMed Central

Jolazadeh, Alireza; Mohammadabadi, Tahereh

2017-01-01

This experiment was conducted to study the effects of various amounts of treated sunflower meal (SFM) with extracted tannins from pistachio hulls on in vitro gas production and ruminal fermentation in ruminants. The SFM was treated with pistachio extract concentrate (PEC), which contained 111.40 g kg-1 total phenol and 71.30 g kg-1 total tannin per dry matter of extract, at six experimental treatment levels of 0, 7, 14, 21, 28 and 35 g PEC per 100 g SFM on a dry matter basis. In vitro gas production, in vitro organic matter digestibility (IVOMD), metabolizable energy (ME) and fermentative parameters of samples were measured. The PEC had no effect on fermentation rate, but asymptotic gas production was linearly decreased with increasing dose of extract. All fermentation parameters (i.e., apparent degraded substrate, short chain fatty acids, gas yield at 24 hr, partitioning factor at 96 hr, IVOMD, ME and microbial protein production (MP) linearly decreased with increasing PEC treatment. Inclusion of PEC linearly decreased ruminal ammonia nitrogen concentration (NH3-N), total protozoa population and pH in the all incubation times. In conclusion, the addition of PEC positively modified some rumen parameters such as NH3-N concentration and protozoa population. PMID:29085607

Positive emotion communication: Fostering well-being at end of life.

PubMed

Terrill, Alexandra L; Ellington, Lee; John, Kevin K; Latimer, Seth; Xu, Jiayun; Reblin, Maija; Clayton, Margaret F

2018-04-01

Little is known about positive emotion communication (PEC) in end-of-life care. This study aims to identify types and patterns of PEC among hospice nurses, caregivers, and patients. A coding system based on positive psychology theory was applied as a secondary analysis to audio recordings of hospice nurse home visits with cancer patients and family caregivers, collected as part of a prospective longitudinal study. Eighty recordings (4 visits from 20 triads) were coded for humor, connection, praise, positive focus, gratitude, taking joy/savoring, and perfunctory statements. Descriptive statistics revealed the greatest proportion of PEC was made by nurses. Humor was most frequently used across all speakers. Cluster analysis revealed four PEC visit types: Savor/Take Joy; Humor; Perfunctory; and Other-focused Expressions of Positive Emotions. Linear mixed effect regression was used to estimate the trajectory of PEC over time, but no significant change was found. We found that positive emotions are common in nurse, caregiver and patient communication at end-of-life and do not decline closer to death. This study is among the first to explore PEC at end-of-life, and offers a way to bring strengths-based approaches into end of life communication research. Copyright © 2017 Elsevier B.V. All rights reserved.

Responsive copolymers for enhanced petroleum recovery. Quarterly technical progress report, December 21, 1994--March 22, 1995

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

McCormick, C.; Hester, R.

The purpose of this study is to extend the concept of micellar polymerization to more complex systems, and to explore the responsive nature of hydrophobically modified polyelectrolytes by tailoring the microstructure. The synthesis of hydrophobically modified acrylamide/acrylic acid copolymer is described. These types of polymers are of interest as thickening agents utilized in enhanced oil recovery.

Multiscale Simulations of Barrier and Aging Properties of Polymer Nanocomposites

DTIC Science & Technology

2013-10-29

Complexation Between Weakly Basic Dendrimers and Linear Polyelectrolytes: Effects of Chain Stiffness, Grafts, and pOH,” Thomas Lewis, Gunja Pandav, Ahmad Omar...November 2012. (c) Presentations 20.0010/29/2013 Venkat Ganesan, Thomas Lewis. Interactions between Grafted Cationic Dendrimers and Anionic Bilayer... dendrimers have shown great promise in drug and gene therapy applications. Despite the advantages realized through positively charged dendrimers , a

Changes in glomerular parietal epithelial cells in mouse kidneys with advanced age

PubMed Central

Roeder, Sebastian S.; Stefanska, Ania; Eng, Diana G.; Kaverina, Natalya; Sunseri, Maria W.; McNicholas, Bairbre A.; Rabinovitch, Peter; Engel, Felix B.; Daniel, Christoph; Amann, Kerstin; Lichtnekert, Julia; Pippin, Jeffrey W.

2015-01-01

Kidney aging is accompanied by characteristic changes in the glomerulus, but little is known about the effect of aging on glomerular parietal epithelial cells (PECs), nor if the characteristic glomerular changes in humans and rats also occur in very old mice. Accordingly, a descriptive analysis was undertaken in 27-mo-old C57B6 mice, considered advanced age. PEC density was significantly lower in older mice compared with young mice (aged 3 mo), and the decrease was more pronounced in juxtamedullary glomeruli compared with outer cortical glomeruli. In addition to segmental and global glomerulosclerosis in older mice, staining for matrix proteins collagen type IV and heparan sulfate proteoglycan were markedly increased in Bowman's capsules of older mouse glomeruli, consistent with increased extracellular matrix production by PECs. De novo staining for CD44, a marker of activated and profibrotic PECs, was significantly increased in aged glomeruli. CD44 staining was more pronounced in the juxtamedullary region and colocalized with phosphorylated ERK. Additionally, a subset of aged PECs de novo expressed the epithelial-to-mesenchymal transition markers α-smooth muscle and vimentin, with no changes in epithelial-to-mesenchymal transition markers E-cadherin and β-catenin. The mural cell markers neural/glial antigen 2, PDGF receptor-β, and CD146 as well as Notch 3 were also substantially increased in aged PECs. These data show that mice can be used to better understand the aging kidney and that PECs undergo substantial changes, especially in juxtamedullary glomeruli, that may participate in the overall decline in glomerular structure and function with advancing age. PMID:26017974

The Regenerative Potential of Parietal Epithelial Cells in Adult Mice

PubMed Central

Berger, Katja; Schulte, Kevin; Boor, Peter; Kuppe, Christoph; van Kuppevelt, Toin H.; Floege, Jürgen; Smeets, Bart

2014-01-01

Previously, we showed that some podocytes in juvenile mice are recruited from cells lining Bowman’s capsule, suggesting that parietal epithelial cells (PECs) are a progenitor cell population for podocytes. To investigate whether PECs also replenish podocytes in adult mice, PECs were genetically labeled in an irreversible fashion in 5-week-old mice. No significant increase in labeled podocytes was observed, even after 18 months. To accelerate a potential regenerative mechanism, progressive glomerular hypertrophy was induced by progressive partial nephrectomies. Again, no significant podocyte replenishment was observed. Rather, labeled PECs exclusively invaded segments of the tuft affected by glomerulosclerosis, consistent with our previous findings. We next reassessed PEC recruitment in juvenile mice using a different reporter mouse and confirmed significant recruitment of labeled PECs onto the glomerular tuft. Moreover, some labeled cells on Bowman’s capsule expressed podocyte markers, and cells on Bowman’s capsule were also directly labeled in juvenile podocyte-specific Pod-rtTA transgenic mice. In 6-week-old mice, however, cells on Bowman’s capsule no longer expressed podocyte-specific markers. Similarly, in human kidneys, some cells on Bowman’s capsule expressed the podocyte marker synaptopodin from 2 weeks to 2 years of age but not at 7 years of age. In summary, podocyte regeneration from PECs could not be detected in aging mice or models of glomerular hypertrophy. We propose that a small fraction of committed podocytes reside on Bowman’s capsule close to the vascular stalk and are recruited onto the glomerular tuft during infancy to adolescence in mice and humans. PMID:24408873

The genome sequence of avian pathogenic Escherichia coli strain O1:K1:H7 shares strong similarities with human extraintestinal pathogenic E. coli genomes.

PubMed

Johnson, Timothy J; Kariyawasam, Subhashinie; Wannemuehler, Yvonne; Mangiamele, Paul; Johnson, Sara J; Doetkott, Curt; Skyberg, Jerod A; Lynne, Aaron M; Johnson, James R; Nolan, Lisa K

2007-04-01

Escherichia coli strains that cause disease outside the intestine are known as extraintestinal pathogenic E. coli (ExPEC) and include human uropathogenic E. coli (UPEC) and avian pathogenic E. coli (APEC). Regardless of host of origin, ExPEC strains share many traits. It has been suggested that these commonalities may enable APEC to cause disease in humans. Here, we begin to test the hypothesis that certain APEC strains possess potential to cause human urinary tract infection through virulence genotyping of 1,000 APEC and UPEC strains, generation of the first complete genomic sequence of an APEC (APEC O1:K1:H7) strain, and comparison of this genome to all available human ExPEC genomic sequences. The genomes of APEC O1 and three human UPEC strains were found to be remarkably similar, with only 4.5% of APEC O1's genome not found in other sequenced ExPEC genomes. Also, use of multilocus sequence typing showed that some of the sequenced human ExPEC strains were more like APEC O1 than other human ExPEC strains. This work provides evidence that at least some human and avian ExPEC strains are highly similar to one another, and it supports the possibility that a food-borne link between some APEC and UPEC strains exists. Future studies are necessary to assess the ability of APEC to overcome the hurdles necessary for such a food-borne transmission, and epidemiological studies are required to confirm that such a phenomenon actually occurs.

A New Water-Soluble Nanomicelle Formed through Self-Assembly of Pectin-Curcumin Conjugates: Preparation, Characterization, and Anticancer Activity Evaluation.

PubMed

Bai, Feng; Diao, Jiajing; Wang, Ying; Sun, Shixin; Zhang, Hongmei; Liu, Yunyun; Wang, Yanqing; Cao, Jian

2017-08-16

Curcumin is a dominating active component of Curcuma longa and has been studied widely because of its prominent biological activities. The extremely low aqueous solubility, stability, and bioavailability of curcumin limit its application in the field of medicine. In this study, we developed pectin-curcumin (PEC-CCM) conjugates that could self-assemble water-soluble nanomicelles in aqueous solution. The structure of PEC-CCM conjugates was characterized by ultraviolet-visible spectra, fluorescence spectra, Fourier transform infrared spectroscopy, and 1 H nuclear magnetic resonance spectroscopy. The thermal property of PEC-CCM conjugates was investigated by thermogravimetric analysis. It was found that PEC-CCM conjugates had formed nanomicelles in aqueous medium via self-assembly. These nanomicelles were observed as small spheres or ellipsoids and aggregated with a size range of 70-190 nm by transmission electron microscopy analysis. In a solution of nanomicelles, the stability of curcumin was improved, and its antioxidant property was preserved. The anticancer activity of PEC-CCM conjugates was quantified by the MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] assay using a hepatic cancer cell line (HepG2), a breast cancer cell line (MCF-7), a cervical cancer cell line (HeLa), and a human normal kidney cell line (293A). It was found that the curcumin of PEC-CCM conjugates had a more significant inhibitory effect on cancer cells and was less cytotoxic to normal cells than free curcumin was. PEC-CCM conjugates have great potential for some food and pharmaceutical applications.

Heterozygous Null Bone Morphogenetic Protein Receptor Type 2 Mutations Promote SRC Kinase-dependent Caveolar Trafficking Defects and Endothelial Dysfunction in Pulmonary Arterial Hypertension*

PubMed Central

Prewitt, Allison R.; Ghose, Sampa; Frump, Andrea L.; Datta, Arumima; Austin, Eric D.; Kenworthy, Anne K.; de Caestecker, Mark P.

2015-01-01

Hereditary pulmonary arterial hypertension (HPAH) is a rare, fatal disease of the pulmonary vasculature. The majority of HPAH patients inherit mutations in the bone morphogenetic protein type 2 receptor gene (BMPR2), but how these promote pulmonary vascular disease is unclear. HPAH patients have features of pulmonary endothelial cell (PEC) dysfunction including increased vascular permeability and perivascular inflammation associated with decreased PEC barrier function. Recently, frameshift mutations in the caveolar structural protein gene Caveolin-1 (CAV-1) were identified in two patients with non-BMPR2-associated HPAH. Because caveolae regulate endothelial function and vascular permeability, we hypothesized that defects in caveolar function might be a common mechanism by which BMPR2 mutations promote pulmonary vascular disease. To explore this, we isolated PECs from mice carrying heterozygous null Bmpr2 mutations (Bmpr2+/−) similar to those found in the majority of HPAH patients. We show that Bmpr2+/− PECs have increased numbers and intracellular localization of caveolae and caveolar structural proteins CAV-1 and Cavin-1 and that these defects are reversed after blocking endocytosis with dynasore. SRC kinase is also constitutively activated in Bmpr2+/− PECs, and localization of CAV-1 to the plasma membrane is restored after treating Bmpr2+/− PECs with the SRC kinase inhibitor 3-(4-chlorophenyl)-1-(1,1-dimethylethyl)-1H-pyrazolo[3,4-d]pyrimidin-4-amine (PP2). Late outgrowth endothelial progenitor cells isolated from HPAH patients show similar increased activation of SRC kinase. Moreover, Bmpr2+/− PECs have impaired endothelial barrier function, and barrier function is restored after treatment with PP2. These data suggest that heterozygous null BMPR2 mutations promote SRC-dependent caveolar trafficking defects in PECs and that this may contribute to pulmonary endothelial barrier dysfunction in HPAH patients. PMID:25411245

The Complete Sequence and Comparative Analysis of a Multidrug-Resistance and Virulence Multireplicon IncFII Plasmid pEC302/04 from an Extraintestinal Pathogenic Escherichia coli EC302/04 Indicate Extensive Diversity of IncFII Plasmids.

PubMed

Ho, Wing Sze; Yap, Kien-Pong; Yeo, Chew Chieng; Rajasekaram, Ganeswrie; Thong, Kwai Lin

2015-01-01

Extraintestinal pathogenic Escherichia coli (ExPEC) that causes extraintestinal infections often harbor plasmids encoding fitness traits such as resistance and virulence determinants that are of clinical importance. We determined the complete nucleotide sequence of plasmid pEC302/04 from a multidrug-resistant E. coli EC302/04 which was isolated from the tracheal aspirate of a patient in Malaysia. In addition, we also performed comparative sequence analyses of 18 related IncFIIA plasmids to determine the phylogenetic relationship and diversity of these plasmids. The 140,232 bp pEC302/04 is a multireplicon plasmid that bears three replication systems (FII, FIA, and FIB) with subtype of F2:A1:B1. The plasmid is self-transmissible with a complete transfer region. pEC302/04 also carries antibiotic resistance genes such as bla TEM-1 and a class I integron containing sul1, cml and aadA resistance genes, conferring multidrug resistance (MDR) to its host, E. coli EC302/04. Besides, two iron acquisition systems (SitABCD and IutA-IucABCD) which are the conserved virulence determinants of ExPEC-colicin V or B and M (ColV/ColBM)-producing plasmids were identified in pEC302/04. Multiple toxin-antitoxin (TA)-based addiction systems (i.e., PemI/PemK, VagC/VagD, CcdA/CcdB, and Hok/Sok) and a plasmid partitioning system, ParAB, and PsiAB, which are important for plasmid maintenance were also found. Comparative plasmid analysis revealed only one conserved gene, the repA1 as the core genome, showing that there is an extensive diversity among the IncFIIA plasmids. The phylogenetic relationship of 18 IncF plasmids based on the core regions revealed that ColV/ColBM-plasmids and non-ColV/ColBM plasmids were separated into two distinct groups. These plasmids, which carry highly diverse genetic contents, are also mosaic in nature. The atypical combination of genetic materials, i.e., the MDR- and ColV/ColBM-plasmid-virulence encoding regions in a single ExPEC plasmid is rare but of clinical importance. Such phenomenon is bothersome when the plasmids are transmissible, facilitating the spread of virulence and resistance plasmids among pathogenic bacteria. Notably, certain TA systems are more commonly found in particular ExPEC plasmid types, indicating the possible relationships between certain TA systems and ExPEC pathogenesis.

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.

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.

Monte Carlo simulations of flexible polyanions complexing with whey proteins at their isoelectric point.

PubMed

de Vries, R

2004-02-15

Electrostatic complexation of flexible polyanions with the whey proteins alpha-lactalbumin and beta-lactoglobulin is studied using Monte Carlo simulations. The proteins are considered at their respective isoelectric points. Discrete charges on the model polyelectrolytes and proteins interact through Debye-Huckel potentials. Protein excluded volume is taken into account through a coarse-grained model of the protein shape. Consistent with experimental results, it is found that alpha-lactalbumin complexes much more strongly than beta-lactoglobulin. For alpha-lactalbumin, strong complexation is due to localized binding to a single large positive "charge patch," whereas for beta-lactoglobulin, weak complexation is due to diffuse binding to multiple smaller charge patches. Copyright 2004 American Institute of Physics

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.

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.

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

Humic substance charge determination by titration with a flexible cationic polyelectrolyte

NASA Astrophysics Data System (ADS)

Tan, Wen-Feng; Norde, Willem; Koopal, Luuk K.

