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Sample records for layer-by-layer covalent attachment

  1. Covalent assembly of poly(ethyleneimine) via layer-by-layer deposition for enhancing surface density of protein and bacteria attachment

    NASA Astrophysics Data System (ADS)

    Xia, Bing; Shi, Jisen; Dong, Chen; Zhang, Wenyi; Lu, Ye; Guo, Ping

    2014-02-01

    Covalently assembly of low molecular weight poly(ethyleneimine) was introduced to glass surfaces via glutaraldehyde crosslinking, with focus on its application on protein immobilization or bacteria attachment. Characterizations of Fourier transform infrared spectroscopy and ellipsometry measurement revealed a stepwise growth of poly(ethyleneimine) films by layer-by-layer deposition. After fluorescein isothiocyanate labelling, photoluminescence spectroscopy measurement indicated that the amount of surface accessible amine groups had been gradually enhanced with increasing poly(ethyleneimine) layers deposition. As compared with traditional aminosilanized surfaces, the surface density of amine groups was enhanced by ∼11 times after five layers grafting, which resulted in ∼9-time increasing of surface density of immobilized bovine serum albumin. Finally, these as-prepared PEI multi-films with excellent biocompatibility were adopted as culture substrates to improve Escherichia coli adherence, which showed that their surface density had been increased by ∼251 times.

  2. Covalent layer-by-layer assembly of hyperbranched polymers on alginate microcapsulesto impart stability and permselectivity.

    PubMed

    Gattás-Asfura, Km; Valdes, M; Celik, E; Stabler, Cl

    2014-12-14

    The microencapsulation of cells has shown promise as a therapeutic vehicle for the treatment of a wide variety of diseases. While alginate microcapsules provide an ideal cell encapsulation material, polycations coatings are commonly employed to enhance stability and impart permselectivity. In this study, functionalized hyperbranched alginate and dendrimer polymers were used to generate discreet nanoscale coatings onto alginate microbeads via covalent layer-by-layer assembly. The bioorthogonal Staudinger ligation scheme was used to chemoselectively crosslink azide functionalized hyperbranched alginate (alginate-hN3) to methyl-2-diphenylphosphino-terephthalate (MDT) linked PAMAM dendrimer (PAMAM-MDT). Covalent layer-by-layer deposition of PAMAM-MDT/alginate-hN3 coatings onto alginate microbeads resulted in highly stable coatings, even after the inner alginate gel was liquefied to form microcapsules. The permselectivity of the coated microcapsules could be manipulated via the charge density of the PAMAM, the number of layers deposited, and the length of the functional arms. The cytocompatibility of the resulting PAMAM-MDT/alginate-hN3 coating was evaluated using a beta cell line, with no significant detrimental response observed. The biocompatibility of the coatings in vivo was also found comparable to uncoated alginate beads. The remarkable stability and versatile nature of these coatings provides an appealing option for bioencapsulation and the release of therapeutic agents. PMID:25478165

  3. Covalent layer-by-layer assembly of polyethyleneimine multilayer for antibacterial applications.

    PubMed

    He, Tao; Chan, Vincent

    2010-11-01

    Polyelectrolyte multilayer film (PMF) is conventionally fabricated by the layer-by-layer (LBL) assembly of a pair of oppositely charged polyelectrolytes on a substrate through electrostatic attractions. However, the lack of long-term stability of PMF under physiological conditions limits its application as antimicrobial coating in medical devices. In this study, a stable PMF composed of only polyethyleneimine (PEI) was constructed by covalent LBL deposition. First, the specific buildup of PEI during covalent LBL assembly was validated by UV-Vis absorption spectroscopy and atomic force microscopy. Second, silver (Ag) nanoparticles were incorporated into PEI multilayers through in situ reduction of Ag(+) by the pre-absorption of NaBH(4). It was also shown that the mass of Ag nanoparticle can be controlled by varying multilayer thickness and loading cycles. Bacterial live/dead assay showed that the PEI multilayers effectively killed Staphylococcus aureus and Escherichia coli upon contact formation. The inclusion of Ag nanoparticles in (PEI) film not only enhanced the antimicrobial property against adherent bacteria but also led to the inhibition of the bacteria growth in suspended culture via the long-term release of Ag(+) into the liquid medium. PMID:20648543

  4. Hemoglobin protein hollow shells fabricated through covalent layer-by-layer technique

    SciTech Connect

    Duan Li; He Qiang; Cui Yue; Wang Kewei; Li Junbai . E-mail: jbli@iccas.ac.cn

    2007-03-09

    Hemoglobin (Hb) protein microcapsules held together by cross-linker, glutaraldehyde (GA), were successfully fabricated by covalent layer-by-layer (LbL) technique. The Schiff base reaction occurred on the colloid templates between the aldehyde groups of GA and free amino sites of Hb results in the formation of GA/Hb microcapsules after the removal of the templates. The structure of obtained monodisperse protein microcapsule was characterized by transmission electron microscopy (TEM) and confocal laser scanning microscopy (CLSM). The UV-Vis spectra measurements demonstrate the existence of Hb in the assembled capsules. Cyclic voltammetry (CV) and potential-controlled amperometric measurements (I-t curve) confirm that hemoglobin microcapsules after fabrication remain their heme electroactivity. Moreover, direct electron transfer process from protein to electrode surface was performed to detect the heme electrochemistry without using any mediator or promoter. The experiments of fluorescence recovery after photobleaching (FRAP) by CLSM demonstrate that the hemoglobin protein microcapsules have an improved permeability comparing to the conventional polyelectrolyte microcapsules.

  5. A facile method for the construction of covalently cross-linked layered double hydroxides layer-by-layer films: Enhanced stability and delayed release of guests

    NASA Astrophysics Data System (ADS)

    Li, Yulong; An, Qi; Hu, Yingmo; Luan, Xinglong; Zhang, Qian; Zhang, Tianhang; Zhang, Yihe

    2015-07-01

    Stable composite films that contain layered double hydroxide (LDH) are appealing materials but are also difficult to prepare. We report here a facile strategy for the fabrication of covalently cross-linked layer-by-layer multilayers that incorporate LDH. The films were first prepared using the traditional LbL method based on non-covalent interactions, followed by infiltration of a photoactive small molecule DAS. UV light was then used to cross-link the multilayers. The stability of the cross-linked film was remarkably enhanced. Furthermore, the release profile of incorporated molecules from layered double hydroxide was significantly delayed.

  6. Fabrication of Covalently Crosslinked and Amine-Reactive Microcapsules by Reactive Layer-by-Layer Assembly of Azlactone-Containing Polymer Multilayers on Sacrificial Microparticle Templates

    PubMed Central

    Saurer, Eric M.; Flessner, Ryan M.; Buck, Maren E.; Lynn, David M.

    2011-01-01

    We report on the fabrication of covalently crosslinked and amine-reactive hollow microcapsules using ‘reactive’ layer-by-layer assembly to deposit thin polymer films on sacrificial microparticle templates. Our approach is based on the alternating deposition of layers of a synthetic polyamine and a polymer containing reactive azlactone functionality. Multilayered films composed of branched poly(ethylene imine) (BPEI) and poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) were fabricated layer-by-layer on the surfaces of calcium carbonate and glass microparticle templates. After fabrication, these films contained residual azlactone functionality that was accessible for reaction with amine-containing molecules. Dissolution of the calcium carbonate or glass cores using aqueous ethylenediamine tetraacetic acid (EDTA) or hydrofluoric acid (HF), respectively, led to the formation of hollow polymer microcapsules. These microcapsules were robust enough to encapsulate and retain a model macromolecule (FITC-dextran) and were stable for at least 22 hours in high ionic strength environments, in low and high pH solutions, and in several common organic solvents. Significant differences in the behaviors of capsules fabricated on CaCO3 and glass cores were observed and characterized using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Whereas capsules fabricated on CaCO3 templates collapsed upon drying, capsules fabricated on glass templates remained rigid and spherical. Characterization using EDS suggested that this latter behavior results, at least in part, from the presence of insoluble metal fluoride salts that are trapped or precipitate within the walls of capsules after etching of the glass cores using HF. Our results demonstrate that the assembly of BPEI/PVDMA films on sacrificial templates can be used to fabricate reactive microcapsules of potential use in a wide range of fields, including catalysis, drug and gene delivery, imaging, and

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

    PubMed Central

    Buck, Maren E.

    2010-01-01

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

  8. What is really driving cell-surface interactions? Layer-by-layer assembled films may help to answer questions concerning cell attachment and response to biomaterials.

    PubMed

    Sergeeva, Yulia N; Huang, Tongtong; Felix, Olivier; Jung, Laura; Tropel, Philippe; Viville, Stephane; Decher, Gero

    2016-06-01

    Layer-by-layer (LbL) assembled multicomponent films offer the opportunity to control and to fine-tune cell attachment and behavior on solid surfaces [Layer-by-Layer Films for Biomedical Applications, edited by Picart et al. (Wiley, Weinheim, 2014) and El-Khouri et al., "Multifunctional layer-by-layer architectures for biological applications," in Functional Polymeric Ultrathin Films, edited by Advincula and Knoll (Wiley, Weinheim, 2011), Vol. 1]. At the same time, these films allow for quite detailed physicochemical characterization of static and dynamic surface properties that are typically not available in classic cell culture. In this report, the authors investigate cell adhesion and cytocompatibility of compositionally and morphologically similar thin films composed of oppositely charged synthetic or natural polyelectrolytes in which different physical parameters such as surface charge or water content are varied through chemical composition and deposition conditions. Human adult dermal fibroblasts were chosen as a model because of the need for chemically defined matrix in the field of primary cell amplification. The growth and the stability of the multilayer films in the incubation media were studied dissipation-enhanced quartz crystal micobalance (QCM-D) and ellipsometry. The QCM-D signals observed during the film deposition were analyzed qualitatively to estimate the viscoelastic properties of the films. The authors used contact angle measurements with water to study the contribution of the chemical functionalities to wetting behavior of the films. Most importantly, they also studied the interaction of the films with serum components. Our results underline that cell adhesion is a highly complex process which is not only governed by the functionality of a surface but also by its morphology, its affinity for serum components, and also by changes of surface properties brought about by adsorbing molecules. Of the many LbL-films tested, poly(4-styrenesulfonate

  9. PAH/DAS covalently cross-linked layer-by-layer multilayers: a "nano-net" superstratum immobilizes nanoparticles and remains permeable to small molecules.

    PubMed

    An, Qi; Nie, Kun; Zhang, Yihe; Wang, Yue; Hu, Yingmo; Dutschk, Victoria; Luan, Xinglong

    2015-09-14

    A "nano-net" superstratum strategy is developed to stabilize layer-by-layer (LbL) films that incorporate nanoparticles. The superstratum immobilizes silica, gold, or magnetic nanoparticles and at the same time is permeable to small molecules. Unlike most strategies to stabilize LbL multilayers reported in the literature, our strategy does not directly cross-link the nanoparticles and polymers in the adjacent layer, thus circumventing the tedious processes of (surface) modification of the nanoparticles or polymers. The unique advantage of our strategy is further employed in the preparation of a model functional device, where mesoporous silica nanoparticles are held in the composite multilayers with enhanced stabilities. A model drug, methylene blue, is then loaded in large amounts due to the porous structure of the silica particles, and could be released in a delayed manner up to 55 h. PMID:26235250

  10. Layer-by-layer cell membrane assembly

    NASA Astrophysics Data System (ADS)

    Matosevic, Sandro; Paegel, Brian M.

    2013-11-01

    Eukaryotic subcellular membrane systems, such as the nuclear envelope or endoplasmic reticulum, present a rich array of architecturally and compositionally complex supramolecular targets that are as yet inaccessible. Here we describe layer-by-layer phospholipid membrane assembly on microfluidic droplets, a route to structures with defined compositional asymmetry and lamellarity. Starting with phospholipid-stabilized water-in-oil droplets trapped in a static droplet array, lipid monolayer deposition proceeds as oil/water-phase boundaries pass over the droplets. Unilamellar vesicles assembled layer-by-layer support functional insertion both of purified and of in situ expressed membrane proteins. Synthesis and chemical probing of asymmetric unilamellar and double-bilayer vesicles demonstrate the programmability of both membrane lamellarity and lipid-leaflet composition during assembly. The immobilized vesicle arrays are a pragmatic experimental platform for biophysical studies of membranes and their associated proteins, particularly complexes that assemble and function in multilamellar contexts in vivo.

  11. Organic self-assembled layer-by-layer thin films for second-order nonlinear optics

    NASA Astrophysics Data System (ADS)

    Guzy, Matthew T.

    Layer-by-layer deposition techniques were used to fabricate films with second order nonlinear optical (NLO) properties. These materials are key to the development of electro-optic modulators used in fiber optic communication systems. Performance benefits and lower manufacturing costs are driving the development of organic NLO materials as replacements for inorganic crystalline materials such as lithium niobate. The layer-by-layer deposition technique in which polyelectrolytes are deposited on a surface by electrostatic effects is called the Ionically Self-Assembled Monolayer or ISAM method. The role of the optically inactive polycation's structure on deposition and chromophore orientation was studied by fabricating films with several different polycations. While the specific interactions responsible for chromophore orientation in ISAM films remains unclear, hydrogen bonding and electrostatic effects are ruled out as the sole sources of orientation. The highest values of chi(2) were observed under pH conditions that resulted in flat and thin layers. The relationship between pH and the optical homogeneity of the film was also explored. Deposition of polymers under pH conditions in which the polymer chains were aggregated in solution results in films that are not suitable for use in devices. In this work, a new layer-by-layer deposition technique was developed. Coined hybrid deposition, it relies on covalent bonds and electrostatic interactions for film fabrication. Optically inactive polyamines were used as sources of positive charges and as binding sites with optically active low molecular weight chromophores functionalized with a reactive triazine ring and negative charged sulfonate groups. Polar ordering of the chromophores was obtained when the deposition was done under conditions in which covalent bonding was the preferred attachment mechanism for the chromophore molecules. pH conditions in which electrostatic attachment dominated resulted in poorer orientation

  12. Burning Graphene Layer-by-Layer

    PubMed Central

    Ermakov, Victor A.; Alaferdov, Andrei V.; Vaz, Alfredo R.; Perim, Eric; Autreto, Pedro A. S.; Paupitz, Ricardo; Galvao, Douglas S.; Moshkalev, Stanislav A.

    2015-01-01

    Graphene, in single layer or multi-layer forms, holds great promise for future electronics and high-temperature applications. Resistance to oxidation, an important property for high-temperature applications, has not yet been extensively investigated. Controlled thinning of multi-layer graphene (MLG), e.g., by plasma or laser processing is another challenge, since the existing methods produce non-uniform thinning or introduce undesirable defects in the basal plane. We report here that heating to extremely high temperatures (exceeding 2000 K) and controllable layer-by-layer burning (thinning) can be achieved by low-power laser processing of suspended high-quality MLG in air in “cold-wall” reactor configuration. In contrast, localized laser heating of supported samples results in non-uniform graphene burning at much higher rates. Fully atomistic molecular dynamics simulations were also performed to reveal details of oxidation mechanisms leading to uniform layer-by-layer graphene gasification. The extraordinary resistance of MLG to oxidation paves the way to novel high-temperature applications as continuum light source or scaffolding material. PMID:26100466

  13. Burning Graphene Layer-by-Layer.

    PubMed

    Ermakov, Victor A; Alaferdov, Andrei V; Vaz, Alfredo R; Perim, Eric; Autreto, Pedro A S; Paupitz, Ricardo; Galvao, Douglas S; Moshkalev, Stanislav A

    2015-01-01

    Graphene, in single layer or multi-layer forms, holds great promise for future electronics and high-temperature applications. Resistance to oxidation, an important property for high-temperature applications, has not yet been extensively investigated. Controlled thinning of multi-layer graphene (MLG), e.g., by plasma or laser processing is another challenge, since the existing methods produce non-uniform thinning or introduce undesirable defects in the basal plane. We report here that heating to extremely high temperatures (exceeding 2000 K) and controllable layer-by-layer burning (thinning) can be achieved by low-power laser processing of suspended high-quality MLG in air in "cold-wall" reactor configuration. In contrast, localized laser heating of supported samples results in non-uniform graphene burning at much higher rates. Fully atomistic molecular dynamics simulations were also performed to reveal details of oxidation mechanisms leading to uniform layer-by-layer graphene gasification. The extraordinary resistance of MLG to oxidation paves the way to novel high-temperature applications as continuum light source or scaffolding material. PMID:26100466

  14. Boosting water oxidation layer-by-layer.

    PubMed

    Hidalgo-Acosta, Jonnathan C; Scanlon, Micheál D; Méndez, Manuel A; Amstutz, Véronique; Vrubel, Heron; Opallo, Marcin; Girault, Hubert H

    2016-04-01

    Electrocatalysis of water oxidation was achieved using fluorinated tin oxide (FTO) electrodes modified with layer-by-layer deposited films consisting of bilayers of negatively charged citrate-stabilized IrO2 NPs and positively charged poly(diallyldimethylammonium chloride) (PDDA) polymer. The IrO2 NP surface coverage can be fine-tuned by controlling the number of bilayers. The IrO2 NP films were amorphous, with the NPs therein being well-dispersed and retaining their as-synthesized shape and sizes. UV/vis spectroscopic and spectro-electrochemical studies confirmed that the total surface coverage and electrochemically addressable surface coverage of IrO2 NPs increased linearly with the number of bilayers up to 10 bilayers. The voltammetry of the modified electrode was that of hydrous iridium oxide films (HIROFs) with an observed super-Nernstian pH response of the Ir(III)/Ir(IV) and Ir(IV)-Ir(IV)/Ir(IV)-Ir(V) redox transitions and Nernstian shift of the oxygen evolution onset potential. The overpotential of the oxygen evolution reaction (OER) was essentially pH independent, varying only from 0.22 V to 0.28 V (at a current density of 0.1 mA cm(-2)), moving from acidic to alkaline conditions. Bulk electrolysis experiments revealed that the IrO2/PDDA films were stable and adherent under acidic and neutral conditions but degraded in alkaline solutions. Oxygen was evolved with Faradaic efficiencies approaching 100% under acidic (pH 1) and neutral (pH 7) conditions, and 88% in alkaline solutions (pH 13). This layer-by-layer approach forms the basis of future large-scale OER electrode development using ink-jet printing technology. PMID:26977761

  15. Covalent attachment of lysozyme to cotton/cellulose materials: protein verses solid support activation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Covalent attachment of enzymes to cellulosic materials like cotton is of interest where either release or loss of enzyme activity over time needs to be avoided. The covalent attachment of an enzyme to a cellulosic substrate requires either activation of a protein side chain or an organic functional ...

  16. Cellular Responses Modulated by FGF-2 Adsorbed on Albumin/Heparin Layer-by-Layer Assemblies

    PubMed Central

    Kumorek, Marta; Kubies, Dana; Filová, Elena; Houska, Milan; Kasoju, Naresh; Mázl Chánová, Eliška; Matějka, Roman; Krýslová, Markéta; Bačáková, Lucie; Rypáček, František

    2015-01-01

    In a typical cell culture system, growth factors immobilized on the cell culture surfaces can serve as a reservoir of bio-signaling molecules, without the need to supplement them additionally into the culture medium. In this paper, we report on the fabrication of albumin/heparin (Alb/Hep) assemblies for controlled binding of basic fibroblast growth factor (FGF-2). The surfaces were constructed by layer-by-layer adsorption of polyelectrolytes albumin and heparin and were subsequently stabilized by covalent crosslinking with glutaraldehyde. An analysis of the surface morphology by atomic force microscopy showed that two Alb/Hep bilayers are required to cover the surface of substrate. The formation of the Alb/Hep assemblies was monitored by the surface plasmon resonance (SPR), the infrared multiinternal reflection spectroscopy (FTIR MIRS) and UV/VIS spectroscopy. The adsorption of FGF-2 on the cross-linked Alb/Hep was followed by SPR. The results revealed that FGF-2 binds to the Alb/Hep assembly in a dose and time-dependent manner up to the surface concentration of 120 ng/cm2. The bioactivity of the adsorbed FGF-2 was assessed in experiments in vitro, using calf pulmonary arterial endothelial cells (CPAE). CPAE cells could attach and proliferate on Alb/Hep surfaces. The adsorbed FGF-2 was bioactive and stimulated both the proliferation and the differentiation of CPAE cells. The improvement was more pronounced at a lower FGF-2 surface concentration (30 ng/cm2) than on surfaces with a higher concentration of FGF-2 (120 ng/cm2). PMID:25945799

  17. Protein attachment to silane-functionalized porous silicon: A comparison of electrostatic and covalent attachment.

    PubMed

    Baranowska, Malgorzata; Slota, Agata J; Eravuchira, Pinkie J; Alba, Maria; Formentin, Pilar; Pallarès, Josep; Ferré-Borrull, Josep; Marsal, Lluís F

    2015-08-15

    Porous silicon (pSi) is a prosperous biomaterial, biocompatible, and biodegradable. Obtaining regularly functionalized pSi surfaces is required in many biotechnology applications. Silane-PEG-NHS (triethoxysilane-polyethylene-glycol-N-hydroxysuccinimide) is useful for single-molecule studies due to its ability to attach to only one biomolecule. We investigate the functionalization of pSi with silane-PEG-NHS and compare it with two common grafting agents: APTMS (3-aminopropylotrimethoxysilane) as electrostatic linker, and APTMS modified with glutaraldehyde as covalent spacer. We show the arrangement of two proteins (collagen and bovine serum albumin) as a function of the functionalization and of the pore size. FTIR is used to demonstrate correct functionalization while fluorescence confocal microscopy reveals that silane-PEG-NHS results in a more uniform protein distribution. Reflection interference spectroscopy (RIfS) is used to estimate the attachment of linker and proteins. The results open a way to obtain homogenous chemical modified silicon supports with a great value in biosensing, drug delivery and cell biology. PMID:25942096

  18. Bioorthogonal layer-by-layer encapsulation of pancreatic islets via hyperbranched polymers.

    PubMed

    Gattás-Asfura, Kerim M; Stabler, Cherie L

    2013-10-23

    Encapsulation of viable tissues via layer-by-layer polymer assembly provides a versatile platform for cell surface engineering, with nanoscale control over the capsule properties. Herein, we report the development of a hyperbranched polymer-based, ultrathin capsule architecture expressing bioorthogonal functionality and tailored physiochemical properties. Random carbodiimide-based condensation of 3,5-dicarboxyphenyl glycineamide on alginate yielded a highly branched polysaccharide with multiple, spatially restricted, and readily functionalizable terminal carboxylate moieties. Poly(ethylene glycol) (PEG) was utilized to link azido end groups to the structured alginate. Together with a phosphine-functionalized poly(amidoamine) dendrimer, nanoscale layer-by-layer coatings, covalently stabilized via Staudinger ligation, were assembled onto solid surfaces and pancreatic islets. The effects of electrostatic and/or bioorthogonal covalent interlayer interactions on the resulting coating efficiency and stability, as well as pancreatic islet viability and function, were studied. These hyperbranched polymers provide a flexible platform for the formation of covalently stabilized, ultrathin coatings on viable cells and tissues. In addition, the hyperbranched nature of the polymers presents a highly functionalized surface capable of bioorthogonal conjugation of additional bioactive or labeling motifs. PMID:24063764

  19. Use of Functionalized Carbon Nanotubes for Covalent Attachment of Nanotubes to Silicon

    NASA Technical Reports Server (NTRS)

    Tour, James M.; Dyke, Christopher A.; Maya, Francisco; Stewart, Michael P.; Chen, Bo; Flatt, Austen K.

    2012-01-01

    The purpose of the invention is to covalently attach functionalized carbon nanotubes to silicon. This step allows for the introduction of carbon nanotubes onto all manner of silicon surfaces, and thereby introduction of carbon nano - tubes covalently into silicon-based devices, onto silicon particles, and onto silicon surfaces. Single-walled carbon nanotubes (SWNTs) dispersed as individuals in surfactant were functionalized. The nano - tube was first treated with 4-t-butylbenzenediazonium tetrafluoroborate to give increased solubility to the carbon nanotube; the second group attached to the sidewall of the nanotube has a silyl-protected terminal alkyne that is de-protected in situ. This gives a soluble carbon nanotube that has functional groups appended to the sidewall that can be attached covalently to silicon. This reaction was monitored by UV/vis/NJR to assure direct covalent functionalization.

  20. Layer-by-layer growth of porphyrin supramolecular thin films

    SciTech Connect

    Nishiyama, Fumitaka; Yokoyama, Takashi; Kamikado, Toshiya; Yokoyama, Shiyoshi; Mashiko, Shinro

    2006-06-19

    Multilayer thin film growth of carboxyphenyl-substituted porphyrin on Au(111) was investigated by means of low-temperature scanning tunneling microscopy. The carboxyphenyl-substituted porphyrins are assembled into supramolecular wires on Au(111) by sequential hydrogen bonding between carboxyphenyl groups, and the dense aggregation of the supramolecular wires results in the formation of the first monolayer film. By further molecular deposition, the layer-by-layer growth of the supramolecular wires has been observed, leading to the supramolecular thin film growth.

  1. Atomic layer-by-layer epitaxy of cuprate superconductors

    SciTech Connect

    Bozovic, I.; Eckstein, J.N.; Virshup, G.F.

    1994-03-01

    A technique for atomic layer-by-layer epitaxy of cuprate superconductors and other complex oxides has been developed at Varian. The samples are engineered by stacking molecular layers of different compounds to assemble multilayers and superlattices, by adding or omitting atomic monolayers to create novel compounds, and by doping within specified atomic monolayers. Apart form manufacturing trilayer Josephson junctions with I{sub c}R{sub n}>5 mV, this technique enables one to address fundamental issues such as the dimensionality of HTSC state, existence of long-range proximity effects, occurrence of resonant tunneling etc., as well as to synthesize novel metastable HTSC compounds. 4 refs., 2 figs.

  2. Stabilization of layer-by-layer engineered multilayered hollow microspheres.

    PubMed

    Liu, Peng

    2014-05-01

    Polymer multilayered hollow microspheres prepared by layer-by-layer (LbL) self-assembly attract more and more interest due to their unique application, especially as drug delivery system (DDS). Unfortunately, the multilayered hollow microspheres assembled via weak linkages could fuse and/or aggregate in high ionic strength media or strong acidic or basic media. This severely restricts the practical applications of the multilayered hollow microspheres as DDS in human physiological medium. In the present work, the progress in stabilization of the multilayered hollow microspheres is reviewed, with emphasis on the assembling process and their crosslinking mechanism. PMID:24321861

  3. Layer-by-Layer Assembly Onto Gold Nanoparticles of Various Size

    NASA Astrophysics Data System (ADS)

    Kilroy, Andrew; Kessler, Sarah; Dobbins, Tabbetha

    This research focuses on the potential applications of coated gold nanoparticles in medicine. By coating gold nanoparticles in layers of polyelectrolytes, with a final layer of antibodies which targets chemicals uniquely exhibited by cancer cells, we eventually hope to selectively attach the nanoparticles to the cancer cells. The coated nanoparticles are assembled through layer-by-layer coulombic attraction due to the passive zeta potential of the particle and the charged nature of the polyelectrolytes. This poster will explore the potential usefulness of variously sized nanoparticles with various thickness of polyelectrolyte layers.

  4. Metal-organic coordination-enabled layer-by-layer self-assembly to prepare hybrid microcapsules for efficient enzyme immobilization.

    PubMed

    Wang, Xiaoli; Jiang, Zhongyi; Shi, Jiafu; Liang, Yanpeng; Zhang, Chunhong; Wu, Hong

    2012-07-25

    A novel layer-by-layer self-assembly approach enabled by metal-organic coordination was developed to prepare polymer-inorganic hybrid microcapsules. Alginate was first activated via N-ethyl-N'-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) coupling chemistry, and subsequently reacted with dopamine. Afterward, the dopamine modified alginate (Alg-DA) and titanium(IV) bis(ammonium lactato) dihydroxide (Ti(IV)) were alternatively deposited onto CaCO3 templates. The coordination reaction between the catechol groups of Alg-DA and the Ti(IV) allowed the alternative assembly to form a series of multilayers. After removing the templates, the alginate-titanium hybrid microcapsules were obtained. The high mechanical stability of hybrid microcapsules was demonstrated by osmotic pressure experiment. Furthermore, the hybrid microcapsules displayed superior thermal stability due to Ti(IV) coordination. Catalase (CAT) was used as model enzyme, either encapsulated inside or covalently attached on the surface of the resultant microcapsules. No CAT leakage from the microcapsules was detected after incubation for 48 h. The encapsulated CAT, with a loading capacity of 450-500 mg g(-1) microcapsules, exhibited desirable long-term storage stability, whereas the covalently attached CAT, with a loading capacity of 100-150 mg g(-1) microcapsules, showed desirable operational stability. PMID:22724538

  5. Multilayer thin films employing electrostatic layer-by- layer self-assembly for optical device applications

    NASA Astrophysics Data System (ADS)

    Lee, Soo-Hyoung

    2000-11-01

    molecules were covalently incorporated into poly(acrylic acid) and subsequently assembled with a polycation employing electrostatic layer-by-layer self-assembly. The sensor is based on the fluorescence quenching of indicator molecules by electron transfer from indicator to electron-deficient analytes such as ferric ions, mercury and 2,4-dinitro toluene. Fluorescence intensities decreased with increasing concentration of analytes. Quenching behavior follows Stern-Volmer bimolecular quenching kinetics. Linear increase in absorbance, film thickness and emission intensity was observed as a function of number of bilayers deposited in all these films.

  6. Layer-by-Layer Assembly of Enzymes on Carbon Nanotubes

    SciTech Connect

    Wang, Jun; Liu, Guodong; Lin, Yuehe

    2008-06-01

    The use of Layer-by-layer techniques for immobilizing several types of enzymes, e.g. glucose oxidase (GOx), horse radish oxidases(HRP), and choline oxidase(CHO) on carbon nanotubes and their applications for biosenseing are presented. The enzyme is immobilized on the negatively charged CNT surface by alternatively assembling a cationic polydiallyldimethyl-ammonium chloride (PDDA) layer and a enzyme layer. The sandwich-like layer structure (PDDA/enzyme/PDDA/CNT) formed by electrostatic assembling provides a favorable microenvironment to keep the bioactivity of enzyme and to prevent enzyme molecule leakage. The morphologies and electrocatalytic acitivity of the resulted enzyme film were characterized using TEM and electrochemical techniques, respectively. It was found that these enzyme-based biosensors are very sensitive, selective for detection of biomolecules, e.g. glucose, choline.

  7. Spraying asymmetry into functional membranes layer-by-layer.

    PubMed

    Krogman, Kevin C; Lowery, Joseph L; Zacharia, Nicole S; Rutledge, Gregory C; Hammond, Paula T

    2009-06-01

    As engineers strive to mimic the form and function of naturally occurring materials with synthetic alternatives, the challenges and costs of processing often limit creative innovation. Here we describe a powerful yet economical technique for developing multiple coatings of different morphologies and functions within a single textile membrane, enabling scientists to engineer the properties of a material from the nanoscopic level in commercially viable quantities. By simply varying the flow rate of charged species passing through an electrospun material during spray-assisted layer-by-layer deposition, individual fibres within the matrix can be conformally functionalized for ultrahigh-surface-area catalysis, or bridged to form a networked sublayer with complimentary properties. Exemplified here by the creation of selectively reactive gas purification membranes, the myriad applications of this technology also include self-cleaning fabrics, water purification and protein functionalization of scaffolds for tissue engineering. PMID:19377464

  8. Natural melanin composites by layer-by-layer assembly

    NASA Astrophysics Data System (ADS)

    Eom, Taesik; Shim, Bong Sub

    2015-04-01

    Melanin is an electrically conductive and biocompatible material, because their conjugated backbone structures provide conducting pathways from human skin, eyes, brain, and beyond. So there is a potential of using as materials for the neural interfaces and the implantable devices. Extracted from Sepia officinalis ink, our natural melanin was uniformly dispersed in mostly polar solvents such as water and alcohols. Then, the dispersed melanin was further fabricated to nano-thin layered composites by the layer-by-layer (LBL) assembly technique. Combined with polyvinyl alcohol (PVA), the melanin nanoparticles behave as an LBL counterpart to from finely tuned nanostructured films. The LBL process can adjust the smart performances of the composites by varying the layering conditions and sandwich thickness. We further demonstrated the melanin loading degree of stacked layers, combination nanostructures, electrical properties, and biocompatibility of the resulting composites by UV-vis spectrophotometer, scanning electron microscope (SEM), multimeter, and in-vitro cell test of PC12, respectively.

  9. Spraying asymmetry into functional membranes layer-by-layer

    NASA Astrophysics Data System (ADS)

    Krogman, Kevin C.; Lowery, Joseph L.; Zacharia, Nicole S.; Rutledge, Gregory C.; Hammond, Paula T.

    2009-06-01

    As engineers strive to mimic the form and function of naturally occurring materials with synthetic alternatives, the challenges and costs of processing often limit creative innovation. Here we describe a powerful yet economical technique for developing multiple coatings of different morphologies and functions within a single textile membrane, enabling scientists to engineer the properties of a material from the nanoscopic level in commercially viable quantities. By simply varying the flow rate of charged species passing through an electrospun material during spray-assisted layer-by-layer deposition, individual fibres within the matrix can be conformally functionalized for ultrahigh-surface-area catalysis, or bridged to form a networked sublayer with complimentary properties. Exemplified here by the creation of selectively reactive gas purification membranes, the myriad applications of this technology also include self-cleaning fabrics, water purification and protein functionalization of scaffolds for tissue engineering.

  10. Fluorescent DNA Nanotags Featuring Covalently Attached Intercalating Dyes: Synthesis, Antibody Conjugation and Intracellular Imaging

    PubMed Central

    Stadler, Andrea L.; Santos, Junriz Delos; Stensrud, Elizabeth S.; Dembska, Anna; Silva, Gloria L.; Liu, Shengpeng; Shank, Nathaniel I.; Kunttas-Tatli, Ezgi; Sobers, Courtney J.; Gramlich, Philipp M. E.; Carell, Thomas; Peteanu, Linda A.; McCartney, Brooke M.; Armitage, Bruce A.

    2011-01-01

    We have synthesized fluorescent DNA duplexes featuring multiple thiazole orange (TO) intercalating dyes covalently attached to the DNA via a triazole linkage. The intercalating dyes stabilize the duplex against thermal denaturation and show bright fluorescence in the green. The emission color can be changed to orange or red by addition of energy-accepting Cy3 or Cy5 dyes attached covalently to the DNA duplex. The dye-modified DNA duplexes were then attached to a secondary antibody for intracellular fluorescence imaging of centrosomes in Drosophila embryos. Bright fluorescent foci were observed at the centrosomes in both the donor (TO) and acceptor (Cy5) channels, due to the fact that the energy transfer efficiency is moderate. Monitoring the Cy5 emission channel significantly minimized the background signal due to the large shift in emission wavelength allowed by energy transfer. PMID:21755981

  11. Covalent attachment of catalyst molecules to conductive diamond: CO2 reduction using "smart" electrodes.

    PubMed

    Yao, Shu A; Ruther, Rose E; Zhang, Linghong; Franking, Ryan A; Hamers, Robert J; Berry, John F

    2012-09-26

    We report here covalent attachment of a catalytically active cobalt complex onto boron-doped, p-type conductive diamond. Peripheral acetylene groups were appended on a cobalt porphyrin complex, and azide-alkyne cycloaddition was used for covalent linking to a diamond surface decorated with alkyl azides. The functionalized surface was characterized by X-ray photoelectron spectroscopy and Fourier transform IR spectroscopy, and the catalytic activity was characterized using cyclic voltammetry and FTIR. The catalyst-modified diamond surfaces were used as "smart" electrodes exhibiting good stability and electrocatalytic activity for electrochemical reduction of CO(2) to CO in acetonitrile solution. PMID:22963046

  12. Osteotropic therapy via targeted Layer-by-Layer nanoparticles

    PubMed Central

    Morton, Stephen W.; Shah, Nisarg J.; Quadir, Mohiuddin A.; Deng, Zhou J.; Poon, Zhiyong

    2014-01-01

    Current treatment options for debilitating bone diseases such as osteosarcoma, osteoporosis, and bone metastatic cancer are suboptimal and have low efficacy. New treatment options for these pathologies require targeted therapy that maximizes exposure to the diseased tissue and minimizes off-target side effects. This work investigates an approach for generating functional and targeted drug carriers specifically for treating primary osteosarcoma, a disease in which recurrence is common and the cure rate has remained around 20%. Our approach utilizes the modularity of Layer-by-Layer (LbL) assembly to generate tissue-specific drug carriers for systemic administration. This is accomplished via surface modification of drug-loaded nanoparticles with an aqueous polyelectrolyte, poly(acrylic acid) (PAA), side-chain functionalized with alendronate, a potent clinically-used bisphosphonate. Nanoparticles coated with PAA-Alendronate are observed to bind and internalize rapidly in human osteosarcoma 143B cells. Encapsulation of doxorubicin, a front-line chemotherapeutic, in an LbL-targeted liposome demonstrates potent toxicity in vitro. Active targeting of 143B xenografts in NCR nude mice with the LbL-targeted doxorubicin liposomes promotes enhanced, prolonged tumor accumulation and significantly improved efficacy. This report represents a tunable approach towards the synthesis of drug carriers, in which LbL can enable surface modification of nanoparticles for tissue-specific targeting and treatment. PMID:24124132

  13. Layer-by-layer assemblies for cancer treatment and diagnosis

    PubMed Central

    Liu, Xi Qiu; Picart, Catherine

    2016-01-01

    The layer-by-layer (LbL) technique was introduced in the early 90s by Profs Moehwald, Lvov and Decher. Since then, it has undergone a series of technological developments, making it possible to engineer various theranostic platforms such as films and capsules, with precise control at the nanometer and micrometer scales. This Research News article highlights recent progress in the applications of LbL assemblies in the field of cancer therapy, diagnosis and fundamental biology study. The potentials of LbL-based systems as drug carriers are discussed, especially with regard to the engineering of innovative stimuli-responsive systems, and their advantageous multifunctionality in the development of new therapeutic tools. Then, the diagnostic functions of LbL assemblies are illustrated for detection and capture of rare cancer cells. Finally, LbL mimicking extracellular environments demonstrate the emerging potential for the study of cancer cell behaviors in vitro. We conclude by highlighting the advantages of LbL systems, important challenges that need to be overcome, and future perspectives in clinical practice. PMID:26390356

  14. Biomimetic layer-by-layer templates for calcium phosphate biomineralization.

    PubMed

    Abdelkebir, K; Morin-Grognet, S; Gaudière, F; Coquerel, G; Labat, B; Atmani, H; Ladam, G

    2012-09-01

    Carboxylated, sulfated and/or phosphorylated surfaces are admitted as potential optimal templates for biomimetic deposition of calcium phosphate (CaP) coatings in view of improving implants' osseointegration. Layer-by-layer films were built up consisting of anionic chondroitin sulfate (ChS), a biological carboxylated and sulfated polysaccharide and cationic poly(l-lysine) (PLL). The films were used as soft matrices to immobilize a model phosphoprotein, phosvitin (PhV). The respective roles of ChS, PLL and PhV terminal layers on the heterogeneous nucleation kinetics and the structure of CaP deposits obtained from supersaturated solutions were inspected. Critical supersaturation ratios and induction times preceding heterogeneous nucleation were precisely determined and interpreted within the framework of classical nucleation theory in order to derive the effective interfacial energies of CaP crystals. It was found that the potency of terminal layers toward CaP nucleation increased in the order: PLL

  15. Controlled Layer-by-Layer Etching of MoS₂.

    PubMed

    Lin, TaiZhe; Kang, BaoTao; Jeon, MinHwan; Huffman, Craig; Jeon, JeaHoo; Lee, SungJoo; Han, Wei; Lee, JinYong; Lee, SeHan; Yeom, GeunYoung; Kim, KyongNam

    2015-07-29

    Two-dimensional (2D) metal dichalcogenides like molybdenum disulfide (MoS2) may provide a pathway to high-mobility channel materials that are needed for beyond-complementary metal-oxide-semiconductor (CMOS) devices. Controlling the thickness of these materials at the atomic level will be a key factor in the future development of MoS2 devices. In this study, we propose a layer-by-layer removal of MoS2 using the atomic layer etching (ALET) that is composed of the cyclic processing of chlorine (Cl)-radical adsorption and argon (Ar)(+) ion-beam desorption. MoS2 etching was not observed with only the Cl-radical adsorption or low-energy (<20 eV) Ar(+) ion-beam desorption steps; however, the use of sequential etching that is composed of the Cl-radical adsorption step and a subsequent Ar(+) ion-beam desorption step resulted in the complete etching of one monolayer of MoS2. Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) indicated the removal of one monolayer of MoS2 with each ALET cycle; therefore, the number of MoS2 layers could be precisely controlled by using this cyclical etch method. In addition, no noticeable damage or etch residue was observed on the exposed MoS2. PMID:26091282

  16. Inkjet Deposition of Layer by Layer Assembled Films

    PubMed Central

    Andres, Christine M.; Kotov, Nicholas A.

    2010-01-01

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

  17. Layer-by-layer nanoencapsulation of camptothecin with improved activity

    PubMed Central

    Parekh, Gaurav; Pattekari, Pravin; Joshi, Chaitanya; Shutava, Tatsiana; DeCoster, Mark; Levchenko, Tatyana; Torchilin, Vladimir; Lvov, Yuri

    2014-01-01

    160 nm nanocapsules containing up to 60% of camptothecin in the core and 7–8 polyelectrolyte bilayers in the shell were produced by washless layer-by-layer assembly of heparin and block-copolymer of poly-L-lysine and polyethylene glycol. The outer surface of the nanocapsules was additionally modified with polyethylene glycol of 5 kDa or 20 kDa molecular weight to attain protein resistant properties, colloidal stability in serum and prolonged release of the drug from the capsules. An advantage of the LbL coated capsules is the preservation of camptothecin lactone form with the shell assembly starting at acidic pH and improved chemical stability of encapsulated drug at neutral and basic pH, especially in the presence of albumin that makes such formulation more active than free camptothecin. LbL nanocapsules preserve the camptothecin lactone form at pH 7.4 resulting in triple activity of the drug toward CRL2303 glioblastoma cell. PMID:24508806

  18. Persistence Length Control of the Polyelectrolyte Layer-by-Layer Self-Assembly on Carbon Nanotubes

    SciTech Connect

    Huang, S J; Artyukhin, A B; Wang, Y; Ju, J; Stroeve, P; Noy, A

    2005-04-30

    One-dimensional inorganic materials such as carbon nanotubes1 and semiconductor nanowires have been central to important advances in materials science in the last decade. Unique mechanical and electronic properties of these molecular-scale wires enabled a variety of applications ranging from novel composite materials, to electronic circuits, to new sensors. Often, these applications require non-covalent modification of carbon nanotubes with organic compounds, DNA and biomolecules, and polymers to change nanotube properties or to add new functionality. We recently demonstrated a versatile and flexible strategy for non-covalent modification of carbon nanotubes using layer-by-layer self-assembly of polyelectrolytes. Researchers used this technique extensively for modification of flat surfaces, micro-, and nano-particles; however, little is known about the mechanism and the factors influencing layer-by-layer self-assembly in one-dimensional nanostructures. The exact conformation of polyelectrolyte chains deposited on single-walled carbon nanotubes (SWNT) is still unknown. There are two possible configurations: flexible polymers wrapping around the nanotube and stretched, rigid chains stacked parallel to the nanotube axis. Several factors, such as polymer rigidity, surface curvature, and strength of polymer-surface interactions, can determine the nature of assembly. Persistence length of the polymer chain should be one of the critical parameters, since it determines the chain's ability to wrap around the nanotube. Indeed, computer simulations for spherical substrates show that polymer rigidity and substrate surface curvature can influence the deposition process. Computational models also show that the persistence length of the polymer must fall below the threshold values determined by target surface curvature in order to initiate polyelectrolyte deposition process. Although these models described the effects of salt concentration and target surface curvature, they

  19. Electron beam controlled covalent attachment of small organic molecules to graphene

    NASA Astrophysics Data System (ADS)

    Markevich, Alexander; Kurasch, Simon; Lehtinen, Ossi; Reimer, Oliver; Feng, Xinliang; Müllen, Klaus; Turchanin, Andrey; Khlobystov, Andrei N.; Kaiser, Ute; Besley, Elena

    2016-01-01

    The electron beam induced functionalization of graphene through the formation of covalent bonds between free radicals of polyaromatic molecules and C&z.dbd;C bonds of pristine graphene surface has been explored using first principles calculations and high-resolution transmission electron microscopy. We show that the energetically strongest attachment of the radicals occurs along the armchair direction in graphene to carbon atoms residing in different graphene sub-lattices. The radicals tend to assume vertical position on graphene substrate irrespective of direction of the bonding and the initial configuration. The ``standing up'' molecules, covalently anchored to graphene, exhibit two types of oscillatory motion - bending and twisting - caused by the presence of acoustic phonons in graphene and dispersion attraction to the substrate. The theoretically derived mechanisms are confirmed by near atomic resolution imaging of individual perchlorocoronene (C24Cl12) molecules on graphene. Our results facilitate the understanding of controlled functionalization of graphene employing electron irradiation as well as mechanisms of attachment of impurities via the processing of graphene nanoelectronic devices by electron beam lithography.The electron beam induced functionalization of graphene through the formation of covalent bonds between free radicals of polyaromatic molecules and C&z.dbd;C bonds of pristine graphene surface has been explored using first principles calculations and high-resolution transmission electron microscopy. We show that the energetically strongest attachment of the radicals occurs along the armchair direction in graphene to carbon atoms residing in different graphene sub-lattices. The radicals tend to assume vertical position on graphene substrate irrespective of direction of the bonding and the initial configuration. The ``standing up'' molecules, covalently anchored to graphene, exhibit two types of oscillatory motion - bending and twisting - caused

  20. Note: Automatic layer-by-layer spraying system for functional thin film coatings

    NASA Astrophysics Data System (ADS)

    Seo, Seongmin; Lee, Sangmin; Park, Yong Tae

    2016-03-01

    In this study, we have constructed an automatic spray machine for producing polyelectrolyte multilayer films containing various functional materials on wide substrates via the layer-by-layer (LbL) assembly technique. The proposed machine exhibits advantages in terms of automation, process speed, and versatility. Furthermore, it has several features that allow a fully automated spraying operation, such as various two-dimensional spraying paths, control of the flow rate and operating speed, air-assist fan-shaped twin-fluid nozzles, and an optical display. The robot uniformly sprays aqueous mixtures containing complementary (e.g., oppositely charged, capable of hydrogen bonding, or capable of covalent bonding) species onto a large-area substrate. Between each deposition of opposite species, samples are spray-rinsed with deionized water and blow-dried with air. The spraying, rinsing, and drying areas and times are adjustable by a computer program. Twenty-bilayer flame-retardant thin films were prepared in order to compare the performance of the spray-assisted LbL assembly with a sample produced by conventional dipping. The spray-coated film exhibited a reduction of afterglow time in vertical flame tests, indicating that the spray-LbL technique is a simple method to produce functional thin film coatings.

  1. Interactions between Chitosan and Alginate Dialdehyde Biopolymers and Their Layer-by-Layer Assemblies.

    PubMed

    Aston, Robyn; Wimalaratne, Medini; Brock, Aidan; Lawrie, Gwendolyn; Grøndahl, Lisbeth

    2015-06-01

    Biopolymers are researched extensively for their applications in biomaterials science and drug delivery including structures and complexes of more than one polymer. Chemical characterization of complexes formed between chitosan (CHI) and alginate dialdehyde (ADA) biopolymers established that while electrostatic interactions dominate (as determined from X-ray photoelectron spectroscopy (XPS)) covalent cross-linking between these biopolymers also contribute to their stability (evidenced from immersion in salt solution). It was furthermore found that imine bond formation could not be directly detected by any of the techniques XPS, FTIR, (1)H NMR, or fluorescence. The layer-by-layer assemblies of the biopolymers formed on silica colloids, glass slides, and alginate hydrogel beads were evaluated using XPS, as well as zeta potential measurements for the silica colloids and changes to hydration properties for the hydrogels. It was found that the degree of oxidation of ADA affected the LbL assemblies in terms of a greater degree of CHI penetration observed when using the more conformationally flexible biopolymer ADA (higher degree of oxidation). PMID:25970641

  2. Controlling interlayer diffusion to achieve sustained, multiagent delivery from layer-by-layer thin films

    PubMed Central

    Wood, Kris C.; Chuang, Helen F.; Batten, Robert D.; Lynn, David M.; Hammond, Paula T.