2011-10-01

The anionic charge of humic substances (HS) plays a major role in the interaction of HS with other components. Therefore, the potential of the polyelectrolyte titration technique to obtain the charge density of HS in simple 1-1 electrolyte solutions has been investigated. Titrations are carried out with an automatic titrator combined with the "Mütek particle charge detector" which allows determination of the Mütek potential and the pH as a function of the added amount of titrant which is a solution of poly-diallyldimethylammonium chloride (polyDADMAC), a cationic strong polyelectrolyte. When the Mütek potential reverses its sign the iso-electric point (IEP) of the polyDADMAC-HS complex is reached. The polyDADMAC/HS mass ratio at the IEP gives information on the HS charge density and from the pH changes in solution an estimate of the charge regulation in the HS-polyDADMAC complex can be obtained. In general, for polyDADMAC-HS complexes an increase in the dissociation of the acid groups of HS is found (charge regulation). The charge regulation decreases with increasing concentration of 1-1 background electrolyte. Cation incorporation can be neglected at 1-1 electrolyte concentrations ⩽ 1 mmol L -1 and a 1-1 stoichiometry exists between the polyDADMAC and HS charge. However, at these low salt concentrations the charge regulation is substantial. A detailed analysis of purified Aldrich humic acid (PAHA) at pH 5 and a range of KCl concentrations reveals that the anionic charge of PAHA in the complex increases at 5 mmol L -1 KCl by 30% and at 150 mmol L -1 KCl by 12%. On the other hand, increasing amounts of K + become incorporated in the complex: at 5 mmol L -1 KCl 5% and at 150 mmol L -1 KCl 24% of the PAHA charge is balanced by K +. By comparing at pH 5 the mass ratios polyDADMAC/PAHA in the complex at the IEP with the theoretical mass ratios of polyDADMAC/PAHA required to neutralize PAHA in the absence of charge regulation and K + incorporation, it is found that at 50 mmol L -1 KCl the extra negative charge due to the interaction between polyDADMAC and PAHA is just compensated by K + incorporation in the complex. Therefore, a pseudo 1-1 stoichiometry exists at about 50 mmol L -1 1-1 electrolyte concentration and only at this salt concentration polyDADMAC titrations and conventional proton titrations give identical results. Most likely this is also true for other HA samples and other pH values. For FA further study is required to reveal the conditions for which polyDADMAC and proton titrations give identical results.

Antigenic modulation of the cytophilic binding of guinea-pig IgG and IgM antibodies to homologous macrophages.

PubMed Central

Webster, R O; Lawrence, D A

1979-01-01

The cytophilic binding of immune complexes by peritoneal exudate cells (PEC) from adjuvant-stimulated guinea-pigs was studied using 125I-labelled guinea-pig IgG1, IgG2 and IgM antibodies to the dinitrophenyl (DNP) group. The influence of hapten density upon cytophilic activity was studied by the addition of DNP-conjugated antigens to antibody in 2-200 molar ratios of DNP:antibody. Only IgG2 binding was enhanced by immune complex formation, and the increased binding of IgG2 anti-DNP was dependent on the number of DNP determinants per antigen molecule. Cytophilic activity with epsilon-DNP-L-lysine (DNP-LYS), alpha,epsilon-di-DNP-L-lysine (DNP-LYS-DNP), or DNP1-8-BSA was no greater than that seen in the absence of hapten. Increased cytophilic binding was noted only with DNP20-41-BSA. The binding of IgG2 and IgG2 anti-DNP:DNP-bovine serum albumin (BSA) complexes was inhibited by monomeric IgG2. The relative cytophilic capacities of guinea-pig immunoglobulins appeared as follows: IgG greater than IgG1 greater than IgM. IgG1 and IgM binding of DNP conjugates did not enhance their cytophilic activity; therefore, IgG1 and IgM cytophilic binding to PEC was considered biologically insignificant. This investigation provides further evidence that cytophilic binding of immune complexes to macrophages is due to the co-operative action of multiple Fc sites rather than a conformational change in the IgG2 antibodies, and serum proteins, notably complement components, can alter the binding and/or phagocytosis of IgG2 anti-DNP:DNP-BSA complexes. PMID:86509

Surface adsorption of oppositely charged C14TAB-PAMPS mixtures at the air/water interface and the impact on foam film stability.

PubMed

Fauser, Heiko; von Klitzing, Regine; Campbell, Richard A

2015-01-08

We have studied the oppositely charged polyelectrolyte/surfactant mixture of poly(acrylamidomethylpropanesulfonate) sodium salt (PAMPS) and tetradecyl trimethylammonium bromide (C14TAB) using a combination of neutron reflectivity and ellipsometry measurements. The interfacial composition was determined using three different analysis methods involving the two techniques for the first time. The bulk surfactant concentration was fixed at a modest value while the bulk polyelectrolyte concentration was varied over a wide range. We reveal complex changes in the surface adsorption behavior. Mixtures with low bulk PAMPS concentrations result in the components interacting synergistically in charge neutral layers at the air/water interface. At the bulk composition where PAMPS and C14TAB are mixed in an equimolar charge ratio in the bulk, we observe a dramatic drop in the surfactant surface excess to leave a large excess of polyelectrolyte at the interface, which we infer to have loops in its interfacial structure. Further increase of the bulk PAMPS concentration leads to a more pronounced depletion of material from the surface. Mixtures containing a large excess of PAMPS in the bulk showed enhanced adsorption, which is attributed to the large increase in total ionic strength of the system and screening of the surfactant headgroup charges. The data are compared to our former results on PAMPS/C14TAB mixtures [Kristen et al. J. Phys. Chem. B, 2009, 23, 7986]. A peak in the surface tension is rationalized in terms of the changing surface adsorption and, unlike in more concentrated systems, is unrelated to bulk precipitation. Also, a comparison between the determined interfacial composition with zeta potential and foam film stability data shows that the highest film stability occurs when there is enhanced synergistic adsorption of both components at the interface due to charge screening when the total ionic strength of the system is highest. The additional contribution to the foam stability of the negatively charged polyelectrolyte within the film bulk is also discussed.

Particles decorated by an ionizable thermoresponsive polymer brush in water: experiments and self-consistent field modeling.

PubMed

Alves, S P C; Pinheiro, J P; Farinha, J P S; Leermakers, F A M

2014-03-20

We have synthesized anionic multistimuli responsive core-shell polymer nanoparticles with low size dispersity composed of glassy poly(methyl methacrylate) (PMMA) cores of ca. 40 nm radius and poly(N-isopropylacrylamide) (PNIPAM) anionic brush-like shells with methacrylic acid comonomers. Using dynamic light scattering, we observed a volume phase transition upon an increase in temperature and this response was pH and ionic strength dependent. Already at room temperature we observed a pronounced polyelectrolyte effect, that is, a shift of the apparent pKa extracted from the degree of dissociation of the acids as a function of the pH. The multiresponsive behavior of the hydrophobic polyelectrolyte brush has been modeled using the Scheutjens-Fleer self-consistent field (SF-SCF) approach. Using a phenomenological relation between the Flory-Huggins χ parameter and the temperature, we confront the predicted change in the brush height with the observed change of the hydrodynamic radius and degree of dissociation and obtain estimates for the average chain lengths (number of Kuhn segments) of the corona chains, the grafting density and charge density distributions. The theory reveals a rich internal structure of the hydrophobic polyelectrolyte brush, especially near the collapse transition, where we find a microphase segregated structure. Considering this complexity, it is fair to state that the theoretical predictions follow the experimental data semiquantitatively, and it is attractive to attribute the observed disparity between theory and experiments to the unknown polydispersity of the chains, the unknown distribution of the charges, or other experimental complications. More likely, however, the deviations point to significant problems of the mean field theory, which focuses solely on the radial distributions and ignores the possibility of the formation of lateral (local) inhomogeneities in partially collapsed polyelectrolyte brushes. We argue that the PNIPAM brush at room temperature is already behaving nonideally.

On the mesoscopic origins of high viscosities in some polyelectrolyte-surfactant mixtures

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

Hoffmann, Ingo, E-mail: ingo.hoffmann@tu-berlin.de; Institut Max von Laue-Paul Langevin; Farago, Bela

Oppositely charged polyelectrolyte (PE) surfactant mixtures allow the control of rheological parameters of a solution even at fairly low concentrations. For example, addition of 0.3 wt. % of anionic surfactant to a 1 wt. % solution of the polycation JR 400 increases the viscosity by 4 orders of magnitude. Recently, we could show that this increase is related to the formation of mixed, rod-like PE/surfactant aggregates which interconnect several polyelectrolyte chains [Hoffmann et al., Europhys. Lett. 104, 28001 (2013)]. In this paper, we refine our structural model of the aggregates to obtain a more consistent picture of their internal structure for differentmore » anionic surfactants. Combining small angle neutron scattering (SANS) and neutron spin-echo (NSE) allows us to determine the size of the aggregates. By comparing different contrasts, the internal structure of the aggregates can be elucidated and it is seen that the PE in the aggregates retains a relatively high freedom of movement. We proceeded to investigate the influence of the surfactant concentration and the surfactant type on structure and dynamics of the mixed aggregates. It is seen that the structural parameters of the aggregates depend very little on the surfactant concentration and headgroup. However, it is crucial to incorporate a sufficient amount of PE in the aggregates to increase the viscosity of the aggregates. By comparing viscous samples at 1 wt. % PE concentration with samples at a PE concentration of 0.3 wt. %, where no significant increase in viscosity is observed, we find that similar aggregates are formed already at this lower PE concentrations. However, the amount of PE incorporated in them is insufficient to interconnect several PE chains and therefore, they do not increase viscosity. So, our detailed investigation combining contrast variation SANS and NSE does not only allow to explain the viscosity behavior but also to deduced detailed information regarding the structures and the dynamics especially of the polyelectrolyte within the complexes.« 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.

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.

Efficient interfacial charge transfer through plasmon sensitized Ag@Bi2O3 hierarchical photoanodes for photoelectrocatalytic degradation of chlorinated phenols.

PubMed

Eswar, Neerugatti KrishnaRao; Adhikari, Sangeeta; Ramamurthy, Praveen C; Madras, Giridhar

2018-01-31

The present work demonstrates an extremely proficient and robust study of efficient interfacial charge transfer through plasmonic Ag decorated Bi 2 O 3 hierarchical photoanodes for the photoelectrochemical treatment of chlorinated phenols. Unique 2D flake-like Bi 2 O 3 hierarchical nanostructures were grown onto a fluorine-doped tin oxide (FTO) substrate by a simple chemical bath deposition method using triethanolamine as complexing agent. The formation of Bi 2 O 3 on FTO was governed by the decomposition of a nucleated bismuth-hydroxyl complex (Bi 2 O 1-x (OH) x ) and modification to the electrode was carried out by the deposition of Ag via a chemical reduction method using hydrazine hydrate. Both the fabricated electrodes were well characterized for their photo- and electro-optical properties. Efficient charge separation was observed due to the surface plasmon resonance phenomenon of silver nanoparticles with the favorable intrinsic properties of Bi 2 O 3 under application of a small electric bias of 1 V preventing the recombination of charge carriers and thereby increasing the rate of photoelectrocatalytic degradation of the chlorinated phenols. PEC degradation using the Ag@Bi 2 O 3 photoelectrode followed the trend 4-CP < 2,4-DCP < 2,4,6-TCP < P-CP due to efficient attack at the chlorinated positions by reactive oxygen species with increasing chlorine substitution and also due to the absence of an expected chain reaction of the generated chlorine radicals (Cl˙) during the PEC reaction. The PEC activity of Ag@Bi 2 O 3 was 1.5 times higher than a Bi 2 O 3 nanoflake electrode for 4-CP over 2 h. The fabricated Ag@Bi 2 O 3 proved to be an efficient photoelectrode with synergistic solar-induced photoactivity. A detailed mechanistic study in the presence of scavengers suggests degradation by produced hydroxyl radical species. Thus, physical insights into the degradation of chlorinated phenols were obtained.

The reaction mechanism with free energy barriers at constant potentials for the oxygen evolution reaction at the IrO 2 (110) surface

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

Ping, Yuan; Nielsen, Robert J.; Goddard, William A.

How to efficiently oxidize H 2O to O 2 (oxygen evolution reaction, OER) in photoelectrochemical cells (PEC) is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. So far no OER mechanism has been fully explained atomistically with both thermodynamic and kinetics. IrO 2 is the only known OER catalyst with both high catalytic activity and stability in acidic conditions. This is important because PEC experiments often operate at extreme pH conditions. In this work, we performed first-principles calculations integrated with implicit solvation at constant potentials to examine the detailed atomistic reaction mechanism of OERmore » at the IrO 2 (110) surface. We determined the surface phase diagram, explored the possible reaction pathways including kinetic barriers, and computed reaction rates based on the microkinetic models. Furthermore, this allowed us to resolve several long-standing puzzles about the atomistic OER mechanism.« less

The reaction mechanism with free energy barriers at constant potentials for the oxygen evolution reaction at the IrO 2 (110) surface

DOE PAGES

Ping, Yuan; Nielsen, Robert J.; Goddard, William A.

2016-12-09

How to efficiently oxidize H 2O to O 2 (oxygen evolution reaction, OER) in photoelectrochemical cells (PEC) is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. So far no OER mechanism has been fully explained atomistically with both thermodynamic and kinetics. IrO 2 is the only known OER catalyst with both high catalytic activity and stability in acidic conditions. This is important because PEC experiments often operate at extreme pH conditions. In this work, we performed first-principles calculations integrated with implicit solvation at constant potentials to examine the detailed atomistic reaction mechanism of OERmore » at the IrO 2 (110) surface. We determined the surface phase diagram, explored the possible reaction pathways including kinetic barriers, and computed reaction rates based on the microkinetic models. Furthermore, this allowed us to resolve several long-standing puzzles about the atomistic OER mechanism.« less

Ultrafast Time-Resolved Photoluminescence Studies of Gallium-Arsenide

NASA Astrophysics Data System (ADS)

Johnson, Matthew Bruce

This thesis concerns the study of ultrafast phenomena in GaAs using time-resolved photoluminescence (PL). The thesis consists of five chapters. Chapter one is an introduction, which discusses the study of ultrafast phenomena in semiconductors. Chapter two is a description of the colliding-pulse mode-locked (CPM) ring dye laser, which is at the heart of the experimental apparatus used in this thesis. Chapter three presents a detailed experimental and theoretical investigation of photoluminescence excitation correlation spectroscopy (PECS), the novel technique which is used to time-resolve ultrafast PL phenomena. Chapters 4 and 5 discuss two applications of the PECS technique. In Chapter 4 the variation of PL intensity in In-alloyed GaAs substrate material is studied, while Chapter 5 discusses the variation of carrier lifetimes in ion-damaged GaAs used in photo-conductive circuit elements (PCEs). PECS is a pulse-probe technique that measures the cross correlation of photo-excited carrier populations. The theoretical model employed in this thesis is based upon the rate equation for a simple three-level system consisting of valence and conduction bands and a single trap level. In the limit of radiative band-to-band dominated recombination, no PECS signal should be observed; while in the capture -dominated recombination limit, the PECS signal from the band-to-band PL measures the cross correlation of the excited electron and hole populations and thus, the electron and hole lifetimes. PECS is experimentally investigated using a case study of PL in semi-insulating (SI) GaAs and In -alloyed GaAs. At 77 K, the PECS signal is characteristic of a capture-dominated system, yielding an electron-hole lifetime of about 200 ps. However, at 5 K the behavior is more complicated and shows saturation effects due to the C acceptor level, which is un-ionized at 5 K. As a first application, PECS is used to investigate the large band-to-band PL contrast observed near dislocations in In-alloyed GaAs. It is found that the PL intensity contrast between bright and dark areas correlates with the ratio of the lifetimes measured using PECS in these areas. Thus, the PL intensity contrast is due to the difference in the carrier lifetimes in the different regions. The carrier lifetimes in the bright and dark regions have different temperature dependences. (Abstract shortened with permission of author.).

Evaluation of Recombinant Attenuated Salmonella Vaccine Strains for Broad Protection against Extraintestinal Pathogenic Escherichia coli.

PubMed

Maddux, Jacob T; Stromberg, Zachary R; Curtiss Iii, Roy; Mellata, Melha

2017-01-01

Antibiotic-resistant bacterial infections are difficult to treat, producing a burden on healthcare and the economy. Extraintestinal pathogenic Escherichia coli (ExPEC) strains frequently carry antibiotic resistance genes, cause infections outside of the intestine, and are causative agents of hospital-acquired infections. Developing a prevention strategy against this pathogen is challenging due to its antibiotic resistance and antigenic diversity. E. coli common pilus (ECP) is frequently found in ExPEC strains and may serve as a common antigen to induce protection against several ExPEC serotypes. In addition, live recombinant attenuated Salmonella vaccine (RASV) strains have been used to prevent Salmonella infection and can also be modified to deliver foreign antigens. Thus, the objective of this study was to design a RASV to produce ECP on its surface and assess its ability to provide protection against ExPEC infections. To constitutively display ECP in a RASV strain, we genetically engineered a vector (pYA4428) containing aspartate-β-semialdehyde dehydrogenase and E. coli ecp genes and introduced it into RASV χ9558. RASV χ9558 containing an empty vector (pYA3337) was used as a control to assess protection conferred by the RASV strain without ECP. We assessed vaccine efficacy in in vitro bacterial inhibition assays and mouse models of ExPEC-associated human infections. We found that RASV χ9558(pYA4428) synthesized the major pilin (EcpA) and tip pilus adhesin (EcpD) on the bacterial surface. Mice orally vaccinated with RASV χ9558(pYA3337) without ECP or χ9558(pYA4428) with ECP, produced anti- Salmonella LPS and anti- E. coli EcpA and EcpD IgG and IgA antibodies. RASV strains showed protective potential against some E. coli and Salmonella strains as assessed using in vitro assays. In mouse sepsis and urinary tract infection challenge models, both vaccines had significant protection in some internal organs. Overall, this work showed that RASVs can elicit an immune response to E . coli and Salmonella antigens in some mice, provide significant protection in some internal organs during ExPEC challenge, and thus this study is a promising initial step toward developing a vaccine for prevention of ExPEC infections. Future studies should optimize the ExPEC antigens displayed by the RASV strain for a more robust immune response and enhanced protection against ExPEC infection.