    2006-01-01

    We present the fabrication of conformal, hydrolytically degradable thin films capable of administering sustained, multiagent release profiles. Films are constructed one molecular layer at a time by using the layer-by-layer, directed-deposition technique; the subsequent hydrolytic surface erosion of these systems results in the release of incorporated materials in a sequence that reflects their relative positions in the film. The position of each species is determined by its ability to diffuse throughout the film architecture, and, as such, the major focus of this work is to define strategies that physically block interlayer diffusion during assembly to create multicomponent, stratified films. By using a series of radiolabeled polyelectrolytes as experimental probes, we show that covalently crosslinked barriers can effectively block interlayer diffusion, leading to compartmentalized structures, although even very large numbers of ionically crosslinked (degradable or nondegradable) barrier layers cannot block interlayer diffusion. By using these principles, we designed degradable films capable of extended release as well as both parallel and serial multiagent release. The ability to fabricate multicomponent thin films with nanoscale resolution may lead to a host of new materials and applications. PMID:16801543

  3. Note: Automatic layer-by-layer spraying system for functional thin film coatings.

    PubMed

    Seo, Seongmin; Lee, Sangmin; Park, Yong Tae

    2016-03-01

    In this study, we have constructed an automatic spray machine for producing polyelectrolyte multilayer films containing various functional materials on wide substrates via the layer-by-layer (LbL) assembly technique. The proposed machine exhibits advantages in terms of automation, process speed, and versatility. Furthermore, it has several features that allow a fully automated spraying operation, such as various two-dimensional spraying paths, control of the flow rate and operating speed, air-assist fan-shaped twin-fluid nozzles, and an optical display. The robot uniformly sprays aqueous mixtures containing complementary (e.g., oppositely charged, capable of hydrogen bonding, or capable of covalent bonding) species onto a large-area substrate. Between each deposition of opposite species, samples are spray-rinsed with deionized water and blow-dried with air. The spraying, rinsing, and drying areas and times are adjustable by a computer program. Twenty-bilayer flame-retardant thin films were prepared in order to compare the performance of the spray-assisted LbL assembly with a sample produced by conventional dipping. The spray-coated film exhibited a reduction of afterglow time in vertical flame tests, indicating that the spray-LbL technique is a simple method to produce functional thin film coatings. PMID:27036843

  4. DNA biosensors based on layer-by-layer self-assembled multilayer films of carbon nanotubes and gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Xiao, Yiyun; Dai, Zhao; Zhang, Jimei; Pang, Jiechun; Xu, Shichao; Zheng, Guo

    2009-07-01

    A novel DNA biosensor based on layer-by-layer self-assembled multi-walled carbon nanotubes (MWNTs) and gold nano-particles (GNPs) was presented in this paper, in which the probe HS-ssDNA oligonucleotides, MWNTs and GNPs were all covalently immobilized by chemical Au-Sulphide bonding. Firstly, the super short MWNTs were prepared and modified with thio groups which could be self-assembled onto the surface of Au elcetrode by Au-sulphide bonding, then the GNPs were chemically adhered to the surfaces of MWNTs by forming Au-sulphide bonding again, at last the selfassamble of probe DNA oligonucleotides were also covalently immobilized via Au-sulphide bonding between thio groups at the ends of the DNA oligonucleotides and GNPs. Hybridization between the probe HS-ssDNA oligonucleotides and target DNA oligonucleotides was confirmed by the changes in the voltammetric peak of an anionic intercalator, anthraquinone-2,6-disulfonic acid (AQDS) as a hybridization indicator. The cyclic voltammetric and differential pulse voltammetry responses demonstrated that the DNA biosensors based on Layer-by-layer self-assembled multilayer films of MWNTs and NGPs offer a higher hybridization efficiency and selectivity compared to those based on only random MWNTs or GNPs.

  5. Electron beam controlled covalent attachment of small organic molecules to graphene.

    PubMed

    Markevich, Alexander; Kurasch, Simon; Lehtinen, Ossi; Reimer, Oliver; Feng, Xinliang; Müllen, Klaus; Turchanin, Andrey; Khlobystov, Andrei N; Kaiser, Ute; Besley, Elena

    2016-02-01

    The electron beam induced functionalization of graphene through the formation of covalent bonds between free radicals of polyaromatic molecules and C=C bonds of pristine graphene surface has been explored using first principles calculations and high-resolution transmission electron microscopy. We show that the energetically strongest attachment of the radicals occurs along the armchair direction in graphene to carbon atoms residing in different graphene sub-lattices. The radicals tend to assume vertical position on graphene substrate irrespective of direction of the bonding and the initial configuration. The "standing up" molecules, covalently anchored to graphene, exhibit two types of oscillatory motion--bending and twisting--caused by the presence of acoustic phonons in graphene and dispersion attraction to the substrate. The theoretically derived mechanisms are confirmed by near atomic resolution imaging of individual perchlorocoronene (C24Cl12) molecules on graphene. Our results facilitate the understanding of controlled functionalization of graphene employing electron irradiation as well as mechanisms of attachment of impurities via the processing of graphene nanoelectronic devices by electron beam lithography. PMID:26757842

  6. Covalent attachment of FeFe hydrogenases to carbon electrodes for direct electron transfer.

    PubMed

    Baffert, Carole; Sybirna, Kateryna; Ezanno, Pierre; Lautier, Thomas; Hajj, Viviane; Meynial-Salles, Isabelle; Soucaille, Philippe; Bottin, Hervé; Léger, Christophe

    2012-09-18

    Direct electron transfer between enzymes and electrodes is now commonly achieved, but obtaining protein films that are very stable may be challenging. This is particularly crucial in the case of hydrogenases, the enzymes that catalyze the biological conversion between dihydrogen and protons, because the instability of the hydrogenase films may prevent the use of these enzymes as electrocatalysts of H(2) oxidation and production in biofuel cells and photoelectrochemical cells. Here we show that two different FeFe hydrogenases (from Chamydomonas reinhardtii and Clostridium acetobutylicum) can be covalently attached to functionalized pyrolytic graphite electrodes using peptidic coupling. In both cases, a surface patch of lysine residues makes it possible to favor an orientation that is efficient for fast, direct electron transfer. High hydrogen-oxidation current densities are maintained for up to one week, the only limitation being the intrinsic stability of the enzyme. We also show that covalent attachment has no effect on the catalytic properties of the enzyme, which means that this strategy can also used be for electrochemical studies of the catalytic mechanism. PMID:22891965

  7. Layer-by-Layer Proteomic Analysis of Mytilus galloprovincialis Shell

    PubMed Central

    Wang, Xin-xing; Bao, Lin-fei; Fan, Mei-hua; Li, Xiao-min; Wu, Chang-wen; Xia, Shu-wei

    2015-01-01

    Bivalve shell is a biomineralized tissue with various layers/microstructures and excellent mechanical properties. Shell matrix proteins (SMPs) pervade and envelop the mineral crystals and play essential roles in biomineralization. Despite that Mytilus is an economically important bivalve, only few proteomic studies have been performed for the shell, and current knowledge of the SMP set responsible for different shell layers of Mytilus remains largely patchy. In this study, we observed that Mytilus galloprovincialis shell contained three layers, including nacre, fibrous prism, and myostracum that is involved in shell-muscle attachment. A parallel proteomic analysis was performed for these three layers. By combining LC-MS/MS analysis with Mytilus EST database interrogations, a whole set of 113 proteins was identified, and the distribution of these proteins in different shell layers followed a mosaic pattern. For each layer, about a half of identified proteins are unique and the others are shared by two or all of three layers. This is the first description of the protein set exclusive to nacre, myostracum, and fibrous prism in Mytilus shell. Moreover, most of identified proteins in the present study are novel SMPs, which greatly extended biomineralization-related protein data of Mytilus. These results are useful, on one hand, for understanding the roles of SMPs in the deposition of different shell layers. On the other hand, the identified protein set of myostracum provides candidates for further exploring the mechanism of adductor muscle-shell attachment. PMID:26218932

  8. Synthesis of covalently attached hexadecaanilines on carbon nanotubes: toward electronic nanocarbon preparation

    NASA Astrophysics Data System (ADS)

    Chiang, Long Y.; Anandakathir, Robinson; Hauck, Tanya S.; Lee, Lawrence; Canteenwala, Taizoon; Padmawar, Prashant A.; Pritzker, Kenneth; Bruno, Ferdinando F.; Samuelson, Lynne A.

    2010-04-01

    We describe the direct covalent-grafting synthesis of well-defined aniline oligomers, such as tetraaniline (A4) and hexadecaaniline (A16, major)/eicosaaniline (A20, minor), on the sidewalls of carbon nanotubes (CNTs), via dediazonization reaction, for achieving highly soluble nanomaterials suitable for printing purposes, with long-term physical stability. Chemically grafting a layer of electroactive hexadecaanilines on CNTs resembles semiconductive encapsulation of functionalized CNTs. The resulting covalent nanoconjugates SWNT-(A4)x, MWNT-(A4)x, SWNT-(A16/20)x, and MWNT-(A16/20)x were characterized by various spectroscopic and microscopic mapping methods. The combination of transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) analyses provided direct evidence for A16/20 attachment to the CNTs, giving confirmation of the presence of heteroatoms surrounding the CNTs that was absent in the parent CNTs. Subsequent atom mapping in the vicinity of the tube structure allowed us to illustrate the 3D distribution of heteroatoms along the CNT surface.We describe the direct covalent-grafting synthesis of well-defined aniline oligomers, such as tetraaniline (A4) and hexadecaaniline (A16, major)/eicosaaniline (A20, minor), on the sidewalls of carbon nanotubes (CNTs), via dediazonization reaction, for achieving highly soluble nanomaterials suitable for printing purposes, with long-term physical stability. Chemically grafting a layer of electroactive hexadecaanilines on CNTs resembles semiconductive encapsulation of functionalized CNTs. The resulting covalent nanoconjugates SWNT-(A4)x, MWNT-(A4)x, SWNT-(A16/20)x, and MWNT-(A16/20)x were characterized by various spectroscopic and microscopic mapping methods. The combination of transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) analyses provided direct evidence for A16/20 attachment to the CNTs, giving confirmation of the presence of heteroatoms surrounding the CNTs

  9. Azidobupramine, an Antidepressant-Derived Bifunctional Neurotransmitter Transporter Ligand Allowing Covalent Labeling and Attachment of Fluorophores

    PubMed Central

    Werner, Anna M.; Cuboni, Serena; Rudolf, Georg C.; Höfner, Georg; Wanner, Klaus T.; Sieber, Stephan A.; Schmidt, Ulrike; Holsboer, Florian; Rein, Theo; Hausch, Felix

    2016-01-01

    The aim of this study was to design, synthesize and validate a multifunctional antidepressant probe that is modified at two distinct positions. The purpose of these modifications was to allow covalent linkage of the probe to interaction partners, and decoration of probe-target complexes with fluorescent reporter molecules. The strategy for the design of such a probe (i.e., azidobupramine) was guided by the need for the introduction of additional functional groups, conveying the required properties while keeping the additional moieties as small as possible. This should minimize the risk of changing antidepressant-like properties of the new probe azidobupramine. To control for this, we evaluated the binding parameters of azidobupramine to known target sites such as the transporters for serotonin (SERT), norepinephrine (NET), and dopamine (DAT). The binding affinities of azidobupramine to SERT, NET, and DAT were in the range of structurally related and clinically active antidepressants. Furthermore, we successfully visualized azidobupramine-SERT complexes not only in SERT-enriched protein material but also in living cells stably overexpressing SERT. To our knowledge, azidobupramine is the first structural analogue of a tricyclic antidepressant that can be covalently linked to target structures and further attached to reporter molecules while preserving antidepressant-like properties and avoiding radioactive isotopes. PMID:26863431

  10. Azidobupramine, an Antidepressant-Derived Bifunctional Neurotransmitter Transporter Ligand Allowing Covalent Labeling and Attachment of Fluorophores.

    PubMed

    Kirmeier, Thomas; Gopalakrishnan, Ranganath; Gormanns, Vanessa; Werner, Anna M; Cuboni, Serena; Rudolf, Georg C; Höfner, Georg; Wanner, Klaus T; Sieber, Stephan A; Schmidt, Ulrike; Holsboer, Florian; Rein, Theo; Hausch, Felix

    2016-01-01

    The aim of this study was to design, synthesize and validate a multifunctional antidepressant probe that is modified at two distinct positions. The purpose of these modifications was to allow covalent linkage of the probe to interaction partners, and decoration of probe-target complexes with fluorescent reporter molecules. The strategy for the design of such a probe (i.e., azidobupramine) was guided by the need for the introduction of additional functional groups, conveying the required properties while keeping the additional moieties as small as possible. This should minimize the risk of changing antidepressant-like properties of the new probe azidobupramine. To control for this, we evaluated the binding parameters of azidobupramine to known target sites such as the transporters for serotonin (SERT), norepinephrine (NET), and dopamine (DAT). The binding affinities of azidobupramine to SERT, NET, and DAT were in the range of structurally related and clinically active antidepressants. Furthermore, we successfully visualized azidobupramine-SERT complexes not only in SERT-enriched protein material but also in living cells stably overexpressing SERT. To our knowledge, azidobupramine is the first structural analogue of a tricyclic antidepressant that can be covalently linked to target structures and further attached to reporter molecules while preserving antidepressant-like properties and avoiding radioactive isotopes. PMID:26863431

  11. Synthesis of covalently attached hexadecaanilines on carbon nanotubes: toward electronic nanocarbon preparation.

    PubMed

    Chiang, Long Y; Anandakathir, Robinson; Hauck, Tanya S; Lee, Lawrence; Canteenwala, Taizoon; Padmawar, Prashant A; Pritzker, Kenneth; Bruno, Ferdinando F; Samuelson, Lynne A

    2010-04-01

    We describe the direct covalent-grafting synthesis of well-defined aniline oligomers, such as tetraaniline (A(4)) and hexadecaaniline (A(16), major)/eicosaaniline (A(20), minor), on the sidewalls of carbon nanotubes (CNTs), via dediazonization reaction, for achieving highly soluble nanomaterials suitable for printing purposes, with long-term physical stability. Chemically grafting a layer of electroactive hexadecaanilines on CNTs resembles semiconductive encapsulation of functionalized CNTs. The resulting covalent nanoconjugates SWNT-(A(4))(x), MWNT-(A(4))(x), SWNT-(A(16/20))(x), and MWNT-(A(16/20))(x) were characterized by various spectroscopic and microscopic mapping methods. The combination of transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) analyses provided direct evidence for A(16/20) attachment to the CNTs, giving confirmation of the presence of heteroatoms surrounding the CNTs that was absent in the parent CNTs. Subsequent atom mapping in the vicinity of the tube structure allowed us to illustrate the 3D distribution of heteroatoms along the CNT surface. PMID:20644756

  12. Stable, Covalent Attachment of Laminin to Microposts Improves the Contractility of Mouse Neonatal Cardiomyocytes

    PubMed Central

    2015-01-01

    The mechanical output of contracting cardiomyocytes, the muscle cells of the heart, relates to healthy and disease states of the heart. Culturing cardiomyocytes on arrays of elastomeric microposts can enable inexpensive and high-throughput studies of heart disease at the single-cell level. However, cardiomyocytes weakly adhere to these microposts, which limits the possibility of using biomechanical assays of single cardiomyocytes to study heart disease. We hypothesized that a stable covalent attachment of laminin to the surface of microposts improves cardiomyocyte contractility. We cultured cells on polydimethylsiloxane microposts with laminin covalently bonded with the organosilanes 3-glycidoxypropyltrimethoxysilane and 3-aminopropyltriethoxysilane with glutaraldehyde. We measured displacement of microposts induced by the contractility of mouse neonatal cardiomyocytes, which attach better than mature cardiomyocytes to substrates. We observed time-dependent changes in contractile parameters such as micropost deformation, contractility rates, contraction and relaxation speeds, and the times of contractions. These parameters were affected by the density of laminin on microposts and by the stability of laminin binding to micropost surfaces. Organosilane-mediated binding resulted in higher laminin surface density and laminin binding stability. 3-glycidoxypropyltrimethoxysilane provided the highest laminin density but did not provide stable protein binding with time. Higher surface protein binding stability and strength were observed with 3-aminopropyltriethoxysilane with glutaraldehyde. In cultured cardiomyocytes, contractility rate, contraction speeds, and contraction time increased with higher laminin stability. Given these variations in contractile function, we conclude that binding of laminin to microposts via 3-aminopropyltriethoxysilane with glutaraldehyde improves contractility observed by an increase in beating rate and contraction speed as it occurs during the

  13. Covalent attachment of functionalized lipid bilayers to planar waveguides for measuring protein binding to biomimetic membranes.

    PubMed Central

    Heyse, S.; Vogel, H.; Sänger, M.; Sigrist, H.

    1995-01-01

    A new method is presented for measuring sensitively the interactions between ligands and their membrane-bound receptors in situ using integrated optics, thus avoiding the need for additional labels. Phospholipid bilayers were attached covalently to waveguides by a novel protocol, which can in principle be used with any glass-like surface. In a first step, phospholipids carrying head-group thiols were covalently immobilized onto SiO2-TiO2 waveguide surfaces. This was accomplished by acylation of aminated waveguides with the heterobifunctional crosslinker N-succinimidyl-3-maleimidopropionate, followed by the formation of thioethers between the surface-grafted maleimides and the synthetic thiolipids. The surface-attached thiolipids served as hydrophobic templates and anchors for the deposition of a complete lipid bilayer either by fusion of lipid vesicles or by lipid self-assembly from mixed lipid/detergent micelles. The step-by-step lipid bilayer formation on the waveguide surface was monitored in situ by an integrated optics technique, allowing the simultaneous determination of optical thickness and one of the two refractive indices of the adsorbed organic layers. Surface coverages of 50-60% were calculated for thiolipid layers. Subsequent deposition of POPC resulted in an overall lipid layer thickness of 45-50 A, which corresponds to the thickness of a fluid bilayer membrane. Specific recognition reactions occurring at cell membrane surfaces were modeled by the incorporation of lipid-anchored receptor molecules into the supported bilayer membranes. (1) The outer POPC layer was doped with biotinylated phosphatidylethanolamine. Subsequent specific binding of streptavidin was optically monitored. (2) A lipopeptide was incorporated in the outer POPC monolayer. Membrane binding of monoclonal antibodies, which were directed against the peptide moiety of the lipopeptide, was optically detected. The specific antibody binding correlated well with the lipopepitde

  14. Nanoscale coatings on wood: polyelectrolyte adsorption and layer-by-layer assembled film formation.

    PubMed

    Renneckar, Scott; Zhou, Yu

    2009-03-01

    Surface chemistry of wood is based on the exposed surface that is the combination of the intact and cut cellular wall material. It is inherently complex and changes with processing history. Modification of wood surfaces through noncovalent attachment of amine containing water soluble polyelectrolytes provides a path to create functional surfaces in a controlled manner. Adsorption of polyethylenimine (PEI) and polydiallydimethylammonium chloride (PDDA) to wood was quantified as a function of solution conditions (pH and ionic strength). Polycation adsorption was maximized under basic pH without the addition of electrolyte. Added salt either had marginal influence or decreased adsorption of polycation, indicating interactions are strongly influenced by Coulombic forces. PEI adsorption could be modeled by both a Langmuir and Freundlich equations, although the wood surface is known to be heterogeneous. After adsorption of polycations, layer-by-layer assembled films were created on the wood surface. Layered films masked ultrastructural features of the cell wall, while leaving the microscale features of wood (cut lumen walls and openings) evident. These findings revealed for the first time that nanoscale films on wood can be deposited without changing the microscopic and macroscopic texture. Functionalized wood surfaces created by nanoscale films may have a future role in adhesives systems for wood composites, wood protection, and creating new functional features on wood. PMID:20355976

  15. Spray Layer-by-Layer Assembled Clay Composite Thin Films as Selective Layers in Reverse Osmosis Membranes.

    PubMed

    Kovacs, Jason R; Liu, Chaoyang; Hammond, Paula T

    2015-06-24

    Spray layer-by-layer assembled thin films containing laponite (LAP) clay exhibit effective salt barrier and water permeability properties when applied as selective layers in reverse osmosis (RO) membranes. Negatively charged LAP platelets were layered with poly(diallyldimethylammonium) (PDAC), poly(allylamine) (PAH), and poly(acrylic acid) (PAA) in bilayer and tetralayer film architectures to generate uniform films on the order of 100 nm thick that bridge a porous poly(ether sulfone) support to form novel RO membranes. Nanostructures were formed of clay layers intercalated in a polymeric matrix that introduced size-exclusion transport mechanisms into the selective layer. Thermal cross-linking of the polymeric matrix was used to increase the mechanical stability of the films and improve salt rejection by constraining swelling during operation. Maximum salt rejection of 89% was observed for the tetralayer film architecture, with an order of magnitude increase in water permeability compared to commercially available TFC-HR membranes. These clay composite thin films could serve as a high-flux alternative to current polymeric RO membranes for wastewater and brackish water treatment as well as potentially for forward osmosis applications. In general, we illustrate that by investigating the composite systems accessed using alternating layer-by-layer assembly in conjunction with complementary covalent cross-linking, it is possible to design thin film membranes with tunable transport properties for water purification applications. PMID:26058008

  16. Covalent Attachment to GaP(110) - Engineering the Chemical Functionalization of a III-V Semiconductor

    NASA Astrophysics Data System (ADS)

    Bradley, A. J.; Ugeda, M. M.; Liu, Wenjun; Yu, Min; Tilley, T. Don; Pérez, Rubén; Neaton, Jeffrey B.; Crommie, M. F.

    2014-03-01

    With its 2.3 eV bulk bandgap, relatively high conduction band edge, and low chemical reactivity, the (110) surface of GaP is an excellent candidate for many UV and visible light applications, such as photo-catalysis and light-induced chemical reduction. However, the reconstruction and resulting charge transfer of the surface makes it difficult to covalently attach the required molecules. Indeed, very little work has been done to understand either covalent functionalization or passivation of this surface. Here we report on a Staudinger-type, thermally-driven covalent attachment of perfluorophenyl azide (pfpa) to GaP(110). We have studied the adsorption of pfpa molecules by means of high-resolution scanning tunneling microscopy and spectroscopy in combination with first principles calculations. We show a progression from a physisorbed state at room temperature to a covalently attached state after exposure to slightly higher temperatures (~ 50°C). The developed approach is expected to be valid for various other functional groups attached to the azide, as well as other III-V semiconductors.

  17. Covalent Attachment of Proteins to Solid Supports and Surfaces via Sortase-Mediated Ligation

    PubMed Central

    Chan, Lilyan; Cross, Hannah F.; She, Joseph K.; Cavalli, Gabriel; Martins, Hugo F. P.; Neylon, Cameron

    2007-01-01

    Background There is growing interest in the attachment of proteins to solid supports for the development of supported catalysts, affinity matrices, and micro devices as well as for the development of planar and bead based protein arrays for multiplexed assays of protein concentration, interactions, and activity. A critical requirement for these applications is the generation of a stable linkage between the solid support and the immobilized, but still functional, protein. Methodology Solid supports including crosslinked polymer beads, beaded agarose, and planar glass surfaces, were modified to present an oligoglycine motif to solution. A range of proteins were ligated to the various surfaces using the Sortase A enzyme of S. aureus. Reactions were carried out in aqueous buffer conditions at room temperature for times between one and twelve hours. Conclusions The Sortase A transpeptidase of S. aureus provides a general, robust, and gentle approach to the selective covalent immobilization of proteins on three very different solid supports. The proteins remain functional and accessible to solution. Sortase mediated ligation is therefore a straightforward methodology for the preparation of solid supported enzymes and bead based assays, as well as the modification of planar surfaces for microanalytical devices and protein arrays. PMID:18000537

  18. Covalent attachment of Arc repressor subunits by a peptide linker enhances affinity for operator DNA.

    PubMed

    Robinson, C R; Sauer, R T

    1996-01-01

    By designing a recombinant gene containing tandem copies of the arc coding sequence with intervening DNA encoding the linker sequence GGGSGGGTGGGSGGG, the two subunits of the P22 Are repressor dimer have been covalently linked to form a single-chain protein called Arc-L1-Arc. The 15-residue linker joins the C-terminus of one monomer to the N-terminus of the second, a distance of approximately 45 A in the Arc-operator cocrystal structure. Arc-L1-Arc is expressed at high levels in Escherichia coli, with no evidence of degradation or proteolytic clipping of the linker, and is more active than wild-type Arc in repression assays. The purified Arc-L1-Arc protein has the molecular weight expected for the designed protein and unfolds cooperatively, reversibly, and with no concentration dependence in thermal-denaturation studies. Arc-L1-Arc protects operator DNA in a manner indistinguishable from that of wild-type Arc in DNase I and copper-phenanthroline footprinting studies, but the covalent attachment of the two monomers results in enhanced affinity for operator DNA. Arc-L1-Arc binds operator DNA half-maximally at a concentration of 1.7 pM, compared with the wild-type value of 185 pM, and also binds DNA fragments containing the left or right operator half-sites more tightly than wild type. Because wild-type Arc is monomeric at sub-nanomolar concentrations and must dimerize before binding to the operator, it was anticipated that Arc-L1-Arc would exhibit a lower half-maximal binding concentration. However, even when the change from a monomeric to a dimeric species is taken into account, the affinity of Arc-L1-Arc for operator and half-operator DNA is greater than the wild-type affinity. This tighter binding appears to result from slower dissociation, as Arc-L1-Arc DNA complexes with full or half-site operators dissociate at rates 5-10 times slower than the corresponding Arc--DNA complexes. Hence, the activity of the designed Arc-L1-Arc protein is substantially increased

  19. Integration of micro nano and bio technologies with layer-by-layer self-assembly

    NASA Astrophysics Data System (ADS)

    Kommireddy, Dinesh Shankar

    In the past decade, layer-by-layer (LbL) nanoassembly has been used as a tool for immobilization and surface modification of materials with applications in biology and physical sciences. Often, in such applications, LbL assembly is integrated with various techniques to form functional surface coatings and immobilized matrices. In this work, integration of LbL with microfabrication and microfluidics, and tissue engineering are explored. In an effort to integrate microfabrication with LbL nanoassembly, microchannels were fabricated using soft-lithography and the surface of these channels was used for the immobilization of materials using LbL and laminar flow patterning. Synthesis of poly(dimethyldiallyl ammonium chloride)/poly(styrene sulfonate) and poly(dimethyldiallyl ammonium chloride)/bovine serum albumin microstrips is demonstrated with the laminar flow microfluidic reactor. Resulting micropatterns are 8-10 mum wide, separated with few micron gaps. The width of these microstrips as well as their position in the microchannel is controlled by varying the flow rate, time of interaction and concentration of the individual components, which is verified by numerical simulation. Spatially resolved pH sensitivity was observed by modifying the surface of the channel with a pH sensitive dye. In order to investigate the integration of LbL assembly with tissue engineering, glass substrates were coated with nanoparticle/polyelectrolyte layers, and two different cell types were used to test the applicability of these coatings for the surface modification of medical implants. Titanium dioxide (TiO 2), silicon dioxide, halloysite and montmorillonite nanoparticles were assembled with oppositely charged polyelectrolytes. In-vitro cytotoxicity tests of the nanoparticle substrates on human dermal firbroblasts (HDFs) showed that the nanoparticle surfaces do not have toxic effects on the cells. HDFs retained their phenotype on the nanoparticle coatings, by synthesizing type

  20. Growth and behavior of chondrocytes on nano engineered surfaces and construction of micropatterned co-culture platforms using layer-by-layer platforms using layer-by-layer assembly lift-off method

    NASA Astrophysics Data System (ADS)

    Shaik, Jameel

    Several approaches such as self-assembled monolayers and layer-by-layer assembled multilayer films are being used as tools to study the interactions of cells with biomaterials in vitro. In this study, the layer-by-layer assembly approach was used to create monolayer, bilayer, trilayer, five, ten and twenty-bilayer beds of eleven different biomaterials. The various biomaterials used were poly(styrene-sulfonate), fibronectin, poly-L-lysine, poly-D-lysine, laminin, bovine serum albumin, chondroitin sulfate, poly(ethyleneimine), polyethylene glycol amine, collagen and poly(dimethyldiallyl-ammonium chloride) with unmodified tissue-culture polystyrene as standard control. Three different cell lines---primary bovine articular chondrocytes, and two secondary cell lines, human chondrosarcoma cells and canine chondrocytes were used in these studies. Chondrocyte morphology and attachment, viability, proliferation, and functionality were determined using bright field microscopy, the Live/Dead viability assay, MTT assay, and immunocytochemistry, respectively. Atomic force microscopy of the nanofilms indicated an increase in surface roughness with increasing number of layers. The most important observations from the studies on primary bovine articular chondrocytes were that these cells exhibited increasing viability and cell metabolic activity with increasing number of bilayers. The increase in viability was more pronounced than the increase in cell metabolic activity. Also, bovine chondrocytes on bilayers of poly(dimethyldiallyl-ammonium chloride, poly-L-lysine, poly(styrene-sulfonate), and bovine serum albumin were substantially bigger in size and well-attached when compared to the cells grown on monolayer and trilayers. Lactate dehydrogenase assay performed on chondrosarcoma cells grown on 5- and 10-bilayer multilayer beds indicated that the 10-bilayer beds had reduced cytotoxicity compared to the 5-bilayer beds. MTT assay performed on canine chondrocytes grown on 5-, 10

  1. Anodic Methods for Covalent Attachment of Ethynylferrocenes to Electrode Surfaces: Comparison of Ethynyl Activation Processes.

    PubMed

    Sheridan, Matthew V; Lam, Kevin; Sharafi, Mona; Schneebeli, Severin T; Geiger, William E

    2016-02-16

    The electrochemical oxidation of ferrocenes having an H- or Li-terminated ethynyl group has been studied, especially as it relates to their covalent anchoring to carbon surfaces. The anodic oxidation of lithioethynylferrocene (1-Li) results in rapid loss of Li(+) and formation of the ethynyl-based radical FeCp(η(5)-C5H4)(C≡C), (1, Cp = η(5)-C5H5), which reacts with the electrode. Chemically modified electrodes (CMEs) were thereby produced containing strongly bonded, ethynyl-linked monolayers and electrochemically controlled multilayers. Strong attachments of ethynylferrocenes to gold and platinum surfaces were also possible. The lithiation/anodic oxidation process is a mirror analogue of the diazonium/cathodic reduction process for preparation of aryl-modified CMEs. A second method produced an ethynylferrocene-modified electrode by direct anodic oxidation of the H-terminated ethynylferrocene (1-H) at a considerably more positive potential. Both processes produced robust modified electrodes with well-defined ferrocene-based surface cyclic voltammetry waves that remained unchanged for as many as 10(4) scans. Ferrocene derivatives in which the ethynyl moiety was separated from the cyclopentadienyl ring by an ether group showed very similar behavior. DFT calculations were performed on the relevant redox states of 1-H, 1-Li, and 1, with emphasis on the ferrocenyl vs ethynyl character of their high valence orbitals. Whereas the HOMOs of both 1-H and 1-Li have some ethynyl character, the SOMOs of the corresponding monocations are strictly ferrocenium in makeup. Predominant ethynyl character returns to the highest valence orbitals after loss of Li(+) from [1-Li](+) or loss of H(+) from [1-H](2+). These anodic processes hold promise for the controlled chemical modification of carbon and other electrode surfaces by a variety of ethynyl or alkynyl-linked organic and metal-containing systems. PMID:26756403

  2. Covalent attachment of polymeric monolith to polyether ether ketone (PEEK) tubing.

    PubMed

    Lv, Chunguang; Heiter, Jaana; Haljasorg, Tõiv; Leito, Ivo

    2016-08-17

    A new method of reproducible preparation of vinylic polymeric monolithic columns with a key step of covalently anchoring the monolith to PEEK surface is described. In order to chemically attach the polymer monolith to the tube wall, methacrylate functional groups were introduced onto PEEK surface by a three-step procedure, including surface etching, surface reduction and surface methacryloylation. The chemical state of the modified tubing surface was characterized by attenuated total reflectance infrared (ATR-IR) spectroscopy. It was found that the etching step is the key to successfully modifying the PEEK tubing surface. Poly(styrene-co-divinylbenzene) monoliths were in situ synthesized by thermally initiated free radical copolymerization within the confines of surface-vinylized PEEK tubings of dimensions close to ones conventionally used in HPLC and UHPLC (1.6 mm internal diameter, 10.0-12.5 cm length). Adhesion test was done by measuring the operating pressure drop, which the prepared stationary phases can withstand. Good pressure resistance, up to 140 bar/10 cm (flow rate 0.5 mL min(-1), acetonitrile as a mobile phase), indicates strong bonding of monolith to the tubing wall. The monolithic material was proven to have a permeability of 1.7 × 10 (-14) m(2), applying acetonitrile-water 70:30 (v/v) as a mobile phase. The column performance was reproducible from column to column and was evaluated via the isocratic separation of a series of alkylbenzenes in the reversed-phase mode (acetonitrile-water 70:30, v/v). The numbers of plates per meter at optimal flow rate were found to be between 26 000 and 32 000 for the different analytes. PMID:27286776

  3. Layer-by-layer assemblies of catechol-functionalized TiO2 nanoparticles and porphyrins through electrostatic interactions.

    PubMed

    Burger, Alexandra; Costa, Rubén D; Lobaz, Volodymyr; Peukert, Wolfgang; Guldi, Dirk M; Hirsch, Andreas

    2015-03-23

    In the current work, we present the successful functionalization and stabilization of P-25 TiO2 nanoparticles by means of N1,N7-bis(3-(4-tert-butyl-pyridium-methyl)phenyl)-4-(3-(3-(4-tert-butyl-pyridinium-methyl)phenylamino)-3-oxopropyl)-4-(3,4-dihydroxybenzamido)heptanediamide tribromide (1). The design of the latter is aimed at nanoparticle functionalization and stabilization with organic building blocks. On one hand, 1 features a catechol anchor to enable its covalent grafting onto the TiO2 surface, and on the other hand, positively charged pyridine groups at its periphery to prevent TiO2 agglomeration through electrostatic repulsion. The success of functionalization and stabilization was corroborated by thermogravimetric analysis, dynamic light-scattering, and zeta potential measurements. As a complement to this, the formation of layer-by-layer assemblies, which are governed by electrostatic interactions, by alternate deposition of functionalized TiO2 nanoparticles and two negatively charged porphyrin derivatives, that is, 5,10,15,20-(phenoxyacetic acid)-porphyrin (2) and 5,10,15,20-(4-(2-ethoxycarbonyl)-4-(2-phenoxyacetamido)heptanedioic acid)-porphyrin (3), is documented. To this end, the layer-by-layer deposition is monitored by UV/Vis spectroscopy, scanning electron microscopy, ellipsometry, and profilometry techniques. The resulting assemblies are utilized for the construction and testing of novel solar cells. From stable and repeatable photocurrents generated during several "on-off" cycles of illumination, we derive monochromatic incident photo-to-current conversion efficiencies of around 3 %. PMID:25684221

  4. Growth of gold/zinc sulphide multilayer films using layer-by-layer assembly of colloidal nanoparticles

    NASA Astrophysics Data System (ADS)

    Promnimit, S.; Cavelius, C.; Mathur, S.; Dutta, J.

    2008-12-01

    Fabrication of multilayer thin films through layer-by-layer (lbl) deposition of charged nanoparticles on tin-doped indium oxide (ITO) coated and uncoated glass substrates are reported. The thin films were constructed by alternately dipping a substrate into a colloidal suspension of chitosan capped zinc sulphide (ZnS) nanoparticles (∼30 nm) and citrate stabilized colloidal gold (Au) nanoparticles (∼20 nm) leading to electrostatic interactions between the oppositely charged nanoparticle layers. Thin films consisting of up to 200 deposition cycles by multiple dipping have been studied and surface morphology, changes in the optical absorption characteristics, thickness, uniformity, roughness and electrical characteristics are reported. The multilayered assemblies, attached to the surface by strong ionic bonds, were highly stable and could not be removed by moderate scratching. The current-voltage characteristics in the forward and reverse bias conditions demonstrated rectifying behaviors in the onset of conduction voltage which makes these films attractive for future electronic devices.

  5. Immobilization of Yarrowia lipolytica Lipase—A Comparison of Stability of Physical Adsorption and Covalent Attachment Techniques

    NASA Astrophysics Data System (ADS)

    Cunha, Aline G.; Fernández-Lorente, Gloria; Bevilaqua, Juliana V.; Destain, Jacqueline; Paiva, Lúcia M. C.; Freire, Denise M. G.; Fernández-Lafuente, Roberto; Guisán, Jose M.

    Lipase immobilization offers unique advantages in terms of better process control, enhanced stability, predictable decay rates and improved economics. This work evaluated the immobilization of a highly active Yarrowia lipolytica lipase (YLL) by physical adsorption and covalent attachment. The enzyme was adsorbed on octyl-agarose and octadecyl-sepabeads supports by hydrophobic adsorption at low ionic strength and on MANAE-agarose support by ionic adsorption. CNBr-agarose was used as support for the covalent attachment immobilization. Immobilization yields of 71, 90 and 97% were obtained when Y. lipolytica lipase was immobilized into octyl-agarose, octadecyl-sepabeads and MANAE-agarose, respectively. However, the activity retention was lower (34% for octyl-agarose, 50% for octadecyl-sepabeads and 61% for MANAE-agarose), indicating that the immobilized lipase lost activity during immobilization procedures. Furthermore, immobilization by covalent attachment led to complete enzyme inactivation. Thermal deactivation was studied at a temperature range from 25 to 45°C and pH varying from 5.0 to 9.0 and revealed that the hydrophobic adsorption on octadecyl-sepabeads produced an appreciable stabilization of the biocatalyst. The octadecyl-sepabeads biocatalyst was almost tenfold more stable than free lipase, and its thermal deactivation profile was also modified. On the other hand, the Y. lipolytica lipase immobilized on octyl-agarose and MANAE-agarose supports presented low stability, even less than the free enzyme.

  6. Surface coating for flame retardant behavior of cotton fabric by layer-by-layer processing

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Flame retardant behavior has been prepared by the layer-by layer assemblies of branched polyethylenimine (BPEI), kaolin, urea, diammonium phosphate (dibasic) on cotton fabrics. Three different kinds of cotton fabrics (print cloth, mercerized print cloth, and mercerized twill fabric) were prepared wi...

  7. Innovative layer-by-layer processing for flame retardant behavior of cotton fabric

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Flame retardant behavior has been prepared by the layer-by layer assemblies of kaolin/casein with inorganic chemicals on cotton fabrics. Three different kinds of cotton fabrics (print cloth, mercerized print cloth, and mercerized twill fabric) were prepared with solutions of mixture of BPEI, urea, ...

  8. Layer-by-Layer Assembly of a pH-Responsive and Electrochromic Thin Film

    ERIC Educational Resources Information Center

    Schmidt, Daniel J.; Pridgen, Eric M.; Hammond, Paula T.; Love, J. Christopher

    2010-01-01

    This article summarizes an experiment on thin-film fabrication with layer-by-layer assembly that is appropriate for undergraduate laboratory courses. The purpose of this experiment is to teach students about self-assembly in the context of thin films and to expose students to the concepts of functional polymeric coatings. Students dip coat…

  9. Covalent attachment of a bioactive hyperbranched polymeric layer to titanium surface for the biomimetic growth of calcium phosphates

    PubMed Central

    Tsiourvas, D.; Arkas, M.; Diplas, S.; Mastrogianni, E.

    2010-01-01

    This work is investigating the chemical grafting on Ti surface of a polymer/calcium phosphate coating of improved adhesion for enhanced bioactivity. For this purpose, a whole new methodology was developed based on covalently attaching a hyperbranched poly(ethylene imine) layer on Ti surface able to promote calcium phosphate formation in a next deposition stage. This was achieved through an intermediate surface silanization step. The research included optimization both of the reaction conditions for covalently grafting the intermediate organosilicon and the subsequent hyperbranched poly(ethylene imine) layers, as well as of the conditions for the mechanical and chemical pretreatment of Ti surface before coating. The reaction steps were monitored employing FTIR and XPS analyses, whereas the surface morphology and structure of the successive coating layers were studied by SEM combined with EDS. The analysis confirmed the successful grafting of the hybrid layer which demonstrated very good ability for hydroxyapatite growth in simulated body fluid. PMID:21069559

  10. Elastodynamic behavior of the three dimensional layer-by-layer metamaterial structure

    SciTech Connect

    Aravantinos-Zafiris, N.; Sigalas, M. M.; Economou, E. N.

    2014-10-07

    In this work, we numerically investigate for the first time the elastodynamic behavior of a three dimensional layer-by-layer rod structure, which is easy to fabricate and has already proved to be very efficient as a photonic crystal. The Finite Difference Time Domain method was used for the numerical calculations. For the rods, several materials were examined and the effects of all the geometric parameters of the structure were also numerically investigated. Additionally, two modifications of the structure were included in our calculations. The results obtained here (for certain geometric parameters), exhibiting a high ratio of longitudinal over transverse sound velocity and therefore a close approach to ideal pentamode behavior over a frequency range, clearly show that the layer-by-layer rod structure, besides being an efficient photonic crystal, is a very serious contender as an elastodynamic metamaterial.

  11. Discrete Layer-by-Layer Magnetic Switching in Fe /MgO (001 ) Superlattices

    NASA Astrophysics Data System (ADS)

    Moubah, R.; Magnus, F.; Warnatz, T.; Palsson, G. K.; Kapaklis, V.; Ukleev, V.; Devishvili, A.; Palisaitis, J.; Persson, P. O. Å.; Hjörvarsson, B.

    2016-04-01

    We report on a discrete layer-by-layer magnetic switching in Fe /MgO superlattices driven by an antiferromagnetic interlayer exchange coupling. The strong interlayer coupling is mediated by tunneling through MgO layers with thicknesses up to at least 1.8 nm, and the coupling strength varies with MgO thickness. Furthermore, the competition between the interlayer coupling and magnetocrystalline anisotropy stabilizes both 90° and 180° periodic alignment of adjacent layers throughout the entire superlattice. The tunable layer-by-layer switching, coupled with the giant tunneling magnetoresistance of Fe /MgO /Fe junctions, is an appealing combination for three-dimensional spintronic memories and logic devices.

  12. Industrial-scale spray layer-by-layer assembly for production of biomimetic photonic systems.

    PubMed

    Krogman, K C; Cohen, R E; Hammond, P T; Rubner, M F; Wang, B N

    2013-12-01

    Layer-by-layer assembly is a powerful and flexible thin film process that has successfully reproduced biomimetic photonic systems such as structural colour. While most of the seminal work has been carried out using slow and ultimately unscalable immersion assembly, recent developments using spray layer-by-layer assembly provide a platform for addressing challenges to scale-up and manufacturability. A series of manufacturing systems has been developed to increase production throughput by orders of magnitude, making commercialized structural colour possible. Inspired by biomimetic photonic structures we developed and demonstrated a heat management system that relies on constructive reflection of near infrared radiation to bring about dramatic reductions in heat content. PMID:24263056

  13. Enforced Layer-by-Layer Stacking of Energetic Salts towards High-Performance Insensitive Energetic Materials.

    PubMed

    Zhang, Jiaheng; Mitchell, Lauren A; Parrish, Damon A; Shreeve, Jean'ne M

    2015-08-26

    Development of modern high-performance insensitive energetic materials is significant because of the increasing demands for both military and civilian applications. Here we propose a rapid and facile strategy called the "layer hydrogen bonding pairing approach" to organize energetic molecules via layer-by-layer stacking, which grants access to tunable energetic materials with targeted properties. Using this strategy, an unusual energetic salt, hydroxylammonium 4-amino-furazan-3-yl-tetrazol-1-olate, with good detonation performances and excellent sensitivities, was designed, synthesized, and fully characterized. In addition, the expected unique layer-by-layer structure with a high crystal packing coefficient was confirmed by single-crystal X-ray crystallography. Calculations indicate that the layer-stacking structure of this material can absorb the mechanical stimuli-induced kinetic energy by converting it to layer sliding, which results in low sensitivity. PMID:26262555

  14. Sandwich-like layer-by-layer assembly of gold nanoparticles with tunable SERS properties.

    PubMed

    Liu, Zhicheng; Bai, Lu; Zhao, Guizhe; Liu, Yaqing

    2016-01-01

    Sandwich-like layer-by-layer thin films consisting of polyelectrolytes and gold nanoparticles were utilized to construct surface-enhanced Raman scattering (SERS) substrates with tunable SERS properties. It is found that both the size of the nanoparticles in the layers and the interlayer distance significantly influence the SERS performance of the multilayered thin film. These simple, low-cost, easily processable and controllable SERS substrates have a promising future in the field of molecular sensing. PMID:27547620

  15. Sandwich-like layer-by-layer assembly of gold nanoparticles with tunable SERS properties

    PubMed Central

    Bai, Lu; Zhao, Guizhe

    2016-01-01

    Summary Sandwich-like layer-by-layer thin films consisting of polyelectrolytes and gold nanoparticles were utilized to construct surface-enhanced Raman scattering (SERS) substrates with tunable SERS properties. It is found that both the size of the nanoparticles in the layers and the interlayer distance significantly influence the SERS performance of the multilayered thin film. These simple, low-cost, easily processable and controllable SERS substrates have a promising future in the field of molecular sensing. PMID:27547620

  16. Layer-by-layer assembly of a metallomesogen by dip-pen nanolithography.

    PubMed

    Radha, Boya; Liu, Guoliang; Eichelsdoerfer, Daniel J; Kulkarni, Giridhar U; Mirkin, Chad A

    2013-03-26

    Palladium alkanethiolates are introduced here as a novel liquid ink for dip-pen nanolithography (DPN). These structures exhibit the unusual characteristic of layer-by-layer assembly, allowing one to deposit a desired number of metal ions on a surface, which can subsequently be reduced via thermolysis to form active catalytic structures. Such structures have been used to generate contiguous metallic or conducting polymer nanoscale architectures by electroless deposition. PMID:23402390

  17. Molecular layer-by-layer assembled thin-film composite membranes for water desalination.

    PubMed

    Gu, Joung-Eun; Lee, Seunghye; Stafford, Christopher M; Lee, Jong Suk; Choi, Wansuk; Kim, Bo-Young; Baek, Kyung-Youl; Chan, Edwin P; Chung, Jun Young; Bang, Joona; Lee, Jung-Hyun

    2013-09-14

    Molecular layer-by-layer (mLbL) assembled thin-film composite membranes fabricated by alternating deposition of reactive monomers on porous supports exhibit both improved salt rejection and enhanced water flux compared to traditional reverse osmosis membranes prepared by interfacial polymerization. Additionally, the well-controlled structures achieved by mLbL deposition further lead to improved antifouling performance. PMID:23847127

  18. Hierarchical fibrillar scaffolds obtained by non-conventional layer-by-layer electrostatic self-assembly.

    PubMed

    Oliveira, Sara M; Silva, Tiago H; Reis, Rui L; Mano, João F

    2013-03-01

    A new application of layer-by-layer assembly is presented, able to create nano/micro fibrils or nanocoatings inside 3D scaffolds using non-fibrillar polyelectrolytes for tissue-engineering applications. This approach shows promise for developing advanced scaffolds with controlled nano/micro environments, and nature and architectures similar to the natural extracellular matrix, leading to improved biological performance. PMID:23184814

  19. "Face-lifting" and "make-up" for microorganisms: layer-by-layer polyelectrolyte nanocoating.

    PubMed

    Fakhrullin, Rawil F; Lvov, Yuri M

    2012-06-26

    Layer-by-layer encapsulation of living biological cells and other microorganisms via sequential adsorption of oppositely charged functional nanoscale components is a promising instrument for engineering cells with enhanced properties and artificial microorganisms. Such nanoarchitectural shells assembled in mild aqueous conditions provide cells with additional abilities, widening their functionality and applications in artificial spore formation, whole-cell biosensors, and fabrication of three-dimensional multicellular clusters. PMID:22612633

  20. Non-covalent attachment of silver nanoclusters onto single-walled carbon nanotubes with human serum albumin as linking molecule

    NASA Astrophysics Data System (ADS)

    Rodríguez-Galván, Andrés; Heredia, Alejandro; Amelines-Sarria, Oscar; Rivera, Margarita; Medina, Luis A.; Basiuk, Vladimir A.

    2015-03-01

    The attachment of silver nanoclusters (AgNCs) onto single-walled carbon nanotubes (SWNTs) for the formation of integrated fluorescence sites has attracted much attention due their potential applications as biological probes and nanovectors in theragnosis. Here, we report the preparation through assembly of fluorescent quasi 1-D nanomaterial based on SWNTs and silver nanoclusters (AgNCs) non-covalently attached to human serum albumin as biological linker. The fluorescent SWNT-AgNCs-HSA conjugates were characterized by atomic force microscopy, high-resolution transmission electron microscopy (HRTEM), high angle annular dark field scanning TEM (HAADF-STEM), fluorescent and UV-vis spectroscopy. The above techniques confirmed that AgNCs were non-covalently attached onto the external surface of SWNTs. In addition, it was observed that the modification did not affect the optical properties of the synthesized AgNCs since the absorption spectra and fluorescence under UV irradiation (λ = 365 nm) remain the same. The effect of the functionalized systems was tested on mammal red blood cells (RBCs) and it was found that their structural integrity was compromised by the conjugates, limiting their biological and medical applications.