Engineering graphene and TMDs based van der Waals heterostructures for photovoltaic and photoelectrochemical solar energy conversion.

PubMed

Li, Changli; Cao, Qi; Wang, Faze; Xiao, Yequan; Li, Yanbo; Delaunay, Jean-Jacques; Zhu, Hongwei

2018-05-08

Graphene and two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted significant interest due to their unique properties that cannot be obtained in their bulk counterparts. These atomically thin 2D materials have demonstrated strong light-matter interactions, tunable optical bandgap structures and unique structural and electrical properties, rendering possible the high conversion efficiency of solar energy with a minimal amount of active absorber material. The isolated 2D monolayer can be stacked into arbitrary van der Waals (vdWs) heterostructures without the need to consider lattice matching. Several combinations of 2D/3D and 2D/2D materials have been assembled to create vdWs heterojunctions for photovoltaic (PV) and photoelectrochemical (PEC) energy conversion. However, the complex, less-constrained, and more environmentally vulnerable interface in a vdWs heterojunction is different from that of a conventional, epitaxially grown heterojunction, engendering new challenges for surface and interface engineering. In this review, the physics of band alignment, the chemistry of surface modification and the behavior of photoexcited charge transfer at the interface during PV and PEC processes will be discussed. We will present a survey of the recent progress and challenges of 2D/3D and 2D/2D vdWs heterojunctions, with emphasis on their applicability to PV and PEC devices. Finally, we will discuss emerging issues yet to be explored for 2D materials to achieve high solar energy conversion efficiency and possible strategies to improve their performance.

Adding a PECS II block for proximal arm arteriovenous access - a randomised study.

PubMed

Quek, K H; Low, E Y; Tan, Y R; Ong, A S C; Tang, T Y; Kam, J W; Kiew, A S C

2018-05-01

Brachial plexus block is often utilised for proximal arm arteriovenous access creation. However, the medial upper arm and axilla are often inadequately anaesthetised, requiring repeated, intraoperative local anaesthetic supplementation, or conversion into general anaesthesia. We hypothesised that the addition of a PECS II block would improve anaesthesia and analgesia for proximal arm arteriovenous access surgery. In this prospective, double-blinded, randomised proof-of-concept study, 36 consenting adults with end-stage renal disease aged between 21 and 90 years received either a combined supraclavicular and PECS II block (Group PECS, n = 18), or combined supraclavicular and sham block (Group SCB, n = 18) for proximal arm arteriovenous access surgery. Primary outcome was whether patients required intraoperative local anaesthetic supplementation by the surgeon. In Group PECS, 33.3% (6/18) needed local anaesthetic supplementation vs. 100% (18/18) in Group SCB. Group SCB had three times (RR 3.0, 95% CI 1.6-5.8; P < 0.001) the risk of requiring intraoperative local anaesthetic supplementation. Group PECS required lower volume of supplemental local anaesthetic compared to Group SCB (0.0 ml, IQR 0.0-6.3 ml vs. 15.0 ml, IQR 7.4-17.8 ml; P < 0.001). Group SCB had twice [RR 2.2, 95% CI 1.1-4.4; (P = 0.019)] the risk of needing additional sedation or analgesia. There were no significant differences between the groups with respect to postoperative visual analogue scale pain scores, time to first rescue analgesia or patient satisfaction. The results suggest that adding a PECS II block to a supraclavicular block improves regional anaesthesia for patients with end-stage renal disease undergoing proximal arm arteriovenous access surgery. © 2018 The Acta Anaesthesiologica Scandinavica Foundation. Published by John Wiley & Sons Ltd.

Development of in vitro models to demonstrate the ability of PecSys®, an in situ nasal gelling technology, to reduce nasal run-off and drip

PubMed Central

2013-01-01

Many of the increasing number of intranasal products available for either local or systemic action can be considered sub-optimal, most notably where nasal drip or run-off give rise to discomfort/tolerability issues or reduced/variable efficacy. PecSys, an in situ gelling technology, contains low methoxy (LM) pectin which gels due to interaction with calcium ions present in nasal fluid. PecSys is designed to spray readily, only forming a gel on contact with the mucosal surface. The present study employed two in vitro models to confirm that gelling translates into a reduced potential for drip/run-off: (i) Using an inclined TLC plate treated with a simulated nasal electrolyte solution (SNES), mean drip length [±SD, n = 10] was consistently much shorter for PecSys (1.5 ± 0.4 cm) than non-gelling control (5.8 ± 1.6 cm); (ii) When PecSys was sprayed into a human nasal cavity cast model coated with a substrate containing a physiologically relevant concentration of calcium, PecSys solution was retained at the site of initial deposition with minimal redistribution, and no evidence of run-off/drip anteriorly or down the throat. In contrast, non-gelling control was significantly more mobile and consistently redistributed with run-off towards the throat. Conclusion In both models PecSys significantly reduced the potential for run-off/drip ensuring that more solution remained at the deposition site. In vivo, this enhancement of retention will provide optimum patient acceptability, modulate drug absorption and maximize the ability of drugs to be absorbed across the nasal mucosa and thus reduce variability in drug delivery. PMID:22803832

Longitudinal dependence of the seasonal variations of the topside ionospheric and plasmaspheric electron content: observations and model results

NASA Astrophysics Data System (ADS)

Zhang, Man-Lian; Liu, Libo; Ning, Baiqi; Wan, Weixing

2016-07-01

Radio signals transmitted from GPS satellite going through the ionization zone above the Earth will be refracted by the ionized components in the ionosphere and the plasmasphere, which would produce additional transfer delay and generate extra errors in satellite navigation and positioning, etc. These errors have strong relation with the total electron content (TEC) along the signal's travelling path. Therefore TEC is one of the most important parameters required by many users for different modern usage purposes. The topside ionospheric and plasmaspheric electron content makes a large contribution to TEC. In the present study, data for the year 2008 of the topside ionospheric and plasmaspheric electron content (PEC) between the height of 800-20200km above the Earth derived from the upward-looking TEC measurements of the precise orbit determination antenna on board the COSMIC low Earth orbit (LEO) satellites to the GPS signals are used to study the longitudinal dependence of the seasonal variations of PEC. A comparison study of the observed PEC with the IZMIRAN_Plas model results is also made. Our study showed that PEC shows different seasonal variations at different longitudinal sectors: for the 240°E-60°E longitudinal sector, PEC shows a strong annual variation with lowest value in the June solstice and highest value in the December solstice months; In contrast, very weak seasonal variations are observed for PEC at 60°E-240°E longitudinal sector; Comparison study showed that this longitudinal dependence feature of the observed PEC's seasonal variation is not well captured by the IZMIRAN_Plas model result. Acknowledgments This research was supported by the National Natural Science Foundation of China (NSFC No. 41274163)

Metagenomic analysis of sediments under seaports influence in the Equatorial Atlantic Ocean.

PubMed

Tavares, Tallita Cruz Lopes; Normando, Leonardo Ribeiro Oliveira; de Vasconcelos, Ana Tereza Ribeiro; Gerber, Alexandra Lehmkuhl; Agnez-Lima, Lucymara Fassarella; Melo, Vânia Maria Maciel

2016-07-01

Maritime ports are anthropogenic interventions capable of causing serious alterations in coastal ecosystems. In this study, we examined the benthic microbial diversity and community structure under the influence of two maritime ports, Mucuripe (MUC) and Pecém (PEC), at Equatorial Atlantic Ocean in Northeast Brazil. Those seaports differ in architecture, time of functioning, cargo handling and contamination. The microbiomes from MUC and PEC were also compared in silico to 11 other globally distributed marine microbiomes. The comparative analysis of operational taxonomic units (OTUs) retrieved by PCR-DGGE showed that MUC presents greater richness and β diversity of Bacteria and Archaea than PEC. In line with these results, metagenomic analysis showed that MUC and PEC benthic microbial communities share the main common bacterial phyla found in coastal environments, although can be distinguish by greater abundance of Cyanobacteria in MUC and Deltaproteobacteria in PEC. Both ports differed in Archaea composition, being PEC port sediments dominated by Thaumarchaeota. The microbiomes showed little divergence in their potential metabolic pathways, although shifts on the microbial taxonomic signatures involved in nitrogen and sulphur metabolic pathways were observed. The comparative analysis of different benthic marine metagenomes from Brazil, Australia and Mexico grouped them by the geographic location rather than by the type of ecosystem, although at phylum level seaport sediments share a core microbiome constituted by Proteobacteria, Cyanobacteria, Actinobacteria, Tenericuteres, Firmicutes, Bacteriodetes and Euryarchaeota. Our results suggest that multiple physical and chemical factors acting on sediments as a result of at least 60years of port operation play a role in shaping the benthic microbial communities at taxonomic level, but not at functional level. Copyright © 2016 Elsevier B.V. All rights reserved.

Escherichia coli isolates from commercial chicken meat and eggs cause sepsis, meningitis and urinary tract infection in rodent models of human infections.

PubMed

Mellata, M; Johnson, J R; Curtiss, R

2018-02-01

The zoonotic potential of Escherichia coli from chicken-source food products is important to define for public health purposes. Previously, genotypic and phenotypic screening of E. coli isolates from commercial chicken meat and shell eggs identified some E. coli strains that by molecular criteria resembled human-source extraintestinal pathogenic E. coli (ExPEC). Here, to clarify the zoonotic risk of such chicken-source E. coli, we compared selected E. coli isolates from chicken meat and eggs, stratified by molecularly defined ExPEC status, to human-source ExPEC and to laboratory E. coli for virulence in rodent models of sepsis, meningitis and UTI, and evaluated whether specific bacterial characteristics predict experimental virulence. Multiple chicken-source E. coli resembled human-source ExPEC in their ability to cause one or multiple different ExPEC-associated infections. Swimming ability corresponded with urovirulence, K1 capsule corresponded with ability to cause neonatal meningitis, and biofilm formation in urine corresponded with ability to cause sepsis. In contrast, molecularly defined ExPEC status and individual genotypic traits were uncorrelated with ability to cause sepsis, and neither complement sensitivity nor growth in human urine corresponded with virulence in any infection model. These findings establish that chicken-derived food products contain E. coli strains that, in rodent models of multiple human-associated ExPEC infections, are able to cause disease comparably to human-source E. coli clinical isolates, which suggests that they may pose a significant food safety threat. Further study is needed to define the level of risk they pose to human health, which if appreciable would justify efforts to monitor for and reduce or eliminate them. © 2017 Blackwell Verlag GmbH.

A brief review of models of DC-DC power electronic converters for analysis of their stability

NASA Astrophysics Data System (ADS)

Siewniak, Piotr; Grzesik, Bogusław

2014-10-01

A brief review of models of DC-DC power electronic converters (PECs) is presented in this paper. It contains the most popular, continuous-time and discrete-time models used for PEC simulation, design, stability analysis and other applications. Both large-signal and small-signal models are considered. Special attention is paid to models that are used in practice for the analysis of the global and local stability of PECs.

A previously unrecognized role of C3a in proteinuric progressive nephropathy

PubMed Central

Morigi, Marina; Locatelli, Monica; Rota, Cinzia; Buelli, Simona; Corna, Daniela; Rizzo, Paola; Abbate, Mauro; Conti, Debora; Perico, Luca; Longaretti, Lorena; Benigni, Ariela; Zoja, Carlamaria; Remuzzi, Giuseppe

2016-01-01

Podocyte loss is the initial event in the development of glomerulosclerosis, the structural hallmark of progressive proteinuric nephropathies. Understanding mechanisms underlying glomerular injury is the key challenge for identifying novel therapeutic targets. In mice with protein-overload induced by bovine serum albumin (BSA), we evaluated whether the alternative pathway (AP) of complement mediated podocyte depletion and podocyte-dependent parietal epithelial cell (PEC) activation causing glomerulosclerosis. Factor H (Cfh−/−) or factor B-deficient mice were studied in comparison with wild-type (WT) littermates. WT+BSA mice showed podocyte depletion accompanied by glomerular complement C3 and C3a deposits, PEC migration to capillary tuft, proliferation, and glomerulosclerosis. These changes were more prominent in Cfh−/− +BSA mice. The pathogenic role of AP was documented by data that factor B deficiency preserved glomerular integrity. In protein-overload mice, PEC dysregulation was associated with upregulation of CXCR4 and GDNF/c-Ret axis. In vitro studies provided additional evidence of a direct action of C3a on proliferation and CXCR4-related migration of PECs. These effects were enhanced by podocyte-derived GDNF. In patients with proteinuric nephropathy, glomerular C3/C3a paralleled PEC activation, CXCR4 and GDNF upregulation. These results indicate that mechanistically uncontrolled AP complement activation is not dispensable for podocyte-dependent PEC activation resulting in glomerulosclerosis. PMID:27345360

Expression of a novel stress-inducible protein, sestrin 2, in rat glomerular parietal epithelial cells

PubMed Central

Hamatani, Hiroko; Sakairi, Toru; Takahashi, Satoshi; Watanabe, Mitsuharu; Maeshima, Akito; Ohse, Takamoto; Pippin, Jeffery W.; Shankland, Stuart J.; Nojima, Yoshihisa

2014-01-01

Sestrin 2, initially identified as a p53 target protein, accumulates in cells exposed to stress and inhibits mammalian target of rapamycin (mTOR) signaling. In normal rat kidneys, sestrin 2 was selectively expressed in parietal epithelial cells (PECs), identified by the marker protein gene product 9.5. In adriamycin nephropathy, sestrin 2 expression decreased in PECs on day 14, together with increased expression of phosphorylated S6 ribosomal protein (P-S6RP), a downstream target of mTOR. Sestrin 2 expression was markedly decreased on day 42, coinciding with glomerulosclerosis and severe periglomerular fibrosis. In puromycin aminonucleoside nephropathy, decreased sestrin 2 expression, increased P-S6RP expression, and periglomerular fibrosis were observed on day 9, when massive proteinuria developed. These changes were transient and nearly normalized by day 28. In crescentic glomerulonephritis, sestrin 2 expression was not detected in cellular crescents, whereas P-S6RP increased. In conditionally immortalized cultured PECs, the forced downregulation of sestrin 2 by short hairpin RNA resulted in increased expression of P-S6RP and increased apoptosis. These data suggest that sestrin 2 is involved in PEC homeostasis by regulating the activity of mTOR. In addition, sestrin 2 could be a novel marker of PECs, and decreased expression of sestrin 2 might be a marker of PEC injury. PMID:25056347

Minute perivascular epithelioid cell (PEC) nests in the abdominal lymph nodes--a putative precursor of PEComa.

PubMed

Nagasaka, Toru; Murakami, Yoshiko; Sasaki, Eiichi; Hosoda, Waki; Nakanishi, Toru; Yatabe, Yasushi

2015-04-01

A perivascular epithelioid cell tumor (PEComa) is a peculiar growth defined as a mesenchymal tumor composed of histologically and immunohistochemically distinct perivascular epithelioid cells (PECs). Because neither normal counterparts nor precursor lesions of PEComa have been identified, we examined minute PEC nests, ranged from 0.8 mm to 10 mm, to investigate the possible origin of the PEComa. We examined a total of 80 677 para-aortic and pelvic lymph nodes that were systematically dissected from 1656 patients for gynecological malignancies. The identified lesions were confirmed immunohistochemically with multiple PEC markers, including smooth muscle actin, HMB45, melan-A, MiTF, ER and PgR. A total of 66 minute PEC nests were found in 21 patients (1.3% of the total population) with an average frequency of 3.1 lesions per patient. In cases of multiple involvement, 11 of 13 nests were located at the same level of multiple lymph node or on continuous levels. The lesions were preferentially distributed at the level of para-aortic and high pelvic lymph nodes. All nests were positive for actin and HMB45, whereas the other markers were positive with varying frequencies. The minute PEC nests may be associated with the possible normal counterpart of PEComas. © 2015 Japanese Society of Pathology and Wiley Publishing Asia Pty Ltd.

Microscopic endometrial perivascular epithelioid cell nodules: a case report with the earliest presentation of a uterine perivascular epithelioid cell tumor

PubMed Central

2012-01-01

Abstract Perivascular epithelioid cell (PEC) tumors (PEComas) are a family of related mesenchymal tumors composed of PECs which co-express melanocytic and smooth muscle markers. Although their distinctive histologic, immunohistochemical, ultrastructural, and genetic features have been clearly demonstrated, their histogenesis and normal counterpart remain largely unknown. Precursor lesions of PEComas have rarely been reported. We herein describe a tuberous sclerosis patient with microscopic PEC nodules in the endometrium of adenomyosis, pelvic endometriosis, an ovarian endometriotic cyst, and the endometrium of the uterine cavity. The nodules showed a mixture of spindle-shaped and epithelioid cells concentrically arranged around small arteries. The cells exhibited uniform nuclei, light eosinophilic cytoplasm, and immunoreactivity with HMB-45 and CD10. Some nodules revealed continuity with a PEComa in the myometrium. These findings support microscopic endometrial PEC nodules possibly being precursor lesions of uterine PEComas. The wide distribution of the nodules in the pelvis may be related to the multicentricity of PEComas in tuberous sclerosis patients. Owing to the immunoreactivity with CD10, microscopic endometrial PEC nodules may be misinterpreted as endothelial stromal cells unless melanocytic markers are stained. To the best of our knowledge, this is a case with the earliest manifestation of PEC lesions occurring in the endometrium. Virtual Slides The virtual slide(s) for this article can be found here: http://www.diagnosticpathology.diagnomx.eu/vs/9658280017862643 PMID:22937790

Microscopic endometrial perivascular epithelioid cell nodules: a case report with the earliest presentation of a uterine perivascular epithelioid cell tumor.