  1. Impact of vacancy defects in single-walled carbon nanotube on the structural properties of covalently attached aromatic diisocyanates

    NASA Astrophysics Data System (ADS)

    Kozlowska, Mariana; Goclon, Jakub; Rodziewicz, Pawel

    2016-01-01

    Ab initio molecular dynamics simulations (AIMD) are used to investigate the influence of the vacancy- and divacancy (5-8-5) defects on the surface of single-walled carbon nanotube (SWCNT)(10,0) on the structural properties of covalently attached aromatic diisocyanate molecules, namely 4,4‧-methylene diphenyl diisocyanate (MDI) and toluene-2,4-diisocyanate (TDI). The structural rearrangements and flexibility of MDI and TDI attached to the defective SWCNTs are analysed and compared with the defect-free SWCNT(10,0). The results obtained indicate more than 4 times higher reactivity of vacancy defective SWCNT(10,0) comparing with the defect-free system. Due to weak C-H⋯O and C-H⋯π hydrogen bonds, formed during the covalent functionalisation, the flexibility of the attached diisocyanates is suppressed. Detailed analysis of the time evolution of the structural parameters during AIMD simulations suggests cyclically repeated mechanism of the structural rearrangements of aromatic diisocyanates on the surface of SWCNTs(10,0).

  2. Augmenting Protein Release from Layer- by-Layer Functionalized Agarose Hydrogels

    PubMed Central

    Lynam, Daniel; Peterson, Chelsea; Maloney, Ryan; Shahriari, Dena; Garrison, Alexa; Saleh, Sara; Mehrotra, Sumit; Chan, Christina; Sakamoto, Jeff

    2014-01-01

    Recent work demonstrated the efficacy of combining layer-by-layer assembly with hydrogels to provide the controlled delivery of proteins for use in nerve repair scaffolds. In this work, we augmented the protein dose response by controlling and increasing the hydrogel internal surface area. Sucrose was added to agarose during gelation to homogenize the nanopore morphology, resulting in increased surface area per unit volume of hydrogel. The surface area of a range of compositions (1.5 to 5.0 wt% agarose and 0, 50 and 65 wt% sucrose) was measured. Gels were supercritically dried to preserve porosity enabling detailed pore morphology measurements using nitrogen adsorption and high resolution scanning electron microscopy. The resulting surface area, normalized by superficial gel volume, ranged between 6 and 56m2/ccgel. Using the layer-by-layer process to load lysozyme, a neurotrophic factor analog, a relationship was observed between surface area and cumulative dose response ranging from 176 to 2556 μg/mL, which is in the range of clinical relevance for the delivery of growth factors. In this work, we demonstrated that the ability to control porosity is key in tuning drug delivery dose response from layer-by-layer modified hydrogels. PMID:24528743

  3. Novel layer-by-layer structured nanofibrous mats coated by protein films for dermal regeneration.

    PubMed

    Xin, Shangjing; Li, Xueyong; Wang, Qun; Huang, Rong; Xu, Xiaoli; Lei, Zhanjun; Deng, Hongbing

    2014-05-01

    Layer-by-layer coating technique is effective in modifying the surface of nanofibrous mats, but overmuch film-coating makes the mats less porous to hardly suit the condition for tissue engineering. We developed novel nanofibrous mats layer-by-layer coated by silk fibroin and lysozyme on the cellulose electrospun template via electrostatic interaction. The film-coating assembled on the mats was not excessive because the charge of the proteins varied in the coating process due to different pH value. In addition, pure nature materials made the mats nontoxic, biodegradable and low-cost. The morphology and composition variation during layer-by-layer coating process was investigated and the results showed that the structure and thickness of film-coatings could be well-controlled. The antibacterial assay and in vitro cell experiments indicated that the mats could actively inhibit bacteria and exhibit excellent biocompatibility. In vivo implant assay further verified the mats cultured with human epidermal cells could promote wound healing and avoid wound infection. Therefore, these mats showed promising prospects when performed for dermal reconstruction. PMID:24734533

  4. Layer-by-Layer Assemblies in Nanoporous Templates: Nano-Organized Design and Applications of Soft Nanotechnology

    PubMed Central

    Azzaroni, Omar; Lau, K.H. Aaron

    2011-01-01

    The synergistic combination of layer-by-layer (LbL) assembly and nanoporous membrane templating has greatly facilitated the creation of complex and functional nanotubular structures. The approach takes advantage of both the new properties conferred by assembling diverse LbL building blocks and the tight dimensional control offered by nanotemplating to enable new functionalities that arise from the highly anisotropic “one-dimensional” LbL-nanotube format. In this review, we aim to convey the key developments and provide a current snap-shot of such templated LbL nanoarchitectures. We survey recent developments that have enabled the assembly of polymers, biomolecules and inorganic nanoparticles “à la carte”, via electrostatic, covalent and specific (bio)recognition interactions. We also discuss the emerging mechanistic understanding of the LbL assembly process within the nanopore environment. Finally, we present a diverse range of LbL nanotube “devices” to illustrate the versatility of the nanotemplated LbL toolbox for generating functional soft nanotechnology. PMID:22216060

  5. Fabrication of graphene/polyaniline composite multilayer films by electrostatic layer-by-layer assembly

    SciTech Connect

    Cong, Jiaojiao; Chen, Yuze; Luo, Jing Liu, Xiaoya

    2014-10-15

    A novel graphene/polyaniline composite multilayer film was fabricated by electrostatic interactions induced layer-by-layer self-assembly technique, using water dispersible and negatively charged chemically converted graphene (CCG) and positively charged polyaniline (PANI) as building blocks. CCG was achieved through partly reduced graphene oxide, which remained carboxyl group on its surface. The remaining carboxyl groups not only retain the dispersibility of CCG, but also allow the growth of the multilayer films via electrostatic interactions between graphene and PANI. The structure and morphology of the obtained CCG/PANI multilayer film are characterized by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, Ultraviolet–visible absorption spectrum (UV–vis), scanning electron microscopy (SEM), Raman spectroscopy and X-Ray Diffraction (XRD). The electrochemical properties of the resulting film are studied using cyclic voltammetry (CV), which showed that the resulting CCG/PANI multilayer film kept electroactivity in neutral solution and showed outstanding cyclic stability up to 100 cycles. Furthermore, the composite film exhibited good electrocatalytic ability toward ascorbic acid (AA) with a linear response from 1×10{sup −4} to 1.2×10{sup −3} M with the detect limit of 5×10{sup −6} M. This study provides a facile and effective strategy to fabricate graphene/PANI nanocomposite film with good electrochemical property, which may find potential applications in electronic devices such as electrochemical sensor. - Graphical abstract: A novel graphene/polyaniline (CCG/PANI) film was prepared by layer-by-layer assembly. - Highlights: • A novel graphene/polyaniline (CCG/PANI) film was prepared by layer-by-layer assembly. • The water dispersible and negatively charged graphene (CCG) was used as building block. • CCG was achieved through partly reduced graphene oxide with carboxyl group on its surface. • CCG/PANI film kept

  6. Layer-by-Layer Assembled 2D Montmorillonite Dielectrics for Solution-Processed Electronics.

    PubMed

    Zhu, Jian; Liu, Xiaolong; Geier, Michael L; McMorrow, Julian J; Jariwala, Deep; Beck, Megan E; Huang, Wei; Marks, Tobin J; Hersam, Mark C

    2016-01-01

    Layer-by-layer assembled 2D montmorillonite nanosheets are shown to be high-performance, solution-processed dielectrics. These scalable and spatially uniform sub-10 nm thick dielectrics yield high areal capacitances of ≈600 nF cm(-2) and low leakage currents down to 6 × 10(-9) A cm(-2) that enable low voltage operation of p-type semiconducting single-walled carbon nanotube and n-type indium gallium zinc oxide field-effect transistors. PMID:26514248

  7. A new generation of electrochemical supercapacitors based on layer-by-layer polymer films

    NASA Astrophysics Data System (ADS)

    Christinelli, Wania Ap.; Gonçalves, Roger; Pereira, Ernesto C.

    2016-01-01

    Here we report supercapacitors fabricated with the layer-by-layer (LBL) technique using two polymers, namely poly(o-methoxyaniline) (POMA) and poly(3-thiophene acetic acid) (PTAA). The electrochemical performances of POMA/PTAA supercapacitors were characterized by cyclic voltammetry and electrochemical impedance spectroscopy. The results were compared with POMA casting film. The specific capacitance of LBL films increases almost linearly with a number of bilayers which were not observed for POMA casting films. The results of this investigation demonstrate that the self-doping effect between POMA and PTAA can change the properties on films and can be successfully used as a supercapacitor technology.

  8. Layer-by-layer design method for soft-X-ray multilayers

    NASA Technical Reports Server (NTRS)

    Yamamoto, Masaki; Namioka, Takeshi

    1992-01-01

    A new design method effective for a nontransparent system has been developed for soft-X-ray multilayers with the aid of graphic representation of the complex amplitude reflectance in a Gaussian plane. The method provides an effective means of attaining the absolute maximum reflectance on a layer-by-layer basis and also gives clear insight into the evolution of the amplitude reflectance on a multilayer as it builds up. An optical criterion is derived for the selection of a proper pair of materials needed for designing a high-reflectance multilayer. Some examples are given to illustrate the usefulness of this design method.

  9. Layer-by-layer films from tartrazine dye with bovine serum albumin

    NASA Astrophysics Data System (ADS)

    de Souza, Nara C.; Flores, Júlio C. Johner; Silva, Josmary R.

    2009-12-01

    We report on the preparation and study of the adsorption process of layer-by-layer films of tartrazine alternated with bovine serum albumin. UV-Vis spectroscopy indicated that the films form J-aggregates of tartrazine. Adsorption kinetics was fitted by the Johnson-Mehl-Avrami equation and surface morphological analyses by atomic force microscopy suggested that the J-aggregates were column-shaped, which was attributed to the column-like symmetry of the tartrazine molecules. The columnar structures that formed probably arose from the juxtaposition of smaller aggregates that were already present at the beginning of film growth.

  10. Layer-by-layer assembly of silica nanoparticles on 3D fibrous scaffolds: enhancement of osteoblast cell adhesion, proliferation, and differentiation.

    PubMed

    Tang, Yanwei; Zhao, Yan; Wang, Xungai; Lin, Tong

    2014-11-01

    Silica nanoparticles were applied onto the fiber surface of an interbonded three-dimensional polycaprolactone fibrous tissue scaffold by an electrostatic layer-by-layer self-assembly technique. The nanoparticle layer was found to improve the fiber wettability and surface roughness. Osteoblast cells were cultured on the fibrous scaffolds to evaluate the biological compatibility. The silica nanoparticle coated scaffold showed enhanced cell attachment, proliferation, and alkaline phosphatase activities. The overall results suggested that interbonded fibrous scaffold with silica nanoparticulate coating could be a promising scaffolding candidate for various applications in bone repair and regeneration. PMID:24288259

  11. Layer-by-layer self-assembly immobilization of catalases on wool fabrics.

    PubMed

    Liu, J; Wang, Q; Fan, X R; Sun, X J; Huang, P H

    2013-04-01

    A new immobilization strategy of catalases on natural fibers was reported in this paper. Catalase (CAT) from Bacillus subtilis was assembled into multiple layers together with poly(diallyldimethylammonium chloride) (PDDA) on wool fabrics via layer-by-layer (LBL) electrostatic self-assembly deposition. The mechanism and structural evaluation of LBL electrostatic self-assembly were studied in terms of scanning electron microscopy (SEM), surface zeta potential, and apparent color depth (K/S). The SEM pictures showed obvious deposits absorbed on the wool surfaces after LBL self-assembly. The surface zeta potential and dyeing depth of CAT/PDDA-assembled wool fabrics presented a regular layer-by-layer alternating trend along with the change of deposited materials, revealing the multilayer structure of the wool fiber immobilized catalases. The V(max) values were found to be 2,500±238 U/mg protein for the free catalase and 1,000±102 U/mg protein for the immobilized catalase. The K(m) value of free catalase (11.25±2.3 mM) was found to be lower than that of the immobilized catalase (222.2±36.5 mM). The immobilized catalase remained high enzymatic activity and showed a measureable amount of reusability, which proved that LBL electrostatic self-assembly deposition is a promising approach to immobilize catalases. PMID:23420488

  12. Calcium-doped ceria/titanate tabular functional nanocomposite by layer-by-layer coating method

    SciTech Connect

    Liu, Xiang W.; Devaraju, M.K.; Yin, Shu; Sato, Tsugio

    2010-07-15

    Ca-doped ceria (CDC)/tabular titanate (K{sub 0.8}Li{sub 0.27}Ti{sub 1.73}O{sub 4}, TT) UV-shielding functional nanocomposite with fairly uniform CDC coating layers was prepared through a polyelectrolyte-associated layer-by-layer (LbL) coating method. TT with lepidocrocite-like layered structure was used as the substrate, poly (diallyldimethylammonium chloride) (PDDA) was used as a coupling agent, CDC nanoparticles were used as the main UV-shielding component. CDC/TT nanocomposites with various coating layers of CDC were obtained through a multistep coating process. The phases were studied by X-ray diffraction. The morphology and coating quality were studied by scanning electron microscopy and element mapping of energy dispersive X-ray analysis. The oxidation catalytic activity, UV-shielding ability and using comfort were characterized by Rancimat test, UV-vis spectra and dynamic friction test, respectively. CDC/TT nanocomposites with low oxidation catalytic activity, high UV-shielding ability and good using comfort were finally obtained. - Graphical abstract: Through the control of surface charge of particles calcium-doped ceria/titanate composites with low oxidation catalytic activity, higher UV-shielding ability and excellent comfort was obtained by a facile layer-by-layer coating method.

  13. Antitumoral materials with regenerative function obtained using a layer-by-layer technique

    PubMed Central

    Ficai, Denisa; Sonmez, Maria; Albu, Madalina Georgiana; Mihaiescu, Dan Eduard; Ficai, Anton; Bleotu, Coralia

    2015-01-01

    A layer-by layer technique was successfully used to obtain collagen/hydroxyapatite-magnetite-cisplatin (COLL/HAn-Fe3O4-CisPt, n=1–7) composite materials with a variable content of hydroxyapatite intended for use in the treatment of bone cancer. The main advantages of this system are the possibility of controlling the rate of delivery of cytostatic agents, the presence of collagen and hydroxyapatite to ensure more rapid healing of the injured bone tissue, and the potential for magnetite to be a passive antitumoral component that can be activated when an appropriate external electromagnetic field is applied. In vitro cytotoxicity assays performed on the COLL/HAn-Fe3O4-CisPt materials obtained using a layer-by layer method confirmed their antitumoral activity. Samples with a higher content of hydroxyapatite had more antitumoral activity because of their better absorption of cisplatin and consequently a higher amount of cisplatin being present in the matrices. PMID:25767374

  14. Layer-by-layer nucleation mechanism for quantum dot formation in strained heteroepitaxy.

    PubMed

    Xiang, Ruoxi; Lung, M T; Lam, Chi-Hang

    2010-08-01

    We study the spontaneous formation of quantum dots in the form of three-dimensional (3D) islands on facetted surfaces in heteroepitaxy. Island development from fast kinetic Monte Carlo (KMC) simulations at low deposition rates is found to follow a layer-by-layer nucleation pathway characterized by energetics driven continuous lateral expansion interrupted by a sequence of independent two-dimensional (2D) upper-layer nucleation events. The process involves only unstable 2D upper-layer nuclei but no unstable 3D nucleus. We have calculated analytically the elastic strain energy of an island in the form of an axisymmetric stepped mound using a small-slope approximation. The total free energy of a system with a 3D island and an adatom bath is obtained. Our theory explains island formation via a free energy driven layer-by-layer nucleation mechanism. Upper-layer nucleation energy barrier, nucleation time, critical radius, and island step spacings are estimated. The relevance of entropic step-step repulsion is discussed. Our theory satisfactorily explains the 3D KMC simulations and may describe the initial evolution of islands in the form of stepped mounds observed in experiments. PMID:20866820

  15. Electrodeposition of alginate/chitosan layer-by-layer composite coatings on titanium substrates.

    PubMed

    Wang, Zhiliang; Zhang, Xueqin; Gu, Juming; Yang, Haitao; Nie, Jun; Ma, Guiping

    2014-03-15

    In this study, alginate/chitosan layer-by-layer composite coatings were prepared on titanium substrates via electrodeposition. The mechanism of anodic deposition of anionic alginate based on the pH decrease at the anode surface, while the pH increase at the cathode surface enabled the deposition of cationic chitosan coatings. The surface of coatings was characterized by using attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The properties of coatings were characterized by X-ray diffraction (XRD) and differential thermal analysis (DTA). Indirect in vitro cytotoxicity test showed that the extracts of coating had no significant effects on cell viability. Moreover, in vitro cytocompatibility test exhibited cell population and spreading tendency, suggesting that the coatings were non-toxic to L929 cells. However, the results revealed that alginate coating was more benefit for cells growing than chitosan coating. The results indicated that the proposed method could be used to fabricate alginate/chitosan layer-by-layer composite coatings on the titanium surface at room temperature and such composite coatings might have potential applications in tissue engineering scaffolds field. PMID:24528698

  16. Clay induced aggregation of a tetra-cationic metalloporphyrin in Layer by Layer self assembled film

    NASA Astrophysics Data System (ADS)

    Banik, Soma; Bhattacharjee, J.; Hussain, S. A.; Bhattacharjee, D.

    2015-12-01

    Porphyrins have a general tendency to form aggregates in ultrathin films. Also electrostatic adsorption of cationic porphyrins onto anionic nano clay platelets results in the flattening of porphyrin moieties. The flattening is evidenced by the red-shifting of Soret band with respect to the aqueous solution. In the present communication, we have studied the clay induced aggregation behaviour of a tetra-cationic metalloporphyrin Manganese (III) 5, 10, 15, 20-tetra (4 pyridyl)-21 H, 23 H-porphine chloride tetrakis (methochloride) (MnTMPyP) in Layer-by-Layer (LbL) self assembled film. The adsorption of dye molecules onto nano clay platelets resulted in the flattening of the meso substituent groups of the dye chromophore. In Layer-by-Layer ultrathin film, the flattened porphyrin molecules tagged nano clay platelets were further associated to form porphyrin aggregates. This has been clearly demonstrated from the UV-vis absorption spectroscopic studies. Atomic Force Microscopic (AFM) studies gave visual evidence of the association of organo-clay hybrid molecules in the LbL film.

  17. Surface functionalization of silica-coated magnetic nanoparticles for covalent attachment of cholesterol oxidase

    NASA Astrophysics Data System (ADS)

    Šulek, Franja; Drofenik, Miha; Habulin, Maja; Knez, Željko

    2010-01-01

    A systematic approach towards the fabrication of highly functionalized silica shell magnetic nanoparticles, presently used for enzyme immobilization, is herein fully presented. The synthesis of bare maghemite (γ-Fe 2O 3) nanoparticles was accomplished by thermal co-precipitation of iron ions in ammonia alkaline solution at harsh reaction conditions, respectively. Primary surface engineering of maghemite nanoparticles was successfully performed by the proper deposition of silica onto nanoparticles surface under strictly regulated reaction conditions. Next, the secondary surface functionalization of the particles was achieved by coating the particles with organosilane followed by glutaraldehyde activation in order to enhance protein immobilization. Covalent immobilization of cholesterol oxidase was attempted afterwards. The structural and magnetic properties of magnetic silica nanocomposites were characterized by TEM and vibrating sample magnetometer (VSM) instruments. X-ray diffraction measurements confirmed the spinel structure and average size of uncoated maghemite nanoparticles to be around 20 nm in diameter. SEM-EDS spectra indicated a strong signal for Si, implying the coating procedure of silica onto the particles surface to be successfully accomplished. Fourier transform infrared (FT-IR) spectra analysis confirmed the binding of amino silane molecules onto the surface of the maghemite nanoparticles mediated Si-O-Si chemical bonds. Compared to the free enzyme, the covalently bound cholesterol oxidase retained 50% of its activity. Binding of enzyme onto chemically modified magnetic nanoparticles via glutaraldehyde activation is a promising method for developing biosensing components in biomedicine.

  18. Detection of water in jet fuel using layer-by-layer thin film coated long period grating sensor.

    PubMed

    Puckett, Sean D; Pacey, Gilbert E

    2009-04-15

    The quantitative measurement of jet fuel additives in the field is of interest to the Air Force. The "smart nozzle" project was designed as a state-of-the-art diagnostics package attached to a single-point refueling nozzle for assessing key fuel properties as the fuel is dispensed. The objective of the work was to show proof of concept that a layer-by-layer thin film and long period grating fibers could be used to detect the presence of water in jet fuel. The data for the nafion/PDMA film and a long period grating fiber is a combination capable of quantitative measurement of water in kerosene. The average response (spectral loss wavelength shift) to the kerosene sample ranged from -6.0 for 15 ppm to -126.5 for 60 ppm water. The average calculated value for the check standard was 21.71 and ranged from 21.25 to 22.00 with a true value of 22.5 ppm water. Potential interferences were observed and are judged to be insignificant in real samples. PMID:19174242

  19. Preparation of novel capsosome with liposomal core by layer-by-Layer self-assembly of sodium hyaluronate and chitosan.

    PubMed

    Yoo, Cha Young; Seong, Joon Seob; Park, Soo Nam

    2016-08-01

    Multi-compartmentalized capsosomes are polyelectrolyte capsules with liposomes as cargo, and are prepared by combining liposomes and polymer capsules. They offer additional functionality while maintaining the advantages and compensating for the weak points of both systems. In this study, a polyelectrolyte multilayered liposome was prepared by alternating adsorption of negatively charged sodium hyaluronate (HA) and positively charged chitosan (CH) on the surface of a cationic core liposome (CL) via layer-by-layer (LbL) deposition. Then, smaller sized liposomes (L) were coated onto the multilayered liposome. Lastly, the particle surfaces were coated with HA as a capping layer to obtain a novel type of capsosome with a liposomal core. The amount of adsorbed liposome was measured for different pH values (pH 2-10) and with liposome solutions of different concentrations (1-3%). The highest liposome adsorption occurred at pH 10 in the 3% solution, respectively. Finally, capsosomes in the size range of 500nm to 2μm were observed and the attached liposomes were located both on the surface and within the polymer shell. In conclusion, the cell-mimicking, liposome-based capsosomes could have infinite applications in the field of medicine, pharmaceuticals, and cosmetics as compartmentalized microreactors, multi-drug delivery systems with controlled release, or functional artificial cells in the future. PMID:27085041

  20. Characterization of the estrogen receptor and its dynamics in MCF-7 human breast cancer cells using a covalently attaching antiestrogen

    SciTech Connect

    Monsma, F.J. Jr.; Katzenellenbogen, B.S.; Miller, M.A.; Ziegler, Y.S.; Katzenellenbogen, J.A.

    1984-07-01

    The authors have used a covalently attaching antiestrogen, tamoxifen aziridine TA to analyze the structure and dynamics of the estrogen receptor in MCF-7 human breast cancer cells. The labeling of receptor with (/sup 3/H)TA is specific, being blocked only by estrogens and antiestrogens, and the labeling is very efficient in that TA labels covalently the same number of receptors that are labeled reversibly by estradiol. In cells exposed to (/sup 3/H)TA for 1 h, most of the covalently associated radioactivity is found in the 0.6 M KCl extract of the nuclear fraction; this receptor has an apparent mol wt of 63,000 +/- 2000 by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and a pI of 5.7 by gel isoelectric focusing in the presence of 8 M urea. The mol wt and pI of cytosol receptor labeled with (/sup 3/H) TA are identical. In cells labeled with (/sup 3/H)TA (20 nM) for 1 h and then exposed to a chase of 10(-6) M estradiol, (3H)TA-labeled nuclear receptor disappears with a half-life of 4 h. Affinity labeled receptor interacts with several monoclonal antibodies to MCF-7 estrogen receptor, and it can be purified extensively by immunoadsorbent chromatography. The findings of similar mol wt and isoelectric points for soluble cytosol and nuclear extracted receptors under strongly denaturing and disaggregating conditions reveal that nuclear localization of receptor after ligand binding is not associated with major structural alterations in the receptor component labeled by TA.

  1. Investigation of human cell response to covalently attached RADA16-I peptide on silicon surfaces.

    PubMed

    Shamsi, Fahimeh

    2016-09-01

    We described a modification of the ionic (RADARADARADARADA)(1) peptide or RADA16-I with 4-azidophenyl isothiocyanate via a specific and gentle reaction. The azidated peptide was covalently immobilized on an alkyne-terminated monolayer on Si(111) via the Cu(I)-catalyzed Huisgen 1,3-dipolar cycloaddition reaction. Detailed characterization using Impedance spectroscopy (IS), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy demonstrated high coverage of the RADA 16-I peptide on silicon surfaces. Scanning electron microscopy (SEM) and methyl tetrazole sulfate (MTS) assay were used to characterize the morphology and proliferation ability of human fibroblast cells on surfaces. Cell adhesion assay was performed to examine cell-substrate interactions. Significant differences in fibroblast cell morphology, adhesion, and viability were observed on the RADA16-I peptide modified surfaces compared to the control surfaces. These results may suggest a potential application of RADA16-I peptide modified surfaces in biomedical applications. PMID:27236098

  2. Chemical reactivity of Synechococcus sp. PCC 7002 and Synechocystis sp. PCC 6803 hemoglobins: covalent heme attachment and bishistidine coordination

    PubMed Central

    Nothnagel, Henry J.; Preimesberger, Matthew R.; Pond, Matthew P.; Winer, Benjamin Y.; Adney, Emily M.

    2011-01-01

    In the absence of an exogenous ligand, the hemoglobins from the cyanobacteria Synechocystis sp. PCC 6803 and Synechococcus sp. PCC 7002 coordinate the heme group with two axial histidines (His46 and His70). These globins also form a covalent linkage between the heme 2-vinyl substituent and His117. The in vitro mechanism of heme attachment to His117 was examined with a combination of site-directed mutagenesis, NMR spectroscopy, and optical spectroscopy. The results supported an electrophilic addition with vinyl protonation being the rate-determining step. Replacement of His117 with a cysteine demonstrated that the reaction could occur with an alternative nucleophile. His46 (distal histidine) was implicated in the specificity of the reaction for the 2-vinyl group as well as protection of the protein from oxidative damage caused by exposure to exogenous H2O2. PMID:21240532

  3. Covalent attachment and growth of nanocrystalline films of photocatalytic TiOF2

    NASA Astrophysics Data System (ADS)

    Zhu, Jian; Lv, Fujian; Xiao, Shengxiong; Bian, Zhenfeng; Buntkowsky, Gerd; Nuckolls, Colin; Li, Hexing

    2014-11-01

    This manuscript describes a synthesis of nanocrystalline TiOF2 film. The nanocrystalline TiOF2 becomes chemically attached to the surface of the glass slide. These films are robust and can be recycled as photocatalysts for the degradation of organic dyes and solvents. These films also have significant antibacterial properties upon irradiation.This manuscript describes a synthesis of nanocrystalline TiOF2 film. The nanocrystalline TiOF2 becomes chemically attached to the surface of the glass slide. These films are robust and can be recycled as photocatalysts for the degradation of organic dyes and solvents. These films also have significant antibacterial properties upon irradiation. Electronic supplementary information (ESI) available: Methods for sample preparation, characterization and Fig. S1-S8. See DOI: 10.1039/c4nr05598e

  4. Characterization of Field Effect Transistor Biosensors Fabricated Using Layer-by-Layer Nanoassembly Process.

    PubMed

    Pathak, Pushparaj; Que, Long

    2015-12-01

    In order to avoid the fabrication complexity involved with a single carbon nanotube (CNT) based immunosensor, herein we report an FET based biosensor, in which the channel is made out of Carbon Nanotube Thin Film (CNTF). The CNTF channel between the source and drain electrodes is assembled using a combination of photolithography and electrostatic layer-by-layer self-assembly (LbL). The fabricated device behaves like a p-type transistor. The bio-affinity interaction between Protein A and rabbit Immunoglobulin G (IgG) is used to model the immunosensing, and our initial results show the device is capable of detecting IgG concentrations as low as 1 pg/mL. PMID:26682397

  5. Manufacturing three-dimensional nickel titanium articles using layer-by-layer laser-melting technology

    NASA Astrophysics Data System (ADS)

    Shishkovsky, I. V.; Yadroitsev, I. A.; Smurov, I. Yu.

    2013-12-01

    Specific features of layer-by-layer synthesis of three-dimensional (3D) nickel titanium (NiTi, nitinol) articles by selective laser melting (SLM) technology have been studied. Nonporous 3D nitinol articles have been obtained for the first time in a single technological cycle. A necessary condition was that the NiTi powder medium was heated to 500°C during sintering. The structure and composition of intermetallic phases in SLM-synthesized samples have been studied by optical metallography, microhardness measurements, scanning electron microscopy, X-ray diffraction, and energy-dispersive x-ray analysis techniques. Optimum SLM regimes for manufacturing NiTi articles and promising medical applications of this material are considered.

  6. Enhanced amplified spontaneous emission using layer-by-layer assembled cowpea mosaic virus

    NASA Astrophysics Data System (ADS)

    Li, Na; Deng, Zhaoqi; Lin, Yuan; Zhang, Xiaojie; Geng, Yanhou; Ma, Dongge; Su, Zhaohui

    2009-01-01

    Layer-by-layer assembly technique was used to construct ultrathin film of cowpea mosaic virus (CPMV) by electrostatic interactions, and the film was employed as a precursor on which an OF8T2 film was deposited by spin coating. Amplified spontaneous emission (ASE) was observed and improved for the OF8T2 film. Compared with OF8T2 film on quartz, the introduction of CPMV nanoparticles reduced the threshold and loss, and remarkably increased the net gain. The threshold, loss, and gain reached 0.05 mJ/pulse, 6.9 cm-1, and 82 cm-1, respectively. CPMV nanoparticles may enormously scatter light, resulting in a positive feedback, thus the ASE is easily obtained and improved.

  7. Layer-by-layer self-assembly of polyelectrolyte functionalized MoS2 nanosheets.

    PubMed

    Shen, Jianfeng; Pei, Yu; Dong, Pei; Ji, Jin; Cui, Zheng; Yuan, Junhua; Baines, Robert; Ajayan, Pulickel M; Ye, Mingxin

    2016-05-01

    Few-layered polyelectrolyte functionalized MoS2 nanosheets were obtained for the first time through in situ polymerization of MoS2 nanosheets with poly(acrylic acid) and poly(acrylamide), both of which demonstrated excellent dispersibility and stability in water. After designing and optimizing the components of this series of polyelectrolyte functionalized MoS2 nanosheets, by exploiting the electrostatic interactions present in the modified MoS2 nanosheets, we further created a series of layer-by-layer (LBL) self-assembling MoS2-based films. To this end, uniform MoS2 nanosheet-based LBL films were precisely deposited on substrates such as quartz, silicon, and ITO. The polyelectrolyte functionalized MoS2 nanosheet assembled LBL film-modified electrodes demonstrated enhanced electrocatalytic activity for H2O2. As such, they are conducive to efficient sensors and advanced biosensing systems. PMID:27102889

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

  9. Direct atomic-scale observation of layer-by-layer oxide growth during magnesium oxidation

    SciTech Connect

    Zheng, He; Wu, Shujing; Sheng, Huaping; Liu, Chun; Liu, Yu; Cao, Fan; Zhou, Zhichao; Zhao, Dongshan E-mail: dszhao@whu.edu.cn; Wang, Jianbo E-mail: dszhao@whu.edu.cn; Zhao, Xingzhong

    2014-04-07

    The atomic-scale oxide growth dynamics are directly revealed by in situ high resolution transmission electron microscopy during the oxidation of Mg surface. The oxidation process is characterized by the layer-by-layer growth of magnesium oxide (MgO) nanocrystal via the adatom process. Consistently, the nucleated MgO crystals exhibit faceted surface morphology as enclosed by (200) lattice planes. It is believed that the relatively lower surface energies of (200) lattice planes should play important roles, governing the growth mechanism. These results facilitate the understanding of the nanoscale oxide growth mechanism that will have an important impact on the development of magnesium or magnesium alloys with improved resistance to oxidation.

  10. Tailored surface engineering of pigments by layer-by-layer coating.

    PubMed

    Dähne, Lars; Schneider, Julia; Lewe, Dirk; Petersen, Henrik

    2015-01-01

    We have evaluated the feasibility of layer-by-layer encapsulation technology for the improvement of dye pigments used for tattoos or permanent make-up. The formation of core-shell structures is possible by coating pigments with thin films of several different polyelectrolytes using this technology. The physicochemical surface properties, such as charge density and chemical functionality, can be reproducibly varied in a wide range. Tailoring the surface properties independently from the pigment core allows one to control the rheological behaviour of pigment suspensions, to prevent aggregation between different pigments, to reduce the cytotoxicity, and to influence the response of phagocytes in order to have similar or the same uptake and bioclearance for all pigments. These properties determine the durability and colour tone stability of tattoos and permanent make-up. PMID:25833634

  11. High {Tc} trilayer tunneling and Josephson junction structures made using atomic layer by layer growth

    SciTech Connect

    Eckstein, J.N.; Bozovic, I.; Virshup, G.F.

    1994-12-31

    Very precise artificial structuring of high {Tc} heterostructures is possible using atomic layer-by-layer molecular beam epitaxy (ALL-MBE). Cuprates are combined with other oxides, such as titanates, to make atomically precise heterostructures for studying transport and interfacial effects. Titanate slabs as thin as one unit cell thick can be grown without pinholes and provide tunneling barriers for c-axis transport. Single doped unit cells of BSCCO-2212 can also be used as barriers. These give SNS Josephson junctions at temperatures as high as 65 K. Since the crystallographic structure of the barrier is identical to the structure of the 2212 electrode material, it is easily possible to stack more than junction in close proximity. This results in phase-locked operation of two junctions together.

  12. Systematic layer-by-layer characterization of multilayers for three-dimensional data storage and logic

    NASA Astrophysics Data System (ADS)

    Petit, Dorothée; Lavrijsen, Reinoud; Lee, JiHyun; Mansell, Rhodri; Fernández-Pacheco, Amalio; Cowburn, Russell P.

    2016-04-01

    Magnetic kink solitons are used as a probe to experimentally measure the layer-by-layer coercivity and interlayer coupling strength of an antiferromagnetically coupled perpendicularly magnetized Co multilayer. The magnetic response is well described by a nearest neighbor Ising macrospin model. By controlling the position of one, two or three solitons in the stack using globally applied magnetic fields, we successfully probe the switching of individual buried layers under different neighboring configurations, allowing us to access individual layer's characteristic parameters. We found the coercivity to increase dramatically up the multilayer, while the interlayer coupling strength decreased slightly. We corroborate these findings with scanning transmission electron microscopy images where a degrading quality of the multilayer is observed. This method provides a very powerful tool to characterize the quality of individual layers in complex multilayers, without the need for depth-sensitive magnetic characterization equipment.

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

    PubMed Central

    2013-01-01

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

  14. Underpotential deposition-mediated layer-by-layer growth of thin films

    SciTech Connect

    Wang, Jia Xu; Adzic, Radoslav R.

    2015-05-19

    A method of depositing contiguous, conformal submonolayer-to-multilayer thin films with atomic-level control is described. The process involves the use of underpotential deposition of a first element to mediate the growth of a second material by overpotential deposition. Deposition occurs between a potential positive to the bulk deposition potential for the mediating element where a full monolayer of mediating element forms, and a potential which is less than, or only slightly greater than, the bulk deposition potential of the material to be deposited. By cycling the applied voltage between the bulk deposition potential for the mediating element and the material to be deposited, repeated desorption/adsorption of the mediating element during each potential cycle can be used to precisely control film growth on a layer-by-layer basis. This process is especially suitable for the formation of a catalytically active layer on core-shell particles for use in energy conversion devices such as fuel cells.

  15. Layer-by-layer Collagen Deposition in Microfluidic Devices for Microtissue Stabilization.

    PubMed

    McCarty, William J; Prodanov, Ljupcho; Bale, Shyam Sundhar; Bhushan, Abhinav; Jindal, Rohit; Yarmush, Martin L; Usta, O Berk

    2015-01-01

    Although microfluidics provides exquisite control of the cellular microenvironment, culturing cells within microfluidic devices can be challenging. 3D culture of cells in collagen type I gels helps to stabilize cell morphology and function, which is necessary for creating microfluidic tissue models in microdevices. Translating traditional 3D culture techniques for tissue culture plates to microfluidic devices is often difficult because of the limited channel dimensions. In this method, we describe a technique for modifying native type I collagen to generate polycationic and polyanionic collagen solutions that can be used with layer-by-layer deposition to create ultrathin collagen assemblies on top of cells cultured in microfluidic devices. These thin collagen layers stabilize cell morphology and function, as shown using primary hepatocytes as an example cell, allowing for the long term culture of microtissues in microfluidic devices. PMID:26485274

  16. Anisotropic behavior of layer-by-layer films using highly disordered copper hexacyanoferrate(II) nanoparticles

    NASA Astrophysics Data System (ADS)

    Soek, Rafael N.; Schmidt, Ariane; Winnischofer, Herbert; Vidotti, Marcio

    2016-08-01

    Copper hexacyanoferrate(II) (Cuhcf(II)) nanoparticles (NPs) were synthesized by using a simple and straightforward methodology using aqueous solution without the need of any further passivating agent. The 15 nm NPs (obtained by TEM) were fully characterized by XRD, FTIR and Raman spectroscopy that revealed a high number of structural defects. These structural defects are responsible to produce a strong internal dipole moment. This leads to an anisotropic growth onto the electrode surface by using the layer-by-layer technique. Specular Reflectance FTIR corroborates with our assumption. The defects are also responsible for the high electroactivity of the Cuhcf(II)NPs modified electrodes in sodium based electrolytes. Our results contrast with others in which the authors attributed the cell distortion as the main phenomenon.

  17. Nanofilms of hyaluronan/chitosan assembled layer-by-layer: An antibacterial surface for Xylella fastidiosa.

    PubMed

    Hernández-Montelongo, Jacobo; Nascimento, Vicente F; Murillo, Duber; Taketa, Thiago B; Sahoo, Prasana; de Souza, Alessandra A; Beppu, Marisa M; Cotta, Monica A

    2016-01-20

    In this work, nanofilms of hyaluronan/chitosan (HA/CHI) assembled layer by layer were synthesized; their application as a potential antimicrobial material was demonstrated for the phytopathogen Xylella fastidiosa, a gram-negative bacterium, here used as a model. For the synthesis, the influence of pH and ionic strength of these natural polymer stem-solutions on final characteristics of the HA/CHI nanofilms was studied in detail. The antibacterial effect was evaluated using widefield fluorescence microscopy. These results were correlated with the chemical properties of the nanofilms, studied by FTIR and Raman spectroscopy, as well as with their morphology and surface properties characterized using SEM and AFM. The present findings can be extended to design and optimize HA/CHI nanofilms with enhanced antimicrobial behavior for other type of phytopathogenic gram-negative bacteria species, such as Xanthomonas citri, Xanthomas campestri and Ralstonia solanacearum. PMID:26572322

  18. Layer-by-layer polysaccharide-coated liposomes for sustained delivery of epidermal growth factor.

    PubMed

    Kaminski, Gabriel A T; Sierakowski, Maria Rita; Pontarolo, Roberto; Santos, Larissa Antoniacomi Dos; de Freitas, Rilton Alves

    2016-04-20

    A three-dimensional layer-by-layer (LbL) structure composed by xanthan and galactomannan biopolymers over dioctadecyldimethylammonium bromide (DODAB) liposome template was proposed and characterized for protein drug delivery. The polymers and the surfactant interaction were sufficiently strong to create a LbL structure up to 8 layers, evaluated using quartz crystal microbalance (QCM) and zeta potential analysis. The polymer-liposome binding enthalpy was determined by isothermal titration calorimetry (ITC). The bilayer of biopolymer-coated liposomes with diameters of 165 (±15)nm, measured by dynamic light scattering (DLS), and ζ-potential of -4 (±13)mV. These bilayer-coated nanoparticles increased up to 5 times the sustained release of epidermal growth factor (EGF) at a first order rate of 0.005min(-1). This system could be useful for improving the release profile of low-stability drugs like EGF. PMID:26876836

  19. Porous Materials with Tunable Structure and Mechanical Properties via Templated Layer-by-Layer Assembly.

    PubMed

    Ziminska, Monika; Dunne, Nicholas; Hamilton, Andrew R

    2016-08-31

    The deposition of stiff and strong coatings onto porous templates offers a novel strategy for fabricating macroscale materials with controlled architectures at the micro- and nanoscale. Here, layer-by-layer assembly is utilized to fabricate nanocomposite-coated foams with highly customizable properties by depositing polymer-nanoclay coatings onto open-cell foam templates. The compressive mechanical behavior of these materials evolves in a predictable manner that is qualitatively captured by scaling laws for the mechanical properties of cellular materials. The observed and predicted properties span a remarkable range of density-stiffness space, extending from regions of very soft elastomer foams to very stiff, lightweight honeycomb and lattice materials. PMID:27513218

  20. Layer-by-layer assembled multilayers using catalase-encapsulated gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Kim, Sungwoo; Park, Jeongju; Cho, Jinhan

    2010-09-01

    We introduce a novel and versatile approach for the preparation of multilayers, based on catalase-encapsulated gold nanoparticles (CAT-AuNP), allowing electrostatic charge reversal and structural transformation through pH adjustment. CAT-AuNP, which are synthesized directly from CAT stabilizer, can be electrostatically assembled with anionic and cationic PEs as a result of the charge reversal of the catalase stabilizers through pH control. In particular, at pH 5.2, near the pI of catalase, dispersed CAT-AuNP are structurally transformed into colloidal or network CAT-AuNP nanocomposites. Furthermore, we demonstrate that the layer-by-layer assembled multilayers composed of PEs and CAT-AuNP induce an effective electron transfer between CAT and the electrode as well as a high loading of CAT and AuNP, and resultantly exhibit a highly catalytic activity toward H2O2.

  1. Enzymatic Degradation of Polysaccharide-Based Layer-by-Layer Structures.

    PubMed

    Cardoso, Matias J; Caridade, Sofia G; Costa, Rui R; Mano, João F

    2016-04-11

    The lack of knowledge on the degradation of layer-by-layer structures is one of the causes hindering its translation to preclinical assays. The enzymatic degradation of chitosan/hyaluronic acid films in the form of ultrathin films, freestanding membranes, and microcapsules was studied resorting to hyaluronidase. The reduction of the thickness of ultrathin films was dependent on the hyaluronidase concentration, leading to thickness and topography variations. Freestanding membranes exhibited accelerated weight loss up to 120 h in the presence of the enzyme, achieving complete degradation. Microcapsules with around 5 μm loaded simultaneously with FITC-BSA and hyaluronidase showed that the coencapsulation of such enzyme and protein mixture led to a FITC-BSA release four times higher than in the absence of hyaluronidase. The results suggest that the degradation of LbL devices may be tuned via embedded enzymes, namely, in the controlled release of active agents in biomedical applications. PMID:26957012

  2. Systematic layer-by-layer characterization of multilayers for three-dimensional data storage and logic.

    PubMed

    Petit, Dorothée; Lavrijsen, Reinoud; Lee, JiHyun; Mansell, Rhodri; Fernández-Pacheco, Amalio; Cowburn, Russell P

    2016-04-15

    Magnetic kink solitons are used as a probe to experimentally measure the layer-by-layer coercivity and interlayer coupling strength of an antiferromagnetically coupled perpendicularly magnetized Co multilayer. The magnetic response is well described by a nearest neighbor Ising macrospin model. By controlling the position of one, two or three solitons in the stack using globally applied magnetic fields, we successfully probe the switching of individual buried layers under different neighboring configurations, allowing us to access individual layer's characteristic parameters. We found the coercivity to increase dramatically up the multilayer, while the interlayer coupling strength decreased slightly. We corroborate these findings with scanning transmission electron microscopy images where a degrading quality of the multilayer is observed. This method provides a very powerful tool to characterize the quality of individual layers in complex multilayers, without the need for depth-sensitive magnetic characterization equipment. PMID:26938688

  3. New type of Reverse Osmosis Membrane via Layer-by-Layer Assembly Process

    NASA Astrophysics Data System (ADS)

    Park, Junwoo; Bang, Joona; Park, Jeongju; Cho, Jinhan

    2009-03-01

    As to the commercial RO membranes for desalination, the polyamide (PA) based membranes have been widely used so far. However, they still have limitations, such as low permeability, bio-fouling, etc. In this work, we propose new types of polyelectrolyte-membranes which can overcome such problems. The membranes were designed by layer-by-layer (LbL) method using polyelectrolytes, including poly(allylamine hydrochloride), poly(styrene sulfonate), poly(acrylic acid), etc. Individual layers were adjusted by pH condition and number of deposition. The resulting multi-layered membranes were crosslinked by heat to provide the good durability. The morphologies were characterized by FE-SEM and AFM and the salt rejection was monitored by ion chromatography. By optimizing the membrane structures, we found that the water permeability was enhanced, while the salt rejection was as efficient as RO membranes. We believe that these results can provide the new protocol to design the advanced RO membrane.

  4. Development of polysaccharides-based edible coatings for citrus fruits: a layer-by-layer approach.

    PubMed

    Arnon, Hadar; Granit, Rina; Porat, Ron; Poverenov, Elena

    2015-01-01

    Biodegradable coatings for citrus fruits that would replace the currently used polyethylene-based waxes, are of great interest. Methylcellulose (MC), hydroxypropyl methylcellulose (HPMC), carboxymethyl cellulose (CMC) and chitosan (CH) coatings were examined on the most sensitive citrus fruit model: mandarins. Among the examined polysaccharides, CMC provided mandarins with the best firmness, lowest weight loss and satisfying gloss, while not affecting natural flavour and the respiration process. To enhance coating performance, glycerol, oleic acid and stearic acid were added; however, mandarin quality generally deteriorated with these additives. Then, a layer-by-layer (LBL) approach was applied. LbL coatings, based on a combination of two polysaccharides, CMC as an internal layer and chitosan as an external layer, gave the best performance. Different concentrations of chitosan were examined. The LbL coatings notably improved all quantified parameters of fruit quality, proving that polysaccharide-based edible coating may offer an alternative to synthetic waxes. PMID:25053081

  5. Spray-assisted layer-by-Layer (LbL) assembly of anisotropic materials

    NASA Astrophysics Data System (ADS)

    de, Souvik; Suarez Martinez, Pilar; Kavarthapu, Avanti; Lutkenhaus, Jodie

    2015-03-01

    Layer-by-layer (LbL) assembly has gained tremendous interest as it allows one to incorporate a large variety of molecules with nano-scale precision and very good reproducibility. In addition to charged polymers, the technique has become extremely popular to fabricate tailor-made thin films containing anisotropic nanomaterials (e.g., graphene oxide sheets). The challenge is that a standard protocol to fabricate ``all-polyelectrolyte'' LbL films may not necessarily give rise to satisfactory film growth when applied to LbL assembly where one of the adsorbing components is an anisotropic nanomaterial. Therefore, in this contribution, we combine polymers and anisotropic nanomaterials via dip- and spray-assisted LbL assembly and investigate the effect of charge density, exfoliation, concentration etc. of the components on the growth behavior and the film quality. The end result is a conformal, pin-hole free coating on model substrates (glass, silicon, metal) over a large area.

  6. Super Gas Barrier Thin Films via Layer-by-Layer Assembly of Polyelectrolytes and Clay

    NASA Astrophysics Data System (ADS)

    Priolo, Morgan; Gamboa, Daniel; Grunlan, Jaime

    2010-03-01

    Thin composite films of branched polyethylenimine (PEI), polyacrylic acid (PAA) and sodium montmorillonite clay (MMT) platelets were prepared using layer-by-layer assembly. Film thickness, mass deposited per layer, and barrier were shown to increase exponentially with the number of deposition cycles. After 32 layers (i.e., eight PEI/PAA/PEI/MMT quadlayers) are deposited, the resulting transparent film exhibits an oxygen transmission rate below the detection limit of commercial instrumentation (< 0.005 cm^3/m^2 . day). This level of oxygen barrier is believed to be due to a nano-brick wall microstructure comprised of exfoliated clay bricks in polymeric mortar, where the enhanced spacing between MMT layers, provided by PEI and PAA, creates channels perpendicular concentration gradient that delay the permeating molecule. These films are good candidates for flexible electronics, food, and pharmaceutical packaging due to their transparency, super gas barrier (that rivals SiOx) and lack of metal.

  7. Thin bacteria/Layered Double Hydroxide films using a layer-by-layer approach.

    PubMed

    Halma, Matilte; Khenifi, Aicha; Sancelme, Martine; Besse-Hoggan, Pascale; Bussière, Pierre-Olivier; Prévot, Vanessa; Mousty, Christine

    2016-07-15

    This paper reports the design of thin bacteria/Layered Double Hydroxides (LDH) films in which bacterial cells of Pseudomonas sp. strain ADP were assembled alternatively with Mg2Al-NO3 LDH nanosheets by a layer-by-layer deposition method. The UV-Vis spectroscopy was used to monitor the assembly process, showing a progressive increase in immobilized bacteria amount upon deposited cycles. The {ADP/LDH}n film was characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy and atomic force microscopy. The metabolic activity of immobilized bacteria was determined using chronoamperometry by measuring the biochemical oxygen demand in presence of glucose using an artificial electron acceptor (Fe(CN)6(3-)) at 0.5V/Ag-AgCl. A steady current of 0.250μAcm(-2) was reached in about 30s after the addition of 5mM glucose. PMID:27124809

  8. Three-Dimensional Nanoprinting via Scanning Probe Lithography-Delivered Layer-by-Layer Deposition.

    PubMed

    Zhao, Jianli; Swartz, Logan A; Lin, Wei-Feng; Schlenoff, Philip S; Frommer, Jane; Schlenoff, Joseph B; Liu, Gang-Yu

    2016-06-28

    Three-dimensional (3D) printing has been a very active area of research and development due to its capability to produce 3D objects by design. Miniaturization and improvement of spatial resolution are major challenges in current 3D printing technology development. This work reports advances in miniaturizing 3D printing to the nanometer scale using scanning probe microscopy in conjunction with local material delivery. Using polyelectrolyte polymers and complexes, we have demonstrated the concept of layer-by-layer nanoprinting by design. Nanometer precision is achieved in all three dimensions, as well as in interlayer registry. The approach enables production of designed functional 3D materials with nanometer resolution and, as such, creates a platform for conducting scientific research in designed 3D nanoenvironments as well. In doing so, it enables production of nanomaterials and scaffolds for photonics devices, biomedicine, and tissue engineering. PMID:27203853

  9. Tunable thermal and flame response of phosphonated oligoallylamines layer by layer assemblies on cotton.

    PubMed

    Carosio, Federico; Negrell-Guirao, Claire; Di Blasio, Alessandro; Alongi, Jenny; David, Ghislain; Camino, Giovanni

    2015-01-22

    In the present paper we have demonstrated how the change of the layer by layer deposition parameters can influence the final properties of cotton fabrics in terms of coating morphology, thermal stability and flammability. To this aim, novel synthetized oligoallylamines and phosphonated oligoallylamines have been assembled on the surface of cotton exploiting different molecular weights and pH conditions. Low molecular weights have yielded an incomplete "island growth" coating while high molecular weight resulted in a homogeneous coating which thickness was controlled by the adopted pH. Both low and high molecular weight assemblies induced a reduction of the cellulose decomposition temperatures that was, conversely, delayed by coatings assembled at pH=10. All assemblies were able to improve cotton flammability by suppressing the afterglow phenomenon; the best results in terms of flame spread and final residue have been achieved by high molecular weight assemblies. PMID:25439958

  10. Nucleation and Early Stages of Layer-by-Layer Growth of Metal Organic Frameworks on Surfaces

    PubMed Central

    2015-01-01

    High resolution atomic force microscopy (AFM) is used to resolve the evolution of crystallites of a metal organic framework (HKUST-1) grown on Au(111) using a liquid-phase layer-by-layer methodology. The nucleation and faceting of individual crystallites is followed by repeatedly imaging the same submicron region after each cycle of growth and we find that the growing surface is terminated by {111} facets leading to the formation of pyramidal nanostructures for [100] oriented crystallites, and triangular [111] islands with typical lateral dimensions of tens of nanometres. AFM images reveal that crystallites can grow by 5–10 layers in each cycle. The growth rate depends on crystallographic orientation and the morphology of the gold substrate, and we demonstrate that under these conditions the growth is nanocrystalline with a morphology determined by the minimum energy surface. PMID:26709359

  11. Layer-by-layer heparinization of decellularized liver matrices to reduce thrombogenicity of tissue engineered grafts

    PubMed Central

    Bruinsma, Bote G; Kim, Yeonhee; Berendsen, Tim A; Ozer, Sinan; Yarmush, Martin L; Uygun, Basak E

    2015-01-01

    Background Tissue-engineered liver grafts may offer a viable alternative to orthotopic liver transplantation and help overcome the donor organ shortage. Decellularized liver matrices (DLM) have a preserved vasculature and sustain hepatocellular function in culture, but graft survival after transplantation remains limited due to thrombogenicity of the matrix. Aim To evaluate the effect of heparin immobilization on DLM thrombogenicity. Methods Heparin was immobilized on DLMs by means of layer-by-layer deposition. Grafts with 4 or 8 bilayers and 2 or 4 g/L of heparin were recellularized with primary rat hepatocytes and maintained in culture for 5 days. Hemocompatibility of the graft was assessed by ex vivo diluted whole-blood perfusion and heterotopic transplantation. Results Heparin was deposited throughout the matrix and the heparin content in the graft was higher with increasing number of bilayers and concentration of heparin. Recellularization and in vitro albumin and urea production were unaffected by heparinization. Resistance to blood flow during ex vivo perfusion was lower with increased heparinization and, macroscopically, no clots were visible in grafts with 8 bilayers. Following transplantation, flow through the graft was limited in all groups. Histological evidence of thrombosis was lower in heparinized DLMs, but transplantation of DLM grafts was not improved. Conclusions Layer-by-layer deposition of heparin on a DLM is an effective method of immobilizing heparin throughout the graft and does not impede recellularization or hepatocellular function in vitro. Thrombogenicity during ex vivo blood perfusion was reduced in heparinized grafts and optimal with 8 bilayers, but transplantation remained unsuccessful with this method. Relevance for patients Tissue engineered liver grafts may offer a viable solution to dramatic shortages in donor organs PMID:26478914

  12. Fluorometric assay for quantitation of biotin covalently attached to proteins and nucleic acids.

    PubMed

    Batchelor, Robert H; Sarkez, Adam; Cox, W Gregory; Johnson, Iain

    2007-10-01

    As a component of the (strept)avidin affinity system, biotin is often covalently linked to proteins or nucleic acids. We describe here a microplate-based high-throughput fluorometric assay for biotin linked to either proteins or nucleic acids based on fluorescence resonance energy transfer (FRET). This assay utilizes a complex of Alexa Fluoro 488 dye-labeled avidin with a quencher dye, 2-(4'-hydroxyazobenzene) benzoic acid (HABA), occupying the biotin binding sites of the avidin. In the absence of biotin, HABA quenches the fluorescence emission of the Alexa Fluor 488 dyes via FRET HABA is displaced when biotin binds to the Alexa Fluor 488 dye-labeled avidin, resulting in decreased FRET efficiency. This mechanism results in an increase in fluorescence intensity directly related to the amount of biotin present in the sample. The assay is able to detect as little as 4 pmol biotin in a 0.1 mL volume within 15 min of adding sample to the reagent, with a Z-factor > 0.9. PMID:18019342

  13. Covalent attachment of microbial lipase onto microporous styrene-divinylbenzene copolymer by means of polyglutaraldehyde.

    PubMed

    Dizge, Nadir; Keskinler, Bülent; Tanriseven, Aziz

    2008-10-01

    A novel method for immobilization of Thermomyces lanuginosus lipase onto polyglutaraldehyde-activated poly(styrene-divinylbenzene) (STY-DVB), which is a hydrophobic microporous support has been successfully developed. The copolymer was prepared by the polymerization of the continuous phase of a high internal phase emulsion (polyHIPE). The concentrated emulsion consists of a mixture of styrene and divinylbenzene containing a suitable surfactant and an initiator as the continuous phase and water as the dispersed phase. Lipase from T. lanuginosus was immobilized covalently with 85% yield on the internal surface of the hydrophobic microporous poly(styrene-divinylbenzene) copolymer and used as a biocatalyst for the transesterification reaction. The immobilized enzyme has been fully active 30 days in storage and retained the activity during the 15 repeated batch reactions. The properties of free and immobilized lipase were studied. The effects of protein concentration, pH, temperature, and time on the immobilization, activity, and stability of the immobilized lipase were also studied. The newly synthesized microporous poly(styrene-divinylbenzene) copolymer constitutes excellent support for lipase. It given rise to high immobilization yield, retains enzymatic activity for 30 days, stable in structure and allows for the immobilization of large amount of protein (11.4mg/g support). Since immobilization is simple yet effective, the newly immobilized lipase could be used in several application including oil hydrolysis, production of modified oils, biodiesel synthesis, and removal of fatty acids from oils. PMID:18571389

  14. Electrical detection of the temperature induced melting transition of a DNA hairpin covalently attached to gold interdigitated microelectrodes

    PubMed Central

    Brewood, Greg P.; Rangineni, Yaswanth; Fish, Daniel J.; Bhandiwad, Ashwini S.; Evans, David R.; Solanki, Raj; Benight, Albert S.

    2008-01-01

    The temperature induced melting transition of a self-complementary DNA strand covalently attached at the 5′ end to the surface of a gold interdigitated microelectrode (GIME) was monitored in a novel, label-free, manner. The structural state of the hairpin was assessed by measuring four different electronic properties of the GIME (capacitance, impedance, dissipation factor and phase angle) as a function of temperature from 25°C to 80°C. Consistent changes in all four electronic properties of the GIME were observed over this temperature range, and attributed to the transition of the attached single-stranded DNA (ssDNA) from an intramolecular, folded hairpin structure to a melted ssDNA. The melting curve of the self-complementary single strand was also measured in solution using differential scanning calorimetry (DSC) and UV absorbance spectroscopy. Temperature dependent electronic measurements on the surface and absorbance versus temperature values measured in solution experiments were analyzed assuming a two-state process. The model analysis provided estimates of the thermodynamic transition parameters of the hairpin on the surface. Two-state analyses of optical melting data and DSC measurements provided evaluations of the thermodynamic transition parameters of the hairpin in solution. Comparison of surface and solution measurements provided quantitative evaluation of the effect of the surface on the thermodynamics of the melting transition of the DNA hairpin. PMID:18628294

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

    NASA Astrophysics Data System (ADS)

    Zhang, Xingcai

    with less powerful sonication. By using polymeric excipients combined with non-ionic and anionic surfactants along with regular sonication, the prepared particle sizes was uniform at around 140-150 nm. Less sonication time (ca 15 minutes) and lower sonication power avoided TiO2 contamination. The amphiphiles attached to the hydrophobic nanoparticles and served as anchors for LbL shell. The inner LbL layers and surfactants minimized the surface free energy, thereby preventing crystal form changes and nanoparticles coalescence, while the outermost layers enhanced colloidal stability. In the third part of the dissertation, LbL shells with PEGylation (using a block copolymer of poly-L-lysine (PLL) and PEG) for lapatinib were developed for enhanced colloidal stability in high molarity PBS buffer. In the above proposed paclitaxel and lapatinib formulation, we obtained 150-200 nm with high drug content of 80-90% due to very thin capsule walls (ca 10 nm). The drug release time from the LbL capsules was found to be between 10 and 20 hours depending on the shell thickness. Washless Layer-by-Layer assembly was used: 1) addition of polycation in the amount that is enough to reverse surface charge of the dispersion to a high positive (+30 mV) value; 2) addition of polyanion in the amount that is enough to reverse surface charge of the dispersion to a high negative (-30 mV) value. No intermediate washing of nanoparticles was done until the shell was complete. The washless method had the advantage of time and energy saving, preservation of the sample structure and no losses of sample. In the last part of the dissertation, we elaborated nanoformulation of two drugs in one nanocapsule locating paclitaxel in the core and lapatinib on the shell periphery. With this formulation, combining in one nanoparticle dual drugs, we reached the drugs' efficiency synergy. In a multidrug-resistant (MDR) ovarian cancer cell line, OVCAR-3, LbL lapatinib/paclitaxel nanocolloids mediated an enhanced cell

  16. Surface chemical study on the covalent attachment of hydroxypropyltrimethyl ammonium chloride chitosan to titanium surfaces

    NASA Astrophysics Data System (ADS)

    Xu, Xiaofen; Wang, Ling; Guo, Shengrong; Lei, Lei; Tang, Tingting

    2011-10-01

    An anti-microbial and bioactive coating could not only reduce the probability of infection related to titanium implants but also support the growth of surrounding osteogenic cells. Our previous study has showed that hydroxypropyltrimethyl ammonium chloride chitosan (HACC) with a DS (degrees of substitution) of 18% had improved solubility and significantly higher antibacterial activities against three bacteria which were usually associated with infections in orthopaedics. In the current study, HACC with a DS of 18% coating was bonded to titanium surface by a three-step process. The titanium surface after each individual reaction step was analyzed by X-ray photoelectron spectroscopy (XPS) and attenuated total reflection (ATR) of Fourier-transformed infrared (FT-IR) spectroscopy. The XPS results demonstrated that there were great changes in the atomic ratios of C/Ti, O/Ti, and N/Ti after each reaction step. The XPS high resolution and corresponding devolution spectra of carbon, oxygen, nitrogen, and titanium were also in good coordination with the anticipated reaction steps. Additionally, the absorption bands around 3365 cm -1 (-OH vibration), 1664 cm -1 (Amide I), 1165 cm -1 ( νas, C-O-C bridge), and the broad absorption bands between 958 cm -1 and 1155 cm -1 (skeletal vibrations involving the C-O stretching of saccharide structure of HACC) verified that HACC was successfully attached to titanium surface.

  17. Assembling semiconducting molecules by covalent attachment to a lamellar crystalline polymer substrate

    PubMed Central

    Machatschek, Rainhard; Ortmann, Patrick; Reiter, Renate; Mecking, Stefan

    2016-01-01

    Summary We have investigated the potential of polymers containing precisely spaced side-branches for thin film applications, particularly in the context of organic electronics. Upon crystallization, the side-branches were excluded from the crystalline core of a lamellar crystal. Thus, the surfaces of these crystals were covered by side-branches. By using carboxyl groups as side-branches, which allow for chemical reactions, we could functionalize the crystal with semiconducting molecules. Here, we compare properties of crystals differing in size: small nanocrystals and large single crystals. By assembling nanocrystals on a Langmuir trough, large areas could be covered by monolayers consisting of randomly arranged nanocrystals. Alternatively, we used a method based on local supersaturation to grow large area single crystals of the precisely side-branched polymer from solution. Attachment of the semiconducting molecules to the lamellar surface of large single crystals was possible, however, only after an appropriate annealing procedure. As a function of the duration of the grafting process, the morphology of the resulting layer of semiconducting molecules changed from patchy to compact. PMID:27335767

  18. Layer-by-layer self-assembly of polyelectrolyte functionalized MoS2 nanosheets

    NASA Astrophysics Data System (ADS)

    Shen, Jianfeng; Pei, Yu; Dong, Pei; Ji, Jin; Cui, Zheng; Yuan, Junhua; Baines, Robert; Ajayan, Pulickel M.; Ye, Mingxin

    2016-05-01

    Few-layered polyelectrolyte functionalized MoS2 nanosheets were obtained for the first time through in situ polymerization of MoS2 nanosheets with poly(acrylic acid) and poly(acrylamide), both of which demonstrated excellent dispersibility and stability in water. After designing and optimizing the components of this series of polyelectrolyte functionalized MoS2 nanosheets, by exploiting the electrostatic interactions present in the modified MoS2 nanosheets, we further created a series of layer-by-layer (LBL) self-assembling MoS2-based films. To this end, uniform MoS2 nanosheet-based LBL films were precisely deposited on substrates such as quartz, silicon, and ITO. The polyelectrolyte functionalized MoS2 nanosheet assembled LBL film-modified electrodes demonstrated enhanced electrocatalytic activity for H2O2. As such, they are conducive to efficient sensors and advanced biosensing systems.Few-layered polyelectrolyte functionalized MoS2 nanosheets were obtained for the first time through in situ polymerization of MoS2 nanosheets with poly(acrylic acid) and poly(acrylamide), both of which demonstrated excellent dispersibility and stability in water. After designing and optimizing the components of this series of polyelectrolyte functionalized MoS2 nanosheets, by exploiting the electrostatic interactions present in the modified MoS2 nanosheets, we further created a series of layer-by-layer (LBL) self-assembling MoS2-based films. To this end, uniform MoS2 nanosheet-based LBL films were precisely deposited on substrates such as quartz, silicon, and ITO. The polyelectrolyte functionalized MoS2 nanosheet assembled LBL film-modified electrodes demonstrated enhanced electrocatalytic activity for H2O2. As such, they are conducive to efficient sensors and advanced biosensing systems. Electronic supplementary information (ESI) available: SEM, AFM and TEM characterization of PAA-MoS2 and PAM-MoS2 nanocomposites. More characterization and electrochemical properties of LBL films

  19. In situ imaging and control of layer-by-layer femtosecond laser thinning of graphene

    NASA Astrophysics Data System (ADS)

    Li, D. W.; Zhou, Y. S.; Huang, X.; Jiang, L.; Silvain, J.-F.; Lu, Y. F.

    2015-02-01

    Although existing methods (chemical vapor deposition, mechanical exfoliation, etc.) are available to produce graphene, the lack of thickness control limits further graphene applications. In this study, we demonstrate an approach to precisely thin graphene films to a specific thickness using femtosecond (fs) laser raster scanning. By using appropriate laser fluence and scanning times, graphene thinning with an atomic layer precision, namely layer-by-layer graphene removal, has been realized. The fs laser used was configured in a four-wave mixing (FWM) system which can be used to distinguish graphene layer thickness and count the number of layers using the linear relationship between the FWM signal intensity and the graphene thickness. Furthermore, FWM imaging has been successfully applied to achieve in situ, real-time monitoring of the fs laser graphene thinning process. This method can not only realize the large-scale thinning of graphene with atomic layer precision, but also provide in situ, rapid imaging capability of graphene for an accurate assessment of the number of layers.Although existing methods (chemical vapor deposition, mechanical exfoliation, etc.) are available to produce graphene, the lack of thickness control limits further graphene applications. In this study, we demonstrate an approach to precisely thin graphene films to a specific thickness using femtosecond (fs) laser raster scanning. By using appropriate laser fluence and scanning times, graphene thinning with an atomic layer precision, namely layer-by-layer graphene removal, has been realized. The fs laser used was configured in a four-wave mixing (FWM) system which can be used to distinguish graphene layer thickness and count the number of layers using the linear relationship between the FWM signal intensity and the graphene thickness. Furthermore, FWM imaging has been successfully applied to achieve in situ, real-time monitoring of the fs laser graphene thinning process. This method can not

  20. Ultrathin Molecular-Layer-by-Layer Polyamide Membranes: Insights from Atomistic Molecular Simulations.

    PubMed

    Liyana-Arachchi, Thilanga P; Sturnfield, James F; Colina, Coray M

    2016-09-01

    In this study, we present an atomistic simulation study of several physicochemical properties of polyamide (PA) membranes formed from interfacial polymerization or from a molecular-layer-by-layer (mLbL) on a silicon wafer. These membranes are composed of meta-phenylenediamine (MPD) and benzene-1,3,5-tricarboxylic acid chloride (TMC) for potential reverse osmosis (RO) applications. The mLbL membrane generation procedure and the force field models were validated, by comparison with available experimental data, for hydrated density, membrane swelling, and pore size distributions of PA membranes formed by interfacial polymerization. Physicochemical properties such as density, free volume, thickness, the degree of cross-linking, atomic compositions, and average molecular orientation (which is relevant for the mLbL membranes) are compared for these different processes. The mLbL membranes are investigated systematically with respect to TMC monomer growth rate per substrate surface area, MPD/TMC ratio, and the number of mLbL deposition cycles. Atomistic simulations show that the mLbL deposition generates membranes with a constant film growth if both the TMC monomer growth rate and MPD/TMC monomer ratio are kept constant. The film growth rate increases with TMC monomer growth rate or MPD/TMC ratio. Furthermore, it was found on one hand that the mLbL membrane density and free volume varies significantly with respect to the TMC monomer growth rate, while on the other hand the degree of cross-linking and the atomic composition varies considerably with the MPD/TMC ratio. Additionally, it was found that both TMC and MPD orient at a tilted angle with respect to the substrate surface, where their angular distribution and average angle orientation depend on both the TMC growth rate and the number of deposition cycles. This study illustrates that molecular simulations can play a crucial role in the understanding of structural properties that can empower the design of the next

  1. Controlled surface functionality of magnetic nanoparticles by layer-by-layer assembled nano-films

    NASA Astrophysics Data System (ADS)

    Choi, Daheui; Son, Boram; Park, Tai Hyun; Hong, Jinkee

    2015-04-01

    Over the past several years, the preparation of functionalized nanoparticles has been aggressively pursued in order to develop desired structures, compositions, and structural order. Among the various nanoparticles, iron oxide magnetic nanoparticles (MNPs) have shown great promise because the material generated using these MNPs can be used in a variety of biomedical applications and possible bioactive functionalities. In this study, we report the development of various functionalized MNPs (F-MNPs) generated using the layer-by-layer (LbL) self-assembly method. To provide broad functional opportunities, we fabricated F-MNP bio-toolbox by using three different materials: synthetic polymers, natural polymers, and carbon materials. Each of these F-MNPs displays distinct properties, such as enhanced thickness or unique morphologies. In an effort to explore their biomedical applications, we generated basic fibroblast growth factor (bFGF)-loaded F-MNPs. The bFGF-loaded F-MNPs exhibited different release mechanisms and loading amounts, depending on the film material and composition order. Moreover, bFGF-loaded F-MNPs displayed higher biocompatibility and possessed superior proliferation properties than the bare MNPs and pure bFGF, respectively. We conclude that by simply optimizing the building materials and the nanoparticle's film composition, MNPs exhibiting various bioactive properties can be generated.Over the past several years, the preparation of functionalized nanoparticles has been aggressively pursued in order to develop desired structures, compositions, and structural order. Among the various nanoparticles, iron oxide magnetic nanoparticles (MNPs) have shown great promise because the material generated using these MNPs can be used in a variety of biomedical applications and possible bioactive functionalities. In this study, we report the development of various functionalized MNPs (F-MNPs) generated using the layer-by-layer (LbL) self-assembly method. To provide

  2. Dual drug delivery microcapsules via layer-by-layer self-assembly.

    PubMed

    Manna, Uttam; Patil, Satish

    2009-09-15

    The integration of hydrophobic and hydrophilic drugs in the polymer microcapsule offers the possibility of developing a new drug delivery system that combines the best features of these two distinct classes of material. Recently, we have reported the encapsulation of an uncharged water-insoluble drug in the polymer membrane. The hydrophobic drug is deposited using a layer-by-layer (LbL) technique, which is based on the sequential adsorption of oppositely charged polyelectrolytes onto a charged substrate. In this paper, we report the encapsulation of two different drugs, which are invariably different in structure and in their solubility in water. We have characterized these dual drug vehicular capsules by confocal laser scanning microscopy, atomic force microscopy, visible microscopy, and transmission electron microscopy. The growth of a thin film on a flat substrate by LbL was monitored by UV-vis spectra. The desorption kinetics of two drugs from the thin film was modeled by a second-order rate model. PMID:19735129

  3. Layer-by-layer assembly of functionalized reduced graphene oxide for direct electrochemistry and glucose detection.

    PubMed

    Mascagni, Daniela Branco Tavares; Miyazaki, Celina Massumi; da Cruz, Nilson Cristino; de Moraes, Marli Leite; Riul, Antonio; Ferreira, Marystela

    2016-11-01

    We report an electrochemical glucose biosensor made with layer-by-layer (LbL) films of functionalized reduced graphene oxide (rGO) and glucose oxidase (GOx). The LbL assembly using positively and negatively charged rGO multilayers represents a simple approach to develop enzymatic biosensors. The electron transport properties of graphene were combined with the specificity provided by the enzyme. rGO was obtained and functionalized using chemical methods, being positively charged with poly(diallyldimethylammonium chloride) to form GPDDA, and negatively charged with poly(styrene sulfonate) to form GPSS. Stable aqueous dispersions of GPDDA and GPSS are easily obtained, enabling the growth of LbL films on various solid supports. The use of graphene in the immobilization of GOx promoted Direct Electron Transfer, which was evaluated by Cyclic Voltammetry. Amperometric measurements indicated a detection limit of 13.4μmol·L(-1) and sensitivity of 2.47μA·cm(-2)·mmol(-1)·L for glucose with the (GPDDA/GPSS)1/(GPDDA/GOx)2 architecture, whose thickness was 19.80±0.28nm, as determined by Surface Plasmon Resonance (SPR). The sensor may be useful for clinical analysis since glucose could be detected even in the presence of typical interfering agents and in real samples of a lactose-free milk and an electrolyte solution to prevent dehydration. PMID:27524075

  4. Layer-by-layer coated gold nanoparticles: size-dependent delivery of DNA into cells.

    PubMed

    Elbakry, Asmaa; Wurster, Eva-Christina; Zaky, Alaa; Liebl, Renate; Schindler, Edith; Bauer-Kreisel, Petra; Blunk, Torsten; Rachel, Reinhard; Goepferich, Achim; Breunig, Miriam

    2012-12-21

    Because nanoparticles are finding uses in myriad biomedical applications, including the delivery of nucleic acids, a detailed knowledge of their interaction with the biological system is of utmost importance. Here the size-dependent uptake of gold nanoparticles (AuNPs) (20, 30, 50 and 80 nm), coated with a layer-by-layer approach with nucleic acid and poly(ethylene imine) (PEI), into a variety of mammalian cell lines is studied. In contrast to other studies, the optimal particle diameter for cellular uptake is determined but also the number of therapeutic cargo molecules per cell. It is found that 20 nm AuNPs, with diameters of about 32 nm after the coating process and about 88 nm including the protein corona after incubation in cell culture medium, yield the highest number of nanoparticles and therapeutic DNA molecules per cell. Interestingly, PEI, which is known for its toxicity, can be applied at significantly higher concentrations than its IC(50) value, most likely because it is tightly bound to the AuNP surface and/or covered by a protein corona. These results are important for the future design of nanomaterials for the delivery of nucleic acids in two ways. They demonstrate that changes in the nanoparticle size can lead to significant differences in the number of therapeutic molecules delivered per cell, and they reveal that the toxicity of polyelectrolytes can be modulated by an appropriate binding to the nanoparticle surface. PMID:22911477

  5. Layer-by-layer engineered nanocapsules of curcumin with improved cell activity.

    PubMed

    Kittitheeranun, Paveenuch; Sajomsang, Warayuth; Phanpee, Sarunya; Treetong, Alongkot; Wutikhun, Tuksadon; Suktham, Kunat; Puttipipatkhachorn, Satit; Ruktanonchai, Uracha Rungsardthong

    2015-08-15

    Nanocarriers based on electrostatic Layer-by-layer (LbL) assembly of CaCO3 nanoparticles (CaCO3 NPs) was investigated. These inorganic nanoparticles was used as templates to construct nanocapsules made from films based on two oppositely charged polyelectrolytes, poly(diallyldimethylammonium chloride), and poly (sodium 4-styrene-sulfonate sodium salt), followed by core dissolution. The naked CaCO3 NPs, CaCO3 NPs coated with the polyelectrolytes and hollow nanocapsules were found with hexagonal shape with average sizes of 350-400 nm. A reversal of the surface charge between positive to negative zeta potential values was found, confirming the adsorption of polyelectrolytes. The loading efficiency and release of curcumin were controlled by the hydrophobic interactions between the drug and the polyelectrolyte matrix of the hollow nanocapsules. The quantity of curcumin released from hollow nanocapsules was found to increase under acidic environments, which is a desirable for anti-cancer drug delivery. The hollow nanocapsules were found to localize in the cytoplasm and nucleus compartment of Hela cancer cells after 24 h of incubation. Hollow nanocapsules were non-toxic to human fibroblast cells. Furthermore, curcumin loaded hollow nanocapsules exhibited higher in vitro cell inhibition against Hela cells than that of free curcumin, suggesting that polyelectrolyte based-hollow nanocapsules can be utilized as new carriers for drug delivery. PMID:26143232

  6. Layer-by-layer films from hyaluronan and amine modified hyaluronan

    PubMed Central

    Schneider, Aurore; Senger, Bernard; Schaaf, Pierre; Voegel, Jean-Claude; Frisch, Benoit

    2008-01-01

    Hyaluronan is a polysaccharide that is increasingly investigated for its role in cellular adhesion and for the preparation of biomimetic matrices for tissue engineering. Hyaluronan gels are prepared for application as space fillers whereas hyaluronan films are usually obtained by adsorbing or grafting a single hyaluronan layer onto a biomaterial surface. Here, we examine the possibility to employ the layer-by-layer technique to deposit thin films of cationic modified hyaluronan (HA+) and hyaluronan (HA) of controlled thicknesses. The buildup conditions are investigated and growth is compared to that of other polyelectrolyte multilayer films containing either HA as polyanion or HA+ as polycation. The films could be formed in a low ionic strength medium but required to be cross-linked prior to be put in contact with physiological medium. NIH3T3 fibroblasts were perfectly viable on self-assembled hyaluronan films with however a preference for hyaluronan ending films. These findings point out the possibility to tune the thickness of thin hyaluronan films at the nanometer scale. Such architectures could be employed for investigating cell/substrate interactions or for functionalizing biomaterial surfaces. PMID:17309215

  7. Sonication-Assisted Layer-by-Layer Assembly for Low Solubility Drug Nanoformulation.

    PubMed

    Santos, Ana C; Pattekari, Pravin; Jesus, Sandra; Veiga, Francisco; Lvov, Yuri; Ribeiro, António J

    2015-06-10

    Sonication-assisted layer-by-layer (LbL) self-assembly is a nanoencapsulation technique based on the alternate adsorption of oppositely charged polyelectrolytes, enabling the encapsulation of low solubility drugs. In this work, a top-down LbL technique was performed using a washless approach and ibuprofen (IBF) as a model class II drug. For each saturated layer deposition, polyelectrolyte concentration was determined by titration curves. The first layer was constituted by cationic poly(allylamine hydrochloride) (PAH), given the IBF negative surface charge, followed by anionic polystyrenesulfonate (PSS). This polyelectrolyte sequence was made up with 2.5, 5.5, and 7.5 bilayer nanoshells. IBF nanoparticles (NPs) coated with 7.5 bilayers of PAH/PSS showed 127.5 ± 38.0 nm of particle size, a PDI of 0.24, and a high zeta potential (+32.7 ± 0.6 mV), allowing for a stable aqueous nanocolloid of the drug. IBF entrapment efficiency of 72.1 ± 5.8% was determined by HPLC quantification. In vitro MTT assay showed that LbL NPs were biocompatible. According to the number of coating layers, a controlled release of IBF from LbL NPs was achieved under simulated intestinal conditions (from 5 h up to 7 days). PAH/PSS-LbL NPs constitute a potential delivery system to improve biopharmaceutical parameters of water low solubility drugs. PMID:25985366

  8. Modifying Randles circuit for analysis of polyoxometalate layer-by-layer films.

    PubMed

    Vyas, Ritesh N; Li, Kuyen; Wang, Bin

    2010-12-01

    Multilayer films with anionic phosphomolybidic acid (PMo(12)) clusters have been fabricated via the electrostatic layer-by-layer (LbL) method. The charged mass transport phenomena of these thin films have been studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) with [Fe(CN)(6)](3-/4-) and [Ru(NH(3))(6)](3+/2+) as the redox probes. By adding a film resistance and a film capacitance to the conventional Randles equivalent circuit, we can calculate the diffusion coefficient values that help understand the microscopic nature of the thin films. When the negatively charged probe [Fe(CN)(6)](3-/4-) was used, lower diffusion coefficients were obtained for multilayers deposited from higher ionic strength solutions. This relationship was less obvious when the positively charged probe [Ru(NH(3))(6)](3+/2+) was used, in which the electrostatic attraction between PMo(12) clusters and the probe ions complicates the mass-transfer process. It is believed that the addition of salt to dipping solutions increases the tortuosity of the films so the mass transport takes longer paths, inducing lower diffusion coefficients. Higher PMo(12) loading causes lower diffusion coefficients due to the polyoxometalate clusters blocking the paths for charged probe ions. PMID:21077668

  9. Sprayable, Paintable Layer-by-Layer Polyaniline Nanofiber/Graphene Electrodes for Electrochemical Energy Storage

    NASA Astrophysics Data System (ADS)

    Kwon, Se Ra; Jeon, Ju-Won; Lutkenhus, Jodie

    2015-03-01

    Sprayable batteries are growing in interest for applications in structural energy storage and power or flexible power. Spray-assisted layer-by-layer (LbL) assembly, in which complementary species are alternately sprayed onto a surface, is particularly amenable toward this application. Here, we report on the fabrication of composite films containing polyaniline nanofibers (PANI NF) and graphene oxide (GO) sheets fabricated via spray-assisted LbL assembly. The resulting films are electrochemical reduced to yield PANI NF/electrochemically reduced graphene (ERGO) electrodes for use as a cathode in non-aqueous energy storage systems. Through the spray-assisted LbL process, the hybrid electrodes could be fabricated 74 times faster than competing dip-assisted LbL assembly. The resulting electrodes are highly porous (0.72 void fraction), and are comprised of 67 wt% PANI NF and 33 wt% ERGO. The sprayed electrodes showed better rate capability, higher specific power, as well as more stable cycle life than dip-assisted LbL electrodes. It is shown here that the spray-assisted LbL approach is well-suited towards the fabrication of paintable electrodes containing polyaniline nanofibers and electrochemically reduced graphene oxide sheets.

  10. Layer-by-layer assembly of UV-resistant poly(3,4-ethylenedioxythiophene) thin films.

    PubMed

    Dawidczyk, Thomas J; Walton, Matthew D; Jang, Woo-Sik; Grunlan, Jaime C

    2008-08-01

    The layer-by-layer assembly technique was used to create electrically conductive films with poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT-PSS) and branched polyethylenimine (BPEI). Titanium dioxide (TiO(2)) and carbon black were used to prevent UV-degradation of these PEDOT-PSS thin film assemblies. Film growth and conductivity were studied, while varying composition and examining the effect of UV absorbing particles on the electrical conductivity. All films showed similar initial sheet resistances, but after exposure to 365 nm UV light for 9 days (correlating to approximately 4 years of sunlight), the films containing TiO(2) were up to 250 times more conductive. Additionally, the TiO(2) containing films were 27% more optically transparent than films made with PEDOT in the absence of TiO(2). The addition of colloidal titania allows the useful life of the PEDOT films to be extended without the detrimental effects of decreased transparency. Doping the PEDOT with dimethylsulfoxide produced eight bilayer films that were almost 6 times more conductive. However, the degradation rate for the doped PEDOT films without TiO(2) was 10 times greater than the doped films with TiO(2). PMID:18590298

  11. Structure analysis of layer-by-layer multilayer films of colloidal particles

    NASA Astrophysics Data System (ADS)

    Batys, Piotr; Nosek, Magdalena; Weroński, Paweł

    2015-03-01

    We have mimicked the layer-by-layer self-assembling process of monodisperse colloidal particles at a solid-liquid interface using the extended random sequential adsorption model of hard spheres. We have studied five multilayer structures of similar thickness, each created at a different single-layer surface coverage. For each multilayer, we have determined its particle volume fraction as a function of distance from the interface. Additionally, we have characterized the film structure in terms of 2D and 3D pair-correlation functions. We have found that the coverage of about 0.3 is optimal for producing a uniform, constant-porosity multilayer in a minimum number of adsorption cycles. The single-layer coverage has also a significant effect on the primary maximum of 2D radial distribution function. In the case of multilayer with the coverage lower than 0.30 the 2D pair-correlation functions of even layers exhibit maxima decreasing with the increase in the layer number. We have verified our theoretical predictions experimentally. We have used fluorescence microscopy to determine the 2D pair-correlation functions for the second, third, and fourth layers of multilayer formed of micron-sized spherical latex particles. We have found a good agreement between our theoretical and experimental results, which confirms the validity of the extended RSA model.

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

    PubMed

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

    2016-08-10

    Self-healing materials, which enable an autonomous repair response to damage, are highly desirable for the long-term reliability of woven or nonwoven textiles. Polyelectrolyte layer-by-layer (LbL) films are of considerable interest as self-healing coatings due to the mobility of the components comprising the film. In this work mechanically stable self-healing films were fabricated through construction of a polyelectrolyte LbL film containing squid ring teeth (SRT) proteins. SRTs are structural proteins with unique self-healing properties and high elastic modulus in both dry and wet conditions (>2 GPa) due to their semicrystalline architecture. We demonstrate LbL construction of multilayers containing native and recombinant SRT proteins capable of self-healing defects. Additionally, we show these films are capable of utilizing functional biomolecules by incorporating an enzyme into the SRT multilayer. Urease was chosen as a model enzyme of interest to test its activity via fluorescence assay. Successful construction of the SRT films demonstrates the use of mechanically stable self-healing coatings, which can incorporate biomolecules for more complex protective functionalities for advanced functional fabrics. PMID:27419265

  13. Layer-by-layer assembly of 3D tissue constructs with functionalized graphene

    PubMed Central

    Shin, Su Ryon; Aghaei-Ghareh-Bolagh, Behnaz; Gao, Xiguang; Nikkhah, Mehdi; Jung, Sung Mi; Dolatshahi-Pirouz, Alireza; Kim, Sang Bok; Kim, Sun Min; Dokmeci, Mehmet R.; Tang, Xiaowu (Shirley); Khademhosseini, Ali

    2014-01-01

    Carbon-based nanomaterials have been considered as promising candidates to mimic certain structure and function of native extracellular matrix materials for tissue engineering. Significant progress has been made in fabricating carbon nanoparticle-incorporated cell culture substrates, but limited studies have been reported on the development of three-dimensional (3D) tissue constructs using these nanomaterials. Here, we present a novel approach to engineer 3D multi-layered constructs using layer-by-layer (LbL) assembly of cells separated with self-assembled graphene oxide (GO)-based thin films. The GO-based structures are shown to serve as cell adhesive sheets that effectively facilitate the formation of multi-layer cell constructs with interlayer connectivity. By controlling the amount of GO deposited in forming the thin films, the thickness of the multi-layer tissue constructs could be tuned with high cell viability. Specifically, this approach could be useful for creating dense and tightly connected cardiac tissues through the co-culture of cardiomyocytes and other cell types. In this work, we demonstrated the fabrication of stand-alone multi-layer cardiac tissues with strong spontaneous beating behavior and programmable pumping properties. Therefore, this LbL-based cell construct fabrication approach, utilizing GO thin films formed directly on cell surfaces, has great potential in engineering 3D tissue structures with improved organization, electrophysiological function, and mechanical integrity. PMID:25419209

  14. Probing nonlinear rheology layer-by-layer in interfacial hydration water

    PubMed Central

    Kim, Bongsu; Kwon, Soyoung; Lee, Manhee; Kim, QHwan; An, Sangmin; Jhe, Wonho

    2015-01-01

    Viscoelastic fluids exhibit rheological nonlinearity at a high shear rate. Although typical nonlinear effects, shear thinning and shear thickening, have been usually understood by variation of intrinsic quantities such as viscosity, one still requires a better understanding of the microscopic origins, currently under debate, especially on the shear-thickening mechanism. We present accurate measurements of shear stress in the bound hydration water layer using noncontact dynamic force microscopy. We find shear thickening occurs above ∼ 106 s−1 shear rate beyond 0.3-nm layer thickness, which is attributed to the nonviscous, elasticity-associated fluidic instability via fluctuation correlation. Such a nonlinear fluidic transition is observed due to the long relaxation time (∼ 10−6 s) of water available in the nanoconfined hydration layer, which indicates the onset of elastic turbulence at nanoscale, elucidating the interplay between relaxation and shear motion, which also indicates the onset of elastic turbulence at nanoscale above a universal shear velocity of ∼ 1 mm/s. This extensive layer-by-layer control paves the way for fundamental studies of nonlinear nanorheology and nanoscale hydrodynamics, as well as provides novel insights on viscoelastic dynamics of interfacial water. PMID:26644571

  15. Photosystem II based multilayers obtained by electrostatic layer-by-layer assembly on quartz substrates.

    PubMed

    Ventrella, Andrea; Catucci, Lucia; Placido, Tiziana; Longobardi, Francesco; Agostiano, Angela

    2014-06-01

    Photosystem II (PSII) proteins from spinach leaves were immobilized onto quartz substrates according to the Layer-by-Layer (LbL) procedure, alternating protein to polyethylenimine (PEI) layers by exploiting electrostatic interactions. The effects of several factors, such as storage conditions, ageing of the PSII-modified substrates, as well as PSII concentration in buffer, on the quality of the prepared multilayers, were investigated by UV-vis Absorption Spectroscopy and Atomic Force Microscopy (AFM). A number of 13 layers was found to be optimal to guarantee intense PSII optical signals with homogeneous morphological distributions of proteins. The multilayers resulted stable if stored in contact with air at 4 °C, as observed by UV-vis Absorption spectra recorded after 48 h. The best results in terms of AFM images and electron transfer efficiency (measured by Hill Reaction assays) were gained by using 5.6 × 10(-7) M chlorophyll concentration, obtaining multilayers with the most ordered protein distributions and the highest electron transfer efficiency, i.e. 85% of an iso-absorbing PSII suspension. The results highlight the possibility to successfully immobilize PSII proteins, without considerable loss of bioactivity, thanks to the mild nature of the electrostatic LbL technique, opening up possibilities of applications in the bioelectrochemical energy conversion and biosensoristic fields. PMID:24550146

  16. Photonic crystal fiber for layer-by-layer assembly and measurements of polyelectrolyte thin films.

    PubMed

    Tian, Fei; Kanka, Jiri; Sukhishvili, Svetlana A; Du, Henry

    2012-10-15

    The cladding air channels of an endlessly single-mode photonic crystal fiber (PCF) and the high-index sensitivity of its long-period gratings (LPG) inscribed by CO(2) laser have been exploited to deposit poly(vinyl pyrrolidone) (PVPON)/poly(methacrylic acid) (PMAA) polyelectrolyte thin films via layer-by-layer assembly (LbL) and to measure the deposition process. We show that LbL can be controllably carried out within the axially aligned air channels. PCF-LPG is highly sensitive to the LbL process as reflected by ~1.625 nm shift in the resonance wavelength per polyelectrolyte layer incorporated. PCF-LPG is also very robust for in situ monitoring of the release of PVPON from cross-linked polyelectrolytes, which results in the formation of pH-responsive PMAA hydrogel. PCF-LPG containing the hydrogel exhibits well-behaved response to changes in solution pH over 2 to 7.5. We demonstrate that PCF-LPG is 2 orders of magnitude more sensitive than its traditional all-solid counterpart through parallel investigation. PMID:23073443

  17. Multifunctional carbon nanotube thin film composites by layer-by-layer assembly technique

    NASA Astrophysics Data System (ADS)

    Shim, Bong Sup

    Polymeric layer-by-layer (LBL) assembly offers a pathway for multifunctional/multicomponent materials with molecular-scale control of stratified structures. Among the wide variety nanoscale building blocks such as nanowires and nanodots, single-walled carbon nanotubes (SWNTs) are regarded as one of the most versatile because of their superior mechanical and electrical properties as well as geometrical perfection. In this thesis, LBL assembled SWNT thin film nanocomposites with high mechanical strength/toughness and with high electrical/optical properties are presented. Exceptional exfoliation state of SWNTs and controlled nm-thick layered structures are the basis for achieving tunable physical properties. Highly anisotropic features of SWNTs are translated into 2 dimensional alignments by meniscus combing technique during LBL assemblies. Advanced LBL assemblies by dewetting methods are also introduced, which significantly accelerate the process with improved lateral organization of nanowires. Furthermore, SWNT composite coating on commodity cotton yarns produced intelligent electronic textiles (e-textiles) with intrinsic humidity sensibility. This e-textile has been further combined with antigen/antibody sensing capability in order to develop a selective albumin biosensor which provides a direct route for the application of these materials as wearable biomonitoring and telemedicine sensors.