PubMed

Fang, Chia-Lang; Lin, Yun-Ho; Chen, Wei-Yu

2012-09-03

Perivascular epithelioid cell (PEC) tumors (PEComas) are a family of related mesenchymal tumors composed of PECs which co-express melanocytic and smooth muscle markers. Although their distinctive histologic, immunohistochemical, ultrastructural, and genetic features have been clearly demonstrated, their histogenesis and normal counterpart remain largely unknown. Precursor lesions of PEComas have rarely been reported. We herein describe a tuberous sclerosis patient with microscopic PEC nodules in the endometrium of adenomyosis, pelvic endometriosis, an ovarian endometriotic cyst, and the endometrium of the uterine cavity. The nodules showed a mixture of spindle-shaped and epithelioid cells concentrically arranged around small arteries. The cells exhibited uniform nuclei, light eosinophilic cytoplasm, and immunoreactivity with HMB-45 and CD10. Some nodules revealed continuity with a PEComa in the myometrium. These findings support microscopic endometrial PEC nodules possibly being precursor lesions of uterine PEComas. The wide distribution of the nodules in the pelvis may be related to the multicentricity of PEComas in tuberous sclerosis patients. Owing to the immunoreactivity with CD10, microscopic endometrial PEC nodules may be misinterpreted as endothelial stromal cells unless melanocytic markers are stained. To the best of our knowledge, this is a case with the earliest manifestation of PEC lesions occurring in the endometrium. Virtual slides: The virtual slide(s) for this article can be found here: http://www.diagnosticpathology.diagnomx.eu/vs/9658280017862643.

Semiconducting Organic-Inorganic Nanodots Heterojunctions: Platforms for General Photoelectrochemical Bioanalysis Application.

PubMed

Wang, Qian; Ruan, Yi-Fan; Zhao, Wei-Wei; Lin, Peng; Xu, Jing-Juan; Chen, Hong-Yuan

2018-03-20

In this study, semiconducting organic polymer dots (Pdots) and inorganic quantum dots (Qdots) were first utilized to construct the organic-inorganic nanodots heterojunction for the photoelectrochemical (PEC) bioanalysis application. Specifically, n-type CdS Qdots, p-type CdTe Qdots, and tetraphenylporphyrin (TPP)-doped poly[(9,9-dioctylfluorenyl-2,7-diyl)- co-(1,4-benzo-{2,1',3}-thiadazole)] (PFBT) Pdots were fabricated, and their energy levels, that is, their valence band (VB)/conduction band (CB) or lowest unoccupied molecular orbital (LUMO)/highest occupied molecular orbital (HOMO) values, were also determined. Then, these nanodots were integrated to construct four types of p-n and p-p organic-inorganic nanodots heterojunctions, that is, CdS Qdots/TPP-doped PFBT Pdots, TPP-doped PFBT Pdots/CdS Qdots, CdTe Qdots/TPP-doped PFBT Pdots, and TPP-doped PFBT Pdots/CdTe Qdots, on the transparent glass electrode. Upon light irradiation, four heterojunctions exhibited different PEC behaviors with some having prominent photocurrent enhancement. With the model molecule l-cysteine (l-cys) as target, the proposed PEC sensor exhibited good performances. In brief, this work presents the first semiconducting organic-inorganic nanodots heterojunction for PEC bioanalysis application, which could be easily used as a general platform for future PEC bioanalysis building. Besides, it is expected to inspire more interest in the design, development, and implementation of various organic-inorganic heterojunctions for advanced PEC bioanalysis in the future.

PECS and VOCAs to enable students with developmental disabilities to make requests: an overview of the literature.

PubMed

Lancioni, Giulio E; O'Reilly, Mark F; Cuvo, Anthony J; Singh, Nirbhay N; Sigafoos, Jeff; Didden, Robert

2007-01-01

This paper provides an overview of the literature dealing with the use of the Picture Exchange Communication System (PECS) and voice output communication aids (VOCAs) for promoting the performance of requests by students with developmental disabilities. Computerized and manual searches were carried out to identify the studies published during the last 15 years (i.e., the period between 1992 and 2006 during which PECS and VOCA approaches became popular). Thirty-seven studies were identified and then divided into three groups concerning the use of the PECS or equivalents, the use of VOCAs or equivalents, and the comparison of both these approaches, respectively. Of the 173 students involved in studies using the PECS or equivalents only three could be considered failures, while a fourth one did not progress in the program due to illness. Similarly, of the 39 students who used VOCAs or equivalents only three could be considered failures, while one was partly successful. Finally, of the 11 students involved in the comparisons between PECS and VOCAs none could be classified as a failure. The results are very encouraging but methodological concerns and the relatively limited use of the systems in terms of request items and request opportunities suggest caution. Caution may also be needed in interpreting the reported similarities between the two systems in usability and effectiveness.

The effectiveness of Picture Exchange Communication System (PECS) training for teachers of children with autism: a pragmatic, group randomised controlled trial.

PubMed

Howlin, Patricia; Gordon, R Kate; Pasco, Greg; Wade, Angie; Charman, Tony

2007-05-01

To assess the effectiveness of expert training and consultancy for teachers of children with autism spectrum disorder in the use of the Picture Exchange Communication System (PECS). Group randomised, controlled trial (3 groups: immediate treatment, delayed treatment, no treatment). 84 elementary school children, mean age 6.8 years. A 2-day PECS workshop for teachers plus 6 half-day, school-based training sessions with expert consultants over 5 months. Rates of: communicative initiations, use of PECS, and speech in the classroom; Autism Diagnostic Observation Schedule-Generic (ADOS-G) domain scores for Communication and Reciprocal Social Interaction; scores on formal language tests. Controlling for baseline age, developmental quotient (DQ) and language; rates of initiations and PECS usage increased significantly immediately post-treatment (Odds Ratio (OR) of being in a higher ordinal rate category 2.72, 95% confidence interval 1.22-6.09, p < .05 and OR 3.90 (95%CI 1.75-8.68), p < .001, respectively). There were no increases in frequency of speech, or improvements in ADOS-G ratings or language test scores. The results indicate modest effectiveness of PECS teacher training/consultancy. Rates of pupils' initiations and use of symbols in the classroom increased, although there was no evidence of improvement in other areas of communication. TREATMENT effects were not maintained once active intervention ceased.

The parietal epithelial cell is crucially involved in human idiopathic focal segmental glomerulosclerosis.

PubMed

Dijkman, Henry; Smeets, Bart; van der Laak, Jeroen; Steenbergen, Eric; Wetzels, Jack

2005-10-01

Focal segmental glomerulosclerosis (FSGS) is one of the most common patterns of glomerular injury encountered in human renal biopsies. Epithelial hyperplasia, which can be prominent in FSGS, has been attributed to dedifferentiation and proliferation of podocytes. Based on observations in a mouse model of FSGS, we pointed to the role of parietal epithelial cells (PECs). In the present study we investigated the relative role of PECs and podocytes in human idiopathic FSGS. We performed a detailed study of lesions from a patient with recurrent idiopathic FSGS by serial sectioning, marker analysis and three-dimensional reconstruction of glomeruli. We have studied the expression of markers for podocytes, PECs, mesangial cells, endothelium, and myofibroblasts. We also looked at proliferation and composition of the deposited extracellular matrix (ECM). We found that proliferating epithelial cells in FSGS lesions are negative for podocyte and macrophage markers, but stain for PEC markers. The composition of the matrix deposited by these cells is identical to Bowman's capsule. Our study demonstrates that PECs are crucially involved in the pathogenesis of FSGS lesions.

Recent Advances in Photoelectrochemical Applications of Silicon Materials for Solar-to-Chemicals Conversion.

PubMed

Zhang, Doudou; Shi, Jingying; Zi, Wei; Wang, Pengpeng; Liu, Shengzhong Frank

2017-11-23

Photoelectrochemical (PEC) technology for the conversion of solar energy into chemicals requires cost-effective photoelectrodes to efficiently and stably drive anodic and/or cathodic half-reactions to complete the overall reactions for storing solar energy in chemical bonds. The shared properties among semiconducting photoelectrodes and photovoltaic (PV) materials are light absorption, charge separation, and charge transfer. Earth-abundant silicon materials have been widely applied in the PV industry, and have demonstrated their efficiency as alternative photoabsorbers for photoelectrodes. Many efforts have been made to fabricate silicon photoelectrodes with enhanced performance, and significant progress has been achieved in recent years. Herein, recent developments in crystalline and thin-film silicon-based photoelectrodes (including amorphous, microcrystalline, and nanocrystalline silicon) immersed in aqueous solution for PEC hydrogen production from water splitting are summarized, as well as applications in PEC CO 2 reduction and PEC regeneration of discharged species in redox flow batteries. Silicon is an ideal material for the cost-effective production of solar chemicals through PEC methods. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessing the acquisition and generalization of two mand forms with adults with severe developmental disabilities.

PubMed

Chambers, Mark; Rehfeldt, Ruth Anne

2003-01-01

The purpose of this study was to determine whether manual sign or the Picture Exchange Communication System (P.E.C.S.) (Frost and Bondy, 1994) would be more effective in teaching mand skills to adults with mental retardation in the severe and profound range. Four participants were taught to mand for four reinforcing items using both communication modalities, in an alternating treatments design. Three of four participants demonstrated criterion performance across all four mands using P.E.C.S. first. Two of those three participants later demonstrated criterion performance for the mands using manual sign. The fourth participant was removed from the study during training due to illness, but her progress indicated greater acquisition with P.E.C.S. Generalization probes conducted at participants' respective residences showed that three participants demonstrated generalization across settings using P.E.C.S., and two participants demonstrated generalization across settings using manual sign. Participants were also more likely to mand for reinforcing items not present using P.E.C.S. than using manual sign.

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.

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

PubMed

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

2008-09-02

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

Effect of gold nanoparticles on the structure and electron-transfer characteristics of glucose oxidase redox polyelectrolyte-surfactant complexes.

PubMed

Cortez, M Lorena; Marmisollé, Waldemar; Pallarola, Diego; Pietrasanta, Lía I; Murgida, Daniel H; Ceolín, Marcelo; Azzaroni, Omar; Battaglini, Fernando

2014-10-06

Efficient electrical communication between redox proteins and electrodes is a critical issue in the operation and development of amperometric biosensors. The present study explores the advantages of a nanostructured redox-active polyelectrolyte-surfactant complex containing [Os(bpy)2Clpy](2+) (bpy=2,2'-bipyridine, py= pyridine) as the redox centers and gold nanoparticles (AuNPs) as nanodomains for boosting the electron-transfer propagation throughout the assembled film in the presence of glucose oxidase (GOx). Film structure was characterized by grazing-incidence small-angle X-ray scattering (GISAXS) and atomic force microscopy (AFM), GOx incorporation was followed by surface plasmon resonance (SPR) and quartz-crystal microbalance with dissipation (QCM-D), whereas Raman spectroelectrochemistry and electrochemical studies confirmed the ability of the entrapped gold nanoparticles to enhance the electron-transfer processes between the enzyme and the electrode surface. Our results show that nanocomposite films exhibit five-fold increase in current response to glucose compared with analogous supramolecular AuNP-free films. The introduction of colloidal gold promotes drastic mesostructural changes in the film, which in turn leads to a rigid, amorphous interfacial architecture where nanoparticles, redox centers, and GOx remain in close proximity, thus improving the electron-transfer process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembled carrageenan/protamine polyelectrolyte nanoplexes-Investigation of critical parameters governing their formation and characteristics.

PubMed

Dul, Maria; Paluch, Krzysztof J; Kelly, Hazel; Healy, Anne Marie; Sasse, Astrid; Tajber, Lidia

2015-06-05

The aim of this work was to investigate the feasibility of cross-linker free polyelectrolyte complex formation at the nanoscale between carrageenan (CAR) and protamine (PROT). The properties of CAR/PROT nanoparticles (NPs) were dependent on the carrageenan type: kappa (KC), iota (IC) and lambda (LC), concentration of components, addition of divalent cations, weight mixing ratio (WMR) of constituents and mode of component addition. In the case of 0.1% w/v solutions, IC-based NPs had the smallest particle sizes (100-150nm) and low polydispersity indices (0.1-0.4). A decrease in the solution concentration from 0.1% to 0.05% w/v enabled the formation of KC/PROT NPs. All carrageenans exhibited the ability to form NPs with surface charge ranging from -190 to 40mV. The inclusion of divalent cations caused an increase in the particle size and zeta potential. Infrared analysis confirmed the presence of a complex between CAR and PROT and showed that IC chains undergo structural changes when forming NPs. Colloidal stability of NPs was related to the initial surface charge of particles and was time- and pH-dependent. IC was found to be the most suitable type of CAR when forming nanoplexes with PROT. Copyright © 2015 Elsevier Ltd. All rights reserved.

Molecular characterization of ESBL-producing Escherichia coli isolates from hospital- and community-acquired infections in NW Mexico.

PubMed

Miranda-Romero, Ana Laura; Silva-Sanchez, Jesus; Garza-Ramos, Ulises; Barrios, Humberto; Sánchez-Pérez, Alejandro; Reyna-Flores, Fernando

2017-01-01

We investigated the molecular characteristics of ESBL-producing E. coli (ESBL-PEc) isolates from two hospitals and community settings in Ciudad Obregon, Sonora, Mexico. Between 2011 and 2014, thirty-seven ESBL-PEc isolates were collected. The major encoded ESBL was the bla CTX-M-15 gene (97%); followed by 13.5% of the bla SHV-12 gene, and 5.5% encoded the bla TLA-1 gene. The PMQR gene aac(6´)-Ib-cr was detected in 97% of the isolates and the qnrB gene, in one isolate. The ESBL-PEc isolates corresponded to phylogenetic group B2, ST131. Our results highlight the dissemination of ESBL-PEc isolates in northwest Mexico (Ciudad Obregon, Sonora). Copyright © 2016 Elsevier Inc. All rights reserved.

Comparative efficacy of the picture exchange communication system (PECS) versus a speech-generating device: effects on social-communicative skills and speech development.

PubMed

Boesch, Miriam C; Wendt, Oliver; Subramanian, Anu; Hsu, Ning

2013-09-01

The Picture Exchange Communication System (PECS) and a speech-generating device (SGD) were compared in a study with a multiple baseline, alternating treatment design. The effectiveness of these methods in increasing social-communicative behavior and natural speech production were assessed with three elementary school-aged children with severe autism who demonstrated extremely limited functional communication skills. Results for social-communicative behavior were mixed for all participants in both treatment conditions. Relatively little difference was observed between PECS and SGD conditions. Although findings were inconclusive, data patterns suggest that Phase II of the PECS training protocol is conducive to encouraging social-communicative behavior. Data for speech outcomes did not reveal any increases across participants, and no differences between treatment conditions were observed.

Electro-actuated hydrogel walkers with dual responsive legs.

PubMed

Morales, Daniel; Palleau, Etienne; Dickey, Michael D; Velev, Orlin D

2014-03-07

Stimuli responsive polyelectrolyte hydrogels may be useful for soft robotics because of their ability to transform chemical energy into mechanical motion without the use of external mechanical input. Composed of soft and biocompatible materials, gel robots can easily bend and fold, interface and manipulate biological components and transport cargo in aqueous solutions. Electrical fields in aqueous solutions offer repeatable and controllable stimuli, which induce actuation by the re-distribution of ions in the system. Electrical fields applied to polyelectrolyte-doped gels submerged in ionic solution distribute the mobile ions asymmetrically to create osmotic pressure differences that swell and deform the gels. The sign of the fixed charges on the polyelectrolyte network determines the direction of bending, which we harness to control the motion of the gel legs in opposing directions as a response to electrical fields. We present and analyze a walking gel actuator comprised of cationic and anionic gel legs made of copolymer networks of acrylamide (AAm)/sodium acrylate (NaAc) and acrylamide/quaternized dimethylaminoethyl methacrylate (DMAEMA Q), respectively. The anionic and cationic legs were attached by electric field-promoted polyion complexation. We characterize the electro-actuated response of the sodium acrylate hydrogel as a function of charge density and external salt concentration. We demonstrate that "osmotically passive" fixed charges play an important role in controlling the bending magnitude of the gel networks. The gel walkers achieve unidirectional motion on flat elastomer substrates and exemplify a simple way to move and manipulate soft matter devices and robots in aqueous solutions.

Confined polyelectrolytes: The complexity of a simple system.