  18. Improved performance of diatomite-based dental nanocomposite ceramics using layer-by-layer assembly

    PubMed Central

    Lu, Xiaoli; Xia, Yang; Liu, Mei; Qian, Yunzhu; Zhou, Xuefeng; Gu, Ning; Zhang, Feimin

    2012-01-01

    To fabricate high-strength diatomite-based ceramics for dental applications, the layer-by-layer technique was used to coat diatomite particles with cationic [poly(allylamine hydrochloride)] and anionic [poly(sodium 4-styrenesulfonate)] polymers to improve the dispersion and adsorption of positively charged nano-ZrO2 (zirconia) as a reinforcing agent. The modified diatomite particles had reduced particle size, narrower size distribution, and were well dispersed, with good adsorption of nano-ZrO2. To determine the optimum addition levels for nano-ZrO2, ceramics containing 0, 20, 25, 30, and 35 wt% nano-ZrO2 were sintered and characterized by the three-point bending test and microhardness test. In addition to scanning electron microscopy, propagation phase-contrast synchrotron X-ray microtomography was used to examine the internal structure of the ceramics. The addition of 30 wt% nano-ZrO2 resulted in the highest flexural strength and fracture toughness with reduced porosity. Shear bond strength between the core and veneer of our diatomite ceramics and the most widely used dental ceramics were compared; the shear bond strength value for the diatomite-based ceramics was found to be significantly higher than for other groups (P < 0.05). Our results show that diatomite-based nanocomposite ceramics are good potential candidates for ceramic-based dental materials. PMID:22619551

  19. Layer-by-Layer Assembly of Stable Aqueous Quantum Dots for Luminescent Planar Plate.

    PubMed

    Zhang, Xuejing; Zhou, Changhua; Zang, Shuaipu; Shen, Huaibin; Dai, Pengpeng; Zhang, Xintong; Li, Lin Song

    2015-07-15

    This work reports the fabrication of a luminescent planar plate based on stable aqueous quantum dots (QDs) and poly(diallyldimethylammonium chloride) (PDDA) via a layer-by-layer (LBL) assembly technique. Preparation of aqueous QDs with facile monoalkyl maleate amphiphilic surfactants as the coating agent is conducted by a robust and efficient phase-transfer method. The as-prepared aqueous QDs exhibit bright emission, and their surface has very large negative zeta potential values, which are useful for electrostatic LBL assembly. Red, green, and blue luminescent planar plates are successfully fabricated via LBL assembly of the monocolor QDs, respectively. Through accurately adjusting the relative proportion of each monocolor luminescent component, we obtain an inspiring luminescent planar plate, which emits bright white light with a color coordinate of (0.3509, 0.3483), a correlated color temperature (CCT) of 4766 K, and a high color rendering index (CRI, Ra) of 89.5 under the irradiation of UV light. Therefore, this paper reports a facile process for the design and preparation of luminescent planar plates, which have potential applications in display and solid-state lighting devices. PMID:26091336

  20. Effect of layer-by-layer polyelectrolyte method on encapsulation of vanillin.

    PubMed

    Noshad, Mohammad; Mohebbi, Mohebbat; Shahidi, Fakhri; Koocheki, Arash

    2015-11-01

    The objective of this work was to microencapsulate vanillin by multilayer emulsion followed by spray drying, aiming to protect it and control its release. An electrostatic layer-by-layer deposition method was used to create the multilayered interfacial membranes around microcapsules with different compositions: (i) one-layer (soy protein isolate); (ii) two-layer (soy protein isolate - OSA starch); (iii) three-layer (soy protein isolate - OSA starch - Chitosan). The morphology of the microcapsules was analyzed by scanning electronic microscopy. The hygroscopicity, solubility, particle size, encapsulation efficiency, Fourier transform infrared spectroscopy and release into water (37°C and 80°C) were also examined. FTIR confirmed the interaction between the wall materials. All microcapsules were not very water-soluble or hygroscopic while three-layer microcapsules compared to one and two layer microcapsules have lower moisture content and predominantly shriveled surfaces. The results indicated it was possible to encapsulate vanillin with the techniques employed and that these protected the vanillin even at 80°C. The reduced solubility and low release rates indicated the enormous potential of the vehicle developed in controlling the release of the vanillin into the food and pharmaceuticals. PMID:26358552

  1. Biocompatibility of layer-by-layer self-assembled nanofilm on silicone rubber for neurons.

    PubMed

    Ai, Hua; Meng, Hongdi; Ichinose, Izumi; Jones, Steven A; Mills, David K; Lvov, Yuri M; Qiao, Xiaoxi

    2003-09-30

    Electrostatic layer-by-layer (LbL) self-assembly, a novel method for ultrathin film coating has been applied to silicone rubber to encourage nerve cell adhesion. The surfaces studied consisted of precursor layers, with alternating cationic poly(ethyleneimine) (PEI) and anionic sodium poly(styrenesulfonate) (PSS) followed by alternating laminin and poly-D-lysine (PDL) layers or fibronectin and PDL layers. Film growth increased linearly with the number of layers. Every fibronectin/PDL and laminin/PDL bilayer was 4.4 and 3.5 nm thick, respectively. All layers were more hydrophilic than the unmodified silicone rubber surface, as determined from contact angle measurements. Of the coatings studied, a PDL layer was the most hydrophilic. A multilayer film with composition [PSS/PEI]3+[fibronectin/PDL]4 or [PSS/PEI]3+[laminin/PDL]4 was highly favorable for neuron adhesion, in contrast to bare silicone rubber substrate. The film coated on silicone rubber is biocompatible for cerebellar neurons with active viability, as shown by lactate dehydrogenase (LDH) assay and fluorescence cellular metabolism observations. These results demonstrate that LbL self-assembly provides an effective approach to apply films with nanometer thickness to silicone rubber. Such only few nanometer thick films are biocompatible with neurons, and may be used to coat devises for long-term implant in the central nervous system. PMID:12948543

  2. Layer-by-layer assembled cell instructive nanocoatings containing platelet lysate.

    PubMed

    Oliveira, Sara M; Santo, Vítor E; Gomes, Manuela E; Reis, Rui L; Mano, João F

    2015-04-01

    Great efforts have been made to introduce growth factors (GFs) onto 2D/3D constructs in order to control cell behavior. Platelet lysate (PL) presents itself as a cost-effective source of multiple GFs and other proteins. The instruction given by a construct-PL combination will depend on how its instructive cues are presented to the cells. The content, stability and conformation of the GFs affect their instruction. Strategies for a controlled incorporation of PL are needed. Herein, PL was incorporated into nanocoatings by layer-by-layer assembling with polysaccharides presenting different sulfation degrees (SD) and charges. Heparin and several marine polysaccharides were tested to evaluate their PL and GF incorporation capability. The consequent effects of those multilayers on human adipose derived stem cells (hASCs) were assessed in short-term cultures. Both nature of the polysaccharide and SD were important properties that influenced the adsorption of PL, vascular endothelial growth factor (VEGF), fibroblast growth factor b (FGFb) and platelet derived growth factor (PDGF). The sulfated polysaccharides-PL multilayers showed to be efficient in the promotion of morphological changes, serum-free adhesion and proliferation of high passage hASCs (P > 5). These biomimetic multilayers promise to be versatile platforms to fabricate instructive devices allowing a tunable incorporation of PL. PMID:25701032

  3. Protein Induces Layer-by-Layer Exfoliation of Transition Metal Dichalcogenides.

    PubMed

    Guan, Guijian; Zhang, Shuangyuan; Liu, Shuhua; Cai, Yongqing; Low, Michelle; Teng, Choon Peng; Phang, In Yee; Cheng, Yuan; Duei, Koh Leng; Srinivasan, Bharathi Madurai; Zheng, Yuangang; Zhang, Yong-Wei; Han, Ming-Yong

    2015-05-20

    Here, we report a general and facile method for effective layer-by-layer exfoliation of transition metal dichalcogenides (TMDs) and graphite in water by using protein, bovine serum albumin (BSA) to produce single-layer nanosheets, which cannot be achieved using other commonly used bio- and synthetic polymers. Besides serving as an effective exfoliating agent, BSA can also function as a strong stabilizing agent against reaggregation of single-layer nanosheets for greatly improving their biocompatibility in biomedical applications. With significantly increased surface area, single-layer MoS2 nanosheets also exhibit a much higher binding capacity to pesticides and a much larger specific capacitance. The protein exfoliation process is carefully investigated with various control experiments and density functional theory simulations. It is interesting to find that the nonpolar groups of protein can firmly bind to TMD layers or graphene to expose polar groups in water, facilitating the effective exfoliation of single-layer nanosheets in aqueous solution. The present work will enable to optimize the fabrication of various 2D materials at high yield and large scale, and bring more opportunities to investigate the unique properties of 2D materials and exploit their novel applications. PMID:25936424

  4. Pulmonary sustained release of insulin from microparticles composed of polyelectrolyte layer-by-layer assembly.

    PubMed

    Amancha, Kiran Prakash; Balkundi, Shantanu; Lvov, Yuri; Hussain, Alamdar

    2014-05-15

    The present study tests the hypothesis that layer-by-layer (LbL) nanoassembly of thin polyelectrolyte films on insulin particles provides sustained release of the drug after pulmonary delivery. LbL insulin microparticles were formulated using cationic and anionic polyelectrolytes. The microparticles were characterized for particle size, particle morphology, zeta potential and in vitro release. The pharmacokinetics and pharmacodynamics of drug were assessed by measuring serum insulin and glucose levels after intrapulmonary administration in rats. Bronchoalveolar lavage (BAL) and evans blue (EB) extravasation studies were performed to investigate the cellular or biochemical changes in the lungs caused by formulation administration. The mass median aerodynamic diameter (MMAD) of the insulin microparticles was 2.7 μm. Confocal image of the formulation particles confirmed the polyelectrolyte deposition around the insulin particles. Zeta potential measurements showed that there was charge reversal after each layering. Pulmonary administered LbL insulin formulation resulted in sustained serum insulin levels and concomitant decrease in serum glucose levels. The BAL and EB extravasation studies showed that the LbL insulin formulation did not elicit significant increase in marker enzymes activities compared to control group. These results demonstrate that the sustained release of insulin could be achieved using LbL nanoassembly around the insulin particles. PMID:24566038

  5. Layer-by-Layer (LBL) Self-Assembled Biohybrid Nanomaterials for Efficient Antibacterial Applications.

    PubMed

    Wu, Yuanhao; Long, Yubo; Li, Qing-Lan; Han, Shuying; Ma, Jianbiao; Yang, Ying-Wei; Gao, Hui

    2015-08-12

    Although antibiotics have been widely used in clinical applications to treat pathogenic infections at present, the problem of drug-resistance associated with abuse of antibiotics is becoming a potential threat to human beings. We report a biohybrid nanomaterial consisting of antibiotics, enzyme, polymers, hyaluronic acid (HA), and mesoporous silica nanoparticles (MSNs), which exhibits efficient in vitro and in vivo antibacterial activity with good biocompatibility and negligible hemolytic side effect. Herein, biocompatible layer-by-layer (LBL) coated MSNs are designed and crafted to release encapsulated antibiotics, e.g., amoxicillin (AMO), upon triggering with hyaluronidase, produced by various pathogenic Staphylococcus aureus (S. aureus). The LBL coating process comprises lysozyme (Lys), HA, and 1,2-ethanediamine (EDA)-modified polyglycerol methacrylate (PGMA). The Lys and cationic polymers provided multivalent interactions between MSN-Lys-HA-PGMA and bacterial membrane and accordingly immobilized the nanoparticles to facilitate the synergistic effect of these antibacterial agents. Loading process was characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and X-ray diffraction spectroscopy (XRD). The minimal inhibition concentration (MIC) of MSN-Lys-HA-PGMA treated to antibiotic resistant bacteria is much lower than that of isodose Lys and AMO. Especially, MSN-Lys-HA-PGMA exhibited good inhibition for pathogens in bacteria-infected wounds in vivo. Therefore, this type of new biohybrid nanomaterials showed great potential as novel antibacterial agents. PMID:26192024

  6. Genipin-cross-linked layer-by-layer assemblies: biocompatible microenvironments to direct bone cell fate.

    PubMed

    Gaudière, Fabien; Morin-Grognet, Sandrine; Bidault, Laurent; Lembré, Pierre; Pauthe, Emmanuel; Vannier, Jean-Pierre; Atmani, Hassan; Ladam, Guy; Labat, Béatrice

    2014-05-12

    The design of biomimetic coatings capable of improving the osseointegration of bone biomaterials is a current challenge in the field of bone repair. Toward this end, layer-by-layer (LbL) films composed of natural components are suitable candidates. Chondroitin sulfate A (CSA), a natural glycosaminoglycan (GAG), was used as the polyanionic component because it promotes osteoblast maturation in vivo. In their native state, GAG-containing LbL films are generally cytophobic because of their low stiffness. To stiffen our CSA-based LbL films, genipin (GnP) was used as a natural cross-linking agent, which is much less cytotoxic than conventional chemical cross-linkers. GnP-cross-linked films display an original combination of microscale topography and tunable mechanical properties. Structural characterization was partly based on a novel donor/acceptor Förster resonance energy transfer (FRET) couple, namely, FITC/GnP, which is a promising approach for further inspection of any GnP-cross-linked system. GnP-cross-linked films significantly promote adhesion, proliferation, and early and late differentiation of preosteoblasts. PMID:24666097

  7. Protein-triggered instant disassembly of biomimetic Layer-by-Layer films.

    PubMed

    Abdelkebir, Khalil; Gaudière, Fabien; Morin-Grognet, Sandrine; Coquerel, Gérard; Atmani, Hassan; Labat, Béatrice; Ladam, Guy

    2011-12-01

    Layer-by-Layer (LbL) coatings are promising tools for the biofunctionalization of biomaterials, as they allow stress-free immobilization of proteins. Here, we explore the possibility to immobilize phosvitin, a highly phosphorylated protein viewed as a model of bone phosphoproteins and, as such, a potential promotive agent of surface-directed biomineralization, into biomimetic LbL architectures. Two immobilization protocols are attempted, first, using phosvitin as the polyanionic component of phosvitin/poly-(L-lysine) films and, second, adsorbing it onto preformed chondroitin sulfate/poly-(L-lysine) films. Surprisingly, it is neither possible to embed phosvitin as the constitutive polyanion of the LbL architectures nor to adsorb it atop preformed films. Instead, phosvitin triggers instant massive film disassembly. This unexpected, incidentally detected behavior constitutes the first example of destructive interactions between LbL films and a third polyelectrolyte, a fortiori a protein, which might open a route toward new stimuli-responsive films for biosensing or drug delivery applications. Interestingly, additional preliminary results still indicate a promotive effect of phosvitin-containing remnant films on calcium phosphate deposition. PMID:22007998

  8. Chondrocyte Behavior on Micropatterns Fabricated Using Layer-by-Layer Lift-Off: Morphological Analysis

    PubMed Central

    Shaik, Jameel; Shaikh Mohammed, Javeed; McShane, Michael J.; Mills, David K.

    2013-01-01

    Cell patterning has emerged as an elegant tool in developing cellular arrays, bioreactors, biosensors, and lab-on-chip devices and for use in engineering neotissue for repair or regeneration. In this study, micropatterned surfaces were created using the layer-by-layer lift-off (LbL-LO) method for analyzing canine chondrocytes response to patterned substrates. Five materials were chosen based on our previous studies. These included: poly(dimethyldiallylammonium chloride) (PDDA), poly(ethyleneimine) (PEI), poly(styrene sulfonate) (PSS), collagen, and chondroitin sulfate (CS). The substrates were patterned with these five different materials, in five and ten bilayers, resulting in the following multilayer nanofilm architectures: (PSS/PDDA)5, (PSS/PDDA)10; (CS/PEI)4/CS, (CS/PEI)9/CS; (PSS/PEI)5, (PSS/PEI)10; (PSS/Collagen)5, (PSS/Collagen)10; (PSS/PEI)4/PSS, (PSS/PEI)9/PSS. Cell characterization studies were used to assess the viability, longevity, and cellular response to the configured patterned multilayer architectures. The cumulative cell characterization data suggests that cell viability, longevity, and functionality were enhanced on micropatterned PEI, PSS, collagen, and CS multilayer nanofilms suggesting their possible use in biomedical applications. PMID:27006918

  9. Silica encapsulation of ferrimagnetic zinc ferrite nanocubes enabled by layer-by-layer polyelectrolyte deposition.

    PubMed

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

    2015-03-24

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

  10. Antibacterial, anti-inflammatory and neuroprotective layer-by-layer coatings for neural implants

    NASA Astrophysics Data System (ADS)

    Zhang, Zhiling; Nong, Jia; Zhong, Yinghui

    2015-08-01

    Objective. Infection, inflammation, and neuronal loss are common issues that seriously affect the functionality and longevity of chronically implanted neural prostheses. Minocycline hydrochloride (MH) is a broad-spectrum antibiotic and effective anti-inflammatory drug that also exhibits potent neuroprotective activities. In this study, we investigated the development of biocompatible thin film coatings capable of sustained release of MH for improving the long term performance of implanted neural electrodes. Approach. We developed a novel magnesium binding-mediated drug delivery mechanism for controlled and sustained release of MH from an ultrathin hydrophilic layer-by-layer (LbL) coating and characterized the parameters that control MH loading and release. The anti-biofilm, anti-inflammatory and neuroprotective potencies of the LbL coating and released MH were also examined. Main results. Sustained release of physiologically relevant amount of MH for 46 days was achieved from the Mg2+-based LbL coating at a thickness of 1.25 μm. In addition, MH release from the LbL coating is pH-sensitive. The coating and released MH demonstrated strong anti-biofilm, anti-inflammatory, and neuroprotective potencies. Significance. This study reports, for the first time, the development of a bioactive coating that can target infection, inflammation, and neuroprotection simultaneously, which may facilitate the translation of neural interfaces to clinical applications.

  11. Functional layer-by-layer design of xerogel-based first-generation amperometric glucose biosensors.

    PubMed

    Poulos, Nicholas G; Hall, Jackson R; Leopold, Michael C

    2015-02-01

    Xerogel-based first-generation amperometric glucose biosensors, constructed through specific layer-by-layer assembly of films featuring glucose oxidase doped xerogel, a diffusion-limiting xerogel layer, and capped with both electropolymerized polyphenol and blended polyurethane semipermeable membranes, are presented. The specific combination of xerogels formed from specific silane precursors, including propyl-trimethoxysilane, isobutyl-trimethoxysilane, octyl-trimethoxysilane, and hydroxymethyl-triethoxysilane, exhibit impressive dynamic and linear ranges of detection (e.g., ≥24-28 mM glucose) and low response times, as well as significant discrimination against common interferent species such as acetaminophen, ascorbic acid, sodium nitrite, oxalic acid, and uric acid as determined by selectivity coefficients. Additionally, systematic electrochemical and contact angle studies of different xerogel silane precursors, varying in structure, chain length, and/or functional group, reveal that sensor performance is more dependent on the tunable porosity/permeability of the layered interfaces rather than the hydrophobic character or functional groups within the films. While the sensing performance largely exceeds that of existing electrochemical glucose sensing schemes in the literature, the presented layered approach establishes the specific functionality of each layer working in concert with each other and suggests that the strategy may be readily adaptable to other clinically relevant targets and is amenable to miniaturization for eventual in situ or in vivo sensing. PMID:25562760

  12. Amperometric detection of lactose using β-galactosidase immobilized in layer-by-layer films.

    PubMed

    Campos, Paula P; Moraes, Marli L; Volpati, Diogo; Miranda, Paulo B; Oliveira, Osvaldo N; Ferreira, Marystela

    2014-07-23

    A direct, low-cost method to determine the concentration of lactose is an important goal with possible impact in various types of industry. In this study, a biosensor is reported that exploits the specific interaction between lactose and the enzyme β-galactosidase (β-Gal) normally employed to process lactose into glucose and galactose for lactose-intolerant people. The biosensor was made with β-Gal immobilized in layer-by-layer (LbL) films with the polyelectrolyte poly(ethylene imine) (PEI) and poly(vinyl sufonate) (PVS) on an indium tin oxide (ITO) electrode modified with a layer of Prussian Blue (PB). With an ITO/PB/(PEI/PVS)1(PEI/β-Gal)30 architecture, lactose could be determined with an amperometric method with sensitivity of 0.31 μA mmol(-1) cm(-2) and detection limit of 1.13 mmol L(-1), which is sufficient for detecting lactose in milk and for clinical exams. Detection occurred via a cascade reaction involving glucose oxidase titrated as electrolytic solution in the electrochemical cell, while PB allowed for operation at 0.0 V versus saturated calomel electrode, thus avoiding effects from interfering species. Sum-frequency generation spectroscopy data for the interface between the LbL film and a buffer containing lactose indicated that β-Gal lost order, which is the first demonstration of structural effects induced by the molecular recognition interaction with lactose. PMID:24991705

  13. Layer-by-Layer Templated Assembly of Silica at the Nanoscale

    SciTech Connect

    Hinestrosa Salazar, Juan P; Sutton, Jonathan; Allison, David P; Doktycz, Mitchel John; Messman, Jamie M; Retterer, Scott T

    2013-01-01

    Bioinspired bottom-up assembly and layer-by-layer (LbL) construction of inorganic materials from lithographically defined organic templates enables the fabrication of nanostructured systems under mild temperature and pH conditions. Such processes open the door to low-impact manufacturing and facile recycling of hybrid materials for energy, biology, and information technologies. Here, templated LbL assembly of silica was achieved using a combination of electron beam lithography, chemical lift-off, and aqueous solution chemistry. Nanopatterns of lines, honeycomb-lattices, and dot arrays were defined in polymer resist using electron beam lithography. Following development, exposed areas of silicon were functionalized with a vapor deposited amine-silane monolayer. Silicic acid solutions of varying pH and salt content were reacted with the patterned organic amine-functional templates. Vapor treatment and solution reaction could be repeated, allowing LbL deposition. Conditions for the silicic acid deposition had a strong effect on thickness of each layer, and the morphology of the amorphous silica formed. Defects in the arrays of silica nanostructures were minor and do not affect the overall organization of the layers. The bioinspired method described here facilitates the bottom-up assembly of inorganic nanostructures defined in three dimensions and provides a path, via LbL processing, for the construction of layered hybrid materials under mild conditions.

  14. Layer-by-layer deposition of vesicles mediated by supramolecular interactions.

    PubMed

    Roling, Oliver; Wendeln, Christian; Kauscher, Ulrike; Seelheim, Patrick; Galla, Hans-Joachim; Ravoo, Bart Jan

    2013-08-13

    Vesicles are dynamic supramolecular structures with a bilayer membrane consisting of lipids or synthetic amphiphiles enclosing an aqueous compartment. Lipid vesicles have often been considered as mimics for biological cells. In this paper, we present a novel strategy for the preparation of three-dimensional multilayered structures in which vesicles containing amphiphilic β-cyclodextrin are interconnected by proteins using cyclodextrin guests as bifunctional linker molecules. We compared two pairs of adhesion molecules for the immobilization of vesicles: mannose-concanavalin A and biotin-streptavidin. Microcontact printing and thiol-ene click chemistry were used to prepare suitable substrates for the vesicles. Successful immobilization of intact vesicles through the mannose-concanavalin A and biotin-streptavidin motifs was verified by fluorescence microscopy imaging and dynamic light scattering, while the vesicle adlayer was characterized by quartz crystal microbalance with dissipation monitoring. In the case of the biotin-streptavidin motif, up to six layers of intact vesicles could be immobilized in a layer-by-layer fashion using supramolecular interactions. The construction of vesicle multilayers guided by noncovalent vesicle-vesicle junctions can be taken as a minimal model for artificial biological tissue. PMID:23898918

  15. Cubical Shape Enhances the Interaction of Layer-by-Layer Polymeric Particles with Breast Cancer Cells.

    PubMed

    Alexander, Jenolyn F; Kozlovskaya, Veronika; Chen, Jun; Kuncewicz, Thomas; Kharlampieva, Eugenia; Godin, Biana

    2015-12-01

    Blood-borne objects display a nonspherical shape with in-flow dimensions much larger than the vascular endothelial fenestrations, yet, at the diseased state, are able to traverse through these fenestrations owing to their elasticity. The role of physical parameters including shape and elasticity in the behavior of objects found in the tumor microenvironment needs to be understood to ultimately enhance chemotherapy and minimize its side effects. In this study, sphere- and cube-shaped biocompatible elastic microparticles (EM) made via layer-by-layer assembly of hydrogen-bonded tannic acid/poly(N-vinylpyrrolidone) (TA/PVPON) as hollow polymer shells and their rigid core-shell precursors (RM) are explored. In contrast to rigid five-bilayer (TA/PVPON) core shells, hollow elastic shells are unrecognized by J774A.1 macrophages, yet interact with endothelial and breast cancer cells. Internalization of cubical shells is fivefold more efficient by HMVEC (human microvascular endothelial cells) and sixfold and 2.5-fold more efficient by MDA-MB-231 and by SUM159 (breast cancer cells), respectively, compared to spherical shells. The interaction of cubical (TA/PVPON)5 shells with endothelial cells is similar under 10 s(-1) (characteristic of tumor vasculature) and 100 s(-1) shear rate (normal vasculature) while it is decreased at 100 s(-1) shear rate for the spherical shells. Our data suggest that cubical geometry promotes interaction of particles with breast cancer cells, while elasticity prevents engulfment by phagocytic cells in the tumor microenvironment. PMID:26424126

  16. Flame-Retardant Paper from Wood Fibers Functionalized via Layer-by-Layer Assembly.

    PubMed

    Köklükaya, Oruç; Carosio, Federico; Grunlan, Jaime C; Wågberg, Lars

    2015-10-28

    The highly flammable character of cellulose-rich fibers from wood limits their use in some advanced materials. To suppress the flammability and introduce flame-retardant properties to individual pulp fibers, we deposited nanometer thin films consisting of cationic chitosan (CH) and anionic poly(vinylphosphonic acid) (PVPA) on fibers using the layer-by-layer (LbL) technique. The buildup of the multilayer film was investigated in the presence and absence of salt (NaCl) using model cellulose surfaces and a quartz crystal microbalance technique. Fibers were then treated with the same strategy, and the treated fibers were used to prepare paper sheets. A horizontal flame test (HFT) and cone calorimetry were conducted to evaluate the combustion behavior of paper sheets as a function of the number of bilayers deposited on fibers. In HFT, paper made of fibers coated with 20 CH/PVPA bilayers (BL), self-extinguished the flame, while uncoated fibers were completely consumed. Scanning electron microscopy of charred paper after HFT revealed that a thin shell of the charred polymeric multilayer remained after the cellulose fibers had been completely oxidized. Cone calorimetry demonstrated that the phosphorus-containing thin films (20 BL is ∼25 nm) reduced the peak heat release rate by 49%. This study identifies a unique and highly effective way to impart flame-retardant characteristic to pulp fibers and the papers made from these fibers. PMID:26457504

  17. Layer-by-Layer Assembly of Supported Lipid Bilayer Poly-L-Lysine Multilayers.

    PubMed

    Heath, George R; Li, Mengqiu; Polignano, Isabelle L; Richens, Joanna L; Catucci, Gianluca; O'Shea, Paul; Sadeghi, Sheila J; Gilardi, Gianfranco; Butt, Julea N; Jeuken, Lars J C

    2016-01-11

    Multilayer lipid membranes perform many important functions in biology, such as electrical isolation (myelination of axons), increased surface area for biocatalytic purposes (thylakoid grana and mitochondrial cristae), and sequential processing (golgi cisternae). Here we develop a simple layer-by-layer methodology to form lipid multilayers via vesicle rupture onto existing supported lipid bilayers (SLBs) using poly l-lysine (PLL) as an electrostatic polymer linker. The assembly process was monitored at the macroscale by quartz crystal microbalance with dissipation (QCM-D) and the nanoscale by atomic force microscopy (AFM) for up to six lipid bilayers. By varying buffer pH and PLL chain length, we show that longer chains (≥300 kDa) at pH 9.0 form thicker polymer supported multilayers, while at low pH and shorter length PLL, we create close packed layers (average lipid bilayers separations of 2.8 and 0.8 nm, respectively). Fluorescence recovery after photobleaching (FRAP) and AFM were used to show that the diffusion of lipid and three different membrane proteins in the multilayered membranes has little dependence on lipid stack number or separation between membranes. These approaches provide a straightforward route to creating the complex membrane structures that are found throughout nature, allowing possible applications in areas such as energy production and biosensing while developing our understanding of the biological processes at play. PMID:26642374

  18. Biocorrosion behavior of biodegradable nanocomposite fibers coated layer-by-layer on AM50 magnesium implant.

    PubMed

    Abdal-Hay, Abdalla; Hasan, Anwarul; Kim, Yu-Kyoung; Yu-Kyoung; Lee, Min-Ho; Hamdy, Abdel Salam; Khalil, Khalil Abdelrazek

    2016-01-01

    This article demonstrates the use of hybrid nanofibers to improve the biodegradation rate and biocompatibility of AM50 magnesium alloy. Biodegradable hybrid membrane fiber layers containing nano-hydroxyapatite (nHA) particles and poly(lactide)(PLA) nanofibers were coated layer-by-layer (LbL) on AM50 coupons using a facile single-step air jet spinning (AJS) approach. The corrosion performance of coated and uncoated coupon samples was investigated by means of electrochemical measurements. The results showed that the AJS 3D membrane fiber layers, particularly the hybrid membrane layers containing a small amount of nHA (3 wt.%), induce a higher biocorrosion resistance and effectively decrease the initial degradation rate compared with the neat AM50 coupon samples. The adhesion strength improved highly due to the presence of nHA particles in the AJS layer. Furthermore, the long biodegradation rates of AM50 alloy in Hank's balanced salt solution (HBSS) were significantly controlled by the AJS-coatings. The results showed a higher cytocompatibility for AJS-coatings compared to that for neat Mg alloys. The nanostructured nHA embedded hybrid PLA nanofiber coating can therefore be a suitable coating material for Mg alloy as a potential material for biodegradable metallic orthopedic implants. PMID:26478426

  19. Layer-by-layer assembly for biomedical applications in the last decade.

    PubMed

    Gentile, P; Carmagnola, I; Nardo, T; Chiono, V

    2015-10-23

    In the past two decades, the design and manufacture of nanostructured materials has been of tremendous interest to the scientific community for their application in the biomedical field. Among the available techniques, layer-by-layer (LBL) assembly has attracted considerable attention as a convenient method to fabricate functional coatings. Nowadays, more than 1000 scientific papers are published every year, tens of patents have been deposited and some commercial products based on LBL technology have become commercially available. LBL presents several advantages, such as (1): a precise control of the coating properties; (2) environmentally friendly, mild conditions and low-cost manufacturing; (3) versatility for coating all available surfaces; (4) obtainment of homogeneous film with controlled thickness; and (5) incorporation and controlled release of biomolecules/drugs. This paper critically reviews the scientific challenge of the last 10 years--functionalizing biomaterials by LBL to obtain appropriate properties for biomedical applications, in particular in tissue engineering (TE). The analysis of the state-of-the-art highlights the current techniques and the innovative materials for scaffold and medical device preparation that are opening the way for the preparation of LBL-functionalized substrates capable of modifying their surface properties for modulating cell interaction to improve substitution, repair or enhancement of tissue function. PMID:26421916

  20. Layer-by-layer polyelectrolyte deposition: a mechanism for forming biocomposite materials

    PubMed Central

    Tan, YerPeng; Yildiz, Umit Hakan; Wei, Wei; Waite, J. Herbert; Miserez, Ali

    2014-01-01

    Complex coacervates prepared from poly-Aspartic acid (polyAsp) and poly-L-Histidine (polyHis) were investigated as models of the metastable protein phases used in the formation of biological structures such as squid beak. When mixed, polyHis and polyAsp form coacervates whereas poly-L-Glutamic acid (polyGlu) forms precipitates with polyHis. Layer-by-layer (LbL) structures of polyHis-polyAsp on gold substrates were compared with those of precipitate-forming polyHis-polyGlu by monitoring with iSPR and QCM-D. PolyHis-polyAsp LbL was found to be stiffer than polyHis-polyGlu LbL with most water evicted from the structure but with sufficient interfacial water remaining for molecular rearrangement to occur. This thin layer is believed to be fluid and like preformed coacervate films, capable of spreading over both hydrophilic ethylene glycol as well as hydrophobic monolayers. These results suggest that coacervate-forming polyelectrolytes deserve consideration for potential LbL applications and point to LbL as an important process by which biological materials form. PMID:23600626

  1. Zinc oxide nanoparticle suspensions and layer-by-layer coatings inhibit staphylococcal growth.

    PubMed

    McGuffie, Matthew J; Hong, Jin; Bahng, Joong Hwan; Glynos, Emmanouil; Green, Peter F; Kotov, Nicholas A; Younger, John G; VanEpps, J Scott

    2016-01-01

    Despite a decade of engineering and process improvements, bacterial infection remains the primary threat to implanted medical devices. Zinc oxide nanoparticles (ZnO-NPs) have demonstrated antimicrobial properties. Their microbial selectivity, stability, ease of production, and low cost make them attractive alternatives to silver NPs or antimicrobial peptides. Here we sought to (1) determine the relative efficacy of ZnO-NPs on planktonic growth of medically relevant pathogens; (2) establish the role of bacterial surface chemistry on ZnO-NP effectiveness; (3) evaluate NP shape as a factor in the dose-response; and (4) evaluate layer-by-layer (LBL) ZnO-NP surface coatings on biofilm growth. ZnO-NPs inhibited bacterial growth in a shape-dependent manner not previously seen or predicted. Pyramid shaped particles were the most effective and contrary to previous work, larger particles were more effective than smaller particles. Differential susceptibility of pathogens may be related to their surface hydrophobicity. LBL ZnO-NO coatings reduced staphylococcal biofilm burden by >95%. From the Clinical Editor: The use of medical implants is widespread. However, bacterial colonization remains a major concern. In this article, the authors investigated the use of zinc oxide nanoparticles (ZnO-NPs) to prevent bacterial infection. They showed in their experiments that ZnO-NPs significantly inhibited bacterial growth. This work may present a new alternative in using ZnO-NPs in medical devices. PMID:26515755

  2. Microporous polymeric 3D scaffolds templated by the layer-by-layer self-assembly.

    PubMed

    Paulraj, Thomas; Feoktistova, Natalia; Velk, Natalia; Uhlig, Katja; Duschl, Claus; Volodkin, Dmitry

    2014-08-01

    Polymeric scaffolds serve as valuable supports for biological cells since they offer essential features for guiding cellular organization and tissue development. The main challenges for scaffold fabrication are i) to tune an internal structure and ii) to load bio-molecules such as growth factors and control their local concentration and distribution. Here, a new approach for the design of hollow polymeric scaffolds using porous CaCO3 particles (cores) as templates is presented. The cores packed into a microfluidic channel are coated with polymers employing the layer-by-layer (LbL) technique. Subsequent core elimination at mild conditions results in formation of the scaffold composed of interconnected hollow polymer microspheres. The size of the cores determines the feature dimensions and, as a consequence, governs cellular adhesion: for 3T3 fibroblasts an optimal microsphere size is 12 μm. By making use of the carrier properties of the porous CaCO3 cores, the microspheres are loaded with BSA as a model protein. The scaffolds developed here may also be well suited for the localized release of bio-molecules using external triggers such as IR-light. PMID:25042776

  3. Layer-by-layer assembly of 3D tissue constructs with functionalized graphene.

    PubMed

    Shin, Su Ryon; Aghaei-Ghareh-Bolagh, Behnaz; Gao, Xiguang; Nikkhah, Mehdi; Jung, Sung Mi; Dolatshahi-Pirouz, Alireza; Kim, Sang Bok; Kim, Sun Min; Dokmeci, Mehmet R; Tang, Xiaowu Shirley; Khademhosseini, Ali

    2014-10-22

    Carbon-based nanomaterials have been considered as promising candidates to mimic certain structure and function of native extracellular matrix materials for tissue engineering. Significant progress has been made in fabricating carbon nanoparticle-incorporated cell culture substrates, but limited studies have been reported on the development of three-dimensional (3D) tissue constructs using these nanomaterials. Here, we present a novel approach to engineer 3D multi-layered constructs using layer-by-layer (LbL) assembly of cells separated with self-assembled graphene oxide (GO)-based thin films. The GO-based structures are shown to serve as cell adhesive sheets that effectively facilitate the formation of multi-layer cell constructs with interlayer connectivity. By controlling the amount of GO deposited in forming the thin films, the thickness of the multi-layer tissue constructs could be tuned with high cell viability. Specifically, this approach could be useful for creating dense and tightly connected cardiac tissues through the co-culture of cardiomyocytes and other cell types. In this work, we demonstrated the fabrication of stand-alone multi-layer cardiac tissues with strong spontaneous beating behavior and programmable pumping properties. Therefore, this LbL-based cell construct fabrication approach, utilizing GO thin films formed directly on cell surfaces, has great potential in engineering 3D tissue structures with improved organization, electrophysiological function, and mechanical integrity. PMID:25419209

  4. Lubricant-Infused Nanoparticulate Coatings Assembled by Layer-by-Layer Deposition

    SciTech Connect

    Sunny, S; Vogel, N; Howell, C; Vu, TL; Aizenberg, J

    2014-09-01

    Omniphobic coatings are designed to repel a wide range of liquids without leaving stains on the surface. A practical coating should exhibit stable repellency, show no interference with color or transparency of the underlying substrate and, ideally, be deposited in a simple process on arbitrarily shaped surfaces. We use layer-by-layer (LbL) deposition of negatively charged silica nanoparticles and positively charged polyelectrolytes to create nanoscale surface structures that are further surface-functionalized with fluorinated silanes and infiltrated with fluorinated oil, forming a smooth, highly repellent coating on surfaces of different materials and shapes. We show that four or more LbL cycles introduce sufficient surface roughness to effectively immobilize the lubricant into the nanoporous coating and provide a stable liquid interface that repels water, low-surface-tension liquids and complex fluids. The absence of hierarchical structures and the small size of the silica nanoparticles enables complete transparency of the coating, with light transmittance exceeding that of normal glass. The coating is mechanically robust, maintains its repellency after exposure to continuous flow for several days and prevents adsorption of streptavidin as a model protein. The LbL process is conceptually simple, of low cost, environmentally benign, scalable, automatable and therefore may present an efficient synthetic route to non-fouling materials.

  5. Polymer Thin Films and Interfaces; a Layer-by-Layer Approach

    NASA Astrophysics Data System (ADS)

    White, Ronald; Lipson, Jane

    2013-03-01

    In this talk we discuss new ways to model polymer films and interfaces, including properties such as density and concentration gradients, interfacial tension, and surface enrichment. We build on recent work where we developed a very simple equation of state approach for polymer thin films, and successfully applied it to determine thermodynamic properties and even to make predictions for the thickness-dependent depression of the thin film glass transition temperature. In that very simplified mean field model, the film properties across the entire interface region were treated as a ``whole sample'' average. Here, we take the next step, and develop a layer-by-layer equation of state model wherein details of the interface region are captured by allowing properties to vary from one discretized layer (within which properties are uniform) to the next. The model can be solved by imposing hydrostatic equilibrium in each layer, which then leads to predictions for the corresponding density gradient and other key interface properties. Work supported by the National Science Foundation.

  6. Layer-by-Layer Assembled Antisense DNA Microsponge Particles for Efficient Delivery of Cancer Therapeutics

    PubMed Central

    2015-01-01

    Antisense oligonucleotides can be employed as a potential approach to effectively treat cancer. However, the inherent instability and inefficient systemic delivery methods for antisense therapeutics remain major challenges to their clinical application. Here, we present a polymerized oligonucleotides (ODNs) that self-assemble during their formation through an enzymatic elongation method (rolling circle replication) to generate a composite nucleic acid/magnesium pyrophosphate sponge-like microstructure, or DNA microsponge, yielding high molecular weight nucleic acid product. In addition, this densely packed ODN microsponge structure can be further condensed to generate polyelectrolyte complexes with a favorable size for cellular uptake by displacing magnesium pyrophosphate crystals from the microsponge structure. Additional layers are applied to generate a blood-stable and multifunctional nanoparticle via the layer-by-layer (LbL) assembly technique. By taking advantage of DNA nanotechnology and LbL assembly, functionalized DNA nanostructures were utilized to provide extremely high numbers of repeated ODN copies for efficient antisense therapy. Moreover, we show that this formulation significantly improves nucleic acid drug/carrier stability during in vivo biodistribution. These polymeric ODN systems can be designed to serve as a potent means of delivering stable and large quantities of ODN therapeutics systemically for cancer treatment to tumor cells at significantly lower toxicity than traditional synthetic vectors, thus enabling a therapeutic window suitable for clinical translation. PMID:25198246

  7. High-Performance Carbon Nanotube/Polymer Composite Fiber from Layer-by-Layer Deposition.

    PubMed

    Wu, Min Le; Chen, Yun; Zhang, Liang; Zhan, Hang; Qiang, Lei; Wang, Jian Nong

    2016-03-30

    So far, preparation of high-performance carbon nanotube (CNT)/polymer composites still faces big challenges mainly due to the limited control of CNT dispersion, fraction, and alignment in polymers. Here, a new "layer-by-layer deposition" method is put forward for preparing CNT/polymer composite fibers using poly(vinyl alcohol) (PVA) as an exemplary polymer. This is based on the continuous production of a hollow cylindrical CNT assembly from a high temperature reactor and its shrinking by a PVA-containing solution and deposition on a removable substrate wire. The in situ mixing of the two composite components at the molecular level allows CNTs to disperse and PVA to infiltrate into the fiber efficiently. As a result, remarkable effects of the CNT reinforcement on the PVA matrix are observed, including a strength improvement from ∼50 to 1255 MPa and electrical conductivity from ∼0 to 1948 S cm(-1). The new method offers good controllability of CNT dispersion and fraction in the polymer matrix, variability for making composite fibers using different polymers, and suitability for scaled up production. This study thus provides a new research direction for preparing CNT-reinforced composites and future performance maximization. PMID:26959406

  8. Biobased nanocomposites from layer-by-layer assembly of cellulose nanowhiskers with chitosan.

    PubMed

    de Mesquita, João P; Donnici, Claudio L; Pereira, Fabiano V

    2010-02-01

    A new biodegradable nanocomposite was obtained from layer-by-layer (LBL) technique using highly deacetylated chitosan and eucalyptus wood cellulose nanowhiskers (CNWs). Hydrogen bonds and electrostatic interactions between the negatively charged sulfate groups on the whisker surface and the ammonium groups of chitosan were the driving forces for the growth of the multilayered films. The film growth was followed by UV-vis spectroscopy through the maximum value of the absorption band at 194 nm and showed the deposition of 14.7 mg.m(-2) of chitosan polymer in each cycle. Scanning electron microscopy showed high density and homogeneous distribution of CNWs adsorbed on each chitosan layer. Cross-section characterization of the assembled films indicates an average of approximately 7 nm of thickness per bilayer. The results presented in this work indicate that the methodology used can be extended to different biopolymers for the design of new biobased nanocomposites in a wide range of applications such as biomedical and food packaging. PMID:20055503

  9. Thermally Induced Charge Reversal of Layer-by-Layer Assembled Single-Component Polymer Films.

    PubMed

    Richardson, Joseph J; Tardy, Blaise L; Ejima, Hirotaka; Guo, Junling; Cui, Jiwei; Liang, Kang; Choi, Gwan H; Yoo, Pil J; De Geest, Bruno G; Caruso, Frank

    2016-03-23

    Temperature can be harnessed to engineer unique properties for materials useful in various contexts and has been shown to affect the layer-by-layer (LbL) assembly of polymer thin films and cause physical changes in preassembled polymer thin films. Herein we demonstrate that exposure to relatively low temperatures (≤ 100 °C) can induce physicochemical changes in cationic polymer thin films. The surface charge of polymer films containing primary and secondary amines reverses after heating (from positive to negative), and different characterization techniques are used to show that the change in surface charge is related to oxidation of the polymer that specifically occurs in the thin film state. This charge reversal allows for single-polymer LbL assembly to be performed with poly(allylamine) hydrochloride (PAH) through alternating heat/deposition steps. Furthermore, the negative charge induced by heating reduces the fouling and cell-association of PAH-coated planar and particulate substrates, respectively. This study highlights a unique property of thin films which is relevant to LbL assembly and biofouling and is of interest for the future development of thin polymer films for biomedical systems. PMID:26953514

  10. Novel Layer-by-Layer Deposition Technique for the Preparation of Double-Chambered Nanoparticle Formulations.

    PubMed

    Sakr, Omar S; Jordan, Olivier; Borchard, Gerrit

    2015-08-01

    In this work, we report a novel method of layer-by-layer (LbL) deposition using concentration tubes that enables faster process and less damage to fragile nanocores than previously described methods. Such methods are generally based on continuous cycles of centrifugation/resuspension for long times and at high speeds, which may eventually lead to the aggregation of the deflocculated suspension of nanoparticles into a compact, non-resuspendable cake. The new method was applied to the preparation of a double-chambered nanocarrier system, which was successfully loaded with a fluorescently labeled model protein (lysozyme) and a model small molecule (fluorescein) in two defined and separate compartments, namely the poly lactide-co-glycolide (PLGA) core (∼110 nm) and an outer shell obtained by LbL surface coating. The new method yielded stable suspensions of drug-loaded, LbL-coated PLGA nanoparticles, while centrifugation at high speeds and long time intervals leads to a compact cake of non-resuspendable aggregates. These nanocarriers were taken up by MDCK cells in vitro, where a colocalization of both model compounds was shown by confocal imaging. PMID:26017561

  11. Selective growth of graphene in layer-by-layer via chemical vapor deposition.

    PubMed

    Park, Jaehyun; An, Hyosub; Choi, Dong-Chul; Hussain, Sajjad; Song, Wooseok; An, Ki-Seok; Lee, Won-Jun; Lee, Naesung; Lee, Wan-Gyu; Jung, Jongwan

    2016-08-14

    Selective and precise control of the layer number of graphene remains a critical issue for the practical applications of graphene. First, it is highly challenging to grow a continuous and uniform few-layer graphene since once the monolayer graphene fully covers a copper (Cu) surface, the growth of the second layer stops, resulting in mostly nonhomogeneous films. Second, from the selective adlayer growth point of view, there is no clear pathway for achieving this. We have developed the selective growth of a graphene adlayer in layer-by-layer via chemical vapor deposition (CVD) which makes it possible to stack graphene on a specific position. The key idea is to deposit a thin Cu layer (∼40 nm thick) on pre-grown monolayer graphene and to apply additional growth. The thin Cu atop the graphene/Cu substrate acts as a catalyst to decompose methane (CH4) gas during the additional growth. The adlayer is grown selectively on the pre-grown graphene, and the thin Cu is removed through evaporation during CVD, eventually forming large-area and uniform double layer graphene. With this technology, highly uniform graphene films with precise thicknesses of 1 to 5 layers and graphene check patterns with 1 to 3 layers were successfully demonstrated. This method provides precise LBL growth for a uniform graphene film and a technique for the design of new graphene devices. PMID:27436358

  12. Flame retardation of cellulose-rich fabrics via a simplified layer-by-layer assembly.

    PubMed

    Yang, Jun-Chi; Liao, Wang; Deng, Shi-Bi; Cao, Zhi-Jie; Wang, Yu-Zhong

    2016-10-20

    Due to the high cellulose content of cotton (88.0-96.5%), the flame retardation of cotton fabrics can be achieved via an approach for the flame retardation of cellulose. In this work, a facile water-based flame retardant coating was deposited on cotton fabrics by a 'simplified' layer-by-layer (LbL) assembly. The novel coating solution was based on a mild reaction between ammonium polyphosphate (APP) and branched polyethyleneimine (BPEI), and the reaction mechanism was studied. TGA results showed that the char residues of coated fabrics were remarkably increased. The fabric with only 5wt% coating showed self-extinguishing in the horizontal flame test, and the peak heat release rate (pHRR) in cone calorimeter test decreased by 51%. Furthermore, this coating overcame a general drawback of flame-retardant LbL assembly which was easily washed away. Therefore, the simplified LbL method provides a fast, low-cost, eco-friendly and wash-durable flame-retardant finishing for the cellulose-rich cotton fabrics. PMID:27474586

  13. Bimodal Tumor-Targeting from Microenvironment Responsive Hyaluronan Layer-by-Layer (LbL) Nanoparticles

    PubMed Central

    2015-01-01

    Active targeting of nanoscale drug carriers can improve tumor-specific delivery; however, cellular heterogeneity both within and among tumor sites is a fundamental barrier to their success. Here, we describe a tumor microenvironment-responsive layer-by-layer (LbL) polymer drug carrier that actively targets tumors based on two independent mechanisms: pH-dependent cellular uptake at hypoxic tumor pH and hyaluronan-directed targeting of cell-surface CD44 receptor, a well-characterized biomarker for breast and ovarian cancer stem cells. Hypoxic pH-induced structural reorganization of hyaluronan-LbL nanoparticles was a direct result of the nature of the LbL electrostatic complex, and led to targeted cellular delivery in vitro and in vivo, with effective tumor penetration and uptake. The nanoscale drug carriers selectively bound CD44 and diminished cancer cell migration in vitro, while co-localizing with the CD44 receptor in vivo. Multimodal targeting of LbL nanoparticles is a powerful strategy for tumor-specific cancer diagnostics and therapy that can be accomplished using a single bilayer of polyamine and hyaluronan that, when assembled, produce a dynamic and responsive cell–particle interface. PMID:25100313

  14. Self-limiting layer-by-layer oxidation of atomically thin WSe2.

    PubMed

    Yamamoto, Mahito; Dutta, Sudipta; Aikawa, Shinya; Nakaharai, Shu; Wakabayashi, Katsunori; Fuhrer, Michael S; Ueno, Keiji; Tsukagoshi, Kazuhito

    2015-03-11

    Growth of a uniform oxide film with a tunable thickness on two-dimensional transition metal dichalcogenides is of great importance for electronic and optoelectronic applications. Here we demonstrate homogeneous surface oxidation of atomically thin WSe2 with a self-limiting thickness from single- to trilayers. Exposure to ozone (O3) below 100 °C leads to the lateral growth of tungsten oxide selectively along selenium zigzag-edge orientations on WSe2. With further O3 exposure, the oxide regions coalesce and oxidation terminates leaving a uniform thickness oxide film on top of unoxidized WSe2. At higher temperatures, oxidation evolves in the layer-by-layer regime up to trilayers. The oxide films formed on WSe2 are nearly atomically flat. Using photoluminescence and Raman spectroscopy, we find that the underlying single-layer WSe2 is decoupled from the top oxide but hole-doped. Our findings offer a new strategy for creating atomically thin heterostructures of semiconductors and insulating oxides with potential for applications in electronic devices. PMID:25646637

  15. Lubricant-infused nanoparticulate coatings assembled by layer-by-layer deposition

    DOE PAGESBeta

    Sunny, Steffi; Vogel, Nicolas; Howell, Caitlin; Vu, Thy L.; Aizenberg, Joanna

    2014-09-01

    Omniphobic coatings are designed to repel a wide range of liquids without leaving stains on the surface. A practical coating should exhibit stable repellency, show no interference with color or transparency of the underlying substrate and, ideally, be deposited in a simple process on arbitrarily shaped surfaces. We use layer-by-layer (LbL) deposition of negatively charged silica nanoparticles and positively charged polyelectrolytes to create nanoscale surface structures that are further surface-functionalized with fluorinated silanes and infiltrated with fluorinated oil, forming a smooth, highly repellent coating on surfaces of different materials and shapes. We show that four or more LbL cycles introducemore » sufficient surface roughness to effectively immobilize the lubricant into the nanoporous coating and provide a stable liquid interface that repels water, low-surface-tension liquids and complex fluids. The absence of hierarchical structures and the small size of the silica nanoparticles enables complete transparency of the coating, with light transmittance exceeding that of normal glass. The coating is mechanically robust, maintains its repellency after exposure to continuous flow for several days and prevents adsorption of streptavidin as a model protein. As a result, the LbL process is conceptually simple, of low cost, environmentally benign, scalable, automatable and therefore may present an efficient synthetic route to non-fouling materials.« less

  16. Lubricant-infused nanoparticulate coatings assembled by layer-by-layer deposition

    SciTech Connect

    Sunny, Steffi; Vogel, Nicolas; Howell, Caitlin; Vu, Thy L.; Aizenberg, Joanna

    2014-09-01

    Omniphobic coatings are designed to repel a wide range of liquids without leaving stains on the surface. A practical coating should exhibit stable repellency, show no interference with color or transparency of the underlying substrate and, ideally, be deposited in a simple process on arbitrarily shaped surfaces. We use layer-by-layer (LbL) deposition of negatively charged silica nanoparticles and positively charged polyelectrolytes to create nanoscale surface structures that are further surface-functionalized with fluorinated silanes and infiltrated with fluorinated oil, forming a smooth, highly repellent coating on surfaces of different materials and shapes. We show that four or more LbL cycles introduce sufficient surface roughness to effectively immobilize the lubricant into the nanoporous coating and provide a stable liquid interface that repels water, low-surface-tension liquids and complex fluids. The absence of hierarchical structures and the small size of the silica nanoparticles enables complete transparency of the coating, with light transmittance exceeding that of normal glass. The coating is mechanically robust, maintains its repellency after exposure to continuous flow for several days and prevents adsorption of streptavidin as a model protein. As a result, the LbL process is conceptually simple, of low cost, environmentally benign, scalable, automatable and therefore may present an efficient synthetic route to non-fouling materials.

  17. Nanocoating for biomolecule delivery using layer-by-layer self-assembly

    PubMed Central

    Keeney, M.; Jiang, X. Y.; Yamane, M.; Lee, M.; Goodman, S.

    2016-01-01

    Since its introduction in the early 1990s, layer-by-layer (LbL) self-assembly of films has been widely used in the fields of nanoelectronics, optics, sensors, surface coatings, and controlled drug delivery. The growth of this industry is propelled by the ease of film manufacture, low cost, mild assembly conditions, precise control of coating thickness, and versatility of coating materials. Despite the wealth of research on LbL for biomolecule delivery, clinical translation has been limited and slow. This review provides an overview of methods and mechanisms of loading biomolecules within LbL films and achieving controlled release. In particular, this review highlights recent advances in the development of LbL coatings for the delivery of different types of biomolecules including proteins, polypeptides, DNA, particles and viruses. To address the need for co-delivery of multiple types of biomolecules at different timing, we also review recent advances in incorporating compartmentalization into LbL assembly. Existing obstacles to clinical translation of LbL technologies and enabling technologies for future directions are also discussed. PMID:27099754

  18. Layer-by-layer assembly for biomedical applications in the last decade

    NASA Astrophysics Data System (ADS)

    Gentile, P.; Carmagnola, I.; Nardo, T.; Chiono, V.

    2015-10-01

    In the past two decades, the design and manufacture of nanostructured materials has been of tremendous interest to the scientific community for their application in the biomedical field. Among the available techniques, layer-by-layer (LBL) assembly has attracted considerable attention as a convenient method to fabricate functional coatings. Nowadays, more than 1000 scientific papers are published every year, tens of patents have been deposited and some commercial products based on LBL technology have become commercially available. LBL presents several advantages, such as (1): a precise control of the coating properties; (2) environmentally friendly, mild conditions and low-cost manufacturing; (3) versatility for coating all available surfaces; (4) obtainment of homogeneous film with controlled thickness; and (5) incorporation and controlled release of biomolecules/drugs. This paper critically reviews the scientific challenge of the last 10 years—functionalizing biomaterials by LBL to obtain appropriate properties for biomedical applications, in particular in tissue engineering (TE). The analysis of the state-of-the-art highlights the current techniques and the innovative materials for scaffold and medical device preparation that are opening the way for the preparation of LBL-functionalized substrates capable of modifying their surface properties for modulating cell interaction to improve substitution, repair or enhancement of tissue function.

  19. Magnetically encoded luminescent composite nanoparticles through layer-by-layer self-assembly.

    PubMed

    Song, Erqun; Han, Weiye; Xu, Hongyan; Jiang, Yunfei; Cheng, Dan; Song, Yang; Swihart, Mark T

    2014-11-01

    Sensitive and rapid detection of multiple analytes and the collection of components from complex samples are important in fields ranging from bioassays/chemical assays, clinical diagnosis, to environmental monitoring. A convenient strategy for creating magnetically encoded luminescent CdTe@SiO2 @n Fe3 O4 composite nanoparticles, by using a layer-by-layer self-assembly approach based on electrostatic interactions, is described. Silica-coated CdTe quantum dots (CdTe@SiO2 ) serve as core templates for the deposition of alternating layers of Fe3 O4 magnetic nanoparticles and poly(dimethyldiallyl ammonium chloride), to construct CdTe@SiO2 @n Fe3 O4 (n=1, 2, 3, …︁) composite nanoparticles with a defined number (n) of Fe3 O4 layers. Composite nanoparticles were characterized by zeta-potential analysis, fluorescence spectroscopy, vibrating sample magnetometry, and transmission electron microscopy, which showed that the CdTe@SiO2 @n Fe3 O4 composite nanoparticles exhibited excellent luminescence properties coupled with well-defined magnetic responses. To demonstrate the utility of these magnetically encoded nanoparticles for near-simultaneous detection and separation of multiple components from complex samples, three different fluorescently labeled IgG proteins, as model targets, were identified and collected from a mixture by using the CdTe@SiO2 @n Fe3 O4 nanoparticles. PMID:25258095

  20. Polyaniline-based organic memristive device fabricated by layer-by-layer deposition technique

    NASA Astrophysics Data System (ADS)

    Erokhina, Svetlana; Sorokin, Vladimir; Erokhin, Victor

    2015-09-01

    Memristors and memristive devices represent a splendid area of research due to the unique possibilities for the realization of new types of computer hardware elements and mimicking several essential properties of the nervous system of living beings. The organic memristive device was developed as an electronic single-device analogue of the synapse, suitable for the realization of circuits allowing Hebbian type of learning. This work is dedicated to the realization of the active channel of organic memristive devices by polyelectrolyte self-assembling (layer-by-layer technique). Stable and reproducible electrical characteristics of the device were obtained when the thickness of the active channel was more than seven bilayers. The device revealed rectifying behaviour and the presence of hysteresis—important properties for the realization of neuromorphic systems with synapse-like properties of the individual elements. Compared to previously reported results on organic memristive devices fabricated using other methods, the present device does not require any additional doping that is usually performed through acid treatment. Such a behaviour is extremely important for the cases in which biological systems (nervous cells, slime mould, etc.) must be interfaced with the system of organic memristive devices, since acid treatment can kill living beings. [Figure not available: see fulltext.

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

    PubMed Central

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

    2016-01-01

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

  2. A 'microfluidic pinball' for on-chip generation of Layer-by-Layer polyelectrolyte microcapsules.

    PubMed

    Kantak, Chaitanya; Beyer, Sebastian; Yobas, Levent; Bansal, Tushar; Trau, Dieter

    2011-03-21

    Inspired by the game of "pinball" where rolling metal balls are guided by obstacles, here we describe a novel microfluidic technique which utilizes micropillars in a flow channel to continuously generate, encapsulate and guide Layer-by-Layer (LbL) polyelectrolyte microcapsules. Droplet-based microfluidic techniques were exploited to generate oil droplets which were smoothly guided along a row of micropillars to repeatedly travel through three parallel laminar streams consisting of two polymers and a washing solution. Devices were prototyped in PDMS and generated highly monodisperse and stable 45±2 µm sized polyelectrolyte microcapsules. A total of six layers of hydrogen bonded polyelectrolytes (3 bi-layers) were adsorbed on each droplet within <3 minutes and a fluorescent intensity measurement confirmed polymer film deposition. AFM analysis revealed the thickness of each polymer layer to be approx. 2.8 nm. Our design approach not only provides a faster and more efficient alternative to conventional LbL deposition techniques, but also achieves the highest number of polyelectrolyte multilayers (PEMs) reported thus far using microfluidics. Additionally, with our design, a larger number of PEMs can be deposited without adding any extra operational or interfacial complexities (e.g. syringe pumps) which are a necessity in most other designs. Based on the aforementioned advantages of our device, it may be developed into a great tool for drug encapsulation, or to create capsules for biosensing where deposition of thin nanofilms with controlled interfacial properties is highly required. PMID:21218225

  3. Layer-by-layer assembly of zeolite imidazolate framework-8 as coating material for capillary electrochromatography.

    PubMed

    Qu, Qishu; Xuan, Han; Zhang, Kehua; Ding, Yi; Xu, Qin

    2016-08-01

    In this work, open-tubular capillary column coated with zeolite imidazolate framework-8 (ZIF-8) nanocrystals was prepared by a layer-by-layer method. The coating was formed by growing ZIF-8 nanocrystals on either bare fused silica capillary wall or the capillary column premodified with amino groups. The shape and the thickness of the coating formed by using these two methods were almost the same. However, the coverage of the ZIF-8 crystals on the bare fused silica capillary wall was higher than that on the capillary column premodified with amino groups. The ZIF-8 coated capillary column was evaluated for open-tubular capillary electrochromatography. The effect of pH value, buffer concentration, and applied voltage on the separation of phenols was investigated. Good separation of nine phenolic isomers was achieved because of the strong interaction between unsaturated Zn sites and phenols. The column performance for o-nitrophenol was as high as 208 860 plates m(-1) . The run-to-run, day-to-day, and column-to-column reproducibility of retention time and resolution for p-nitrophenol and o-nitrophenol were very good with RSDs of less than 6.5%. PMID:27174427

  4. Layer-by-layer assembly of epidermal growth factors on polyurethane films for wound closure.

    PubMed

    Kulkarni, Abhilash; Diehl-Jones, William; Ghanbar, Sadegh; Liu, Song

    2014-02-13

    To facilitate the healing of chronic wounds, growth factors such as epidermal growth factor need to be safely encapsulated for their sustained and effective delivery to the wound bed. Using a layer-by-layer assembly technique, epidermal growth factor is successfully encapsulated on the surface of poly(acrylic acid)-modified polyurethane film. The amount of encapsulated epidermal growth factor is controlled by adjusting the number of chitosan/epidermal growth factor bilayers. A controlled release of epidermal growth factor from the surface of polyurethane film for a period of five days is achieved with well-retained bioactivity (over 90%) as evidenced by a cell proliferation assay. In an in vitro cellular wounding assay, the cell gap covered with the epidermal growth factor-loaded polyurethane film closes at a rate more than twice as fast as that covered with a control polyurethane film. Fluorescent staining of F-actin reveals that the released epidermal growth factor induces differences in cytoskeletal organization, suggesting that stimulated cell migration also contributes to the close of the cell gap. PMID:24525716

  5. Ion-Exchange Membranes Prepared Using Layer-by-Layer Polyelectrolyte Deposition

    PubMed Central

    Liu, Guanqing; Dotzauer, David M.; Bruening, Merlin L

    2010-01-01

    Layer-by-layer polyelectrolyte adsorption in porous polymeric membranes provides a simple way to create ion-exchange sites without greatly decreasing hydraulic permeability (<20% reduction in permeability). At 80% breakthrough, membranes coated with 3-bilayer poly(styrene sulfonate) (PSS)/polyethyleneimine (PEI) films bind 37±6 mg of negatively charged Au colloids per mL of membrane volume. The binding capacity of membranes coated with 1-bilayer films decreases in the order PSS/PEI>PSS/poly(diallyldimethyl ammonium chloride)>PSS/poly(allylamine hydrochloride). Films terminated with a polyanion present cation-exchange sites that bind lysozyme, and the lysozyme-binding capacities of (PSS/PEI)3/PSS films increase with the ionic strength of the solution from which the last PSS layer is deposited. Charge screening during deposition of the terminal PSS layer gives rise to a larger number of ion-exchange sites and lysozyme binding capacities as high as 16 mg per mL of membrane. At 10% breakthrough, a stack of 3 membranes binds 3 times as much lysozyme as a single membrane, showing that stacking is an effective way to increase capacity. PMID:20606722

  6. Development of the layer-by-layer biosensor using graphene films: application for cholesterol determination

    NASA Astrophysics Data System (ADS)

    Binh Nguyen, Hai; Chuc Nguyen, Van; Nguyen, Van Tu; Doan Le, Huu; Quynh Nguyen, Van; Thanh Tam Ngo, Thi; Phuc Do, Quan; Nghia Nguyen, Xuan; Phan, Ngoc Minh; Tran, Dai Lam

    2013-03-01

    The preparation and characterization of graphene films for cholesterol determination are described. The graphene films were synthesized by thermal chemical vapor deposition (CVD) method. Methane gas (CH4) and copper tape were used as carbon source and catalyst in the graphene growth process, respectively. The intergrated array was fabricated by using micro-electro-mechanical systems (MEMS) technology in which Fe3O4-doped polyaniline (PANi) film was electropolymerized on Pt/Gr electrodes. The properties of the Pt/Gr/PANi/Fe3O4 films were investigated by field-emission scanning electron microscopy (FE-SEM), Raman spectroscopy and electrochemical techniques. Cholesterol oxidase (ChOx) has been immobilized onto the working electrode with glutaraldehyde agent. The cholesterol electrochemical biosensor shows high sensitivity (74 μA mM-1 cm-2) and fast response time (<5 s). A linear calibration plot was obtained in the wide cholesterol concentration range from 2 to 20 mM and correlation coefficient square (R2) of 0.9986. This new layer-by-layer biosensor based on graphene films promises many practical applications.

  7. Drug nano-reservoirs synthesized using layer-by-layer technologies.

    PubMed

    Costa, Rui R; Alatorre-Meda, Manuel; Mano, João F

    2015-11-01

    The pharmaceutical industry has been able to tackle the emergence of new microorganisms and diseases by synthesizing new specialized drugs to counter them. Their administration must ensure that a drug is effectively encapsulated and protected until it reaches its target, and that it is released in a controlled way. Herein, the potential of layer-by-layer (LbL) structures to act as drug reservoirs is presented with an emphasis to "nano"-devices of various geometries, from planar coatings to fibers and capsules. The inherent versatile nature of this technique allows producing carriers resorting to distinct classes of materials, variable geometry and customized release profiles that fit within adequate criteria required for disease treatment or for novel applications in the tissue engineering field. The production methods of LbL reservoirs are varied and allow for different kinds of molecules to be incorporated, such as antibiotics, growth factors and biosensing substances, not limited to water-soluble molecules but including hydrophobic drugs. We will also debate the future of LbL in the pharmaceutical industry. Currently, multilayered structures are yet to be covered by the regulatory guidelines that govern the fabrication of nanotechnology products. However, as they stand now, LbL nanodevices have already shown usefulness for antifouling applications, gene therapy, nanovaccines and the formation of de novo tissues. PMID:25900197

  8. Effects of geometrical confinement in membrane pores on enzyme-based layer-by-layer assemblies

    NASA Astrophysics Data System (ADS)

    Ramírez-Wong, Diana G.; Coelho-Diogo, Cristina; Aimé, Carole; Bonhomme, Christian; Jonas, Alain M.; Demoustier-Champagne, Sophie

    2015-05-01

    Micro- and nanoporous systems incorporating bioactive molecules, such as enzymes, are very promising supports for biocatalysis. Here, we investigate the influence of geometrical confinement on the layer-by-layer (LbL) assembly of enzyme-based thin films, using the polyionic couple (chitosan/β-lactamase)n. Thin films with different number of layers were prepared on flat silicon wafers and within cylindrical submicron pores of polycarbonate membranes to determine the impact of the confinement of macromolecules on: (i) the LbL film growth, (ii) the enzyme loading, and (iii) the biocatalytic efficiency. Solid-state NMR is employed to estimate the amount of enzyme loaded in the different types of LbL films, and the enzyme activity is determined by the study of the kinetics of nitrocefin hydrolysis. Film growth and loading of enzyme occur faster in the confined medium, until pores reach saturation. Moreover, when LbL films are grown within nanopores, the weight fraction of enzyme is very high and remains constant along the build-up. Conversely, the relative amount of enzyme in flat films significantly decreases with the number of layers due to the partial exchange during the growth. Finally, our study emphasizes that the immobilization of enzymes through LbL assembly in confined media can lead to very active surfaces with a restricted number of LbL cycles.

  9. Local and Sustained Activity of Doxycycline Delivered with Layer-by-Layer Microcapsules.

    PubMed

    Luo, Dong; Gould, David J; Sukhorukov, Gleb B

    2016-04-11

    Achieving localized delivery of small molecule drugs has the potential to increase efficacy and reduce off target and side effects associated with systemic distribution. Herein, we explore the potential use of layer-by-layer (LbL) assembled microcapsules for the delivery of doxycycline. Absorbance of doxycycline onto core dextran sulfate of preassembled microcapsules provides an efficient method to load both synthetic and biodegradable microcapsules with the drug. Application of an outer layer lipid coat enhances the sustained in vitro release of doxycycline from both microcapsule types. To monitor doxycycline delivery in a biological system, C2C12 mouse myoblasts are engineered to express EGFP under the control of the optimized components of the tetracycline regulated gene expression system. Microcapsules are not toxic to these cells, and upon delivery to the cells, EGFP is more efficiently induced in those cells that contain engulfed microcapsules and monitored EGFP expression clearly demonstrates that synthetic microcapsules with a DPPC coat are the most efficient for sustain intracellular delivery. Doxycycline released from microcapsules also displayed sustained activity in an antimicrobial growth inhibition assay compared with doxycycline solution. This study reveals the potential for LbL microcapsules in small molecule drug delivery and their feasible use for achieving prolonged doxycycline activity. PMID:26967921

  10. Resistive switching memory properties of layer-by-layer assembled enzyme multilayers.

    PubMed

    Baek, Hyunhee; Lee, Chanwoo; Lim, Kwang-il; Cho, Jinhan

    2012-04-20

    The properties of enzymes, which can cause reversible changes in currents through redox reactions in solution, are of fundamental and practical importance in bio-electrochemical applications. These redox properties of enzymes are often associated with their charge-trap sites. Here, we demonstrate that reversible changes in resistance in dried lysozyme (LYS) films can be generated by an externally applied voltage as a result of charge trap/release. Based on such changes, LYS can be used as resistive switching active material for nonvolatile memory devices. In this study, cationic LYS and anionic poly(styrene sulfonate) (PSS) layers were alternately deposited onto Pt-coated silicon substrates using a layer-by-layer assembly method. Then, top electrodes were deposited onto the top of LYS/PSS multilayers to complete the fabrication of the memory-like device. The LYS/PSS multilayer devices exhibited typical resistive switching characteristics with an ON/OFF current ratio above 10(2), a fast switching speed of 100 ns and stable performance. Furthermore, the insertion of insulating polyelectrolytes (PEs) between the respective LYS layers significantly enhanced the memory performance of the devices showing a high ON/OFF current ratio of ~10(6) and low levels of power consumption. PMID:22456233

  11. Starch-Based Layer by Layer Assembly: Efficient and Sustainable Approach to Cotton Fire Protection.

    PubMed

    Carosio, F; Fontaine, G; Alongi, J; Bourbigot, S

    2015-06-10

    Starch has been employed via layer by layer assembly for building an efficient and sustainable biobased coatings capable of protecting cotton from fire. In order to obtain a better understanding of the coating to substrate relationship, the coating efficiency has been tested on cotton fabrics having different densities (i.e., 100, 200, and 400 g/m(2)). The adopted deposition conditions allow for the buildup of a homogeneous coating even at a low number of deposition steps. The physical and chemical mechanisms are described and related to the achieved results. The coating can greatly enhance the char forming ability of cellulose, nearly doubling the amount of thermally stable organic residue produced by cotton at high temperatures, as assessed by thermogravimetric analyses. After only 2 bilayers deposited, this biobased system is capable of self-extinguishing a flame during flammability tests with less than 5% in weight deposited on cotton. This high efficiency is kept even when the coating is deposited on cotton with the highest density. By cone calorimetry, all treated cottons showed significant reductions (up to 40%) of the total heat released during combustion, thus demonstrating the high efficiency achieved. PMID:25978652

  12. Layer-by-layer assembly of nanowires for three-dimensional, multifunctional electronics.

    PubMed

    Javey, Ali; Nam, SungWoo; Friedman, Robin S; Yan, Hao; Lieber, Charles M

    2007-03-01

    We report a general approach for three-dimensional (3D) multifunctional electronics based on the layer-by-layer assembly of nanowire (NW) building blocks. Using germanium/silicon (Ge/Si) core/shell NWs as a representative example, ten vertically stacked layers of multi-NW field-effect transistors (FETs) were fabricated. Transport measurements demonstrate that the Ge/Si NW FETs have reproducible high-performance device characteristics within a given device layer, that the FET characteristics are not affected by sequential stacking, and importantly, that uniform performance is achieved in sequential layers 1 through 10 of the 3D structure. Five-layer single-NW FET structures were also prepared by printing Ge/Si NWs from lower density growth substrates, and transport measurements showed similar high-performance characteristics for the FETs in layers 1 and 5. In addition, 3D multifunctional circuitry was demonstrated on plastic substrates with sequential layers of inverter logical gates and floating gate memory elements. Notably, electrical characterization studies show stable writing and erasing of the NW floating gate memory elements and demonstrate signal inversion with larger than unity gain for frequencies up to at least 50 MHz. The ability to assemble reproducibly sequential layers of distinct types of NW-based devices coupled with the breadth of NW building blocks should enable the assembly of increasing complex multilayer and multifunctional 3D electronics in the future. PMID:17266383

  13. Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes.

    PubMed

    Lindemann, Peter; Träutlein, Yannick; Wöll, Christof; Tsotsalas, Manuel

    2015-01-01

    CMP as large surface area materials have attracted growing interest recently, due to their high variability in the incorporation of functional groups in combination with their outstanding thermal and chemical stability, and low densities. However, their insoluble nature causes problems in their processing since usually applied techniques such as spin coating are not available. Especially for membrane applications, where the processing of CMP as thin films is desirable, the processing problems have hindered their commercial application. Here we describe the interfacial synthesis of CMP thin films on functionalized substrates via molecular layer-by-layer (l-b-l) synthesis. This process allows the preparation of films with desired thickness and composition and even desired composition gradients. The use of sacrificial supports allows the preparation of freestanding membranes by dissolution of the support after the synthesis. To handle such ultra-thin freestanding membranes the protection with sacrificial coatings showed great promise, to avoid rupture of the nanomembranes. To transfer the nanomembranes to the desired substrate, the coated membranes are upfloated at the air-liquid interface and then transferred via dip coating. PMID:26710232

  14. Preparation and characterization of directly compactible layer-by-layer nanocoated cellulose.

    PubMed

    Strydom, Schalk J; Otto, Daniel P; Liebenberg, Wilna; Lvov, Yuri M; de Villiers, Melgardt M

    2011-02-14

    Microcrystalline cellulose is a commonly used direct compression tablet diluent and binder. It is derived from purified α-cellulose in an environmentally unfriendly process that involves mineral acid catalysed hydrolysis. In this study Kraft softwood fibers was nanocoated using a layer-by-layer self-assembling process. Powder flow and compactibility results showed that the application of nano-thin polymer layers on the fibers turned non-flowing, non-compacting cellulose into powders that can be used in the direct compression of tablets. The powder flow properties and tableting indices of compacts compressed from these nanocoated microfibers were similar or better than that of directly compactible microcrystalline cellulose powders. Cellulose microfibers coated with four PSS/PVP bilayers had the best compaction properties while still producing tablets that were able to absorb water and disintegrate and did not retard the dissolution of a model drug acetaminophen. The advantages of nanocoating rather than traditional pharmaceutical coating are that it add less than 1% to the weight of the fibers and allows control of the molecular properties of the surface and the thickness of the coat to within a few nanometers. This process is potentially friendlier to the environment because of the type and quantity of materials used. Also, it does not involve acid-catalyzed hydrolysis and neutralization of depolymerized cellulose. PMID:21056645

  15. Conductive wood microfibres for smart paper through layer-by-layer nanocoating

    NASA Astrophysics Data System (ADS)

    Agarwal, Mangilal; Lvov, Yuri; Varahramyan, Kody

    2006-11-01

    A layer-by-layer (LbL) self-assembly of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) on lignocellulose wood microfibres was used to make conductive fibres and paper. Polycations such as poly(allylamine hydrochloride) (PAH), and poly(ethyleneimine) (PEI) were used in alternate deposition with anionic conductive polythiophene (PEDOT-PSS) to construct the multilayer nanofilms on wood microfibres. Current-voltage characterization was measured on single fibres using a Keithley probe measurement system after deposition of every PEDOT-PSS monolayer to study the electrical properties of the coating. The conductivity of the microfibres increased linearly with increasing number of bilayers of PEDOT-PSS/polycation. The measured conductivities of the coated microfibres ranged from 1 to 10 S cm-1. It was also observed that the conductivity of the fibres (i.e., coating of PEDOT-PSS) depends upon the type of polycations used to alternate with the polythiophene. In this work we have demonstrated successful scale integration from nano to micro and macroscale (nanocoating-microfibres-macropaper) in developing new paper material. The conductive paper that has been produced (and its fabrication method) can be used for the development of smart paper technology on monitoring of electrical, and optical/electrical signals.

  16. Layer-by-layer fully printed Zn-MnO2 batteries with improved internal resistance and cycle life

    NASA Astrophysics Data System (ADS)

    Kim, B.; Winslow, R.; Lin, I.; Gururangan, K.; Evans, J.; Wright, P.

    2015-12-01

    This research created direct layer-by-layer printed zinc-based secondary batteries with an ionic liquid-based gel polymer electrolyte to power micro- and meso-scale devices. The use of a gel polymer electrolyte composed of [BMIM][Otf] ionic liquid, ZnOtf salt, and PVDF-HFP polymer binder enabled direct layer-by-layer printing of functional cells. The effects of additive printing methods on cell discharge capacity, cycle life, and internal resistance are discussed. Fully printed cells have demonstrated average discharge capacities of 0.548 mAh/cm2, energy densities of 8.20 mWh/cm3, and specific energies of 2.46 mWh/g with some cells achieving over 1000 cycles without catastrophic failure. Layer-by-layer printed devices exhibited decreased DC internal resistance and longer cycle life over previous mechanically assembled cells.

  17. The use of native chemical functional groups presented by wound beds for the covalent attachment of polymeric microcarriers of bioactive factors

    PubMed Central

    Jain, Rishabh; Agarwal, Ankit; Kierski, Patricia R.; Schurr, Michael J.; Murphy, Christopher J.; McAnulty, Jonathan F.; Abbott, Nicholas L.

    2012-01-01

    The development of versatile methods that provide spatial and temporal control over the presentation of physical and biochemical cues on wound beds can lead to new therapeutic approaches that expedite wound healing by favorably influencing cellular behaviors. Towards that goal, we report that native chemical functional groups presented by wound beds can be utilized for direct covalent attachment of polymeric microbeads. Specifically, we demonstrated the covalent attachment of maleimide-functionalized and catechol-functionalized microbeads, made of either polystyrene (non-degradable) or poly(lactic-co-glycolic acid) ((PLGA), degradable), to sulfhydryl and amine groups present on porcine dermis used here as an ex vivo model wound bed. A pronounced increase (10–70 fold) in the density and persistence of the covalently reactive microbeads was observed relative to microbeads that adsorb via non-covalent interactions. Complementary characterization of the surface chemistry of the ex vivo wound beds using Raman microspectroscopy provides support for our conclusion that the increased adherence of the maleimide-functionalized beads results from their covalent bond formation with sulfhydryl groups on the wound bed. The attachment of maleimide-functionalized microbeads to wounds created in live wild-type and diabetic mice led to observations of differential immobilization of microbeads on them and were consistent with anticipated differences in the presentation of sulfhydryl groups on the two different wound types. Finally, the incorporation of maleimide-functionalized microbeads in wounds created in wild-type mice did not impair the rate of wound closure relative to an untreated wound. Overall, the results presented in this paper enable a general and facile approach to the engineering of wound beds in which microbeads are covalently immobilized to wound beds. Such immobilized microbeads could be used in future studies to release bioactive factors (e.g., antimicrobial

  18. 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

  19. Enzymatic amplification-free nucleic acid hybridisation sensing on nanostructured thick-film electrodes by using covalently attached methylene blue.

    PubMed

    García-González, Raquel; Costa-García, Agustín; Fernández-Abedul, M Teresa

    2015-09-01

    Amplification-free (referring to enzymatic amplification step) detection methodologies are increasing in biosensor development due to the need of faster and simpler protocols. However, for maintaining sensitivity without this step, highly detectable molecules or very sensitive detection techniques are required. The nanostructuration of transducer surfaces with carbon nanotubes (CNTs), gold nanoparticles (AuNPs) or both in nanohybrid configurations has been employed in this work for DNA hybridisation sensing purposes. Methylene blue (MB), covalently attached to single stranded DNA, (ssDNA) was incubated with a complementary sequence immobilized on nanostructured screen-printed electrodes (AuSPEs). Although CNTs can increase notoriously the signal of the marker, adsorptive properties should also be considered when bioassays are performed because non-specific adsorption (NSA) phenomena are magnified. In this work, strategies for decreasing NSA were thoroughly evaluated for the detection of Mycoplasma pneumoniae (MP) on CNTs-nanostructured screen-printed electrodes. Among them, the employ of UV-radiation or long incubation times (72h) allowed obtaining higher signals for the complementary strand with respect to the non-complementary one. The use of CNTs/AuNPs nanohybrids, together with the use of streptavidin-biotin (ST-B) interaction allows the higher differentiation (with a 3.5 ratio) in the genosensing of M. pneumoniae. PMID:26003686

  20. Perfluorinated poly(dimethylsiloxane) via the covalent attachment of perfluoroalkylsilanes on the oxidized surface: Effects on zeta-potential values

    NASA Astrophysics Data System (ADS)

    Sun, Peiling; Horton, J. Hugh

    2013-04-01

    Poly(dimethylsiloxane) (PDMS) is a widely-used polymer in microfluidic devices due to its range of physical and chemical properties suitable for molding micron-sized features. However, its hydrophobicity also leads to some limitations: it poorly supports electro-osmotic flow, and can be incompatible with biomolecules and with many organic solvents. Surface modification is commonly used to vary PDMS surface properties to make it more suitable for specific microfluidic applications. Here, we report on the surface modification of PDMS using perfluoroalkane-triethoxysilanes, via the covalent attachment of triethoxysilane groups on plasma-oxidized PDMS. A device constructed from such fluorinated materials could be used for separating fluorous-tagged proteins or peptides. Modified PDMS were characterized using a range of surface analytical methods. In particular, zeta- (ζ-) potential values at the interfaces of both modified and unmodified PDMS and under varying pH conditions were measured, as ζ-potential is an essential parameter to support electroosmotic flow (EOF), a common pumping method in microfluidic devices. The results showed the length of fluorinated alkane chain has significant effect on the density of surface modifying species and topography following modification. In addition, the perfluorinated modification increases the magnitude of the ζ-potential at the PDMS interface when compared to that of native PDMS, increasing the electro-osmotic flow rate, over a wide pH range. The modified surface is resistant to the diffusion of PDMS oligomers that affects other PDMS surface modification processes.

  1. Development of a Dehalogenase-Based Protein Fusion Tag Capable of Rapid, Selective and Covalent Attachment to Customizable Ligands

    PubMed Central

    Encell, Lance P; Friedman Ohana, Rachel; Zimmerman, Kris; Otto, Paul; Vidugiris, Gediminas; Wood, Monika G; Los, Georgyi V; McDougall, Mark G; Zimprich, Chad; Karassina, Natasha; Learish, Randall D; Hurst, Robin; Hartnett, James; Wheeler, Sarah; Stecha, Pete; English, Jami; Zhao, Kate; Mendez, Jacqui; Benink, Hélène A; Murphy, Nancy; Daniels, Danette L; Slater, Michael R; Urh, Marjeta; Darzins, Aldis; Klaubert, Dieter H; Bulleit, Robert F; Wood, Keith V

    2012-01-01

    Our fundamental understanding of proteins and their biological significance has been enhanced by genetic fusion tags, as they provide a convenient method for introducing unique properties to proteins so that they can be examinedin isolation. Commonly used tags satisfy many of the requirements for applications relating to the detection and isolation of proteins from complex samples. However, their utility at low concentration becomes compromised if the binding affinity for a detection or capture reagent is not adequate to produce a stable interaction. Here, we describe HaloTag® (HT7), a genetic fusion tag based on a modified haloalkane dehalogenase designed and engineered to overcome the limitation of affinity tags by forming a high affinity, covalent attachment to a binding ligand. HT7 and its ligand have additional desirable features. The tag is relatively small, monomeric, and structurally compatible with fusion partners, while the ligand is specific, chemically simple, and amenable to modular synthetic design. Taken together, the design features and molecular evolution of HT7 have resulted in a superior alternative to common tags for the overexpression, detection, and isolation of target proteins. PMID:23248739

  2. Development of a dehalogenase-based protein fusion tag capable of rapid, selective and covalent attachment to customizable ligands.

    PubMed

    Encell, Lance P; Friedman Ohana, Rachel; Zimmerman, Kris; Otto, Paul; Vidugiris, Gediminas; Wood, Monika G; Los, Georgyi V; McDougall, Mark G; Zimprich, Chad; Karassina, Natasha; Learish, Randall D; Hurst, Robin; Hartnett, James; Wheeler, Sarah; Stecha, Pete; English, Jami; Zhao, Kate; Mendez, Jacqui; Benink, Hélène A; Murphy, Nancy; Daniels, Danette L; Slater, Michael R; Urh, Marjeta; Darzins, Aldis; Klaubert, Dieter H; Bulleit, Robert F; Wood, Keith V

    2012-01-01

    Our fundamental understanding of proteins and their biological significance has been enhanced by genetic fusion tags, as they provide a convenient method for introducing unique properties to proteins so that they can be examinedin isolation. Commonly used tags satisfy many of the requirements for applications relating to the detection and isolation of proteins from complex samples. However, their utility at low concentration becomes compromised if the binding affinity for a detection or capture reagent is not adequate to produce a stable interaction. Here, we describe HaloTag® (HT7), a genetic fusion tag based on a modified haloalkane dehalogenase designed and engineered to overcome the limitation of affinity tags by forming a high affinity, covalent attachment to a binding ligand. HT7 and its ligand have additional desirable features. The tag is relatively small, monomeric, and structurally compatible with fusion partners, while the ligand is specific, chemically simple, and amenable to modular synthetic design. Taken together, the design features and molecular evolution of HT7 have resulted in a superior alternative to common tags for the overexpression, detection, and isolation of target proteins. PMID:23248739

  3. The Effect of Covalently-Attached ATRP-Synthesized Polymers on Membrane Stability and Cytoprotection in Human Erythrocytes

    PubMed Central

    Clafshenkel, William P.; Murata, Hironobu; Andersen, Jill; Creeger, Yehuda; Russell, Alan J.

    2016-01-01

    Erythrocytes have been described as advantageous drug delivery vehicles. In order to ensure an adequate circulation half-life, erythrocytes may benefit from protective enhancements that maintain membrane integrity and neutralize oxidative damage of membrane proteins that otherwise facilitate their premature clearance from circulation. Surface modification of erythrocytes using rationally designed polymers, synthesized via atom-transfer radical polymerization (ATRP), may further expand the field of membrane-engineered red blood cells. This study describes the fate of ATRP-synthesized polymers that were covalently attached to human erythrocytes as well as the effect of membrane engineering on cell stability under physiological and oxidative conditions in vitro. The biocompatible, membrane-reactive polymers were homogenously retained on the periphery of modified erythrocytes for at least 24 hours. Membrane engineering stabilized the erythrocyte membrane and effectively neutralized oxidative species, even in the absence of free-radical scavenger-containing polymers. The targeted functionalization of Band 3 protein by NHS-pDMAA-Cy3 polymers stabilized its monomeric form preventing aggregation in the presence of the crosslinking reagent, bis(sulfosuccinimidyl)suberate (BS3). A free radical scavenging polymer, NHS-pDMAA-TEMPO˙, provided additional protection of surface modified erythrocytes in an in vitro model of oxidative stress. Preserving or augmenting cytoprotective mechanisms that extend circulation half-life is an important consideration for the use of red blood cells for drug delivery in various pathologies, as they are likely to encounter areas of imbalanced oxidative stress as they circuit the vascular system. PMID:27331401

  4. Selective growth of graphene in layer-by-layer via chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Park, Jaehyun; An, Hyosub; Choi, Dong-Chul; Hussain, Sajjad; Song, Wooseok; An, Ki-Seok; Lee, Won-Jun; Lee, Naesung; Lee, Wan-Gyu; Jung, Jongwan

    2016-07-01

    Selective and precise control of the layer number of graphene remains a critical issue for the practical applications of graphene. First, it is highly challenging to grow a continuous and uniform few-layer graphene since once the monolayer graphene fully covers a copper (Cu) surface, the growth of the second layer stops, resulting in mostly nonhomogeneous films. Second, from the selective adlayer growth point of view, there is no clear pathway for achieving this. We have developed the selective growth of a graphene adlayer in layer-by-layer via chemical vapor deposition (CVD) which makes it possible to stack graphene on a specific position. The key idea is to deposit a thin Cu layer (~40 nm thick) on pre-grown monolayer graphene and to apply additional growth. The thin Cu atop the graphene/Cu substrate acts as a catalyst to decompose methane (CH4) gas during the additional growth. The adlayer is grown selectively on the pre-grown graphene, and the thin Cu is removed through evaporation during CVD, eventually forming large-area and uniform double layer graphene. With this technology, highly uniform graphene films with precise thicknesses of 1 to 5 layers and graphene check patterns with 1 to 3 layers were successfully demonstrated. This method provides precise LBL growth for a uniform graphene film and a technique for the design of new graphene devices.Selective and precise control of the layer number of graphene remains a critical issue for the practical applications of graphene. First, it is highly challenging to grow a continuous and uniform few-layer graphene since once the monolayer graphene fully covers a copper (Cu) surface, the growth of the second layer stops, resulting in mostly nonhomogeneous films. Second, from the selective adlayer growth point of view, there is no clear pathway for achieving this. We have developed the selective growth of a graphene adlayer in layer-by-layer via chemical vapor deposition (CVD) which makes it possible to stack graphene

  5. Fabrication of biofuel cell containing enzyme catalyst immobilized by layer-by-layer method

    NASA Astrophysics Data System (ADS)

    Hyun, Kyu Hwan; Han, Sang Won; Koh, Won-Gun; Kwon, Yongchai

    2015-07-01

    Enzymatic biofuel cell (EBC) employing a layer-by-layer (LbL) structure consisting of multiple layers of glucose oxidase (GOx) and poly(ethyleneimine) (PEI) at carbon nanotube (CNT) ([GOx/PEI]n/CNT) is fabricated. The [GOx/PEI]n/CNT serves as anode catalyst for promoting glucose reaction, while Pt is employed as cathode catalyst. To evaluate effect of [GOx/PEI]n/CNT on EBC performance and stability, several characterizations are conducted. The optimal GOx/PEI layer is determined electrochemically, and it turns out that [GOx/PEI]2/CNT is the best. Electron transfer rate constant of the optimal layer is 11.3 s-1, its glucose sensitivity is 83 μAmM-1cm-2, and maximum power density of EBC adopting [GOx/PEI]2/CNT is 1.34 mWcm-2. The values are superior to those of other reference structures, indicating that the [GOx/PEI]2/CNT can produce excellent reactivity, followed by improved EBC performance. In terms of redox reaction mechanism of flavin adenine dinucleotide (FAD) within [GOx/PEI]2/CNT, glucose does not affect the redox reaction of FAD, while oxygen serves as mediator in transferring electrons and protons produced by glucose oxidation into those for reduction reaction of FAD. It is also found that the [GOx/PEI]2/CNT is confined by surface reaction and the reaction is quasi-reversible. Regarding long-term stability, [GOx/PEI]2/CNT maintains ∼83% of initial activity even after two weeks.

  6. Cross-linked Bioreducible Layer-by-layer Films for Increased Cell Adhesion and Transgene Expression

    PubMed Central

    Blacklock, Jenifer; Sievers, Torsten K.; Handa, Hitesh; You, Ye-Zi; Oupický, David; Mao, Guangzhao; Möhwald, Helmuth

    2010-01-01

    The effect of cross-linking layer-by-layer (LbL) films consisting of bioreducible poly(2-dimethylaminoethyl methacrylate) (rPDMAEMA) and DNA is examined with regards to rigidity, biodegradability, cell adhesion, and transfection activity using 1,5-diiodopentane (DIP) cross-linker. DIP chemically reacts with the tertiary amines of rPDMAEMA, altering the chemical composition of these LbL films. The result is a change in surface morphology, film swelling behavior and film rigidity, measured with AFM and ellipsometry. It is found that the apparent Young’s modulus is increased more than four times its original value upon cross-linking. Cross-linking mass is additionally confirmed with quartz crystal microbalance with dissipation (QCM-D). Comprehensive analyses of these experimental values were investigated to calculate the degree of cross-linking using the rubber elasticity theory and the Flory-Rehner theory. Additionally, the Flory-Huggins parameter, χ, was calculated. Good agreement in the two methods yields a cross-linking density of ~0.82 mmol/cm3. The Flory-Huggins parameter increased upon cross-linking from 1.07 to 1.2, indicating increased hydrophobicity of the network and formation of bulk water droplets within the films. In addition, the effects of cross-linking on film disassembly by 1,4-dithiothreitol (DTT) is found to be insignificant despite the alteration in film rigidity. Mouse fibroblast cells and smooth muscle cells are used to study the effect of cross-linking on cell adhesion and cell transfection activity. In vitro transfection activity up to seven days is quantified using secreted alkaline phosphatase (SEAP) DNA. Film cross-linking is found to enhance cell adhesion and prolong the duration of cellular transfection. These results contribute to the development of bioreducible polymer coatings for localized gene delivery. PMID:20369813

  7. Layer-by-Layer Assembled Multilayer Films for Transcutaneous Drug and Vaccine Delivery

    PubMed Central

    Su, Xingfang; Kim, Byeong-Su; Kim, Sara R.; Hammond, Paula T.; Irvine, Darrell J.

    2011-01-01

    We describe protein- and oligonucleotide-loaded layer-by-layer (LbL)-assembled multiplayer films incorporating a hydrolytically degradable polymer for transcutaneous drug or vaccine delivery. Films were constructed based on electrostatic interactions between a cationic poly(β-amino ester) (denoted Poly-1) with a model protein antigen, ovalbumin (ova), and/or immunostimulatory CpG (Cytosine–phosphate diester—Guanine rich) DNA oligonucleotide adjuvant molecules. Linear growth of nanoscale Poly-1/ova bilayers was observed. Dried ova protein-loaded films rapidly deconstructed when rehydrated in saline solutions, releasing ova as non-aggregated/non-degraded protein, suggesting that the structure of biomolecules integrated into these multilayer films are preserved during release. Using confocal fluorescence microscopy and an in vivo murine ear skin model, we demonstrated delivery of ova from LbL films into barrier-disrupted skin, uptake of the protein by skin-resident antigen-presenting cells (Langerhans cells), and transport of the antigen to the skin-draining lymph nodes. Dual incorporation of ova and CpG oligonucleotides into the nanolayers of LbL films enabled dual release of the antigen and adjuvant with distinct kinetics for each component; ova was rapidly released while CpG was released in a relatively sustained manner. Applied as skin patches, these films delivered ova and CpG to Langerhans Cells in the skin. To our knowledge, this is the first demonstration of LbL films applied for the delivery of biomolecules into skin. This approach provides a new route for storage of vaccines and other immunotherapeutics in a solid-state thin film for subsequent delivery into the immunologically-rich milieu of the skin. PMID:19824655

  8. Strength improvement via coating of a cylindrical hole by layer-by-layer assembled polymer particles.

    PubMed

    Wu, Shuqing; Garfield, Lucas B; Rupert, Nicholas E; Grady, Brian P; Funkhouser, Gary P

    2010-04-01

    Negatively charged colloidal poly(methyl methacrylate-co-butyl acrylate) (P(MMA-BA)) particles and positively charged dissolved poly(ethyleneimine) (PEI) were adsorbed onto a cement block using a layer-by-layer (LBL) assembly technique. The block was fashioned so as to have a cylindrical hole running from one face to another along the long axis of the rectangular block, and a fluid containing either of the two charged materials was pumped through the block. The result was a film tens of micrometers thick, and the pressure required to crack the cement block was measured after one end of the hole was sealed. Latex particles with a T(g) near the use temperature showed the maximum improvement in the cracking stress of the blocks. In a multilayer coating with identically sized particles, the cracking stress of the blocks increased to an improvement of 25% and then dropped off with increasing number of layers, even though the relationship between film thickness and the number of layers was linear. An improvement of about 30% in the cracking stress of the coated blocks was obtained when using multiple layers with different particle sizes. The effects of the number of layers and particle size on the cracking stress suggest that both the morphology and the thickness of the film play a role in performance. Tests done under confinement, e.g., with an external stress applied to the outside of the blocks, suggest that not only does a film-forming mechanism contribute to performance but that filling of microcracks in the rock may also play a role. PMID:20423142

  9. Conductive paper fabricated by layer-by-layer assembly of polyelectrolytes and ITO nanoparticles.

    PubMed

    Peng, C Q; Thio, Y S; Gerhardt, R A

    2008-12-17

    A new salt-free approach was developed for fabricating conductive paper by layer-by-layer (LBL) assembly of conductive indium tin oxide (ITO) nanoparticles and polyelectrolytes onto wood fibers. Subsequent to the coating procedure, the fibers were manufactured into conductive paper using traditional paper making methods. The wood fibers were first coated with polyethyleneimine (PEI) and then LBL assembled with poly(sodium 4-styrenesulfonate) (PSS) and ITO for several bilayers. The surface charge intensity of both the ITO nanoparticles and the coated wood fibers were evaluated by measuring the zeta-potential of the nanoparticles and short fibers, respectively. The ITO nanoparticles were found to preferentially aggregate on defects on the fiber surfaces and formed interconnected paths, which led to the formation of conductive percolation paths throughout the whole paper. With ten bilayer coatings, the as-made paper was made DC conductive, and its sigma(dc) was measured to be 5.2 x 10(-6) S cm(-1) in the in-plane (IP) direction, while the conductivity was 1.9 x 10(-8) S cm(-1) in the through-the-thickness (TT) direction. The percolation phenomena in these LBL-assembled ITO-coated paper fibers was evaluated using scanning electron microscopy (SEM), current atomic force microscopy (I-AFM), and impedance measurements. The AC electrical properties are reported for frequencies ranging from 0.01 Hz to 1 MHz. A clear transition from insulating to conducting behavior is observed in the AC conductivity. PMID:19942775

  10. Layer-by-layer deposited organic/inorganic hybrid multilayer films containing noncentrosymmetrically orientated azobenzene chromophores.

    PubMed

    Kang, En-Hua; Bu, Tianjia; Jin, Pengcheng; Sun, Junqi; Yang, Yanqiang; Shen, Jiacong

    2007-07-01

    Organic/inorganic hybrid multilayer films with noncentrosymmetrically orientated azobenzene chromophores were fabricated by the sequential deposition of ZrO2 layers by a surface sol-gel process and subsequent layer-by-layer (LbL) adsorption of the nonlinear optical (NLO)-active azobenzene-containing polyanion PAC-azoBNS and poly(diallyldimethylammonium chloride) (PDDA). Noncentrosymmetric orientation of the NLO-active azobenzene chromophores was achieved because of the strong repulsion between the negatively charged ZrO(2) and the sulfonate groups of the azobenzene chromophore in PAC-azoBNS. Regular deposition of ZrO(2)/PAC-azoBNS/PDDA multilayer films was verified by UV-vis absorption spectroscopy and quartz crystal microbalance measurements. Both UV-vis absorption spectroscopy and transmission second harmonic generation (SHG) measurements confirmed the noncentrosymmetric orientation of the azobenzene chromophores in the as-prepared ZrO2/PAC-azoBNS/PDDA multilayer films. The square root of the SHG signal (I(2omega)(1/2)) increases with the increase of the azobenzene graft ratio in PAC-azoBNS as the number of deposition cycles of the ZrO(2)/PAC-azoBNS/PDDA films remains the same, while the second-order susceptibility chi(zzz)(2) of the film decreases with the increase of the azobenzene graft ratio. Furthermore, the present method was successfully extended to realize the noncentrosymmetric orientation of azobenzene chromophores in multilayer films when small organic azobenzene compounds with carboxylic acid and/or hydroxyl groups at one end and sulfonate groups at the other end were used. The present method was characterized by its simplicity and flexibility in film preparation, and it is anticipated to be a facile way to fabricate second-order nonlinear optical film materials. PMID:17555337

  11. Layer-by-layer fabrication of AgCl-PANI hybrid nanocomposite films for electronic tongues.

    PubMed

    Manzoli, Alexandra; Shimizu, Flavio M; Mercante, Luiza A; Paris, Elaine C; Oliveira, Osvaldo N; Correa, Daniel S; Mattoso, Luiz H C

    2014-11-28

    The fabrication of nanostructured films with tailored properties is essential for many applications, particularly with materials such as polyaniline (PANI) whose electrical characteristics may be easily tuned. In this study we report the one-step synthesis of AgCl-PANI nanocomposites that could form layer-by-layer (LbL) films with poly(sodium 4-styrenesulfonate) (PSS) and be used for electronic tongues (e-tongues). The first AgCl-PANI layer was adsorbed on a quartz substrate according to a nucleation-and-growth mechanism explained using the Johnson-Mehl-Avrami (JMA) model, revealing a 3D film growth confirmed by atomic force microscopy (AFM) measurements for the AgCl-PANI/PSS LbL films. In contrast to conventional PANI-containing films, the AgCl-PANI/PSS LbL films deposited on interdigitated electrodes exhibited electrical resistance that was practically unaffected by changes in pH from 4 to 9, and therefore these films can be used in e-tongues for both acidic and basic media. With a sensor array made of AgCl-PANI/PSS LbL films with different numbers of bilayers, we demonstrated the suitability of the AgCl-PANI nanocomposite for an e-tongue capable of clearly discriminating the basic tastes from salt, acid and umami solutions. Significantly, the hybrid AgCl-PANI nanocomposite is promising for any application in which PANI de-doping at high pH is to be avoided. PMID:25298297

  12. Novel layer-by-layer interfacial [Ni(salen)]-polyelectrolyte hybrid films.

    PubMed

    Patrício, Sónia; Cruz, Ana I; Biernacki, Krzysztof; Ventura, João; Eaton, Peter; Magalhães, Alexandre L; Moura, Cosme; Hillman, A Robert; Freire, Cristina

    2010-07-01

    A novel multilayer film containing a cationic phosphonium-derivatized Ni(salen)-type complex and poly(sodium-4-styrenesulfonate (NaPSS) was assembled onto quartz, mica, and metal surfaces using the layer-by-layer (LbL) technique. Spectroscopic (UV-vis) and gravimetric (QCM) responses for the multilayer films show regular stepwise growth and the signature of strong electrostatic interactions between the component layers. The gravimetric responses indicate the presence of substantial additional (net neutral) material in the PSS layers, which XPS shows is not polyelectrolyte or salt, so charge compensation is intrinsic; we deduce the presence of space-filling solvent. Direct electrostatic interaction of the two-component layers is enhanced by a secondary noncovalent interaction between the delocalized pi-systems of the two components. Permeability of the film to the redox probe [Fe(CN)(6)](3-/4-) was studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Qualitatively similar results were obtained in the absence and presence of a precursor PSS/PAH multilayer, but with a general shift in kinetic and diffusional processes to longer time scales (lower frequencies) in the presence of the precursor layer and with increasing numbers of PSS/[Ni(salen)] bilayers. Quantitatively, the EIS data were interpreted using a capillary membrane model (CMM) to yield values of coverage, apparent charge transfer resistance, double-layer capacitance, pore size, and diffusion coefficient. The coverage values were consistent with a model in which there are no preferential growth sites and the surface charge density is independent of the number of bilayers. PMID:20476725

  13. Protein adsorption on polyanion/polycation layer-by-layer assembled polyelectrolyte films.

    PubMed

    Yang, Jen Ming; Tsai, Rong-Ze; Hsu, Chih-Chin

    2016-06-01

    As layer-by-layer self-assembly deposition (LbL) is a versatile technique for surface modification, protein adsorption on the LbL modified glass is evaluated in this study. At the beginning, glass slides was silanized by 3-aminopropyltriethoxysilane (APTES). Sodium alginate (Alg), poly(γ-glutamic acid) (PGA) and poly(aspartic acid) (PAsp) were selected as polyanion electrolytes and chitosan (CS) was used as the polycation electrolyte. Both polyanion and polycation electrolytes alternately deposited on the silanized glass slide surface by the LbL technique to get three different polyanion/chitosan series of LbL films ([Alg/CS], [PGA/CS], and [PAsp/CS]). Three kinds of kinetic model including pseudo-first-order, second-order kinetic and intraparticle diffusion model were used to evaluate the adsorption of albumin on the three different polyanion/chitosan series of LbL films. It is found that the adsorption of albumin on the polyanion/chitosan series of LbL films can be described well with the pseudo-second-order kinetic mechanism. To make sure if the pseudo-second-order kinetic mechanism of protein adsorbed on the other polyanion/polycation LbL films is also suitable, poly(allylamine hydrochloride) (PAH) and poly(L-lysine) (PLL) are used as two other polycations. The [polyanion/PAH] and [polyanion/PLL] series of LbL films were prepared with the same LbL technique for albumin, fibrinogen, and fibronectin adsorption. From the results, it is found that albumin, fibrinogen, and fibronectin adsorption on the various polyanion/polycation LbL films can be described well with the pseudo-second-order kinetic mechanism. The protein adsorbed at equilibrium and rate constant of protein adsorbed on the various LbL films can be determined. PMID:26938325

  14. [Electrochemical sensor for acetaminophen based on layer-by-layer self assembly technique].