PubMed

Nunes, Sandra C C; Skepö, Marie; Pais, Alberto A C C

2015-08-05

The interaction between polyelectrolytes and counterions in confined situations and the mutual relationship between chain conformation and ion condensation is an important issue in several areas. In the biological field, it assumes particular relevance in the understanding of the packaging of nucleic acids, which is crucial in the design of gene delivery systems. In this work, a simple coarse-grained model is used to assess the cooperativity between conformational change and ion condensation in spherically confined backbones, with capsides permeable to the counterions. It is seen that the variation on the degree of condensation depends on counterion valence. For monovalent counterions, the degree of condensation passes through a minimum before increasing as the confining space diminishes. In contrast, for trivalent ions, the overall tendency is to decrease the degree of condensation as the confinement space also decreases. Most of the particles reside close to the spherical wall, even for systems in which the density is higher closer to the cavity center. This effect is more pronounced, when monovalent counterions are present. Additionally, there are clear variations in the charge along the concentric layers that cannot be totally ascribed to polyelectrolyte behavior, as shown by decoupling the chain into monomers. If both chain and counterions are confined, the formation of a counterion rich region immediately before the wall is observed. Spool and doughnut-like structures are formed for stiff chains, within a nontrivial evolution with increasing confinement. © 2015 Wiley Periodicals, Inc.

Occupational leg oedema is more reduced by antigraduated than by graduated stockings.

PubMed

Mosti, G; Partsch, H

2013-05-01

Elastic compression stockings exerting a progressive pressure, higher at the calf than at the ankle (progressive elastic compression stockings, PECS), have already proved to be more comfortable, easier to put on and more effective in improving venous pumping function compared to graduated compression elastic stockings (GECS). Nevertheless, PECS could have a negative effect on the prevention and treatment of oedema or even favour oedema formation. The aim of the present study was to investigate if, in normal volunteers, PECS are able to prevent leg swelling during their working shift. A total of 30 normal volunteers (14 males, 16 females aged 36.4 ± 6.6 years) staying standing or sitting during their shift were enrolled into the study. Their leg volume was measured at the beginning and at the end of their working shift on 2 consecutive days. On one day, the volunteers did not put on any stockings; on the other day, they wore GECS on one leg and PECS on the other. The difference between the leg volume measured at the end of the shift and the basal volume in the morning was called 'occupational oedema'. Interface pressure at points B1 and C was measured immediately after stockings' application and before removal. The volunteers were asked to report about difficulty of putting on the stockings and comfort during wearing time. The results were submitted to statistical analysis. The GECS and PECS groups had similar baseline leg volumes (3143 vs. 3154 ml) and occupational oedema (134 vs. 137.5 ml); after putting on the stockings, occupational oedema was reduced in both legs but the reduction was significantly greater with PECS (20 vs. 40 ml with GECS) (P < 0.05). Interface pressure at ankle level is higher with GECS both in supine and in standing position while at calf level it is higher with PECS both in supine and standing position. PECS are easier to put on and slightly more comfortable. PECS are easier to put on and more comfortable and produce a significantly higher reduction of occupational oedema compared with GECS in normal volunteers. Nevertheless leg volumetry, providing a global leg-volume evaluation, is not able to localise the oedema reduction and to assess if it occurs more in the calf or the ankle area. Theoretically, despite a global volume reduction, PECS could even promote a slight oedema formation at ankle level over-compensated by a greater oedema reduction at calf level. Further studies need to concentrate on patients with venous disease and on the local distribution of this global effect. Copyright © 2013 European Society for Vascular Surgery. Published by Elsevier Ltd. All rights reserved.

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.

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.

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.

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.

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).

Phylogenetic Backgrounds and Virulence-Associated Traits of Escherichia coli Isolates from Surface Waters and Diverse Animals in Minnesota and Wisconsin.

PubMed

Johnson, James R; Johnston, Brian D; Delavari, Parissa; Thuras, Paul; Clabots, Connie; Sadowsky, Michael J

2017-12-15

Possible external reservoirs for extraintestinal pathogenic Escherichia coli (ExPEC) strains that cause infections in humans are poorly defined. Because of the tremendous human health importance of ExPEC infections, we assessed surface waters and domesticated and wild animals in Minnesota and Wisconsin as potential reservoirs of ExPEC of human health relevance. We characterized 595 E. coli isolates (obtained from 1999 to 2002; 280 from seven surface water sites, 315 from feces of 13 wild and domesticated animal species) for phylogroup and virulence genotype, including inferred ExPEC status, by using multiplex PCR-based methods. We also compared the pulsed-field gel electrophoresis (PFGE) profiles of the isolates with a large private PFGE profile library. We found a predominance of non-ExPEC strains (95% and 93% among water and animal isolates, respectively), which were mainly from phylogroups A and B1, plus a minority of ExPEC strains (5% and 7% among water isolates and animal isolates, respectively), predominantly from phylogroup B2. The ExPEC strains, although significantly associated with cats, dogs, and turkeys, occurred in several additional animal species (goat, horse, chicken, pig) and were distributed broadly across all surface water sites. Virulence gene content among the animal source ExPEC isolates segregated significantly in relation to host species, following established patterns. PFGE analysis indicated that 11 study isolates closely matched (94% to 100% profile similarity) reference human clinical and fecal isolates. These findings imply what probably is a low but non-zero risk to humans from environmental and animal source E. coli isolates, especially those from specific human-associated animal species. IMPORTANCE Our detection of potentially pathogenic strains that may pose a health threat to humans among E. coli isolates from surface waters and wild and domesticated animals suggests a need for heightened attention to these reservoirs as possible sources for human acquisition of disease-causing E. coli Although cats, dogs, and turkeys were especially high-prevalence sources, the presence of such strains in other animal species and at all sampled water sites suggests that this potential risk may be widespread. Copyright © 2017 American Society for Microbiology.

A Water-Borne Adhesive Modeled after the Sandcastle Glue of P. californicaa

PubMed Central

Shao, Hui; Bachus, Kent N.

2010-01-01

Polyacrylate glue protein analogs of the glue secreted by Phragmatopoma californica, a marine polycheate, were synthesized with phosphate, primary amine, and catechol sidechains with molar ratios similar to the natural glue proteins. Aqueous mixtures of the mimetic polyelectrolytes condensed into liquid complex coacervates around neutral pH. Wet cortical bone specimens bonded with the coacervates, oxidatively crosslinked through catechol sidechains, had bond strengths nearly 40% of the strength of a commercial cyanoacrylate. The unique material properties of complex coacervates may be ideal for development of clinically useful adhesives and other biomaterials. PMID:19040222

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.

Photoelectrochemical hydrogen production from biomass derivatives and water.

PubMed

Lu, Xihong; Xie, Shilei; Yang, Hao; Tong, Yexiang; Ji, Hongbing

2014-11-21

Hydrogen, a clean energy carrier with high energy capacity, is a very promising candidate as a primary energy source for the future. Photoelectrochemical (PEC) hydrogen production from renewable biomass derivatives and water is one of the most promising approaches to producing green chemical fuel. Compared to water splitting, hydrogen production from renewable biomass derivatives and water through a PEC process is more efficient from the viewpoint of thermodynamics. Additionally, the carbon dioxide formed can be re-transformed into carbohydrates via photosynthesis in plants. In this review, we focus on the development of photoanodes and systems for PEC hydrogen production from water and renewable biomass derivatives, such as methanol, ethanol, glycerol and sugars. We also discuss the future challenges and opportunities for the design of the state-of-the-art photoanodes and PEC systems for hydrogen production from biomass derivatives and water.

Effects of pressure and temperature on sintering of Cr-doped Al2O3 by pulsed electric current sintering process

NASA Astrophysics Data System (ADS)

Dang, K. Q.; Nanko, M.

2011-03-01

The aluminium oxide crystal, Al2O3, which contains a small amount of chromium, Cr, is called ruby. Pulsed electric current sintering (PECS) was applied to sinter ruby polycrystals. Cr2O3-Al2O3 powder mixture prepared by drying an aqueous slurry containing amounts of Al2O3 and Cr(NO3)3 was consolidated by PECS process. The PECS process was performed in vacuum at sintering temperature raging from 1100 to 1300°C with heating rate of 2 K/min under applied uniaxial pressure varied from 40 to 100 MPa. This study found that highly densified and transparent Cr-doped Al2O3 can be obtained by the PECS process with the high applied pressure at sintering temperature of 1200°C.

Surface Interrogation Scanning Electrochemical Microscopy for a Photoelectrochemical Reaction: Water Oxidation on a Hematite Surface.

PubMed

Kim, Jae Young; Ahn, Hyun S; Bard, Allen J

2018-03-06

To understand the pathway of a photoelectrochemical (PEC) reaction, quantitative knowledge of reaction intermediates is important. We describe here surface interrogation scanning electrochemical microscopy for this purpose (PEC SI-SECM), where a light pulse to a photoactive semiconductor film at a given potential generates intermediates that are then analyzed by a tip generated titrant at known times after the light pulse. The improvements were demonstrated for photoelectrochemical water oxidation (oxygen evolution) reaction on a hematite surface. The density of photoactive sites, proposed to be Fe 4+ species, on a hematite surface was successfully quantified, and the photoelectrochemical water oxidation reaction dynamics were elucidated by time-dependent redox titration experiments. The new configuration of PEC SI-SECM should find expanded usage to understand and investigate more complicated PEC reactions with other materials.

All-inorganic perovskite quantum dot/TiO2 inverse opal electrode platform: stable and efficient photoelectrochemical sensing of dopamine under visible irradiation.

PubMed

Chen, Xu; Li, Dongyu; Pan, Gencai; Zhou, Donglei; Xu, Wen; Zhu, Jinyang; Wang, He; Chen, Cong; Song, Hongwei

2018-06-07

CsPbX3 (X = Cl, Br or I) perovskite quantum dots (PQDs) have attracted tremendous attention due to their extraordinarily excellent optical properties. However, there is still an obstacle for their bio-application, which is limited by their water-instability. In this work, we have designed a novel visible light triggered photoelectrochemical (PEC) sensor for dopamine (DA) based on CsPbBr1.5I1.5 PQD immobilized three-dimensional (3D) TiO2 inverse opal photonic crystals (IOPCs). Supported by the TiO2 IOPCs, the water-stability of the PQDs as well as that of the PEC sensor was considerably improved. Furthermore, employed as a photoactive material in PEC sensor, CsPbBr1.5I1.5 PQDs can expand the photocurrent response of the PEC sensor to the whole visible region. In addition, the modulation of the photonic stop band effect of TiO2 IOPCs on the incident light and the emission of PQDs could further enhance the photocurrent response. Such a PEC sensor demonstrates sensitive detection of DA in phosphate buffer saline solution and serum, with a good linear range from 0.1 μM to 250 μM and a low detection limit of approximately 0.012 μM. Our strategy opens an alternative horizon for PQD based PEC sensing, which could be more sensitive, convenient and inexpensive for clinical and biological analysis.

Photoelectrochemical devices for solar water splitting - materials and challenges.

PubMed

Jiang, Chaoran; Moniz, Savio J A; Wang, Aiqin; Zhang, Tao; Tang, Junwang

2017-07-31

It is widely accepted within the community that to achieve a sustainable society with an energy mix primarily based on solar energy we need an efficient strategy to convert and store sunlight into chemical fuels. A photoelectrochemical (PEC) device would therefore play a key role in offering the possibility of carbon-neutral solar fuel production through artificial photosynthesis. The past five years have seen a surge in the development of promising semiconductor materials. In addition, low-cost earth-abundant co-catalysts are ubiquitous in their employment in water splitting cells due to the sluggish kinetics of the oxygen evolution reaction (OER). This review commences with a fundamental understanding of semiconductor properties and charge transfer processes in a PEC device. We then describe various configurations of PEC devices, including single light-absorber cells and multi light-absorber devices (PEC, PV-PEC and PV/electrolyser tandem cell). Recent progress on both photoelectrode materials (light absorbers) and electrocatalysts is summarized, and important factors which dominate photoelectrode performance, including light absorption, charge separation and transport, surface chemical reaction rate and the stability of the photoanode, are discussed. Controlling semiconductor properties is the primary concern in developing materials for solar water splitting. Accordingly, strategies to address the challenges for materials development in this area, such as the adoption of smart architectures, innovative device configuration design, co-catalyst loading, and surface protection layer deposition, are outlined throughout the text, to deliver a highly efficient and stable PEC device for water splitting.

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.

Comparative Genomics of Escherichia coli Isolated from Skin and Soft Tissue and Other Extraintestinal Infections.

PubMed

Ranjan, Amit; Shaik, Sabiha; Nandanwar, Nishant; Hussain, Arif; Tiwari, Sumeet K; Semmler, Torsten; Jadhav, Savita; Wieler, Lothar H; Alam, Munirul; Colwell, Rita R; Ahmed, Niyaz

2017-08-15

Escherichia coli , an intestinal Gram-negative bacterium, has been shown to be associated with a variety of diseases in addition to intestinal infections, such as urinary tract infections (UTIs), meningitis in neonates, septicemia, skin and soft tissue infections (SSTIs), and colisepticemia. Thus, for nonintestinal infections, it is categorized as extraintestinal pathogenic E. coli (ExPEC). It is also an opportunistic pathogen, causing cross infections, notably as an agent of zoonotic diseases. However, comparative genomic data providing functional and genetic coordinates for ExPEC strains associated with these different types of infections have not proven conclusive. In the study reported here, ExPEC E. coli isolated from SSTIs was characterized, including virulence and drug resistance profiles, and compared with isolates from patients suffering either pyelonephritis or septicemia. Results revealed that the majority of the isolates belonged to two pathogenic phylogroups, B2 and D. Approximately 67% of the isolates were multidrug resistant (MDR), with 85% producing extended-spectrum beta-lactamase (ESBL) and 6% producing metallo-beta-lactamase (MBL). The bla CTX-M-15 genotype was observed in at least 70% of the E. coli isolates in each category, conferring resistance to an extended range of beta-lactam antibiotics. Whole-genome sequencing and comparative genomics of the ExPEC isolates revealed that two of the four isolates from SSTIs, NA633 and NA643, belong to pandemic sequence type ST131, whereas functional characteristics of three of the ExPEC pathotypes revealed that they had equal capabilities to form biofilm and were resistant to human serum. Overall, the isolates from a variety of ExPEC infections demonstrated similar resistomes and virulomes and did not display any disease-specific functional or genetic coordinates. IMPORTANCE Infections caused by extraintestinal pathogenic E. coli (ExPEC) are of global concern as they result in significant costs to health care facilities management. The recent emergence of a multidrug-resistant pandemic clone, Escherichia coli ST131, is of primary concern as a global threat. In developing countries, such as India, skin and soft tissue infections (SSTIs) associated with E. coli are marginally addressed. In this study, we employed both genomic analysis and phenotypic assays to determine relationships, if any, among the ExPEC pathotypes. Similarity between antibiotic resistance and virulence profiles was observed, ST131 isolates from SSTIs were reported, and genomic similarities among strains isolated from different disease conditions were detected. This study provides functional molecular infection epidemiology insight into SSTI-associated E. coli compared with ExPEC pathotypes. Copyright © 2017 Ranjan et al.

Low temperature oxidative desulfurization with hierarchically mesoporous titaniumsilicate Ti-SBA-2 single crystals.

PubMed

Shi, Chengxiang; Wang, Wenxuan; Liu, Ni; Xu, Xueyan; Wang, Danhong; Zhang, Minghui; Sun, Pingchuan; Chen, Tiehong

2015-07-21

Hierarchically porous Ti-SBA-2 with high framework Ti content (up to 5 wt%) was firstly synthesized by employing organic mesomorphous complexes of a cationic surfactant (CTAB) and an anionic polyelectrolyte (PAA) as templates. The material exhibited excellent performance in oxidative desulfurization of diesel fuel at low temperature (40 °C or 25 °C) due to the unique hierarchically porous structure and high framework Ti content.

CDC42 is required for epicardial and pro-epicardial development by mediating FGF receptor trafficking to the plasma membrane

PubMed Central

Li, Jingjing; Miao, Lianjie; Zhao, Chen; Shaikh Qureshi, Wasay Mohiuddin; Shieh, David; Guo, Hua; Lu, Yangyang; Hu, Saiyang; Huang, Alice; Zhang, Lu; Cai, Chen-leng; Wan, Leo Q.; Xin, Hongbo; Vincent, Peter; Singer, Harold A.; Zheng, Yi; Cleaver, Ondine; Fan, Zhen-Chuan

2017-01-01

The epicardium contributes to multiple cardiac lineages and is essential for cardiac development and regeneration. However, the mechanism of epicardium formation is unclear. This study aimed to establish the cellular and molecular mechanisms underlying the dissociation of pro-epicardial cells (PECs) from the pro-epicardium (PE) and their subsequent translocation to the heart to form the epicardium. We used lineage tracing, conditional deletion, mosaic analysis and ligand stimulation in mice to determine that both villous protrusions and floating cysts contribute to PEC translocation to myocardium in a CDC42-dependent manner. We resolved a controversy by demonstrating that physical contact of the PE with the myocardium constitutes a third mechanism for PEC translocation to myocardium, and observed a fourth mechanism in which PECs migrate along the surface of the inflow tract to reach the ventricles. Epicardial-specific Cdc42 deletion disrupted epicardium formation, and Cdc42 null PECs proliferated less, lost polarity and failed to form villous protrusions and floating cysts. FGF signaling promotes epicardium formation in vivo, and biochemical studies demonstrated that CDC42 is involved in the trafficking of FGF receptors to the cell membrane to regulate epicardium formation. PMID:28465335

Fracture mode, microstructure and temperature-dependent elastic moduli for thermoelectric composites of PbTe-PbS with SiC nanoparticle additions

NASA Astrophysics Data System (ADS)

Ni, Jennifer E.; Case, Eldon D.; Schmidt, Robert D.; Wu, Chun-I.; Hogan, Timothy P.; Trejo, Rosa M.; Lara-Curzio, Edgar; Kanatzidis, Mercouri G.