    PubMed

    Ru, Hui-ying; Xu, Fen; Sun, Li-xian; Liu, Qing-shan; Liu, Na

    2011-10-01

    A novel type of carbon nanotube-coated Au nanoparticle and [bmim]BF4 composite modified glassy carbon electrode was fabricated by a layer-by-layer self-assembly technique. The electrochemical performance of acetaminophen (ACOP) on the modified electrode was investigated by cyclic voltammetry. The Nafion/GNPs/RTIL/MWNTs/GC electrode showed an excellent electrocatalytic activity for the oxidation of ACOP and accelerated electron transfer between the electrode and ACOP. For ACOP, the reversible electrochemical process was observed on the Nafion/GNPs/RTIL/MWNTs/GC electrode, while irreversible electrochemical process occurred on the GC electrode. For the Nafion/GNPs/RTIL/MWNTs/GC electrode, the anodic peak potential of ACOP was moved from 0.562 V to 0.413 V, with a potential drop of 149 mV. At the same time, the reduction peak potential was 0.384 V, and the potential difference was only 29 mV. It was shown that the modified electrode possessed higher electrocatalytic activity and more sensitive effect for the detection of ACOP than both MWNTs/GC electrode and GC electrode. The effects of the different experimental conditions on the electrochemical behaviors of ACOP were explored. Under the optimum conditions of preparation and experimental, the linear calibration curves of ACOP were obtained in a wide range of 2 x 10(-1) to 4.0 x 10(-4) mol x L(-1) with a correlation coefficient 0.999 2 and a detection limit of 2.6 x 10(-8) mol x L(-1) (the ratio of signal to noise, 3:1). The recovery rate was 97.9%-100.8%. This method can be used to determine ACOP in paracetamol tablets with satisfactory results. PMID:22242455

  15. Tissue Integration of Growth Factor-Eluting Layer-by-Layer Polyelectrolyte Multilayer Coated Implants

    PubMed Central

    Macdonald, Mara L.; Samuel, Raymond E.; Shah, Nisarg J.; Padera, Robert; Beben, Yvette M.; Hammond, Paula T.

    2011-01-01

    Drug eluting coatings that can direct the host tissue response to implanted medical devices have the potential to ameliorate both the medical and financial burden of complications from implantation. However, because many drugs useful in this arena are biologic in nature, a paucity of delivery strategies for biologics, including growth factors, currently limits the control that can be exerted on the implantation environment. Layer-by-Layer (LbL) polyelectrolyte multilayer films are highly attractive as ultrathin biologic reservoirs, due to conformal coating of difficult geometries, aqueous processing likely to preserve fragile protein function, and tenability of incorporation and release profiles. Herein, we describe the first LbL films capable of microgram-scale release of the biologic Bone Morphogenetic Protein 2 (BMP-2), which is capable of directing the host tissue response to create bone from native progenitor cells. Ten micrograms of BMP-2 are released over a period of two weeks in vitro; less than 1% is released in the first 3 hours (compared with commercial collagen matrices which can release up to 60% of BMP-2, too quickly to induce differentiation). BMP-2 released from LbL films retains its ability to induce bone differentiation in MC3T3 E1S4 preosteoblasts, as measured by induction of alkaline phosphatase and stains for calcium (via Alizarin Red) and calcium matrix (via Von Kossa). In vivo, BMP-2 film coated scaffolds were compared with film coated scaffolds lacking BMP-2. BMP-2 coatings implanted intramuscularly were able to initiate host progenitor cells to differentiate into bone, which matured and expanded from four to nine weeks as measured by MicroCT and histology. Such LbL films represent new steps towards controlling and tuning host response to implanted medical devices, which may ultimately increase the success of implanted devices, provide alternative new approaches toward bone wound healing, and lay the foundation for development of a multi

  16. The effect of electrostatic heparin/collagen layer-by-layer coating degradation on the biocompatibility

    NASA Astrophysics Data System (ADS)

    Chen, Jialong; Huang, Nan; Li, Quanli; Chu, Chun H.; Li, Jun; Maitz, Manfred F.

    2016-01-01

    Electrostatic layer-by-layer coatings of heparin and collagen have been suggested before to improve the biocompatibility of blood-contacting devices. However, to our knowledge, there have been no systematic studies about the effect of degradation of this coating on its biocompatibility, anticoagulant properties and the cyto-compatibility. The purpose of this study was to design an in vitro experiment in this regard that can assess the degradation behavior and the biocompatibility change of the coating. The coating degradation in physiological saline (PS) under static and dynamic condition was monitored by DR-FTIR, SEM, AFM and water contact angle, moreover, heparin densities on the topmost surface and the release heparin every day were measured by toluidine blue O (TBO) assay. The results showed that the degradation rate of the coating in is much faster under flow and shear conditions than during static incubation, and only very limited collagen and heparin remain on the surface after 15 days incubation in dynamic condition. With the degradation, the hemocompatibility of the coating got worse, especially when incubated under dynamic conditions. The degradation products of the coating do not lead to coagulation but behave -as heparin- anticoagulant. The compatibility of the coating to endothelial cells improved within 15d incubation in static medium, but it for degradation under dynamic conditions, it improved for 5d but at 15d incubation, it was almost as low as for the bare substrate. These results highlight the necessity for appropriate testing of newly developed coatings not only in the initial state but also after extended exposure to a physiological ambient.

  17. Bioactive coronary stent coating based on layer-by-layer technology for siRNA release.

    PubMed

    Hossfeld, S; Nolte, A; Hartmann, H; Recke, M; Schaller, M; Walker, T; Kjems, J; Schlosshauer, B; Stoll, D; Wendel, H-P; Krastev, R

    2013-05-01

    One procedure to treat stenotic coronary arteries is the percutaneous transluminal coronary angioplasty (PTCA). In recent years, drug-eluting stents (DESs) have demonstrated elaborate ways to improve outcomes of intravascular interventions. To enhance DESs, the idea has evolved to design stents that elute specific small interfering RNA (siRNA) for better vascular wall regeneration. Layer-by-layer (LbL) technology offers the possibility of incorporating siRNA nanoplexes (NPs) to achieve bioactive medical implant coatings. The LbL technique was used to achieve hyaluronic acid/chitosan (HA/Chi) films with incorporated Chi-siRNA NPs. The multilayer growth was monitored by quartz crystal microbalance. The coating on the stents and its thickness were analyzed using fluorescence and scanning electron microscopy. All stents showed a homogeneous coating, and the polyelectrolyte multilayers (PEMs) were not disrupted after ethylene oxide sterilization or expansion. The in vitro uptake of fluorescent-labeled NPs from PEMs in primary human endothelial cells (ECs) was analyzed by flow cytometry for 2, 6 and 9 days. Furthermore, stents coated with HA/Chi and Chi-siRNA NPs were expanded into porcine arteries and showed ex vivo delivery of NPs. The films showed no critical results in terms of hemocompatibility. This study demonstrates that Chi-siRNA NPs can be incorporated into PEMs consisting of HA and Chi. We conclude that the NPs were delivered to ECs under in vitro conditions. Furthermore, under ex vivo conditions, NPs were transferred into porcine artery walls. Due to their good hemocompatibility, they might make an innovative tool for achieving bioactive coatings for coronary stents. PMID:23333865

  18. Photoactive layer-by-layer films of cellulose phosphate and titanium dioxide containing phosphotungstic acid

    NASA Astrophysics Data System (ADS)

    Ullah, Sajjad; Acuña, José Javier Sáez; Pasa, André Avelino; Bilmes, Sara A.; Vela, Maria Elena; Benitez, Guillermo; Rodrigues-Filho, Ubirajara Pereira

    2013-07-01

    A versatile layer-by-layer (LbL) procedure for the preparation of highly dispersed, adherent and porous multilayer films of TiO2 nanoparticles (NPs) and phosphotungstic acid (HPW) on a variety of substrates at room temperature was developed based on the use of cellulose phosphate (CP) as an efficient and non-conventional polyelectrolyte. UV/vis absorption spectroscopy confirmed the linear and regular growth of the films with the number of immersion cycles and a strong adsorption ability of CP towards TiO2 NPs. FTIR spectroscopy showed that HPW binds to the surface of TiO2 through the oxygen atom at the corner of the Keggin structure. XPS results showed that the interaction between TiO2 and CP is through Ti-O-P linkage. A model is proposed for the TiO2-HPW interaction based on XPS and FTIR results. FEG/SEM study of the surface morphology revealed a porous film structure with a homogenous distribution of the TiO2 NPs induced by CP. HRTEM studies showed that the resulting composite films consist of crystalline anatase and rutile phases and poly-nano-crystalline HPW with a semi-crystalline TiO2-HPW interface. These CP/TiO2 and CP/TiO2/HPW LbL films showed good photoactivity against both saturated and unsaturated species, for instance, stearic acid (SA), crystal violet (CV) and methylene blue (MB) under UV irradiation. The CP/HPW films formed on bacterial cellulose (BC) showed good photochromic response which is enhanced in presence of TiO2 due to an interfacial electron transfer from TiO2 to HPW. This simple and environmentally safe method can be used to form coatings on a variety of surfaces with photoactive TiO2 and TiO2/HPW films.

  19. Assembly-Controlled Permeability of Layer-by-Layer Polymeric Microcapsules Using a Tapered Fluidized Bed.

    PubMed

    Noi, Ka Fung; Roozmand, Ali; Björnmalm, Mattias; Richardson, Joseph J; Franks, George V; Caruso, Frank

    2015-12-23

    Nano- and microcapsules engineered through layer-by-layer (LbL) assembly are finding an increasingly large number of applications as catalysts, electrochemical biosensors, bioreactors, artificial cells and drug delivery vehicles. While centrifugation-based LbL assembly is the most common method for coating template particles and preparing capsules, it is a batch process and requires frequent intervention that renders the system challenging to automate and scale up. Here, we report the use of a tapered fluidized bed (TFB) for the preparation of multilayered polymer capsules. This is a significant improvement over our recent approach of fluidizing particles in cylindrical fluidized beds (CFB) for LbL assembly. We demonstrate that TFB is compatible with particles <3 μm in diameter (an order-of-magnitude improvement compared with CFB), which can be fluidized with minimal entrainment. Additionally, layering materials were expanded to include both electrostatic and hydrogen-bonding polymer pairs (e.g., poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate) (PSS), and thiol-modified poly(methacrylic acid) (PMASH) and poly(N-vinylpyrrolidone) (PVPON), respectively). Finally, differences between capsules prepared via centrifugation-based and TFB LbL assembly were investigated. The obtained TFB microcapsules demonstrate increased film thickness and roughness compared with those prepared using centrifugation-based LbL assembly. Furthermore, PMASH microcapsules exhibit lower swelling and permeability when prepared via TFB LbL assembly compared with centrifugation-based LbL assembly due to enhanced multilayer deposition, entanglement, and cross-linking. Therefore, polymeric capsules fabricated via TFB LbL assembly may be useful for encapsulation and retention of relatively low molecular weight (∼20 kDa) hydrophilic biomacromolecules to passively or responsively release the payload for drug delivery applications. PMID:26651354

  20. Surface activation of CNT Webs towards layer by layer assembly of biosensors.

    PubMed

    Musameh, Mustafa; Huynh, Chi P; Hickey, Mark; Kyratzis, Ilias Louis

    2016-04-25

    Several surface activation methods such as chemical, electrochemical and plasma have been used for enhancing the electrochemical performance of carbon based electrodes for various applications. However, some of these surface activation methods may not be useful depending on the chemical and physical properties of the activated surface. Herein we investigate the surface activation of carbon nanotube (CNT) webs by electrochemical and plasma techniques to enhance their electrochemical performance and enable the fabrication of a biosensor using the layer-by-layer (LBL) approach. The pretreated CNT webs were characterized by SEM, TEM, Raman, XPS and electrochemical methods. TEM images and Raman analysis showed an increase in the level of surface defects upon pretreatment with higher number of defects after electrochemical pretreatment. XPS analysis showed an increase in the level of oxygen functional groups after pretreatment (4 to 5 times increase) which resulted in enhanced water wettability especially for plasma pretreated CNT webs. The pretreated CNT web electrodes also showed an enhanced electrochemical activity towards the oxidation and reduction of different redox probes with higher sensitivity for the electrochemically pretreated CNT web electrode that was accompanied by a higher level of noise in amperometric measurements. A highly linear response was obtained for the untreated and the electrochemically pretreated CNT web electrodes towards the amperometric detection of NADH (R(2) of 0.9996 and 0.9986 respectively) while a non-linear response was observed for the plasma pretreated CNT web electrode (R(2) of 0.8538). The pretreated CNT web electrodes enabled the fabrication of a LBL biosensor for alcohol detection with highest operational stability obtained for the plasma pretreated CNT web surface. PMID:26818435

  1. Layer-by-layer assembly of aquaporin Z-incorporated biomimetic membranes for water purification.

    PubMed

    Wang, Miaoqi; Wang, Zhining; Wang, Xida; Wang, Shuzheng; Ding, Wande; Gao, Congjie

    2015-03-17

    We fabricated a biomimetic nanofiltration (NF) membrane by immobilizing an Aquaporin Z (AqpZ)-incorporated supported lipid bilayer (SLB) on a layer-by-layer (LbL) complex polyelectrolyte membrane to achieve excellent permeability and salt rejection with a high stability. The polyelectrolyte membranes were prepared by LbL assembly of poly(ethylenimine) (PEI) with positive charges and poly(sodium 4-styrenesulfonate) (PSS) with negative charges alternately on a porous hydrolyzed polyacrylonitrile (H-PAN) substrate. AqpZ-incorporated 1,2-dioleloyl-sn-glycero-3-phosphocholine (DOPC)/1,2-dioleoyl-3-trimethylammo-nium-propane (chloride salt) (DOTAP) vesicles with positive charges were deposited on the H-PAN/PEI/PSS polyelectrolytes membrane surface. The resulting biomimetic membrane exhibited a high flux of 22 L·m(-2)·h(-1) (LMH), excellent MgCl2 rejection of ∼97% and NaCl rejection of ∼75% under an operation pressure of 0.4 MPa. Due to the attractive electrostatic interaction between SLB and the polyelectrolyte membrane, the biomimetic membrane showed satisfactory stability and durability as well as stable NF flux and rejection for at least 36 h. In addition, the AqpZ-containing biomimetic membrane was immersed in a 0.24 mM (critical micellar concentration, CMC) Triton X-100 solution for 5 min. The flux and rejection were slightly influenced by the Triton X-100 treatment. The current investigation demonstrated that the AqpZ-incorporated biomimetic membranes fabricated by the LbL method led to excellent separation performances and robust structures that withstand a high operation pressure for a relatively long time. PMID:25730158

  2. Layer-by-layer Assembly of Thick, Cu2+-Chelating Films

    PubMed Central

    Wijeratne, Salinda; Bruening, Merlin L.; Baker, Gregory L.

    2013-01-01

    Layer-by-layer adsorption of protonated poly(allylamine) (PAH) and deprotonated poly(N,N-dicarboxymethylallyl amine) (PDCMAA) yields thick films with a high density of iminodiacetic acid (IDA) ligands that bind metal ions. When film deposition occurs at pH 3.0, PAH/PDCMAA bilayer thicknesses reach 200 nm, and Cu2+ binding capacities are ~2.5 mmoles per cm3 of film. (PAH/PDCMAA)10 films deposited at pH 3.0 are 4- to 8-fold thicker than films formed at pH 5.0, 7.0, or 9.0, presumably because of the low charge density on PDCMAA chains at pH 3.0. However, with normalization to film thickness, all films bind similar amounts of Cu2+ from pH 4.1 solutions of CuSO4. In μm-thick films, equilibration of binding sites with Cu2+ requires ~4 h due to a low Cu2+ diffusion coefficient (~2.6×10−12 cm2/sec). Sorption isotherms determined at several temperatures show that Cu2+ binding is endothermic with a positive entropy (binding constants increase with increasing temperature), presumably because metal-ion complexation involves displacement of both a proton from IDA and water molecules from Cu2+. (PAH/PDCMAA)10 films retain their binding capacity over 4 absorption/elution cycles and may prove useful in metal-ion scavenging, catalysis, and protein binding. PMID:24044576

  3. Fabrication of polyelectrolyte multilayered nano-capsules using a continuous layer-by-layer approach.

    PubMed

    Elizarova, Iuliia S; Luckham, Paul F

    2016-05-15

    The layer-by-layer approach is a highly versatile method for the fabrication of multilayered polymeric films and capsules. It has been widely investigated in research for various polyelectrolyte pairs and core template particles. However, the fabrication of nano-sized capsules at the larger scale is difficult and time consuming, due to the necessity of washing and centrifugation steps before the deposition of each polyelectrolyte layer. This results not only in a very long fabrication time, but also in the partial loss of particles during those intermediate steps. In this study, we introduced a continuous approach for the fabrication of multilayer polyelectrolyte based nano-capsules using calcium phosphate core nanoparticles and a tubular flow type reactor with the potential for synthesizing tens of milligrams of capsules per hour. Adsorption of the polyelectrolyte layer occurred in the tubing where particles and polyelectrolyte solution of choice were mixed, creating a layer of polyelectrolyte on the particles. After this, these newly surfaced-modified particles passed into the next segment of tubing, where they were mixed with a second polyelectrolyte of opposite charge. This process can be continuously repeated until the desired number of layers is achieved. One potential problem with this method concerned the presence of any excess polyelectrolyte in the tubing, so careful control of the amount of polymer added was crucial. It was found that slightly under dosing the amount of added polyelectrolyte ensured that negligible unadsorbed polyelectrolyte remained in solution. The particles created at each deposition step were stable, as they all had a zeta potential of greater than ±25mV. Furthermore the zeta potential measurements showed that charge reversal occurred at each stage. Having achieved the necessary number of polyelectrolyte layers, the calcium phosphate cores were easily removed via dissolution in either hydrochloric or acetic acid. PMID:26939072

  4. Logical enzyme triggered (LET) layer-by-layer nanocapsules for drug delivery system

    NASA Astrophysics Data System (ADS)

    Kelley, Marie-Michelle

    Breast cancer is the second leading cause of morbidity and mortality among women in the United States. Early detection and treatment methods have resulted in 100% 5-year survival rates for stage 0-I breast cancer. Unfortunately, the 5-year survival rate of metastatic breast cancer (stage IV) is reduced fivefold. The most challenging issues of metastatic breast cancer treatment are the ability to selectively target the adenoma and adenocarcinoma cells both in their location of origin and as they metastasize following initial treatment. Multilayer/Layer-by-Layer (LbL) nanocapsules have garnered vast interest as anticancer drug delivery systems due to their ability to be easily modified, their capacity to encapsulate a wide range of chemicals and proteins, and their improved pharmacokinetics. Multilayer nanocapsule formation requires the layering of opposing charged polyelectrolytic polymers over a removable core nanoparticle. Our goal is to have a programmable nanocapsules degrade only after receiving and validating specific breast cancer biomarkers. The overall objective is to fabricate a novel programmable LbL nanocapsule with a specific logical system that will enhance functions pertinent to drug delivery systems. Our central hypothesis is that LbL technology coupled with extracellular matrix (ECM) protein substrates will result in a logical enzyme triggered LbL nanocapsule drug delivery system. This platform represents a novel approach toward a logically regulated nano-encapsulated cancer therapy that can selectively follow and deliver chemotherapeutics to cancer cells. The rationale for this project is to overcome a crucial limitation of existing drug delivery systems where chemotherapeutic can be erroneously delivered to non-carcinogenic cells.

  5. Layer-by-layer electrostatic self-assembly of single-wall carbon nanotube polyelectrolytes.

    PubMed

    Paloniemi, Hanna; Lukkarinen, Marjo; Aäritalo, Timo; Areva, Sami; Leiro, Jarkko; Heinonen, Markku; Haapakka, Keijo; Lukkari, Jukka

    2006-01-01

    We have used anionic and cationic single-wall carbon nanotube polyelectrolytes (SWNT-PEs), prepared by the noncovalent adsorption of ionic naphthalene or pyrene derivatives on nanotube sidewalls, for the layer-by-layer self-assembly to prepare multilayers from carbon nanotubes with polycations, such as poly(diallyldimethylammonium) or poly(allylamine hydrochloride) (PDADMA or PAH, respectively), and polyanions (poly(styrenesulfonate), PSS). This is a general and powerful technique for the fabrication of thin carbon nanotube films of arbitrary composition and architecture and allows also an easy preparation of all-SWNT (SWNT/SWNT) multilayers. The multilayers were characterized with vis-near-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), surface plasmon resonance (SPR) measurements, atomic force microscopy (AFM), and imaging ellipsometry. The charge compensation in multilayers is mainly intrinsic, which shows the electrostatic nature of the self-assembly process. The multilayer growth is linear after the initial layers, and in SWNT/polyelectrolyte films it can be greatly accelerated by increasing the ionic strength in the SWNT solution. However, SWNT/SWNT multilayers are much more inert to the effect of added electrolyte. In SWNT/SWNT multilayers, the adsorption results in the deposition of 1-3 theoretical nanotube monolayers per adsorbed layer, whereas the nominal SWNT layer thickness is 2-3 times higher in SWNT/polyelectrolyte films prepared with added electrolyte. AFM images show that the multilayers contain a random network of nanotube bundles lying on the surface. Flexible polyelectrolytes (e.g., PDADMA, PSS) probably surround the nanotubes and bind them together. On macroscopic scale, the surface roughness of the multilayers depends on the components and increases with the film thickness. PMID:16378403

  6. Effect of pirfenidone delivered using layer-by-layer thin film on excisional wound healing.

    PubMed

    Mandapalli, Praveen Kumar; Labala, Suman; Bojja, Jagadeesh; Venuganti, Venkata Vamsi Krishna

    2016-02-15

    The aim of this study was to evaluate the effect of a new anti-fibrotic agent, pirfenidone (PFD), delivered using polyelectrolyte multilayer films on excisional wound healing. Polyelectrolyte multilayer films were prepared by layer-by-layer (LbL) sequential adsorption of chitosan and sodium alginate. The UV-spectrophotometer, FTIR and differential scanning calorimeter were used to characterize the LbL thin films. The PFD was entrapped within the LbL thin films and its effect on excisional wound healing was studied in C57BL/6. The total protein, collagen content and TGF-β expression within the wound tissue were determined after application of PFD using LbL thin films, chitosan hydrogel and polyethylene glycol hydrogel. UV-spectrophotometer and FTIR studies showed a sequential adsorption of chitosan and alginate polymer layers to form LbL thin films. The thickness of LbL thin films with 15 bilayers was found to be 15 ± 2 μm. HPLC analysis showed a PFD loading efficiency of 1.0 ± 0.1mg in 1cm(2) area of LbL thin film. In vivo wound healing studies in C57BL/6 mice showed an accelerated (<9 days) wound contraction after treatment with the PFD compared with blank LbL thin film and commercial povidone-iodine gel (12 days). The collagen content within the wound tissue was significantly (p<0.05) less after treatment with PFD compared with blank film application. Western blot analysis showed gradual decrease in TGF-β expression within the wound tissue after treatment with PFD. This study for the first time demonstrated that new anti-fibrotic agent PFD loaded in LbL thin films can be utilized for excisional wound healing. PMID:26723907

  7. Layer-by-Layer Enabled Nanomaterials for Chemical Sensing and Energy Conversion

    NASA Astrophysics Data System (ADS)

    Paterno, Leonardo G.; Soler, Maria A. G.

    2013-06-01

    The layer-by-layer (LbL) technique is a wet chemical method for the assembly of ultrathin films, with thicknesses up to 100 nm. This method is based on the successive transfer of molecular layers to a solid substrate that is dipped into cationic and anionic solutions in an alternating fashion. The adsorption is mainly driven by electrostatic interactions so that many molecular and nanomaterial systems can be engineered under this method. Moreover, it is inexpensive, can be easily performed, and does not demand sophisticated equipment or clean rooms. The most explored use of the LbL technique is to build up molecular devices for chemical sensing and energy conversion. Both applications require ultrathin films where specific elements must be organized with high control of thickness and spatial distribution, preferably in the nanolength and mesolength scales. In chemical sensors, the LbL technique is employed to assemble specific sensoactive materials such as conjugated polymers, enzymes, and immunological elements onto appropriated electrodes. Molecular recognition events are thus transduced by the assembled sensoactive layer. In energy-conversion devices, the LbL technique can be employed to fabricate different device's parts including electrodes, active layers, and auxiliary layers. In both applications, the devices' performance can be fully modulated and improved by simply varying film thickness and molecular architecture. The present review article highlights the main features of the LbL technique and provides a brief description of different (bio)chemical sensors, solar cells, and organic light-emitting diodes enabled by the LbL approach.

  8. Improved pharmacokinetics and enhanced tumor growth inhibition using a nanostructured lipid carrier loaded with doxorubicin and modified with a layer-by-layer polyelectrolyte coating.

    PubMed

    Mussi, Samuel V; Parekh, Gaurav; Pattekari, Pravin; Levchenko, Tatyana; Lvov, Yuri; Ferreira, Lucas A M; Torchilin, Vladimir P

    2015-11-10

    A nanostructured lipid carrier (NLC) loaded with doxorubicin (DOX) has been shown to be cytotoxic against the human cancer cell lines A549 and MCF-7/Adr. In attempts to improve formulation characteristics, enhance pharmacokinetics and antitumor effects, we modified the surface of these NLC with an alternating layer-by-layer (LbL) assembly of polycation and polyanion polyelectrolytes and an additional coating with PEG using a simple method of core shell attachment. The formulation had a narrow size distribution, longer residence in the blood, lower accumulation in the liver, higher accumulation in tumors and a significant tumor growth inhibition effect. Thus, NLC-DOX nanopreparations complexes modified by LbL coating have the potential to enhance the anticancer effects of DOX against tumors. PMID:26325314

  9. Surface coating for flame-retardant behavior of cotton fabric using a continuous layer-by-layer process

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cotton’s exceptional softness, breathability, and absorbency have made it America’s best selling textile fiber; however, cotton textiles are generally more combustible than their synthetic counterparts. In this study, a continuous layer-by-layer self-assembly technique was used to deposit polymer-cl...

  10. Part I. improve flame retardant textile. Part II. novel approach layer-by-layer processing for flame retardant textile.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this presentation, new approaches for flame retardant textile by using supercritical carbon dioxide (scCO2) and layer-by-layer processing will be discussed. Due to its environmentally benign character, the scCO2 is considered in green chemistry as a substitute for organic solvents in chemical rea...

  11. Part I. Improved flame retardant textiles. Part II. Novel approach to layer-by-layer processing for flame retardant textiles.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this presentation, new approaches for flame retardant textile by using supercritical carbon dioxide (scCO2) and layer-by-layer processing will be discussed. Due to its environmentally benign character, the scCO2 is considered in green chemistry as a substitute for organic solvents in chemical re...

  12. Hybrid white light sources based on layer-by-layer assembly of nanocrystals on near-UV emitting diodes

    NASA Astrophysics Data System (ADS)

    Nizamoglu, Sedat; Demir, Hilmi Volkan

    2007-10-01

    We present the design, growth, fabrication, integration and characterization of alternative hybrid white light sources based on the controlled layer-by-layer assembly of nanocrystals on UV-emitting nitride diodes for adjustable white light parameters. We hybridize CdSe/ZnS core-shell nanocrystals of different sizes (1.9-3.2-5.2 nm) on InGaN/GaN LEDs as a near-UV excitation source at 383 nm for efficient pumping. The first device includes layer-by-layer assembly of dichromatic cyan- and red-emitting nanocrystals (λPL = 504-615 nm) leading to the tristimulus coordinates (x = 0.37,y = 0.46); the second device uses the trichromatic combination of layer-by-layer hybridized cyan-, yellow- and red-emitting nanocrystals (λPL = 504-580-615 nm), yielding (x = 0.38,y = 0.48). Such layer-by-layer hybridization offers the advantages of precisely controlling individual nanocrystal film thicknesses and order in addition to concentrations. By utilizing such multiple combinations of nanocrystals in the assembly, the light parameters are well controlled and adjusted. Leveraging rapidly advancing UV technology into efficient lighting with nanocrystal based color conversion, it is critical to develop and demonstrate hybrid light sources on UV pumping platforms.

  13. Layer-by-layer assembly of nanostructured composites: Mechanics and applications

    NASA Astrophysics Data System (ADS)

    Podsiadlo, Paul

    The development of efficient methods for preparation of nanometer-sized materials and our evolving ability to manipulate the nanoscale objects have brought about a scientific and technological revolution called: nanotechnology. This revolution has been especially driven by discovery of unique nanoscale properties of the nanomaterials which are governed by their inherent size. Today, the total societal impact of nanotechnology is expected to be greater than the combined influences that the silicon integrated circuit, medical imaging, computer-aided engineering, and man-made polymers have had in the last century. Many nanomaterials were also found to possess exceptional mechanical properties. This led to tremendous interest into developing composite materials by exploiting the mechanical properties of these building blocks. In spite of a tremendous volume of work done in the field, preparation of such nanocomposites (NCs) has proven to be elusive due to inability of traditional "top-down" fabrication approaches to effectively harness properties of the nano-scale building blocks. This thesis focuses on preparation of organic/inorganic and solely organic NCs via a bottom-up nano-manufacturing approach called the layer-by-layer (LBL) assembly. Two natural and inexpensive nanoscale building blocks are explored: nanosheets of Na+-montmorillonite clay (MTM) and rod-shaped nanocrystals of cellulose (CNRs). In the first part of the thesis, we present results from systematic study of mechanics of MTM-based NCs. Different compositions are explored with a goal of understanding the nanoscale mechanics. Ultimately, development of a transparent composite with record-high strength and stiffness is presented. In the second part, we present results from LBL assembly of the CNRs. We demonstrate feasibility of assembly and mechanical properties of the resulting films. We also demonstrate preparation of LBL films with anti- reflective properties from tunicate (a sea animal) CNRs. In the

  14. Fabrication of ceramic layer-by-layer infrared wavelength photonic band gap crystals

    NASA Astrophysics Data System (ADS)

    Kang, Henry Hao-Chuan

    Photonic band gap (PBG) crystals, also known as photonic crystals, are periodic dielectric structures which form a photonic band gap that prohibit the propagation of electromagnetic (EM) waves of certain frequencies at any incident angles. Photonic crystals have several potential applications including zero-threshold semiconductor lasers, the inhibiting spontaneous emission, dielectric mirrors, and wavelength filters. If defect states are introduced in the crystals, light can be guided from one location to another or even a sharp bending of light in submicron scale can be achieved. This generates the potential for optical waveguide and optical circuits, which will contribute to the improvement in the fiber-optic communications and the development of high-speed computers. The goal of this dissertation research is to explore techniques for fabricating 3D ceramic layer-by-layer (LBL) photonic crystals operating in the infrared frequency range, and to characterize the infilling materials properties that affect the fabrication process as well as the structural and optical properties of the crystals. While various approaches have been reported in literature for the fabrication of LBL structure, the uniqueness of this work ties with its cost-efficiency and relatively short process span. Besides, very few works have been reported on fabricating ceramic LBL crystals at mid-IR frequency range so far. The fabrication techniques reported here are mainly based on the concepts of microtransfer molding with the use of polydimethyl siloxane (PDMS) as molds/stamps. The infilling materials studied include titanium alkoxide precursors and aqueous suspensions of nanosize titania particles (slurries). Various infilling materials were synthesized to determine viscosities, effects on drying and firing shrinkages, effects on film surface roughness, and their moldability. Crystallization and phase transformation of the materials were also monitored using DTA, TGA and XRD. Mutilayer crystal

  15. Layer-by-layer assembled carbon nanotube-acetylcholinesterase/biopolymer renewable interfaces: SPR and electrochemical characterization.

    PubMed

    Zhang, Yuanyuan; Arugula, Mary A; Kirsch, Jeffrey S; Yang, Xiaoyun; Olsen, Eric; Simonian, Aleksandr L

    2015-02-01

    Developing simple, reliable, and cost-effective methods of renewing an inhibited biocatalyst (e.g., enzymatic interfaces) on biosensors is needed to advance multiuse, reusable sensor applications. We report a method for the renewal of layer-by-layer (LbL) self-assembled inhibition-based enzymatic interfaces in multiwalled carbon nanotube (MWCNT) armored acetylcholinesterase (AChE) biosensors. The self-assembly process of MWCNT dispersed enzymes/biopolymers was investigated using surface plasmon resonance (SPR). The LbL fabrication consisted of alternating cushion layers of positively charged CNT-polyethylenimine (CNT-PEI) and negatively charged CNT-deoxyribonucleic acid (CNT-DNA) and a functional interface consisting of alternating layers of CNT-PEI and negatively charged CNT-acetylcholine esterase (CNT-AChE, pH 7.4). The observed SPR response signal increased while assembling the different layers, indicating the buildup of multiple layers on the Au surface. A partial desorption of the top enzymatic layer in the LbL structure was observed with a desorption strategy employing alkaline treatment. This indicates that the strong interaction of CNT-biopolymer conjugates with the Au surface was a result of both electrostatic interactions between biopolymers and the surface binding energy from CNTs: the closer the layers are to the Au surface, the stronger the interactions. In contrast, a similar LbL assembly of soluble enzyme/polyelectrolytes resulted in stronger desorption on the surface after the alkaline treatment; this led to the investigation of AChE layer removal, permanently inhibited after pesticide exposure on glassy carbon (GC) electrodes, while keeping the cushion layers intact. The desorption strategy permitted the SPR and electrochemical electrode surfaces to be regenerated multiple times by the subsequent self-assembly of fresh PEI/AChE layers. Flow-mode electrochemical amperometric analysis demonstrated good stability toward the determination of

  16. Superhydrophobic Thin Films Fabricated by Reactive Layer-by-Layer Assembly of Azlactone-Functionalized Polymers

    PubMed Central

    Buck, Maren E.; Schwartz, Sarina C.

    2010-01-01

    We report an approach to the fabrication of superhydrophobic thin films that is based on the ‘reactive’ layer-by-layer assembly of azlactone-containing polymer multilayers. We demonstrate that films fabricated from alternating layers of the azlactone functionalized polymer poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) and poly(ethyleneimine) (PEI) exhibit micro- and nanoscale surface features that result in water contact angles in excess of 150º. Our results reveal that the formation of these surface features is (i) dependent upon film thickness (i.e., the number of layers of PEI and PVDMA deposited) and (ii) that it is influenced strongly by the presence (or absence) of cyclic azlactone-functionalized oligomers that can form upon storage of the 2-vinyl-4,4-dimethylazlactone (VDMA) used to synthesize PVDMA. For example, films fabricated using polymers synthesized in the presence of these oligomers exhibited rough, textured surfaces and superhydrophobic behavior (i.e., advancing contact angles in excess of 150º). In contrast, films fabricated from PVDMA polymerized in the absence of this oligomer (e.g., using freshly distilled monomer) were smooth and only moderately hydrophobic (i.e., advancing contact angles of ~75º). The addition of authentic, independently synthesized oligomer to samples of distilled VDMA at specified and controlled concentrations permitted reproducible fabrication of superhydrophobic thin films on the surfaces of a variety of different substrates. The surfaces of these films were demonstrated to be superhydrophobic immediately after fabrication, but they became hydrophilic after exposure to water for six days. Additional experiments demonstrated that it was possible to stabilize and prolong the superhydrophobic properties of these films (e.g., advancing contact angles in excess of 150° even after complete submersion in water for at least six weeks) by exploiting the reactivity of residual azlactones to functionalize the surfaces of the

  17. Composite Layer-by-Layer (LBL) assembly with inorganic nanoparticles and nanowires.

    PubMed

    Srivastava, Sudhanshu; Kotov, Nicholas A

    2008-12-01

    New assembly techniques are required for creating advanced materials with enough structural flexibility to be tuned for specific applications, and to be practical, the techniques must be implemented at relatively low cost. Layer-by-layer (LBL) assembly is a simple, versatile, and significantly inexpensive approach by which nanocomponents of different groups can be combined to coat both macroscopically flat and non-planar (e.g., colloidal core-shell particles) surfaces. Compared with other available assembly methods, LBL assembly is simpler and more universal and allows more precise thickness control at the nanoscale. LBL can be used to combine a wide variety of species--including nanoparticles (NPs), nanosheets, and nanowires (NWs)--with polymers, thus merging the properties of each type of material. This versatility has led to recent exceptional growth in the use of LBL-generated nanocomposites. This Account will focus on the materials and biological applications of introducing inorganic nanocrystals into polymer thin films. Combining inorganic NPs and NWs with organic polymers allows researchers to manipulate the unique properties in the nanomaterial. We describe the LBL assembly technique for introducing metallic NPs into polymers in order to generate a material with combined optomechanical properties. Similarly, LBL assembly of highly luminescent semiconductor NPs like HgTe or CdTe with poly(diallyldimethylammonium chloride) (PDDA) was used to create uniform optical-quality coatings made on optical fibers and tube interiors. In addition, LBL assembly with inorganic nanosheets or clay molecules is reported for fabricating films with strong mechanical and ion transport properties, and the technique can also be employed to prepare Au/TiO(2) core/sheath NWs. The LBL approach not only will be useful for assembly of inorganic nanocrystals with various polymers but can be further applied to introduce specific functions. We discuss how the expanded use of NWs and

  18. Molecular Composite Coatings on Nafion Using Layer-by-Layer Self-Assembly.

    PubMed

    Lefaux, Christophe J; Kim, Byoung-Suhk; Venkat, Narayanan; Mather, Patrick T

    2015-05-20

    Controlled growth of nanometer-scale multilayered coatings of negatively charged sulfonated poly(benzobisimidazole) (SPBI), complexed with positively charged poly(2-vinylpyridine) (P2VP) on quartz, and Nafion membrane as substrates has been explored. Both polymers, SPBI and P2VP, possess a net charge in methanol as a result of the dissolution of SPBI by complexation with triethylamine (TEA) and the protonation of P2VP with HCl, respectively, and thereby can form a multilayered molecular composite of alternating anionic SPBI and cationic P2VP via an electrostatic layer-by-layer (LbL) self-assembly. UV-vis absorption spectrophotometry was used to monitor the buildup and growth rate of such SPBI/P2VP multilayer films. Atomic force microscopy (AFM) was used to determine the roughness and thickness of the resulting SPBI/P2VP multilayers. As a result, it was found that a steady-state linear growth regime for the LbL self-assembled SPBI/P2VP multilayer films and coatings onto quartz and Nafion membranes was observed after completion of the first few deposition cycles, indicating the successful formation of the SPBI/P2VP multilayered assembly in methanol solutions. In addition, the SPBI/P2VP multilayer films in the perpendicular direction (flat view) demonstrated isotropic orientation distribution on the Nafion membrane, while the SPBI/P2VP multilayer films examined by X-ray scattering in the parallel direction (edge view) revealed anisotropic orientation, the combined observations indicating confinement of SPBI rods to the plane of the coating. We further found that the SPBI/P2VP multilayer coated Nafion possesses good thermal stability, as indicated by isothermal gravimetric analysis at 310 °C, and it was further observed that SPBI/P2VP multilayer coatings using the LbL self-assembly technique on Nafion membrane significantly increased the membrane stiffness, despite the small coating thickness employed. PMID:25923689

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

    NASA Astrophysics Data System (ADS)

    Escobar-Ferrand, Luis

    Layer by Layer (LbL) deposition using primarily inorganic silica nanoparticles is employed for the modification of polymeric micro and ultrafiltration (MF/UF) membranes to produce thin film composites (TFC) with potential nanofiltration (NF) and reverse osmosis (RO) capabilities.. A variety of porous substrate membranes with different membrane surface characteristics are employed, but exhibiting in common that wicking of water does not readily occur into the pore structure, including polycarbonate track etched (PCTE), polyethersulfone (PES) and sulfonated PES (SPEES) MF/UF membranes. Both spherical (cationic/anionic) and eccentric elongated (anionic) silica nanoparticles are deposited using conditions similar to those reported by Lee et al. Appropriate selection of the pH's for anionic and cationic particle deposition enables the construction of nanoparticle only layers 100--1200 nm in thickness atop the original membrane substrates. The surface layer thickness varies monotonically with the number of bilayers (anionic/cationic deposition cycles) as expected. The deposition process is optimized to eliminate drying induced cracking and to improve mechanical durability via thickness control and post-deposition hydro-thermal treatment. The hydrodynamic permeability of these TFC membranes is measured to evaluate their performance under typical NF operating conditions using dead-end permeation experiments and their performance compared quantitatively with realistic hydrodynamic models, with favorable results. For track etched polycarbonate MF substrates, surface modification causes a permeability reduction of approximately two orders of magnitude with respect to the bare substrates, to values comparable to those for typical commercial NF membranes. Good quantitative agreement with hydrodynamic models with no adjustable parameters was also established for this case, providing indirect confirmation that the LbL deposited surface layers are largely defect (crack) free

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

    NASA Astrophysics Data System (ADS)

    Mehrotra, Sumit

    Tissues and organs in vivo are structured in three dimensional (3-D) ordered assemblies to maintain their metabolic functions. In the case of an injury, certain tissues lack the regenerative abilities without an external supportive environment. In order to regenerate the natural in vivo environment post-injury, there is a need to design three-dimensional (3-D) tissue engineered constructs of appropriate dimensions along with strategies that can deliver growth factors or drugs at a controlled rate from such constructs. This thesis focuses on the applications of hydrogen bonded (H-bonded) nanoscale layer-by-layer (LbL) assembled multilayers for time controlled drug delivery, fabrication of polymeric nanoparticles as drug delivery carriers, and engineering 3-D cellular constructs. Axonal regeneration in the central nervous system after spinal cord injury is often disorganized and random. To support linear axonal growth into spinal cord lesion sites, certain growth factors, such as brain-derived neurotrophic factor (BDNF), needs to be delivered at a controlled rate from an array of uniaxial channels patterned in a scaffold. In this study, we demonstrate for the first time that H-bonded LbL assembled degradable thin films prepared over agarose hydrogel, whereby the protein was loaded separately from the agarose fabrication, provided sustained release of protein under physiological conditions for more than four weeks. Further, patterned agarose scaffolds implanted at the site of a spinal cord injury forms a reactive cell layer of leptomeningeal fibroblasts in and around the scaffold. This limits the ability of axons to reinnervate the spinal cord. To address this challenge, we demonstrate the time controlled release of an anti-mitotic agent from agarose hydrdgel to control the growth of the reactive cell layer of fibroblasts. Challenges in tissue engineering can also be addressed using gene therapy approaches. Certain growth factors in the body are known to inhibit

  1. Covalent attachment of cell-adhesive peptide Gly-Arg-Gly-Asp (GRGD) to poly(etheretherketone) surface by tailored silanization layers technique

    NASA Astrophysics Data System (ADS)

    Zheng, Yanyan; Xiong, Chengdong; Li, Xiaoyu; Zhang, Lifang

    2014-11-01

    Poly(etheretherketone) (PEEK) is a rigid semicrystalline polymer that combines excellent mechanical properties, broad chemical resistance and bone-like stiffness and is widely used in biomedical fields. However, PEEK is naturally bioinert, leading to limited biomedical applications, especially when a direct bone-implant osteointegration is desired. In this study, a three-step reaction procedure was employed to immobilize the cell-adhesive peptide Gly-Arg-Gly-Asp (GRGD) on the surface of PEEK sheet by covalent chemical attachment to favor cell adhesion and proliferation. First, hydroxylation-pretreated PEEK surfaces were silanized with 7-Oct-1-enyltrichlorosilane (OETS) in dry cyclohexane, resulting in a silanization layer with terminal ethenyl. Second, the terminal ethylenic double bonds of the silanization layer on PEEK surface were converted to carboxyl groups through acidic potassium manganate oxidation. Finally, GRGD was covalently attached by carbodiimide mediated condensation between the carboxyl on PEEK surface and amine presents in GRGD. X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, surface profiler and water contact angle measurements were applied to characterize the modified surfaces. The effect of cells attachment and proliferation on each specimen was investigated. Pre-osteoblast cells (MC3T3-E1) attachment, spreading and proliferation were improved effectively on GRGD-modified PEEK surface. PEEK modified with GRGD on its surface has potential use in orthopedic or dental implants.

  2. Modifying of Cotton Fabric Surface with Nano-ZnO Multilayer Films by Layer-by-Layer Deposition Method.

    PubMed

    Uğur, Sule S; Sarıışık, Merih; Aktaş, A Hakan; Uçar, M Ciğdem; Erden, Emre

    2010-01-01

    ZnO nanoparticle-based multilayer nanocomposite films were fabricated on cationized woven cotton fabrics via layer-by-layer molecular self-assembly technique. For cationic surface charge, cotton fabrics were pretreated with 2,3-epoxypropyltrimethylammonium chloride (EP3MAC) by pad-batch method. XPS and SEM were used to examine the deposited nano-ZnO multilayer films on the cotton fabrics. The nano-ZnO films deposited on cotton fabrics exhibited excellent antimicrobial activity against Staphylococcus aureus bacteria. The results also showed that the coated fabrics with nano-ZnO multilayer films enhanced the protection of cotton fabrics from UV radiation. Physical tests (tensile strength of weft and warp yarns, air permeability and whiteness values) were performed on the fabrics before and after the treatment with ZnO nanoparticles to evaluate the effect of layer-by-layer (LbL) process on cotton fabrics properties. PMID:20596450

  3. Modifying of Cotton Fabric Surface with Nano-ZnO Multilayer Films by Layer-by-Layer Deposition Method

    PubMed Central

    2010-01-01

    ZnO nanoparticle–based multilayer nanocomposite films were fabricated on cationized woven cotton fabrics via layer-by-layer molecular self-assembly technique. For cationic surface charge, cotton fabrics were pretreated with 2,3-epoxypropyltrimethylammonium chloride (EP3MAC) by pad-batch method. XPS and SEM were used to examine the deposited nano-ZnO multilayer films on the cotton fabrics. The nano-ZnO films deposited on cotton fabrics exhibited excellent antimicrobial activity against Staphylococcus aureus bacteria. The results also showed that the coated fabrics with nano-ZnO multilayer films enhanced the protection of cotton fabrics from UV radiation. Physical tests (tensile strength of weft and warp yarns, air permeability and whiteness values) were performed on the fabrics before and after the treatment with ZnO nanoparticles to evaluate the effect of layer-by-layer (LbL) process on cotton fabrics properties. PMID:20596450

  4. Layer-by-layer thinning of two-dimensional MoS2 films by using a focused ion beam.

    PubMed

    Wang, Ding; Wang, Yuqiu; Chen, Xiaodong; Zhu, Yuankun; Zhan, Ke; Cheng, Hongbin; Wang, Xianying

    2016-02-21

    A layer-controlled two-dimensional (2D) molybdenum disulfide (MoS2) film with tunable bandgaps is highly desired for the fabrication of electronic/photoelectronic devices. In this work, we demonstrate that a focused ion beam (FIB) can be applied to thin MoS2 films layer-by-layer. The layer number can be controlled by simply changing the Ga(+) beam exposure time and the thinning speed is about half a layer per second. OM, AFM, PL and Raman spectra were used to monitor the change of layer numbers and characterize the morphology, thickness, and homogeneity of MoS2 films. The FIB layer-by-layer thinning technology will establish a new methodology for rationally thinning all kinds of 2D layered materials. PMID:26821788

  5. Construction of antibacterial poly(ethylene terephthalate) films via layer by layer assembly of chitosan and hyaluronic acid.