2013-12-01

Twenty-six (Pb0.95Sn0.05Te)0.92(PbS)0.08-0.055% PbI2-SiC nanoparticle (SiCnp) composite thermoelectric specimens were either hot pressed or pulsed electric current sintered (PECS). Bloating (a thermally induced increase in porosity, P, for as-densified specimens) was observed during annealing at temperatures >603 K for hot-pressed specimens and PECS-processed specimens from wet milled powders, but in contrast seven out of seven specimens densified by PECS from dry milled powders showed no observable bloating following annealing at temperatures up to 936 K. In this study, bloating in the specimens was accessed via thermal annealing induced changes in (i) porosity measured by scanning electron microscopy on fractured specimen surfaces, (ii) specimen volume and (iii) elastic moduli. The moduli were measured by resonant ultrasound spectroscopy. SiCnp additions (1-3.5 vol.%) changed the fracture mode from intergranular to transgranular, inhibited grain growth, and limited bloating in the wet milled PECS specimens. Inhibition of bloating likely occurs due to cleaning of contamination from powder particle surfaces via PECS processing which has been reported previously in the literature.

Simplified human model and pedestrian simulation in the millimeter-wave region

NASA Astrophysics Data System (ADS)

Han, Junghwan; Kim, Seok; Lee, Tae-Yun; Ka, Min-Ho

2016-02-01

The 24 GHz and 77 GHz radar sensors have been studied as a strong candidate for advanced driver assistance systems(ADAS) because of their all-weather capability and accurate range and radial velocity measuring scheme. However, developing a reliable pedestrian recognition system hasmany obstacles due to the inaccurate and non-trivial radar responses at these high frequencies and the many combinations of clothes and accessories. To overcome these obstacles, many researchers used electromagnetic (EM) simulation to characterize the radar scattering response of a human. However, human simulation takes so long time because of the electrically huge size of a human in the millimeter-wave region. To reduce simulation time, some researchers assumed the skin of a human is the perfect electric conductor (PEC) and have simulated the PEC human model using physical optics (PO) algorithm without a specific explanation about how the human body could be modeled with PEC. In this study, the validity of the assumption that the surface of the human body is considered PEC in the EM simulation is verified, and the simulation result of the dry skin human model is compared with that of the PEC human model.

Partitionable-space enhanced coagulation (PEC) reactor and its working mechanism: a new prospective chemical technology for phosphorus pollution control.

PubMed

Zhang, Meng; Zheng, Ping; Abbas, Ghulam; Chen, Xiaoguang

2014-02-01

Phosphorus pollution control and phosphorus recycling, simultaneously, are focus of attention in the wastewater treatment. In this work, a novel reactor named partitionable-space enhanced coagulation (PEC) was invented for phosphorus control. The working performance and process mechanism of PEC reactor were investigated. The results showed that the PEC technology was highly efficient and cost-effective. The volumetric removal rate (VRR) reached up to 2.86 ± 0.04 kg P/(m(3) d) with a phosphorus removal rate of over 97%. The precipitant consumption was reduced to 2.60-2.76 kg Fe(II)/kg P with low operational cost of $ 0.632-0.673/kg P. The peak phosphorus content in precipitate was up to 30.44% by P2O5, which reveal the benefit of the recycling phosphorus resource. The excellent performance of PEC technology was mainly attributed to the partitionable-space and 'flocculation filter'. The partition limited the trans-regional back-mixing of reagents along the reactor, which promoted the precipitation reaction. The 'flocculation filter' retained the microflocs, enhancing the flocculation process. Copyright © 2013 Elsevier Ltd. All rights reserved.

Surface- and interface-engineered heterostructures for solar hydrogen generation

NASA Astrophysics Data System (ADS)

Chen, Xiangyan; Li, Yanrui; Shen, Shaohua

2018-04-01

Photoelectrochemical (PEC) water splitting based on semiconductor photoelectrodes provides a promising platform for reducing environmental pollution and solving the energy crisis by developing clean, sustainable and environmentally friendly hydrogen energy. In this context, metal oxides with their advantages including low cost, good chemical stability and environmental friendliness, have attracted extensive attention among the investigated candidates. However, the large bandgap, poor charge transfer ability and high charge recombination rate limit the PEC performance of metal oxides as photoelectrodes. To solve this limitation, many approaches toward enhanced PEC water splitting performance, which focus on surface and interface engineering, have been presented. In this topical review, we concentrate on the heterostructure design of some typical metal oxides with narrow bandgaps (e.g. Fe2O3, WO3, BiVO4 and Cu2O) as photoelectrodes. An overview of the surface- and interface-engineered heterostructures, including semiconductor heterojunctions, surface protection, surface passivation and cocatalyst decoration, will be given to introduce the recent advances in metal oxide heterostructures for PEC water splitting. This article aims to provide fundamental references and principles for designing metal oxide heterostructures with high activity and stability as photoelectrodes for PEC solar hydrogen generation.

Graphene-doped Bi2S3 nanorods as visible-light photoelectrochemical aptasensing platform for sulfadimethoxine detection.

PubMed

Okoth, Otieno Kevin; Yan, Kai; Liu, Yong; Zhang, Jingdong

2016-12-15

Bismuth sulphide (Bi2S3) nanorods doped with graphene (G) were synthesized and explored as photoactive materials for constructing a photoelectrochemical (PEC) aptasensor for sulfadimethoxine (SDM) detection. The formation of Bi2S3 nanorods and G nanosheets was observed by scanning electron microscopy (SEM) and further characterized by X-ray diffraction (XRD) spectroscopy. The PEC measurements indicated that the photocurrent response of Bi2S3 was obviously improved by doping suitable amount of G. The G-Bi2S3 composite coated electrode was utilized for fabricating a PEC aptasensor by covalently immobilizing a 5'-amino-terminated SDM aptamer on the electrode surface. Based on the specific interaction between SDM and the aptamer, a PEC sensor responsive to SDM was obtained. Under optimal conditions, the proposed sensor showed a linear photocurrent response to SDM in the concentration range of 1.0-100nM, with a low detection limit (3S/N) of 0.55nM. Moreover, the sensor showed high sensitivity, stability and reproducibility. The potential applicability of the PEC aptasensor was confirmed by detecting SDM in veterinary drug formulation and milk. Copyright © 2016 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.

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.

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.

Risk factors for post-colorectal endoscopic submucosal dissection (ESD) coagulation syndrome: a multicenter, prospective, observational study

PubMed Central

Arimoto, Jun; Higurashi, Takuma; Kato, Shingo; Fuyuki, Akiko; Ohkubo, Hidenori; Nonaka, Takashi; Yamaguchi, Yoshikazu; Ashikari, Keiichi; Chiba, Hideyuki; Goto, Shungo; Taguri, Masataka; Sakaguchi, Takashi; Atsukawa, Kazuhiro; Nakajima, Atsushi

2018-01-01

Background and study aims  Colorectal cancer (CRC) is one of the most common neoplasms and endoscopic submucosal dissection (ESD) is an effective treatment for early-stage CRC. However, it has been observed that patients undergoing ESD often complain of pain, even if ESD has been successfully performed. Risk factors for such pain still remain unknown. The aim of this study was to explore the risk factors for post-colorectal ESD coagulation syndrome (PECS). Patients and methods  This was a prospective multicenter observational trial (UMIN000016781) conducted in 106 of 223 patients who underwent ESD between March 2015 and April 2016. We investigated age, sex, tumor location, ESD operation time, lesion size, duration of hospitalization, and frequency of PECS. We defined PECS as local abdominal pain (evaluated on a visual analogue scale) in the region corresponding to the site of the ESD that occurred within 4 days of the procedure. Results  PECS occurred in 15/106 (14.2 %), and 10 were women ( P  = 0.01, OR: 7.74 [1.6 – 36.4]), 7 had lesions in the cecum ( P  < 0.001, OR: 20.6 [3.7 – 115.2]), and 9 in whom ESD operation time was > 90 min ( P  = 0.002, OR: 10.3 [2.4 – 44.6]). Frequency of deviation from the prescribed clinical path was significantly higher (47 % [7/15] vs. 2 % [2/91], P  < 0.001, OR: 38.9 [6.9 – 219.6]), and hospital stay was significantly longer in the PECS group.  Conclusions  Female gender, location of lesion in the cecum, and ESD operation time > 90 minutes were significant risk factors independent of PECS. These findings are important to management of PECS.  PMID:29527556

Prospective double blind randomized placebo-controlled clinical trial of the pectoral nerves (Pecs) block type II.

PubMed

Versyck, Barbara; van Geffen, Geert-Jan; Van Houwe, Patrick

2017-08-01

The aim of this clinical trial was to test the hypothesis whether adding the pectoral nerves (Pecs) block type II to the anesthetic procedure reduces opioid consumption during and after breast surgery. A prospective randomized double blind placebo-controlled study. A secondary hospital. 140 breast cancer stage 1-3 patients undergoing mastectomy or tumorectomy with sentinel node or axillary node dissection. Patients were randomized to receive either a Pecs block with levobupivacaine 0.25% (n=70) or placebo block with saline (n=70). The pain levels were evaluated by Numeric Rating Scale (NRS) pain scores at 15-minute intervals during the post anesthesia care unit stay time (PACU), at 2-hour intervals for the first 24h on the ward and at 4-hour intervals for the next 24h. Intraoperative and postoperative opioid consumption were recorded during the full stay. Patient satisfaction was evaluated upon discharge using a 10-point scale. Intraoperative sufentanil requirements were comparable for the Pecs and placebo group (8.0±3.5μg and 7.8±3.0μg, P=0.730). Patients in the Pecs group experienced significantly less pain than patients in the control group (P=0.048) during their PACU stay. Furthermore, patients in the Pecs group required significant less postoperative opioids (9.16±10.15mg and 14.97±14.38mg morphine equivalent, P=0.037) and required significant fewer postsurgical opioid administration interventions than patients in the control group (P=0.045). Both patient-groups were very satisfied about their management (9.6±0.6 and 9.1±1.8 on a 10-point scale, P=0.211). The Pecs block reduces postsurgical opioid consumption during the PACU stay time for patients undergoing breast surgery. Copyright © 2017 Elsevier Inc. All rights reserved.

Frequency of hepatitis E virus, rotavirus and porcine enteric calicivirus at various stages of pork carcass processing in two pork processing plants.

PubMed

Jones, Tineke H; Muehlhauser, Victoria

2017-10-16

Hepatitis E virus (HEV), rotavirus (RV), and porcine enteric calicivirus (PEC) infections are common in swine and raises concerns about the potential for zoonotic transmission through undercooked meat products. Enteric viruses can potentially contaminate carcasses during meat processing operations. There is a lack of information on the prevalence and control of enteric viruses in the pork processing chain. This study compared the incidence and levels of contamination of hog carcasses with HEV, RV and PEC at different stages of the dressing process. A total of 1000 swabs were collected from 2 pork processing plants on 10 separate occasions over the span of a year. The samples were obtained from random sites on hog carcasses at 4 dressing stages (plant A: bleeding, dehairing, pasteurization, and evisceration; plant B: bleeding, skinning, evisceration, and washing) and from meat cuts. Numbers of genome copies (gc) of HEV, RV and PEC were determined by RT-qPCR. RV and PEC were detected in 100%, and 18% of samples, respectively, after bleeding for plant A and in 98%, and 36% of samples, respectively, after bleeding for plant B. After evisceration, RV and PEC were detected in 21% and 3% of samples, respectively, for plant A and in 1%, and 0% of samples, respectively for plant B. RV and PEC were detected on 1%, and 5% of pork cuts, respectively, for plant A and on 0%, and 0% of pork cuts, respectively, for plant B. HEV was not detected in any pork carcass or retail pork samples from plants A or B. The frequency of PEC and RV on pork is progressively reduced along the pork processing chain but the viruses were not completely eliminated. The findings suggest that consumers could be at risk when consuming undercooked meat contaminated with pathogenic enteric viruses. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Combining Quantitative Genetic Footprinting and Trait Enrichment Analysis to Identify Fitness Determinants of a Bacterial Pathogen

PubMed Central

Wiles, Travis J.; Norton, J. Paul; Russell, Colin W.; Dalley, Brian K.; Fischer, Kael F.; Mulvey, Matthew A.

2013-01-01

Strains of Extraintestinal Pathogenic Escherichia c oli (ExPEC) exhibit an array of virulence strategies and are a major cause of urinary tract infections, sepsis and meningitis. Efforts to understand ExPEC pathogenesis are challenged by the high degree of genetic and phenotypic variation that exists among isolates. Determining which virulence traits are widespread and which are strain-specific will greatly benefit the design of more effective therapies. Towards this goal, we utilized a quantitative genetic footprinting technique known as transposon insertion sequencing (Tn-seq) in conjunction with comparative pathogenomics to functionally dissect the genetic repertoire of a reference ExPEC isolate. Using Tn-seq and high-throughput zebrafish infection models, we tracked changes in the abundance of ExPEC variants within saturated transposon mutant libraries following selection within distinct host niches. Nine hundred and seventy bacterial genes (18% of the genome) were found to promote pathogen fitness in either a niche-dependent or independent manner. To identify genes with the highest therapeutic and diagnostic potential, a novel Trait Enrichment Analysis (TEA) algorithm was developed to ascertain the phylogenetic distribution of candidate genes. TEA revealed that a significant portion of the 970 genes identified by Tn-seq have homologues more often contained within the genomes of ExPEC and other known pathogens, which, as suggested by the first axiom of molecular Koch's postulates, is considered to be a key feature of true virulence determinants. Three of these Tn-seq-derived pathogen-associated genes—a transcriptional repressor, a putative metalloendopeptidase toxin and a hypothetical DNA binding protein—were deleted and shown to independently affect ExPEC fitness in zebrafish and mouse models of infection. Together, the approaches and observations reported herein provide a resource for future pathogenomics-based research and highlight the diversity of factors required by a single ExPEC isolate to survive within varying host environments. PMID:23990803

Photoelectrocatalytic degradation of methylene blue using F doped TiO2 photoelectrode under visible light irradiation.

PubMed

Liu, Dong; Tian, Renwen; Wang, Jianqiao; Nie, Er; Piao, Xianqing; Li, Xin; Sun, Zhuo

2017-10-01

Photoelectrocatalysis (PEC) has attracted great interest due to cost effectiveness and high efficiency in water treatment. In this study, F doped TiO 2 (F-TiO 2 ) photoelectrodes with honeycomb like morphology were prepared, and the PEC performance was investigated. F-TiO 2 particles that showed enhanced absorption of visible light were synthesized via a sol-gel method. F-TiO 2 particles were anchored onto the surface of F-doped SnO 2 glass by a screen-printing method to prepare the F-TiO 2 photoelectrodes. The PEC performance of the F-TiO 2 photoelectrodes was investigated via the degradation of methylene blue (MB) under visible light irradiation. The results show that the F-TiO 2 photoelectrodes exhibited an excellent PEC performance that was affected by the F doping content, applied bias and solution pH. A maximum decolorization percentage of 97.8% was achieved by the FT-15 photoelectrode, with a 1.4 V bias at pH 9.94 after 4.0 h of visible light irradiation. The high PEC performance of the F-TiO 2 photoelectrodes is mainly ascribed to the efficient separation of electron-hole (e - -h + ) pairs and the creation of active radicals such as hydroxyl radicals (OH). The PEC decolorization kinetic data were analyzed using the first-order kinetic model and the Langmuir-Hinshelwood (L-H) model. The data indicates that the PEC degradation of MB molecules mainly occurred on the surface of the F-TiO 2 photoelectrodes, and the MB molecules were discolored mainly by h + (41.5%) and OH (46.5%). In addition, 8.2% of the MB molecules were discolored by other oxidative species, and 3.8% of the MB molecules were discolored by self-sensitized oxidation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Heme oxygenase-1-mediated autophagy protects against pulmonary endothelial cell death and development of emphysema in cadmium-treated mice

PubMed Central

Surolia, Ranu; Karki, Suman; Kim, Hyunki; Yu, Zhihong; Kulkarni, Tejaswini; Mirov, Sergey B.; Carter, A. Brent; Rowe, Steven M.; Matalon, Sadis; Thannickal, Victor J.; Agarwal, Anupam

2015-01-01

Pulmonary exposure to cadmium, a major component of cigarette smoke, has a dramatic impact on lung function and the development of emphysema. Cigarette smoke exposure induces heme oxygenase-1 (HO-1), a cytoprotective enzyme. In this study, we employed a truncated mouse model of emphysema by intratracheal instillation of cadmium (CdCl2) solution (0.025% per 1 mg/kg body wt) in HO-1+/+, HO-1−/−, and overexpressing humanized HO-1 bacterial artificial chromosome (hHO-1BAC) mice. We evaluated the role of HO-1 in cadmium-induced emphysema in mice by analyzing histopathology, micro-computed tomography scans, and lung function tests. CdCl2-exposed HO-1−/− mice exhibited more severe emphysema compared with HO-1+/+ or hHO-1BAC mice. Loss of pulmonary endothelial cells (PECs) from the alveolar capillary membrane is recognized to be a target in emphysema. PECs from HO-1+/+, HO-1−/−, and hHO-1BAC were employed to define the underlying molecular mechanism for the protection from emphysema by HO-1. Electron microscopy, expression of autophagic markers (microtubule-associated protein 1B-light chain 3 II, autophagy protein 5, and Beclin1) and apoptotic marker (cleaved caspase 3) suggested induction of autophagy and apoptosis in PECs after CdCl2 treatment. CdCl2-treated HO-1−/− PECs exhibited downregulation of autophagic markers and significantly increased cleaved caspase 3 expression and activity (∼4-fold higher). Moreover, hHO-1BAC PECs demonstrated upregulated autophagy and absence of cleaved caspase 3 expression or activity. Pretreatment of HO-1+/+ PECs with rapamycin induced autophagy and resulted in reduced cell death upon cadmium treatment. Induction of autophagy following CdCl2 treatment was found to be protective from apoptotic cell death. HO-1 induced protective autophagy in PECs and mitigated cadmium-induced emphysema. PMID:26071551

Heme oxygenase-1-mediated autophagy protects against pulmonary endothelial cell death and development of emphysema in cadmium-treated mice.

PubMed

Surolia, Ranu; Karki, Suman; Kim, Hyunki; Yu, Zhihong; Kulkarni, Tejaswini; Mirov, Sergey B; Carter, A Brent; Rowe, Steven M; Matalon, Sadis; Thannickal, Victor J; Agarwal, Anupam; Antony, Veena B

2015-08-01

Pulmonary exposure to cadmium, a major component of cigarette smoke, has a dramatic impact on lung function and the development of emphysema. Cigarette smoke exposure induces heme oxygenase-1 (HO-1), a cytoprotective enzyme. In this study, we employed a truncated mouse model of emphysema by intratracheal instillation of cadmium (CdCl2) solution (0.025% per 1 mg/kg body wt) in HO-1(+/+), HO-1(-/-), and overexpressing humanized HO-1 bacterial artificial chromosome (hHO-1BAC) mice. We evaluated the role of HO-1 in cadmium-induced emphysema in mice by analyzing histopathology, micro-computed tomography scans, and lung function tests. CdCl2-exposed HO-1(-/-) mice exhibited more severe emphysema compared with HO-1(+/+) or hHO-1BAC mice. Loss of pulmonary endothelial cells (PECs) from the alveolar capillary membrane is recognized to be a target in emphysema. PECs from HO-1(+/+), HO-1(-/-), and hHO-1BAC were employed to define the underlying molecular mechanism for the protection from emphysema by HO-1. Electron microscopy, expression of autophagic markers (microtubule-associated protein 1B-light chain 3 II, autophagy protein 5, and Beclin1) and apoptotic marker (cleaved caspase 3) suggested induction of autophagy and apoptosis in PECs after CdCl2 treatment. CdCl2-treated HO-1(-/-) PECs exhibited downregulation of autophagic markers and significantly increased cleaved caspase 3 expression and activity (∼4-fold higher). Moreover, hHO-1BAC PECs demonstrated upregulated autophagy and absence of cleaved caspase 3 expression or activity. Pretreatment of HO-1(+/+) PECs with rapamycin induced autophagy and resulted in reduced cell death upon cadmium treatment. Induction of autophagy following CdCl2 treatment was found to be protective from apoptotic cell death. HO-1 induced protective autophagy in PECs and mitigated cadmium-induced emphysema. Copyright © 2015 the American Physiological Society.

Modeling the Inactivation of Intestinal Pathogenic Escherichia coli O157:H7 and Uropathogenic E. coli in Ground Chicken by High Pressure Processing and Thymol

PubMed Central

Chien, Shih-Yung; Sheen, Shiowshuh; Sommers, Christopher H.; Sheen, Lee-Yan

2016-01-01

Disease causing Escherichia coli commonly found in meat and poultry include intestinal pathogenic E. coli (iPEC) as well as extraintestinal types such as the Uropathogenic E. coli (UPEC). In this study we compared the resistance of iPEC (O157:H7) to UPEC in chicken meat using High Pressure Processing (HPP) in with (the hurdle concept) and without thymol essential oil as a sensitizer. UPEC was found slightly more resistant than E. coli O157:H7 (iPEC O157:H7) at 450 and 500 MPa. A central composite experimental design was used to evaluate the effect of pressure (300–400 MPa), thymol concentration (100–200 ppm), and pressure-holding time (10–20 min) on the inactivation of iPEC O157:H7 and UPEC in ground chicken. The hurdle approach reduced the high pressure levels and thymol doses imposed on the food matrices and potentially decreased food quality damaged after treatment. The quadratic equations were developed to predict the impact (lethality) on iPEC O157:H7 (R2 = 0.94) and UPEC (R2 = 0.98), as well as dimensionless non-linear models [Pr > F (<0.0001)]. Both linear and non-linear models were validated with data obtained from separated experiment points. All models may predict the inactivation/lethality within the same order of accuracy. However, the dimensionless non-linear models showed potential applications with parameters outside the central composite design ranges. The results provide useful information of both iPEC O157:H7 and UPEC in regard to how they may survive HPP in the presence or absence of thymol. The models may further assist regulatory agencies and food industry to assess the potential risk of iPEC O157:H7 and UPEC in ground chicken. PMID:27379050

Ni-doped TiO2 nanotubes photoanode for enhanced photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Dong, Zhenbiao; Ding, Dongyan; Li, Ting; Ning, Congqin

2018-06-01

Photoelectrochemical (PEC) water splitting hydrogen production provides a promising way for sustainable development. In this work, we prepared Ni-doped TiO2 (Ti-Ni-O) nanotubes through anodizing different Ti-Ni alloys and further annealing them at elevated temperatures, and reported their PEC water splitting performance. It was found that Ni doping could improve light absorption and facilitate separation of photo-excited electron-hole pair. The nanotubes fabricated on Ti-1 wt.% Ni alloy and annealed at 550 °C exhibited better PEC water splitting performance than those on Ti-10 wt.% Ni alloy. The photoconversion efficiency was 0.67%, which was 3.35 times the photoconversion efficiency of undoped TiO2. It demonstrated that it was feasible to fabricate high-performance Ti-Ni-O nanotubes on Ti-Ni alloys and used as photoanode for improving PEC water splitting.

A Comparison of PECS and iPad to Teach Requesting to Pre-schoolers with Autistic Spectrum Disorders.

PubMed

Agius, May M; Vance, Margaret

2016-01-01

Few studies have compared the efficacy of the Picture Exchange Communication System (PECS) and iPads used as speech generating devices (SGDs), and none have targeted preschoolers. This study compares the relative efficacy of PECS and an iPad/SGD with three preschool-aged children with autism spectrum disorder and limited functional speech who lived in Malta. The study utilized an adapted alternating treatment design embedded in a multiple baseline design, with requesting of reinforcers as the dependent variable. Visual analysis of the results indicated that all participants required more prompted trials and sessions for the iPad/SGD condition. All participants learned a three step navigational sequence on the iPad. Participant preference probes were inconclusive and were not linked to speed of acquisition of requesting skills. Results suggest that both PECS and an iPad could be appropriate for teaching requesting skills to beginning communicators.

Using an adapted form of the picture exchange communication system to increase independent requesting in deafblind adults with learning disabilities.

PubMed

Bracken, Maeve; Rohrer, Nicole

2014-02-01

The current study assessed the effectiveness of an adapted form of the Picture Exchange Communication System (PECS) in increasing independent requesting in deafblind adults with learning disabilities. PECS cards were created to accommodate individual needs, including adaptations such as enlarging photographs and using swelled images which consisted of images created on raised line drawing paper. Training included up to Phase III of PECS and procedures ensuring generalizations across individuals and contexts were included. The effects of the intervention were evaluated using a multiple baseline design across participants. Results demonstrated an increase in independent requesting with each of the participants reaching mastery criterion. These results suggest that PECS, in combination with some minor adaptations, may be an effective communicative alternative for individuals who are deafblind and have learning impairments. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

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.

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.

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.

Effects of horticultural therapy on mood and heart rate in patients participating in an inpatient cardiopulmonary rehabilitation program.

PubMed

Wichrowski, Matthew; Whiteson, Jonathan; Haas, François; Mola, Ana; Rey, Mariano J

2005-01-01

To assess the effects of horticultural therapy (HT) on mood state and heart rate (HR) in patients participating in an inpatient cardiac rehabilitation program. Cardiac rehabilitation inpatients (n = 107) participated in the study. The HT group consisted of 59 subjects (34 males, 25 females). The control group, which participated in patient education classes (PECs), consisted of 48 subjects (31 males, 17 females). Both HT sessions and PEC are components of the inpatient rehabilitation program. Each group was evaluated before and after a class in their respective modality. Evaluation consisted of the completion of a Profile of Mood States (POMS) inventory, and an HR obtained by pulse oximetry. Changes in the POMS total mood disturbance (TMD) score and HR between preintervention and postintervention were compared between groups. There was no presession difference in either TMD score (16 +/- 3.6 and 19.0 +/- 3.2, PEC and HT, respectively) or HR (73.5 +/- 2.5 and 79 +/- 1.8, PEC and HT, respectively). Immediately following the intervention, the HT TMD was significantly reduced (post-TMD = 1.6 +/- 3.2, P < .001), while PEC TMD was not significantly changed (TMD = 17.0 +/- 28.5). After intervention, HR fell in HT by 4 +/- 9.6 bpm (P < .001) but was unchanged in PEC. These findings indicate that HT improves mood state, suggesting that it may be a useful tool in reducing stress. Therefore, to the extent that stress contributes to coronary heart disease, these findings support the role of HT as an effective component of cardiac rehabilitation.

Examination of the Source and Extended Virulence Genotypes of Escherichia coli Contaminating Retail Poultry Meat

PubMed Central

Johnson, Timothy J.; Logue, Catherine M.; Wannemuehler, Yvonne; Kariyawasam, Subhashinie; Doetkott, Curt; DebRoy, Chitrita; White, David G.

2009-01-01

Abstract Extraintestinal pathogenic Escherichia coli (ExPEC) are major players in human urinary tract infections, neonatal bacterial meningitis, and sepsis. Recently, it has been suggested that there might be a zoonotic component to these infections. To determine whether the E. coli contaminating retail poultry are possible extraintestinal pathogens, and to ascertain the source of these contaminants, they were assessed for their genetic similarities to E. coli incriminated in colibacillosis (avian pathogenic E. coli [APEC]), E. coli isolated from multiple locations of apparently healthy birds at slaughter, and human ExPEC. It was anticipated that the retail poultry isolates would most closely resemble avian fecal E. coli since only apparently healthy birds are slaughtered, and fecal contamination of carcasses is the presumed source of meat contamination. Surprisingly, this supposition proved incorrect, as the retail poultry isolates exhibited gene profiles more similar to APEC than to fecal isolates. These isolates contained a number of ExPEC-associated genes, including those associated with ColV virulence plasmids, and many belonged to the B2 phylogenetic group, known to be virulent in human hosts. Additionally, E. coli isolated from the crops and gizzards of apparently healthy birds at slaughter also contained a higher proportion of ExPEC-associated genes than did the avian fecal isolates examined. Such similarities suggest that the widely held beliefs about the sources of poultry contamination may need to be reassessed. Also, the presence of ExPEC-like clones on retail poultry meat means that we cannot yet rule out poultry as a source of ExPEC human disease. PMID:19580453

Effect of electro-acupuncture intervention on cognition attention bias in heroin addiction abstinence-a dot-probe-based event-related potential study.

PubMed

Jiang, Ying-Ping; Liu, Hao; Xu, Ping; Wang, Yan; Lu, Guang-Hua

2011-04-01

To study the changes of cognitive attention-related brain function in the heroin addicts before and after electro-acupuncture (EA) intervention for exploring the concerned neuro-mechanism of addictive relapse and the central action role of EA intervention. Adopting event-related potential (ERP) technique, the ERP at 64 electrode spots in 10 heroin addicts (test group) were recorded before and after EA intervention with dot-probe experimental form during implementing cognitive task on positive emotional clue (PEC), negative emotional clues (NEC), and heroin-related clue (HRC). The P200 amplitude components on the selected observation points (Fz, Cz, and Pz) were analyzed and compared with those obtained from 10 healthy subjects as the control. Before EA, the ERP of attention on HRC in the test group was higher than that on PEC and NEC (P<0.05) and significantly higher than that in the control group (P<0.05); after EA, the P200 amplitude of attention on HRC at Cz and Pz was significantly lowered (P<0.05) and that on PEC at Fz was significantly elevated (P<0.05). After EA, the P200 amplitude at Pz was ranked as NEC > PEC > HRC, but in the control group, it showed PEC > HRC at all three observation points and PEC > NEC at Pz. Heroin addicts show attention bias to HRC, which could be significantly reduced by EA intervention, illustrating that EA could effectively inhibit the attention bias to heroin and so might have potential for lowering the relapse rate.

PATHOGEN EQUIVALENCY COMMITTEE (PEC)

EPA Science Inventory

The U.S. Environmental Protection Agency created the PEC in 1985 to make recommendations to EPA and State managers on the equivalency of unproven sewage sludge disinfection technologies/processes to either a Process to Significantly Reduce Pathogens (PSRP) or a Process to Further...

The parietal epithelial cell: a key player in the pathogenesis of focal segmental glomerulosclerosis in Thy-1.1 transgenic mice.

PubMed

Smeets, Bart; Te Loeke, Nathalie A J M; Dijkman, Henry B P M; Steenbergen, Mark L M; Lensen, Joost F M; Begieneman, Mark P V; van Kuppevelt, Toin H; Wetzels, Jack F M; Steenbergen, Eric J

2004-04-01

Focal segmental glomerulosclerosis (FSGS) is a hallmark of progressive renal disease. Podocyte injury and loss have been proposed as the critical events that lead to FSGS. In the present study, the authors have examined the development of FSGS in Thy-1.1 transgenic (tg) mice, with emphasis on the podocyte and parietal epithelial cell (PEC). Thy-1.1 tg mice express the Thy-1.1 antigen on podocytes. Injection of anti-Thy-1.1 mAb induces an acute albuminuria and development of FSGS lesions that resemble human collapsing FSGS. The authors studied FSGS lesions at days 1, 3, 6, 7, 10, 14, and 21, in relation to changes in the expression of specific markers for normal podocytes (WT-1, synaptopodin, ASD33, and the Thy-1.1 antigen), for mouse PEC (CD10), for activated podocytes (desmin), for macrophages (CD68), and for proliferation (Ki-67). The composition of the extracellular matrix (ECM) that forms tuft adhesions or scars was studied using mAb against collagen IV alpha2 and alpha4 chains and antibodies directed against different heparan sulfate species. The first change observed was severe PEC injury at day 1, which increased in time, and resulted in denuded segments of Bowman's capsule at days 6 and 7. Podocytes showed foot process effacement and microvillous transformation. There was no evidence of podocyte loss or denudation of the GBM. Podocytes became hypertrophic at day 3, with decreased expression of ASD33 and synaptopodin and normal expression of WT-1 and Thy-1.1. Podocyte bridges were formed by attachment of hypertrophic podocytes to PEC and podocyte apposition against denuded segments of Bowman's capsule. At day 6, there was a marked proliferation of epithelial cells in Bowman's space. These proliferating cells were negative for desmin and all podocyte markers, but stained for CD10, and thus appeared to be PEC. The staining properties of the early adhesions were identical to that of Bowman's capsule, suggesting that the ECM in the adhesions was produced by PEC. In conclusion, the authors propose the following sequence of events leading to FSGS lesions in the Thy1.1 tg mice: (1) PEC damage and denudation of Bowman's capsule segments; (2) podocyte hypertrophy and bridging; and (3) PEC proliferation with ECM production.

PehN, a Polygalacturonase Homologue with a Low Hydrolase Activity, Is Coregulated with the Other Erwinia chrysanthemi Polygalacturonases

PubMed Central

Hugouvieux-Cotte-Pattat, Nicole; Shevchik, Vladimir E.; Nasser, William

2002-01-01

Erwinia chrysanthemi 3937 secretes an arsenal of pectinolytic enzymes, including at least eight endo-pectate lyases encoded by pel genes, which play a major role in the soft-rot disease caused by this bacterium on various plants. E. chrysanthemi also produces some hydrolases that cleave pectin. Three adjacent hydrolase genes, pehV, pehW, and pehX, encoding exo-poly-α-d-galacturonosidases, have been characterized. These enzymes liberate digalacturonides from the nonreducing end of pectin. We report the identification of a novel gene, named pehN, encoding a protein homologous to the glycosyl hydrolases of family 28, which includes mainly polygalacturonases. PehN has a low hydrolase activity on polygalacturonate and on various pectins. PehN action favors the activity of the secreted endo-pectate lyases, mainly PelB and PelC, and that of the periplasmic exo-pectate lyase PelX. However, removal of the pehN gene does not significantly alter the virulence of E. chrysanthemi. Regulation of pehN transcription was analyzed by using gene fusions. Like other pectinase genes, pehN transcription is dependent on several environmental conditions. It is induced by pectic catabolic products and is affected by growth phase, catabolite repression, osmolarity, anaerobiosis, nitrogen starvation, and the presence of calcium ions. The transcription of pehN is modulated by the repressor KdgR, which controls almost all the steps of pectin catabolism, and by cyclic AMP receptor protein (CRP), the global activator of sugar catabolism. The regulator PecS, which represses the transcription of the pel genes but activates that of pehV, pehW, and pehX, also activates transcription of pehN. The three regulators KdgR, PecS, and CRP act by direct interaction with the pehN promoter region. The sequences involved in the binding of these three regulators and of RNA polymerase have been precisely defined. Analysis of the simultaneous binding of these proteins indicates that CRP and RNA polymerase bind cooperatively and that the binding of KdgR could prevent pehN transcription. In contrast, the activator effect of PecS is not linked to competition with KdgR or to cooperation with CRP or RNA polymerase. This effect probably results from competition between PecS and an unidentified repressor involved in peh regulation. PMID:11976295

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.

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.

The evolution of cyclopropenium ions into functional polyelectrolytes

PubMed Central

Jiang, Yivan; Freyer, Jessica L.; Cotanda, Pepa; Brucks, Spencer D.; Killops, Kato L.; Bandar, Jeffrey S.; Torsitano, Christopher; Balsara, Nitash P.; Lambert, Tristan H.; Campos, Luis M.

2015-01-01

Versatile polyelectrolytes with tunable physical properties have the potential to be transformative in applications such as energy storage, fuel cells and various electronic devices. Among the types of materials available for these applications, nanostructured cationic block copolyelectrolytes offer mechanical integrity and well-defined conducting paths for ionic transport. To date, most cationic polyelectrolytes bear charge formally localized on heteroatoms and lack broad modularity to tune their physical properties. To overcome these challenges, we describe herein the development of a new class of functional polyelectrolytes based on the aromatic cyclopropenium ion. We demonstrate the facile synthesis of a series of polymers and nanoparticles based on monomeric cyclopropenium building blocks incorporating various functional groups that affect physical properties. The materials exhibit high ionic conductivity and thermal stability due to the nature of the cationic moieties, thus rendering this class of new materials as an attractive alternative to develop ion-conducting membranes. PMID:25575214

Lateral Structure Formation in Polyelectrolyte Brushes Induced by Multivalent Ions

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

Brettmann, Blair; Pincus, Philip; Tirrell, Matthew

2017-01-13

We provide a theoretical model for the collapse of polyelectrolyte brushes in the presence of multivalent ions, focusing on the formation of lateral inhomogeneties in the collapsed state. Polyelectrolyte brushes are important in a variety of applications, including stabilizing colloidal particles and lubricating surfaces. Many uses rely on the extension of the densely grafted polymer chains from the surface in the extended brush morphology. In the presence Extended Brush of multivalent ions, brushes are significantly shorter than in monovalent ionic solutions, which greatly affects their properties. We base our theoretical analysis on an analogous collapse of polyelectrolyte brushes in amore » poor solvent, providing an energy balance representation for pinned micelles and cylindrical bundles. The equilibrium brush heights predicted for these structures are of a similar magnitude to those measured experimentally. The formation of lateral structures can open new avenues for stimuli-responsive applications that rely on nanoscale pattern formation on surfaces.« less

Structure of Weakly Charged Polyelectrolyte Brushes: Monomer Density Profiles

NASA Astrophysics Data System (ADS)

Borisov, O. V.; Zhulina, E. B.

1997-03-01

The internal structure (the monomer density profiles) of weakly charged polyelectrolyte brushes of different morphologies has been analyzed on the basis of the self-consistent-field approach. In contrast to previous studies based on the local electroneutrality approximation valid for sufficiently strongly charged or densely grafted (“osmotic") brushes we consider the opposite limit of sparse brushes which are unable to retain the counterions inside the brush. We have shown that an exact analytical solution of the SCF-equations is available in the case of a planar brush. In contrast to Gaussian monomer density profile known for “osmotic" polyelectrolyte brushes we have found that weakly charged brushes are characterized by constant monomer density. At the same time free ends of grafted polyions are distributed throughout the brush. Thus, the structural cross-over between polyelectrolyte “mushrooms" and dense brush regimes is established.

The evolution of cyclopropenium ions into functional polyelectrolytes

DOE PAGES

Jiang, Yivan; Freyer, Jessica L.; Cotanda, Pepa; ...

2015-01-09

We report that versatile polyelectrolytes with tunable physical properties have the potential to be transformative in applications such as energy storage, fuel cells and various electronic devices. Among the types of materials available for these applications, nanostructured cationic block copolyelectrolytes offer mechanical integrity and well-defined conducting paths for ionic transport. To date, most cationic polyelectrolytes bear charge formally localized on heteroatoms and lack broad modularity to tune their physical properties. To overcome these challenges, we describe herein the development of a new class of functional polyelectrolytes based on the aromatic cyclopropenium ion.We demonstrate the facile synthesis of a series ofmore » polymers and nanoparticles based on monomeric cyclopropenium building blocks incorporating various functional groups that affect physical properties. In conclusion, the materials exhibit high ionic conductivity and thermal stability due to the nature of the cationic moieties, thus rendering this class of new materials as an attractive alternative to develop ion-conducting membranes.« less

PHD TUTORIAL: A complete numerical approach to electron hydrogen collisions

NASA Astrophysics Data System (ADS)

Bartlett, Philip L.

2006-11-01

This tutorial presents an extensive computational study of electron-impact scattering and ionization of atomic hydrogen and hydrogenic ions, through the solution of the non-relativistic Schrödinger equation in coordinate space using propagating exterior complex scaling (PECS). It details the complete numerical and computational development of the PECS method, which enables highly computationally-efficient solution of these collision systems. Benchmark results are presented for a complete range of electron-hydrogen collisions, including discrete elastic and inelastic scattering both below and above the ionization threshold energy, very low-energy ionizing collisions through to moderately high-energy ionizing collisions, ground-state and excited-state targets and charged hydrogenic targets with Z <= 4. Total ionization cross sections through to fully differential cross sections, both in-plane and out-of-plane, are given and are found to be in excellent accord with other state-of-the-art methods and measurements, where available. We also review our recent confirmation (Bartlett and Stelbovics 2004 Phys. Rev. Lett. 93 233201) of the Wannier and related threshold laws for e-H collisions.

Assembly of Functional Porous Solids in Complex Hybrid Composites

DTIC Science & Technology

2004-03-19

synthesis … 30 7.1.2 Grafting … 34 7.2 Surface functionalization of 3DOM oxide supports with polyelectrolytes and nanoparticles of another oxide … 34...incorporating hydrothermally prepared rutile/anatase nanoparticles (᝿ nm) within the walls of 3DOM silica, varying the titania content from ca. 0.5-20 wt... nanoparticles showing the bright colors that can be obtained and varied through synthesis parameters. 5.7 Effects of 3DOM particle sizes on optical

Preparation of the polyelectrolyte complex hydrogel of biopolymers via a semi-dissolution acidification sol-gel transition method and its application in solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Zhao, Jian; Chen, Yu; Yao, Ying; Tong, Zong-Rui; Li, Pu-Wang; Yang, Zi-Ming; Jin, Shao-Hua

2018-02-01

Hydrogels have drawn many attentions as the solid-state electrolytes in flexible solid-state supercapacitors (SCs) recently. Among them, the polyelectrolyte complex hydrogel (PECH) electrolytes of natural polymers are more competitive because of their environmentally friendly property and low cost. However, while mixing two biopolymer solutions with opposite charges, the strong electrostatic interactions between the cationic and anionic biopolymers may result in precipitates instead of hydrogels. Here we report a novel method, semi-dissolution acidification sol-gel transition (SD-A-SGT), for the preparation of the PECH of chitosan (CTS) and sodium alginate (SA), with the controllable sol-gel transition and uniform composition and successfully apply it as the hydrogel electrolyte of solid-state supercapacitors (SCs). The CTS-SA PECH exhibits an extremely high ionic conductivity of 0.051 S·cm-1 and reasonable mechanical properties with a tensile strength of 0.29 MPa and elongation at break of 109.5%. The solid-state SC fabricated with the CTS-SA PECH and conventional polyaniline (PANI) nanowire electrodes provided a high specific capacitance of 234.6 F·g-1 at 5 mV·s-1 and exhibited excellent cycling stability with 95.3% capacitance retention after 1000 cycles. Our work may pave a novel avenue to the preparation of biodegradable PECHs of full natural polymers, and promote the development of environmentally friendly electronic devices.

Self-consistent-field calculations of proteinlike incorporations in polyelectrolyte complex micelles

NASA Astrophysics Data System (ADS)

Lindhoud, Saskia; Stuart, Martien A. Cohen; Norde, Willem; Leermakers, Frans A. M.

2009-11-01

Self-consistent field theory is applied to model the structure and stability of polyelectrolyte complex micelles with incorporated protein (molten globule) molecules in the core. The electrostatic interactions that drive the micelle formation are mimicked by nearest-neighbor interactions using Flory-Huggins χ parameters. The strong qualitative comparison with experimental data proves that the Flory-Huggins approach is reasonable. The free energy of insertion of a proteinlike molecule into the micelle is nonmonotonic: there is (i) a small repulsion when the protein is inside the corona; the height of the insertion barrier is determined by the local osmotic pressure and the elastic deformation of the core, (ii) a local minimum occurs when the protein molecule is at the core-corona interface; the depth (a few kBT ’s) is related to the interfacial tension at the core-corona interface and (iii) a steep repulsion (several kBT ) when part of the protein molecule is dragged into the core. Hence, the protein molecules reside preferentially at the core-corona interface and the absorption as well as the release of the protein molecules has annealed rather than quenched characteristics. Upon an increase of the ionic strength it is possible to reach a critical micellization ionic (CMI) strength. With increasing ionic strength the aggregation numbers decrease strongly and only few proteins remain associated with the micelles near the CMI.

A Novel Chitosan-γPGA Polyelectrolyte Complex Hydrogel Promotes Early New Bone Formation in the Alveolar Socket Following Tooth Extraction

PubMed Central

Chang, Hao-Hueng; Wang, Yin-Lin; Chiang, Yu-Chih; Chen, Yen-Liang; Chuang, Yu-Horng; Tsai, Shang-Jye; Heish, Kuo-Huang; Lin, Feng-Huei; Lin, Chun-Pin

2014-01-01

A novel chitosan-γPGA polyelectrolyte complex hydrogel (C-PGA) has been developed and proven to be an effective dressing for wound healing. The purpose of this study was to evaluate if C-PGA could promote new bone formation in the alveolar socket following tooth extraction. An animal model was proposed using radiography and histomorphology simultaneously to analyze the symmetrical sections of Wistar rats. The upper incisors of Wistar rats were extracted and the extraction sockets were randomly treated with gelatin sponge, neat chitosan, C-PGA, or received no treatment. The extraction sockets of selected rats from each group were evaluated at 1, 2, 4, or 6 wk post-extraction. The results of radiography and histopathology indicated that the extraction sockets treated with C-PGA exhibited lamellar bone formation (6.5%) as early as 2 wk after the extraction was performed. Moreover, the degree of new bone formation was significantly higher (P < 0.05) in the extraction sockets treated with C-PGA at 6 wk post-extraction than that in the other study groups. In this study, we demonstrated that the proposed animal model involving symmetrical sections and simultaneous radiography and histomorphology evaluation is feasible. We also conclude that the novel C-PGA has great potential for new bone formation in the alveolar socket following tooth extraction. PMID:24658174

Flexible polyelectrolyte chain in a strong electrolyte solution: Insight into equilibrium properties and force-extension behavior from mesoscale simulation

NASA Astrophysics Data System (ADS)

Malekzadeh Moghani, Mahdy; Khomami, Bamin

2016-01-01

Macromolecules with ionizable groups are ubiquitous in biological and synthetic systems. Due to the complex interaction between chain and electrostatic decorrelation lengths, both equilibrium properties and micro-mechanical response of dilute solutions of polyelectrolytes (PEs) are more complex than their neutral counterparts. In this work, the bead-rod micromechanical description of a chain is used to perform hi-fidelity Brownian dynamics simulation of dilute PE solutions to ascertain the self-similar equilibrium behavior of PE chains with various linear charge densities, scaling of the Kuhn step length (lE) with salt concentration cs and the force-extension behavior of the PE chain. In accord with earlier theoretical predictions, our results indicate that for a chain with n Kuhn segments, lE ˜ cs-0.5 as linear charge density approaches 1/n. Moreover, the constant force ensemble simulation results accurately predict the initial non-linear force-extension region of PE chain recently measured via single chain experiments. Finally, inspired by Cohen's extraction of Warner's force law from the inverse Langevin force law, a novel numerical scheme is developed to extract a new elastic force law for real chains from our discrete set of force-extension data similar to Padè expansion, which accurately depicts the initial non-linear region where the total Kuhn length is less than the thermal screening length.

Flexible polyelectrolyte chain in a strong electrolyte solution: Insight into equilibrium properties and force-extension behavior from mesoscale simulation.

PubMed

Malekzadeh Moghani, Mahdy; Khomami, Bamin

2016-01-14

Macromolecules with ionizable groups are ubiquitous in biological and synthetic systems. Due to the complex interaction between chain and electrostatic decorrelation lengths, both equilibrium properties and micro-mechanical response of dilute solutions of polyelectrolytes (PEs) are more complex than their neutral counterparts. In this work, the bead-rod micromechanical description of a chain is used to perform hi-fidelity Brownian dynamics simulation of dilute PE solutions to ascertain the self-similar equilibrium behavior of PE chains with various linear charge densities, scaling of the Kuhn step length (lE) with salt concentration cs and the force-extension behavior of the PE chain. In accord with earlier theoretical predictions, our results indicate that for a chain with n Kuhn segments, lE ∼ cs (-0.5) as linear charge density approaches 1/n. Moreover, the constant force ensemble simulation results accurately predict the initial non-linear force-extension region of PE chain recently measured via single chain experiments. Finally, inspired by Cohen's extraction of Warner's force law from the inverse Langevin force law, a novel numerical scheme is developed to extract a new elastic force law for real chains from our discrete set of force-extension data similar to Padè expansion, which accurately depicts the initial non-linear region where the total Kuhn length is less than the thermal screening length.

Solution rheology of polyelectrolytes and polyelectrolyte-surfactant systems

NASA Astrophysics Data System (ADS)

Plucktaveesak, Nopparat

The fundamental understanding of polyelectrolytes in aqueous solutions is an important branch of polymer research. In this work, the rheological properties of polyelectrolytes and polyelectrolyte/surfactant systems are studied. Various synthetic poly electrolytes are chosen with varied hydrophobicity. We discuss the effects of adding various surfactants to aqueous solutions of poly(ethylene oxide)-b-poly(propylene oxide)- b-polyethylene oxide)-g-poly(acrylic acid) (PEO-PPO-PAA) in the first chapter. Thermogelation in aqueous solutions of PEO-PPO-PAA is due to micellization caused by aggregation of poly(propylene oxide) (PPO) blocks resulting from temperature-induced dehydration of PPO. When nonionic surfactants with hydrophilic-lipophilic balance (HLB) parameter exceeding 11 or Cn alkylsulfates; n-octyl (C8), n-decyl (C 10) and n-dodecyl (C12) sulfates are added, the gelation threshold temperature (Tgel) of 1.0wt% PEO-PPO-PAA in aqueous solutions increases. In contrast, when nonionic surfactants with HLB below 11 are added, the gelation temperature decreases. On the other hand, alkylsulfates with n = 16 or 18 and poly(ethylene oxide) (PEO) do not affect the Tgel. The results imply that both hydrophobicity and tail length of the added surfactant play important roles in the interaction of PEO-PPO-PAA micelles and the surfactant. In the second chapter, the solution behavior of alternating copolymers of maleic acid and hydrophobic monomer is studied. The alternating structure of monomers with two-carboxylic groups and hydrophobic monomers make these copolymers unique. Under appropriate conditions, these carboxylic groups dissociate leaving charges on the chain. The potentiometric titrations of copolymer solutions with added CaCl2 reveal two distinct dissociation processes corresponding to the dissociation of the two adjacent carboxylic acids. The viscosity data as a function of polymer concentration of poly(isobutylene-alt-sodium maleate), poly(styrene-alt-sodium maleate) and poly(diisobutylene- alt-sodium maleate) show the polyelectrolyte behavior as predicted. However, the viscosity as a function of concentration of sodium maleate based copolymers with 1-alkenes; 1-octene (C8), 1-decene (C10), 1-dodecene (C12) and 1-hexene (C14) exhibit an abnormal scaling power, which might be caused by aggregation of the alkene tails to form micelles. In the last chapter, we report the rheological properties of aqueous solutions of poly(acrylic acid) and oppositely charged surfactant, dodecyl trimethylammonium bromide (C12TAB). The solution viscosity decreases as surfactant is added, partly because the polyelectrolyte wraps around the surface of the spherical surfactant micelles, shortening the effective chain length. The effects of polymer molecular weight, polymer concentration, and polymer charge have been studied with no added salt. The results are compared with the predictions of a simple model based on the scaling theory for the viscosity of dilute and unentangled semidilute polyelectrolyte solutions in good solvent. This model takes into account two effects of added surfactant. The effective chain length of the polyelectrolyte is shortened when a significant fraction of the chain wraps around micelles. Another effect is the change of solution ionic strength resulting from surfactant addition that further lowers the viscosity. The parameters used in this model are independently determined, allowing the model to make a quantitative prediction of solution viscosity with no adjustable parameters. The model is also applied to predict the decrease in viscosity of various polyelectrolyte/oppositely charged surfactant systems reported in literature. The results are in good agreement with experimental data, proving that our model applies to all polyelectrolytes mixed with oppositely charged surfactants that form spherical micelles.