    PubMed

    Del Hoyo-Gallego, Sara; Pérez-Álvarez, Leyre; Gómez-Galván, Flor; Lizundia, Erlantz; Kuritka, Ivo; Sedlarik, Vladimir; Laza, Jose Manuel; Vila-Vilela, Jose Luis

    2016-06-01

    Polyelectrolytic multilayers (PEMs) with enhanced antibacterial properties were built up onto commercial poly(ethylene terephthalate) (PET) films based on the layer by layer assembling of bacterial contact killing chitosan and bacterial repelling highly hydrated hyaluronic acid. The optimization of the aminolysis modification reaction of PET was carried out by the study of the mechanical properties and the surface characterization of the modified polymers. The layer by layer assembly was successfully monitored by TEM microscopy, surface zeta-potential, contact angle measurements and, after labeling with fluorescein isothiocyanate (FTIC) by absorption spectroscopy and confocal fluorescent microscopy. Beside, the stability of the PEMs was studied at physiological conditions in absence and in the presence of lysozyme and hyaluronidase enzymes. Antibacterial properties of the obtained PEMs against Escherichia coli were compared with original commercial PET. PMID:27083341

  6. Template-Free 3D Microprinting of Metals Using a Force-Controlled Nanopipette for Layer-by-Layer Electrodeposition.

    PubMed

    Hirt, Luca; Ihle, Stephan; Pan, Zhijian; Dorwling-Carter, Livie; Reiser, Alain; Wheeler, Jeffrey M; Spolenak, Ralph; Vörös, János; Zambelli, Tomaso

    2016-03-23

    A novel 3D printing method for voxel-by-voxel metal printing is presented. Hollow atomic force microscopy (AFM) cantilevers are used to locally supply metal ions in an electrochemical cell, enabling a localized electroplating reaction. By exploiting the deflection feedback of these probes, electrochemical 3D metal printing is, for the first time, demonstrated in a layer-by-layer fashion, enabling the fabrication of arbitrary-shaped geometries. PMID:26783090

  7. Layer-by-layer thinning of two-dimensional MoS2 films by using a focused ion beam

    NASA Astrophysics Data System (ADS)

    Wang, Ding; Wang, Yuqiu; Chen, Xiaodong; Zhu, Yuankun; Zhan, Ke; Cheng, Hongbin; Wang, Xianying

    2016-02-01

    A layer-controlled two-dimensional (2D) molybdenum disulfide (MoS2) film with tunable bandgaps is highly desired for the fabrication of electronic/photoelectronic devices. In this work, we demonstrate that a focused ion beam (FIB) can be applied to thin MoS2 films layer-by-layer. The layer number can be controlled by simply changing the Ga+ beam exposure time and the thinning speed is about half a layer per second. OM, AFM, PL and Raman spectra were used to monitor the change of layer numbers and characterize the morphology, thickness, and homogeneity of MoS2 films. The FIB layer-by-layer thinning technology will establish a new methodology for rationally thinning all kinds of 2D layered materials.A layer-controlled two-dimensional (2D) molybdenum disulfide (MoS2) film with tunable bandgaps is highly desired for the fabrication of electronic/photoelectronic devices. In this work, we demonstrate that a focused ion beam (FIB) can be applied to thin MoS2 films layer-by-layer. The layer number can be controlled by simply changing the Ga+ beam exposure time and the thinning speed is about half a layer per second. OM, AFM, PL and Raman spectra were used to monitor the change of layer numbers and characterize the morphology, thickness, and homogeneity of MoS2 films. The FIB layer-by-layer thinning technology will establish a new methodology for rationally thinning all kinds of 2D layered materials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05768j

  8. Layer-by-Layer Assembled C/S Cathode with Trace Binder for Li-S Battery Application.

    PubMed

    Wang, Qian; Yan, Na; Wang, Meiri; Qu, Chao; Yang, Xiaofei; Zhang, Hongzhang; Li, Xianfeng; Zhang, Huamin

    2015-11-18

    The C/S cathode with only 0.5 wt % binder, composed with Nafion and PVP, was assembled layer-by-layer for lithium-sulfur battery (Li-S) application. It achieved excellent binding strength and battery performance compared to the cathode with 10 wt % PVDF, which is promising to further increase the practical energy density of Li-S batteries. PMID:26541216

  9. Inorganic-organic hybrid coatings on stainless steel by layer-by-layer deposition and surface-initiated atom-transfer-radical polymerization for combating biocorrosion.

    PubMed

    Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

    2009-03-01

    To improve the biocorrosion resistance of stainless steel (SS) and to confer the bactericidal function on its surface for inhibiting bacterial adhesion and biofilm formation, well-defined inorganic-organic hybrid coatings, consisting of the inner compact titanium oxide multilayers and outer dense poly(vinyl-N-hexylpyridinium) brushes, were successfully developed. Nanostructured titanium oxide multilayer coatings were first built up on the SS substrates via the layer-by-layer sol-gel deposition process. The trichlorosilane coupling agent, containing the alkyl halide atom-transfer-radical polymerization (ATRP) initiator, was subsequently immobilized on the titanium oxide coatings for surface-initiated ATRP of 4-vinylpyridine (4VP). The pyridium nitrogen moieties of the covalently immobilized 4VP polymer, or P(4VP), brushes were quaternized with hexyl bromide to produce a high concentration of quaternary ammonium salt on the SS surfaces. The excellent antibacterial efficiency of the grafted polycations, poly(vinyl-N-pyridinium bromide), was revealed by viable cell counts and atomic force microscopy images of the surface. The effectiveness of the hybrid coatings in corrosion protection was verified by the Tafel plot and electrochemical impedance spectroscopy measurements. PMID:20355986

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

    PubMed

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

    2012-11-01

    As one of the most effective synthesis tools, layer-by-layer (LbL) self-assembly technology can provide a strong non-covalent integration and accurate assembly between homo- or hetero-phase compounds or oppositely charged polyelectrolytes, resulting in highly-ordered nanoscale structures or patterns with excellent functionalities and activities. It has been widely used in the developments of novel materials and nanostructures or patterns from nanotechnologies to medical fields. However, the application of LbL self-assembly in the development of highly efficient electrocatalysts, specific functionalized membranes for proton exchange membrane fuel cells (PEMFCs) and electrode materials for supercapacitors is a relatively new phenomenon. In this review, the application of LbL self-assembly in the development and synthesis of key materials of PEMFCs including polyelectrolyte multilayered proton-exchange membranes, methanol-blocking Nafion membranes, highly uniform and efficient Pt-based electrocatalysts, self-assembled polyelectrolyte functionalized carbon nanotubes (CNTs) and graphenes will be reviewed. The application of LbL self-assembly for the development of multilayer nanostructured materials for use in electrochemical supercapacitors will also be reviewed and discussed (250 references). PMID:22945597

  11. A method for the second-site screening of K-Ras in the presence of a covalently attached first-site ligand.

    PubMed

    Sun, Qi; Phan, Jason; Friberg, Anders R; Camper, DeMarco V; Olejniczak, Edward T; Fesik, Stephen W

    2014-09-01

    K-Ras is a well-validated cancer target but is considered to be "undruggable" due to the lack of suitable binding pockets. We previously discovered small molecules that bind weakly to K-Ras but wanted to improve their binding affinities by identifying ligands that bind near our initial hits that we could link together. Here we describe an approach for identifying second site ligands that uses a cysteine residue to covalently attach a compound for tight binding to the first site pocket followed by a fragment screen for binding to a second site. This approach could be very useful for targeting Ras and other challenging drug targets. PMID:25087006

  12. Facile synthesis of novel magnetic silica nanoparticles functionalized with layer-by-layer detonation nanodiamonds for secretome study.

    PubMed

    Li, Hong; Wang, Yi; Zhang, Lei; Lu, Haojie; Zhou, Zhongjun; Wei, Liming; Yang, Pengyuan

    2015-12-01

    Novel magnetic silica nanoparticles functionalized with layer-by-layer detonation nanodiamonds (dNDs) were prepared by coating single submicron-size magnetite particles with silica and subsequently modified with dNDs. The resulting layer-by-layer dND functionalized magnetic silica microspheres (Fe3O4@SiO2@[dND]n) exhibit a well-defined magnetite-core-silica-shell structure and possess a high content of magnetite, which endow them with high dispersibility and excellent magnetic responsibility. Meanwhile, dNDs are known for their high affinity and biocompatibility towards peptides or proteins. Thus, a novel convenient, fast and efficient pretreatment approach of low-abundance peptides or proteins was successfully established with Fe3O4@SiO2@[dND]n microspheres. The signal intensity of low-abundance peptides was improved by at least two to three orders of magnitude in mass spectrometry analysis. The novel microsphere also showed good tolerance to salt. Even with a high concentration of salt, peptides or proteins could be isolated effectively from samples. Therefore, the convenient and efficient enrichment process of this novel layer-by-layer dND-functionalized microsphere makes it a promising candidate for isolation of protein in a large volume of culture supernatant for secretome analysis. In the application of Fe3O4@SiO2@[dND]n in the secretome of hepatoma cells, 1473 proteins were identified and covered a broad range of pI and molecular weight, including 377 low molecular weight proteins. PMID:26468487

  13. Electrodeposition of catalytic and magnetic gold nanoparticles on dendrimer-carbon nanotube layer-by-layer films.

    PubMed

    Siqueira, José R; Gabriel, Rayla C; Zucolotto, Valtencir; Silva, Anielle C A; Dantas, Noelio O; Gasparotto, Luiz H S

    2012-11-01

    Magnetic and catalytic gold nanoparticles were electrodeposited through potential pulse on dendrimer-carbon nanotube layer-by-layer (LbL) films. A plasmon absorption band at about 550 nm revealed the presence of nanoscale gold in the film. The location of the Au nanoparticles in the film was clearly observed by selecting the magnetic force microscopy mode. To our knowledge, this is the first report on the electrochemical synthesis of magnetic Au nanoparticles. In addition to the magnetic properties, the Au nanoparticles also exhibited high catalytic activity towards ethanol and glycerol oxidation in alkaline medium. PMID:23007196

  14. Layer-by-Layer Assembly of Metal-Organic Frameworks in Macroporous Polymer Monolith and Their Use for Enzyme Immobilization.

    PubMed

    Wen, Liyin; Gao, Aicong; Cao, Yao; Svec, Frantisek; Tan, Tianwei; Lv, Yongqin

    2016-03-01

    New monolithic materials comprising zeolitic imidazolate framework (ZIF-8) located on the pore surface of poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolith previously functionalized with N-(3-aminopropyl)-imidazole have been prepared via a layer-by-layer self-assembly strategy. These new ZIF-8@monolith hybrids are used as solid-phase carriers for enzyme immobilization. Their performance is demonstrated with immobilization of a model proteolytic enzyme trypsin. The best of the conjugates enable very efficient digestion of proteins that can be achieved in mere 43 s. PMID:26806691

  15. An ultrasensitive and low-cost graphene sensor based on layer-by-layer nano self-assembly

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Cui, Tianhong

    2011-02-01

    The flexible cancer sensor based on layer-by-layer self-assembled graphene reported in this letter demonstrates features including ultrahigh sensitivity and low cost due to graphene material properties in nature, self-assembly technique, and polyethylene terephthalate substrate. According to the conductance change of self-assembled graphene, the label free and labeled graphene sensors are capable of detecting very low concentrations of prostate specific antigen down to 4 fg/ml (0.11 fM) and 0.4 pg/ml (11 fM), respectively, which are three orders of magnitude lower than carbon nanotube sensors under the same conditions of design, manufacture, and measurement.

  16. Layer by layer removal of Au atoms from passivated Au(111) surfaces using the scanning tunneling microscope: Nanoscale ``paint stripping''

    NASA Astrophysics Data System (ADS)

    Keel, J. M.; Yin, J.; Guo, Q.; Palmer, R. E.

    2002-04-01

    Layer by layer removal of gold atoms from the (111) surface of gold has been performed using the scanning tunneling microscope. The process is made possible by a chemisorbed self-assembled monolayer (SAM) of dodecanethiol molecules on the surface, which gives rise to a reduced bonding strength between the top two layers of gold atoms. The gold atoms and associated adsorbed molecules are peeled off and displaced laterally by the STM tip, and the size of the modified area (down to ˜10×10 nm) is more or less determined by the scan size.

  17. Ultra-Fast Layer-by-Layer Approach for Depositing Flame Retardant Coatings on Flexible PU Foams within Seconds.

    PubMed

    Carosio, F; Alongi, J

    2016-03-16

    In this letter, we are presenting a novel approach for the deposition of layer-by-layer (LbL) coatings capable of conferring flame retardant properties to flexible polyurethane foams exploiting subsecond deposition times. The process yields nanoscale coatings able to reduce by 33% one of the main fire safety parameters, namely the heat release rate peak, with a total treatment time of only 2.5 s. This new approach turned out to be three to 4 orders of magnitude faster than conventional LbL treatments. Such results make it possible for the exploit of LbL as a competitive, efficient and ecofriendly technology at industrial scale. PMID:26925855

  18. Gold nanorod-photosensitizer complex obtained by layer-by-layer method for photodynamic/photothermal therapy in vitro.

    PubMed

    Kim, Seung Beom; Lee, Tae Heon; Yoon, Il; Shim, Young Key; Lee, Woo Kyoung

    2015-03-01

    Gold nanorod (GNR)-photosensitizer (PS) complex was prepared using anionic PS (sodium salt of purpurin-18) and cationic poly(allylamine hydrochloride) by layer-by-layer method, and was characterized by transmission electron microscopy, UV-vis spectroscopy, and zeta potential. The GNR-PS complex is a promising agent for synergistic (photothermal and photodynamic) therapy (PTT/PDT), in which PTT generates heat as well as operates the PS release which maximize the following PDT activity. The combined dual therapy, PTT followed by PDT, exhibits a significantly higher photocytotoxicity result based on synergistic effect of hyperthermia from PTT as well as singlet oxygen photogeneration from PDT. PMID:25630881

  19. A novel pulsed drug-delivery system: polyelectrolyte layer-by-layer coating of chitosan–alginate microgels

    PubMed Central

    Zhou, Guichen; Lu, Ying; Zhang, He; Chen, Yan; Yu, Yuan; Gao, Jing; Sun, Duxin; Zhang, Guoqing; Zou, Hao; Zhong, Yanqiang

    2013-01-01

    Purpose The aim of this report was to introduce a novel “core-membrane” microgel drug-delivery device for spontaneously pulsed release without any external trigger. Methods The microgel core was prepared with alginate and chitosan. The semipermeable membrane outside the microgel was made of polyelectrolytes including polycation poly(allylamine hydrochloride) and sodium polystyrene sulfonate. The drug release of this novel system was governed by the swelling pressure of the core and the rupture of the outer membrane. Results The size of the core-membrane microgel drug-delivery device was 452.90 ± 2.71 μm. The surface charge depended on the layer-by-layer coating of polyelectrolytes, with zeta potential of 38.6 ± 1.4 mV. The confocal microscope exhibited the layer-by-layer outer membrane and inner core. The in vitro release profile showed that the content release remained low during the first 2.67 hours. After this lag time, the cumulative release increased to 80% in the next 0.95 hours, which suggested a pulsed drug release. The in vivo drug release in mice showed that the outer membrane was ruptured at approximately 3 to 4 hours, as drug was explosively released. Conclusion These data suggest that the encapsulated substance in the core-membrane microgel delivery device can achieve a massive drug release after outer membrane rupture. This device was an effective system for pulsed drug delivery. PMID:23486565

  20. 3D Printing of Human Tissue Mimics via Layer-by-Layer Assembly of Polymer/Hydrogel Biopapers

    NASA Astrophysics Data System (ADS)

    Ringeisen, Bradley

    2015-03-01

    The foundations of tissue engineering were built on two fundamental areas of research: cells and scaffolds. Multipotent cells and their derivatives are traditionally randomly seeded into sophisticated polymer or hydrogel scaffolds, ultimately with the goal of forming a tissue-like material through cell differentiation and cell-material interactions. One problem with this approach is that no matter how complex or biomimetic the scaffold is, the cells are still homogeneously distributed throughout this three dimensional (3D) material. Natural tissue is inherently heterogeneous on both a microscopic and macroscopic level. It also contains different types of cells in close proximity, extracellular matrix, voids, and a complex vascularized network. Recently developed 3D cell and organ printers may be able to enhance traditional tissue engineering experiments by building scaffolds layer-by-layer that are crafted to mimic the microscopic and macroscopic structure of natural tissue or organs. Over the past decade, my laboratory has developed a capillary-free, live cell printer termed biological laser printing, or BioLP. We find that printed cells do not express heat shock protein and retain >99% viability. Printed cells also incur no DNA strand fracture and preserve their ability to differentiate. Recent work has used a layer-by-layer approach, stacking sheets of hybrid polymer/hydrogel biopapers in conjunction with live cell printing to create 3D tissue structures. Our specific work is now focused on the blood-brain-barrier and air-lung interface and will be described during the presentation.

  1. Mechanically durable, superoleophobic coatings prepared by layer-by-layer technique for anti-smudge and oil-water separation

    NASA Astrophysics Data System (ADS)

    Brown, Philip S.; Bhushan, Bharat

    2015-03-01

    Superoleophobic surfaces are of interest for anti-fouling, self-cleaning, anti-smudge, low-drag, anti-fog, and oil-water separation applications. Current bioinspired surfaces are of limited use due to a lack of mechanical durability. A so-called layer-by-layer approach, involving charged species with electrostatic interactions between layers, can provide the flexibility needed to improve adhesion to the substrate while providing a low surface tension coating at the air interface. In this work, a polyelectrolyte binder, SiO2 nanoparticles, and a fluorosurfactant are spray deposited separately to create a durable, superoleophobic coating. Polydiallyldimethylammonium chloride (PDDA) polyelectrolyte was complexed with a fluorosurfactant layer (FL), which provides oil repellency while being hydrophilic. This oleophobic/superhydrophilic behavior was enhanced through the use of roughening with SiO2 particles resulting in a superoleophobic coating with hexadecane contact angles exceeding 155° and tilt angles of less than 4°. The coating is also superhydrophilic, which is desirable for oil-water separation applications. The durability of these coatings was examined through the use of micro- and macrowear experiments. These coatings currently display characteristics of transparency. Fabrication of these coatings via the layer-by-layer technique results in superoleophobic surfaces displaying improved durability compared to existing work where either the durability or the oil-repellency is compromised.

  2. Mechanically durable, superoleophobic coatings prepared by layer-by-layer technique for anti-smudge and oil-water separation.

    PubMed

    Brown, Philip S; Bhushan, Bharat

    2015-01-01

    Superoleophobic surfaces are of interest for anti-fouling, self-cleaning, anti-smudge, low-drag, anti-fog, and oil-water separation applications. Current bioinspired surfaces are of limited use due to a lack of mechanical durability. A so-called layer-by-layer approach, involving charged species with electrostatic interactions between layers, can provide the flexibility needed to improve adhesion to the substrate while providing a low surface tension coating at the air interface. In this work, a polyelectrolyte binder, SiO2 nanoparticles, and a fluorosurfactant are spray deposited separately to create a durable, superoleophobic coating. Polydiallyldimethylammonium chloride (PDDA) polyelectrolyte was complexed with a fluorosurfactant layer (FL), which provides oil repellency while being hydrophilic. This oleophobic/superhydrophilic behavior was enhanced through the use of roughening with SiO2 particles resulting in a superoleophobic coating with hexadecane contact angles exceeding 155° and tilt angles of less than 4°. The coating is also superhydrophilic, which is desirable for oil-water separation applications. The durability of these coatings was examined through the use of micro- and macrowear experiments. These coatings currently display characteristics of transparency. Fabrication of these coatings via the layer-by-layer technique results in superoleophobic surfaces displaying improved durability compared to existing work where either the durability or the oil-repellency is compromised. PMID:25731716

  3. Layer-by-layer fabrication of supramolecular dyes on TiO2 surfaces for optoelectronic applications

    NASA Astrophysics Data System (ADS)

    Kong, Xiaoqing; Maguire, Shawn; Lye, Diane; Weck, Marcus; Lee, Stephanie

    We present a modular layer-by-layer approach based on metal coordination chemistry to assemble supramolecular dyes exhibiting increased absorption in the visible range on electrode surfaces. Specifically, palladiated bis-pincer complexes (Pd-BPCs) were employed as linkers between pyridyl-terminated organic molecules via dative bonding. By alternately immersing mesoporous TiO2-coated glass substrates in solutions containing dissolved zinc porphyin (ZnP) and Pd-BPCs, supramolecular dyes were assembled layer-by-layer on the TiO2 surfaces. UV-visible absorption spectra of these assembled structures revealed a linear increase in the Soret and Q bands of ZnP after each immersion of the substrate in the ZnP solution. Coordination of the ZnP layers with Pd-BPC resulted in a slight red shift (<10 nm) of the absorption bands. The modular nature of the assembly process afforded the incorporation of other pyridyl-terminated organic molecules in specific layers of the supramolecular assemblies. By assembling unique organic dyes that absorb different wavelengths of light, we expect to expand light absorption across the visible region of the solar spectrum for solar cell applications.

  4. Mechanically durable, superoleophobic coatings prepared by layer-by-layer technique for anti-smudge and oil-water separation

    PubMed Central

    Brown, Philip S.; Bhushan, Bharat

    2015-01-01

    Superoleophobic surfaces are of interest for anti-fouling, self-cleaning, anti-smudge, low-drag, anti-fog, and oil-water separation applications. Current bioinspired surfaces are of limited use due to a lack of mechanical durability. A so-called layer-by-layer approach, involving charged species with electrostatic interactions between layers, can provide the flexibility needed to improve adhesion to the substrate while providing a low surface tension coating at the air interface. In this work, a polyelectrolyte binder, SiO2 nanoparticles, and a fluorosurfactant are spray deposited separately to create a durable, superoleophobic coating. Polydiallyldimethylammonium chloride (PDDA) polyelectrolyte was complexed with a fluorosurfactant layer (FL), which provides oil repellency while being hydrophilic. This oleophobic/superhydrophilic behavior was enhanced through the use of roughening with SiO2 particles resulting in a superoleophobic coating with hexadecane contact angles exceeding 155° and tilt angles of less than 4°. The coating is also superhydrophilic, which is desirable for oil-water separation applications. The durability of these coatings was examined through the use of micro- and macrowear experiments. These coatings currently display characteristics of transparency. Fabrication of these coatings via the layer-by-layer technique results in superoleophobic surfaces displaying improved durability compared to existing work where either the durability or the oil-repellency is compromised. PMID:25731716

  5. Corrosion protection and improved cytocompatibility of biodegradable polymeric layer-by-layer coatings on AZ31 magnesium alloys.

    PubMed

    Ostrowski, Nicole; Lee, Boeun; Enick, Nathan; Carlson, Benjamin; Kunjukunju, Sangeetha; Roy, Abhijit; Kumta, Prashant N

    2013-11-01

    Composite coatings of electrostatically assembled layer-by-layer anionic and cationic polymers combined with an Mg(OH)2 surface treatment serve to provide a protective coating on AZ31 magnesium alloy substrates. These ceramic conversion coating and layer-by-layer polymeric coating combinations reduced the initial and long-term corrosion progression of the AZ31 alloy. X-ray diffraction and Fourier transform infrared spectroscopy confirmed the successful application of coatings. Potentiostatic polarization tests indicate improved initial corrosion resistance. Hydrogen evolution measurements over a 2 week period and magnesium ion levels over a 1 week period indicate longer range corrosion protection and retention of the Mg(OH)2 passivation layer in comparison to the uncoated substrates. Live/dead staining and DNA quantification were used as measures of biocompatibility and proliferation while actin staining and scanning electron microscopy were used to observe the cellular morphology and integration with the coated substrates. The coatings simultaneously provided improved biocompatibility, cellular adhesion and proliferation in comparison to the uncoated alloy surface utilizing both murine pre-osteoblast MC3T3 cells and human mesenchymal stem cells. The implementation of such coatings on magnesium alloy implants could serve to improve the corrosion resistance and cellular integration of these implants with the native tissue while delivering vital drugs or biological elements to the site of implantation. PMID:23684762

  6. Patterning of gold nanoparticles on fluoropolymer films by using patterned surface grafting and layer-by-layer deposition techniques.

    PubMed

    Jung, Chang-Hee; Hwang, In-Tae; Jung, Chan-Hee; Choi, Jae-Hak; Kwon, Oh-Sun; Shin, Kwanwoo

    2013-09-11

    The patterning of gold nanoparticles (GNPs) on the surface of a fluoropolymer substrate by using patterned surface grafting and layer-by-layer deposition techniques is described. The surface of a poly(tetrafluoroethylene-co-perfluorovinyl ether) (PFA) substrate was selectively implanted with 150 keV proton ions. Peroxide groups were successfully formed on the implanted PFA surface, and their concentration depended on the fluence. Acrylic acid was graft polymerized onto the implanted regions of the PFA substrate, resulting in well-defined patterns of poly(acrylic acid) (PAA) on the PFA substrate. The surface properties of the PAA-patterned PFA surface, such as chemical compositions, wettability, and morphology, were investigated. The surface analysis results revealed that PAA was definitely present on the implanted regions of the PFA surface, and the degree of grafting was dependent on three factors: fluence, grafting time, and monomer concentration. Furthermore, GNP patterns were generated on the prepared PAA-patterned PFA surface by layer-by-layer deposition of GNPs and poly(diallyldimethyl ammonium chloride). The multilayers of GNPs were deposited only onto the PAA-grafted regions separated by bare PFA regions, and the resulting GNP patterns exhibited good electrical conductivity. PMID:23927646

  7. Layer-by-layer self-assembly of functionalized graphene nanoplates for glucose sensing in vivo integrated with on-line microdialysis system.

    PubMed

    Gu, Hui; Yu, Yanyan; Liu, Xiaoqian; Ni, Bing; Zhou, Tianshu; Shi, Guoyue

    2012-02-15

    In this work, a novel amperometric biosensor for hydrogen peroxide was fabricated through the layer-by-layer (LBL) self-assembling of amine-terminated ionic liquid (IL-NH(2)), and sulfonic acid (SO(3)(-)) functionalized graphene by covalent bonding. The modification of the two functionalities introduced positive and negative charge onto the surface of graphene respectively, thus facilitating the formation of a multilayer film denoted with {IL-RGO/S-RGO}(n) through electrostatic interaction and further immobilization of glucose oxidase (GOx). The resulting {IL-RGO/S-RGO}(n)/GOx/Nafion biosensor displayed an excellent response to glucose at a potential of -200 mV. Combined with on-line microdialysis system, the glucose biosensor in the on-line system showed good linear range from 10 μM to 500 μM with the detection limit of 3.33 μM (S/N=3). Consequently, the basal level of glucose in the striatum of anesthetic rats was calculated to be 0.376 ± 0.028 mM (mean ± s.d., n=3). The {IL-RGO/S-RGO}(n)/GOx/Nafion biosensor was further applied for in vivo sensing of the glucose level in the striatum when rats received intraperitoneal (i.p.) injection of 30 μL insulin, which resulted in an obvious decrease in the extracellular concentration of glucose within 30 min. The method was proved to be sensitive and reproducible, which enabled its promising application in physiology and pathology. PMID:22209068

  8. Functionalization of Fibers Using Azlactone-Containing Polymers: Layer-by-Layer Fabrication of Reactive Thin Films on the Surfaces of Hair and Cellulose-Based Materials

    PubMed Central

    Buck, Maren E.

    2010-01-01

    We report an approach to the functionalization of fibers and fiber-based materials that is based on the deposition of reactive azlactone-functionalized polymers and the ‘reactive’ layer-by-layer assembly of azlactone-containing thin films. We demonstrate (i) that the azlactone-functionalized polymer poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) can be used to modify the surfaces of a model protein-based fiber (horsehair) and cellulose-based materials (e.g., cotton and paper), and (ii) that fibers functionalized in this manner can be used to support the fabrication of covalently crosslinked and reactive polymer multilayers assembled using PVDMA and poly(ethyleneimine) (PEI). The growth, chemical reactivity, and uniformity of films deposited on these substrates were characterized using fluorescence microscopy, confocal microscopy, and scanning electron microscopy (SEM). In addition to the direct functionalization of fibers, we demonstrate that the residual azlactone functionality in PVDMA-treated or film-coated fibers can be exploited to chemically modify the surface chemistry and physicochemical properties of fiber-based materials post-fabrication using amine functionalized molecules. For example, we demonstrate that this approach permits control over the surface properties of paper (e.g., absorption of water) by simple post-fabrication treatment of film-coated paper with the hydrophobic amine n-decylamine. The azlactone functionality present in these materials provides a platform for the modification of polymer-treated and film-coated fibers with a broad range of other chemical and biological species (e.g., enzymes, peptides, catalysts, etc.). The results of this investigation thus provide a basis for the functionalization of fibers and fiber-based materials (e.g., textile fabrics or non-woven mats) of potential utility in a broad range of consumer, industrial, and biomedical contexts. PMID:20402471

  9. Fabrication and optoelectronic properties of novel films based on functionalized multiwalled carbon nanotubes and (phthalocyaninato)ruthenium(II) via coordination bonded layer-by-layer self-assembly.

    PubMed

    Zhao, Wei; Tong, Bin; Shi, Jianbing; Pan, Yuexiu; Shen, Jinbo; Zhi, Junge; Chan, Wai Kin; Dong, Yuping

    2010-10-19

    4-(2-(4-pyridinyl)Ethynyl)benzenic diazonium salt (PBD) was used to modify multiwalled carbon nanotubes (MWCNTs) by the self-assembly technique. After the decomposition of the diazonium group in PBD under UV irradiation, the PBD monolayer film covalently anchored on multiwalled carbon nanotubes is very stable. The obtained pyridine-modified MWCNTs (Py(Ar)-MWCNTs) have good solubility in common organic solvents. Furthermore, the layer-by-layer (LBL) self-assembled fully conjugated films of Py(Ar)-MWCNTs and (phthalocyaninato)ruthenium(II) (RuPc) were fabricated on the PBD-modified substrates, and characterized using UV-vis absorption spectroscopy, scanning electron microscopy (SEM), and electrochemistry. The UV-vis analysis results indicate that the LBL RuPc/Py(Ar)-MWCNTs self-assembled multilayer films with axial ligands between the ruthenium atom and pyridine group were successfully fabricated, and the progressive assembly runs regularly with almost equal amounts of deposition in each cycle. A top view SEM image shows a random and homogeneous distribution of Py(Ar)-MWCNTs over the PBD-modified silicon substrate, which indicates well independence between all Py(Ar)-MWCNTs. Moreover, the opto-electronic conversion was also studied by assembling RuPc/Py(Ar)-MWCNTs multilayer films on PBD-modified ITO substrate. Under illumination, the LBL self-assembled films on ITO showed an effective photoinduced charge transfer because of their conjugated structure and the ITO current density changed with the number of bilayer. As the number of bilayers was increased, the photocurrent increases and reaches its maximum value (∼300 nA/cm(2)) at nine bilayers. These results allow us to design novel materials for applications in optoelectronic devices by using LBL self-assembly techniques. PMID:20853832

  10. Electrostatic Layer-By-Layer Self-Assembled Graphene/Multi-Walled Carbon Nanotubes Hybrid Multilayers as Efficient 'All Carbon' Supercapacitors.

    PubMed

    Gupta, Sanju; Heintzman, Eli; Price, Carson

    2016-05-01

    In this work, covalently bonded graphene/carbon nanotube (Gr/CNT) conjoined materials are fabricated as engineered three-dimensional hybrid multilayer supercapacitors for high-performance integrated electrochemical energy storage. Stable aqueous dispersion of polymer-modified graphene sheets are prepared in the presence of cationic poly(ethyleneimine), PEI (PEI-Gr) for sequential or electrostatic layer-by-layer (E-LBL) self-assembly with negatively charged acid-oxidized or functionalized multi-walled CNT (fMWCNT), forming (PEI-Gr/fMWCNT)n architecture as "all carbon" super-capacitor, where n = 1, 2, 4, 6, 9, 12 and 15. These films possess an interconnected network of mesoporous nanocarbon structure with well-defined interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. They exhibit nearly rectangular cyclic voltammograms at an exceedingly high scan rate of 1 V/s with an average specific capacitance of -450 F g(-1) and specific energy density of 75.5 Wh kg(-1) based on electrode weight, measured at a current density of 0.3 A g(-1), comparable to that of Ni metal hydride battery and charged/discharged within a few seconds or a minute. This is attributed to the maximized synergistic effect of the highest specific surface areas by preventing re-aggregation of PEI-Gr or PEI-rGO via fMWCNT as spacers. We also determined relative contributions of the interfacial capacitance (C(dl)) and charge transfer (R(ct)) properties of the hybrids and investigated interfacial properties by SECM technique. PMID:27483821

  11. Covalent attachment of a three-dimensionally printed thermoplast to a gelatin hydrogel for mechanically enhanced cartilage constructs.

    PubMed

    Boere, Kristel W M; Visser, Jetze; Seyednejad, Hajar; Rahimian, Sima; Gawlitta, Debby; van Steenbergen, Mies J; Dhert, Wouter J A; Hennink, Wim E; Vermonden, Tina; Malda, Jos

    2014-06-01

    Hydrogels can provide a suitable environment for tissue formation by embedded cells, which makes them suitable for applications in regenerative medicine. However, hydrogels possess only limited mechanical strength, and must therefore be reinforced for applications in load-bearing conditions. In most approaches the reinforcing component and the hydrogel network have poor interactions and the synergetic effect of both materials on the mechanical properties is not effective. Therefore, in the present study, a thermoplastic polymer blend of poly(hydroxymethylglycolide-co-ε-caprolactone)/poly(ε-caprolactone) (pHMGCL/PCL) was functionalized with methacrylate groups (pMHMGCL/PCL) and covalently grafted to gelatin methacrylamide (gelMA) hydrogel through photopolymerization. The grafting resulted in an at least fivefold increase in interface-binding strength between the hydrogel and the thermoplastic polymer material. GelMA constructs were reinforced with three-dimensionally printed pHMGCL/PCL and pMHMGCL/PCL scaffolds and tested in a model for a focal articular cartilage defect. In this model, covalent bonds at the interface of the two materials resulted in constructs with an improved resistance to repeated axial and rotational forces. Moreover, chondrocytes embedded within the constructs were able to form cartilage-specific matrix both in vitro and in vivo. Thus, by grafting the interface of different materials, stronger hybrid cartilage constructs can be engineered. PMID:24590160

  12. Covalent heme attachment to the protein in human heme oxygenase-1 with selenocysteine replacing the His25 proximal iron ligand.

    PubMed

    Jiang, Yongying; Trnka, Michael J; Medzihradszky, Katalin F; Ouellet, Hugues; Wang, Yongqiang; Ortiz de Montellano, Paul R

    2009-03-01

    To characterize heme oxygenase with a selenocysteine (SeCys) as the proximal iron ligand, we have expressed truncated human heme oxygenase-1 (hHO-1) His25Cys, in which Cys-25 is the only cysteine, in the Escherichia coli cysteine auxotroph strain BL21(DE3)cys. Selenocysteine incorporation into the protein was demonstrated by both intact protein mass measurement and mass spectrometric identification of the selenocysteine-containing tryptic peptide. One selenocysteine was incorporated into approximately 95% of the expressed protein. Formation of an adduct with Ellman's reagent (DTNB) indicated that the selenocysteine in the expressed protein was in the reduced state. The heme-His25SeCys hHO-1 complex could be prepared by either (a) supplementing the overexpression medium with heme, or (b) reconstituting the purified apoprotein with heme. Under reducing conditions in the presence of imidazole, a covalent bond is formed by addition of the selenocysteine residue to one of the heme vinyl groups. No covalent bond is formed when the heme is replaced by mesoheme, in which the vinyls are replaced by ethyl groups. These results, together with our earlier demonstration that external selenolate ligands can transfer an electron to the iron [Y. Jiang, P.R. Ortiz de Montellano, Inorg. Chem. 47 (2008) 3480-3482 ], indicate that a selenyl radical is formed in the hHO-1 His25SeCys mutant that adds to a heme vinyl group. PMID:19135260

  13. The potential use of a layer-by-layer strategy to develop LDPE antimicrobial films coated with silver nanoparticles for packaging applications.

    PubMed

    Azlin-Hasim, Shafrina; Cruz-Romero, Malco C; Cummins, Enda; Kerry, Joseph P; Morris, Michael A

    2016-01-01

    Commercial low-density polyethylene (LDPE) films were UV/ozone treated and coated using a layer-by-layer (LbL) technique by alternating the deposition of polyethyleneimine (PEI) and poly(acrylic acid) (PAA) polymer solutions and antimicrobial silver (Ag). The effects of the initial pH of the PEI/PAA polymer solutions alternating layers (pH 10.5/4 or 9/6.5) on the antimicrobial activity of the developed LbL coatings combined with Ag against Gram-negative and Gram-positive bacteria were investigated. The results from fourier transform infrared spectroscopy and toluidine blue O assay showed that LDPE LbL coated using PEI/PAA polymer solutions with initial pH of 10.5/4 significantly increased the presence of carboxylic acid groups and after Ag attachment the coating had higher antimicrobial activity against both Gram-negative and Gram-positive bacteria compared to the LDPE LbL coated using PEI/PAA polymer solutions with initial pH of 9/6.5. The LDPE LbL coated films using non-modified pH PEI/PAA polymer solutions decreased the water contact-angle indicating an increased hydrophilicity of the film, also increased the tensile strength and roughness of LDPE LbL coated films compared to uncoated LbL samples. The LDPE LbL coated films attached with Ag(+) were UV/ozone treated for 20 min to oxidise Ag(+) to Ag(0). The presence of Ag(0) (Ag nanoparticles (NPs)) on the LDPE LbL coated films was confirmed by XRD, UV-vis spectrophotometer and colour changes. The overall results demonstrated that the LbL technique has the potential to be used as a coating method containing antimicrobial Ag NPs and that the manufactured films could potentially be applied as antimicrobial packaging. PMID:26402783

  14. Recent Advances in Gas Barrier Thin Films via Layer-by-Layer Assembly of Polymers and Platelets.

    PubMed

    Priolo, Morgan A; Holder, Kevin M; Guin, Tyler; Grunlan, Jaime C

    2015-05-01

    Layer-by-layer (LbL) assembly has emerged as the leading non-vacuum technology for the fabrication of transparent, super gas barrier films. The super gas barrier performance of LbL deposited films has been demonstrated in numerous studies, with a variety of polyelectrolytes, to rival that of metal and metal oxide-based barrier films. This Feature Article is a mini-review of LbL-based multilayer thin films with a 'nanobrick wall' microstructure comprising polymeric mortar and nano-platelet bricks that impart high gas barrier to otherwise permeable polymer substrates. These transparent, water-based thin films exhibit oxygen transmission rates below 5 × 10(-3) cm(3) m(-2) day(-1) atm(-1) and lower permeability than any other barrier material reported. In an effort to put this technology in the proper context, incumbent technologies such as metallized plastics, metal oxides, and flake-filled polymers are briefly reviewed. PMID:25800245

  15. Regulating Cell Apoptosis on Layer-by-Layer Assembled Multilayers of Photosensitizer-Coupled Polypeptides and Gold Nanoparticles

    NASA Astrophysics Data System (ADS)

    Xing, Ruirui; Jiao, Tifeng; Ma, Kai; Ma, Guanghui; Möhwald, Helmuth; Yan, Xuehai

    2016-05-01

    The design of advanced, nanostructured materials by layer-by-layer (LbL) assembly at the molecular level is of great interest because of the broad application of these materials in the biomedical field especially in regulating cell growth, adhesion, movement, differentiation and detachment. Here, we fabricated functional hybrid multilayer films by LbL assembly of biocompatible photosensitizer-coupled polypeptides and collagen-capped gold nanoparticles. The resulting multilayer film can well accommodate cells for adhesion, growth and proliferation. Most significantly, controlled cell apoptosis (detachment) and patterning of the multilayer film is achieved by a photochemical process yielding reactive oxygen species (ROS). Moreover, the site and shape of apoptotic cells can be controlled easily by adjusting the location and shape of the laser beam. The LbL assembled multilayer film with integration of functions provides an efficient platform for regulating cell growth and apoptosis (detachment).

  16. Inhomogeneity of phase transition in lead titanate thin films formed by magnetron layer-by-layer deposition

    NASA Astrophysics Data System (ADS)

    Iljinas, Aleksandras; Stankus, Vytautas; Čyvienė, Jurgita; Abakevičienė, Brigita

    2015-10-01

    The formation of deposited ferroelectric perovskite PbTiO3 thin films using layer-by-layer reactive magnetron sputtering was investigated in this work. Deposition rates of each layer (PbO and TiO2) for 7.2 and 9.2 nm/min, respectively, were chosen there. Silicon (110) substrate with the heater was moved periodically and parallel to the magnetron cathodes during deposition. The heater temperature (380 °C-700 °C) has influence on the stoichiometry of thin films. Perovskite phase of lead titanate was not obtained without post annealing. The reasons for this are discussed in the work. The results of the structure of thin layers deposited on silicon substrates at 380 °C and annealed for one hour at 700 °C in air have shown that a pure perovskite phase of PbTiO3 is formed there.

  17. Regulating Cell Apoptosis on Layer-by-Layer Assembled Multilayers of Photosensitizer-Coupled Polypeptides and Gold Nanoparticles

    PubMed Central

    Xing, Ruirui; Jiao, Tifeng; Ma, Kai; Ma, Guanghui; Möhwald, Helmuth; Yan, Xuehai

    2016-01-01

    The design of advanced, nanostructured materials by layer-by-layer (LbL) assembly at the molecular level is of great interest because of the broad application of these materials in the biomedical field especially in regulating cell growth, adhesion, movement, differentiation and detachment. Here, we fabricated functional hybrid multilayer films by LbL assembly of biocompatible photosensitizer-coupled polypeptides and collagen-capped gold nanoparticles. The resulting multilayer film can well accommodate cells for adhesion, growth and proliferation. Most significantly, controlled cell apoptosis (detachment) and patterning of the multilayer film is achieved by a photochemical process yielding reactive oxygen species (ROS). Moreover, the site and shape of apoptotic cells can be controlled easily by adjusting the location and shape of the laser beam. The LbL assembled multilayer film with integration of functions provides an efficient platform for regulating cell growth and apoptosis (detachment). PMID:27211344

  18. Stimuli-Responsive Layer-by-Layer Tellurium-Containing Polymer Films for the Combination of Chemotherapy and Photodynamic Therapy.

    PubMed

    Fan, Fuqiang; Wang, Lu; Li, Feng; Fu, Yu; Xu, Huaping

    2016-07-01

    Tellurium-containing photoresponsive polyelectrolyte multilayer films were fabricated by layer-by-layer assembly of a tellurium-containing polymer, photosensitizer, and poly(styrenesulfonate). The resulting films were investigated by UV/vis spectroscopy, XPS, EPR, and fluorescence spectroscopy. Under visible light, the photosensitizer in the film is excited and transforms triplet oxygen into singlet oxygen in aqueous solution. Singlet oxygen oxidizes -Te- to high valence state (Te═O) on the polymer backbone. The generated (Te═O) group makes the micelles more hydrophilic and looser, thereby facilitating the controlled release of the loaded cargo of micelles. These results show that the film has the potential to be used for cargo loading and controlled release, thus may provide a new way to combine photodynamic therapy and chemotherapy. PMID:27301845

  19. Tunable green oxygen barrier through layer-by-layer self-assembly of chitosan and cellulose nanocrystals.

    PubMed

    Li, Fei; Biagioni, Paolo; Finazzi, Marco; Tavazzi, Silvia; Piergiovanni, Luciano

    2013-02-15

    We address the oxygen-barrier properties of a nanocomposite created by layer-by-layer assembly of two biopolymers, chitosan (CS) and cellulose, in nanocrystals form (CNs), on an amorphous PET substrate. We systematically investigated the oxygen permeability, morphology, and thickness of the nanocomposite grown under two different pH combinations and with different number of deposition cycles, up to 30 bilayers. Noticeably, the thickness of each deposited bilayer can be largely tuned by the pH value of the solution, from ~7 up to ~26 nm in the tested conditions. By our analysis, it is reliably concluded that such CS/CNs nanocomposite holds promises for gas barrier applications in food and drug packaging as a clear coating on plastic films and tridimensional objects, improving performance and sustainability of the final packages. PMID:23399267

  20. Regulating Cell Apoptosis on Layer-by-Layer Assembled Multilayers of Photosensitizer-Coupled Polypeptides and Gold Nanoparticles.

    PubMed

    Xing, Ruirui; Jiao, Tifeng; Ma, Kai; Ma, Guanghui; Möhwald, Helmuth; Yan, Xuehai

    2016-01-01

    The design of advanced, nanostructured materials by layer-by-layer (LbL) assembly at the molecular level is of great interest because of the broad application of these materials in the biomedical field especially in regulating cell growth, adhesion, movement, differentiation and detachment. Here, we fabricated functional hybrid multilayer films by LbL assembly of biocompatible photosensitizer-coupled polypeptides and collagen-capped gold nanoparticles. The resulting multilayer film can well accommodate cells for adhesion, growth and proliferation. Most significantly, controlled cell apoptosis (detachment) and patterning of the multilayer film is achieved by a photochemical process yielding reactive oxygen species (ROS). Moreover, the site and shape of apoptotic cells can be controlled easily by adjusting the location and shape of the laser beam. The LbL assembled multilayer film with integration of functions provides an efficient platform for regulating cell growth and apoptosis (detachment). PMID:27211344

  1. Layer-by-layer assembly of hemoglobin and gold nanoparticles for enhancing the ability of oxygen carrying

    NASA Astrophysics Data System (ADS)

    Sun, Lijun; Liu, Xiaojun; Sun, Qiaoling; Cai, Meng; Zhou, Jiajing; Dong, Zenglin; Bao, Ning; Gu, Haiying; He, Hong

    2016-02-01

    This paper reports layer-by-layer films fabricated with hemoglobin (Hb) and gold nanoparticles (AuNPs) as well as their applications in carrying oxygen. The characterization of {Hb/AuNPs}n multilayer films at different layers revealed that the formation of films was step-by-step. Meanwhile, the study showed that the {Hb/AuNPs}n modified glass carbon electrode can maintain the biological activity of Hb. The capacity of carrying oxygen was associated with the number of assembled layers. The {Hb/AuNPs}3 multilayer films displayed a good storing and releasing ability of oxygen. The study can provide an alternative method for construction of hemoglobin function interface with high-efficiency oxygen carrying capacity.

  2. An automated spin-assisted approach for molecular layer-by-layer assembly of crosslinked polymer thin films

    SciTech Connect

    Chan, Edwin P.; Chung, Jun Young; Stafford, Christopher M.; Lee, Jung-Hyun

    2012-11-15

    We present the design of an automated spin-coater that facilitates fabrication of polymer films based on molecular layer-by-layer (mLbL) assembly. Specifically, we demonstrate the synthesis of ultrathin crosslinked fully-aromatic polyamide (PA) films that are chemically identical to polymer membranes used in water desalination applications as measured by X-ray photoelectron spectroscopy. X-ray reflectivity measurements indicate that the automated mLbL assembly creates films with a constant film growth rate and minimal roughness compared with the traditional interfacial polymerization of PA. This automated spin-coater improves the scalability and sample-to-sample consistency by reducing human involvement in the mLbL assembly.

  3. All-optical poling and second harmonic generation diagnostic of layer-by-layer assembled photoactive polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Aldea-Nunzi, G.; Chan, S. W.; Man, K. Y. K.; Nunzi, J. M.

    2013-07-01

    Layer-by-layer (LBL) self-assembling was employed to produce dye-containing multilayer films with a nonlinear optical maleic acid copolymer containing Disperse Red 1 moieties. By alternate adsorption of maleic acid copolymer derivative and polyethyleneimine, films made from 1 to 30 bilayers were prepared and characterized. The effect of salt addition to the polyelectrolyte on the LBL self-assembly process was also studied. Second order optical nonlinearity χ(2) of LBL films was studied by second harmonic generation and its stability was assessed by all-optical poling. A 'restoring force' model for the chromophore orientation in the LBL films is proposed to simulate the rotational motion. It clarifies the origin of the stability of the noncentrosymmetry in LBL films.

  4. Process Conditions of Forming the Surface Layer of Aluminum Powder Product by Layer-by-layer Laser Sintering

    NASA Astrophysics Data System (ADS)

    Saprykina, N. A.; Saprykin, A. A.; Ibragimov, E. A.; Arkhipova, D. A.

    2016-07-01

    The paper presents data on state of the art in selective laser sintering of products. Layer-by-layer sintering is shown to be a future-oriented technology, making it possible to synthesize products of metal powder materials. Factors, influencing the quality of a sintered product, are revealed in the paper. It presents outcomes of experiments, focused on the dependence of surface layer thickness of sintered aluminum powder PA-4 on laser processing conditions. Basic factors, influencing the quality of a sintered surface layer include laser power, speeds of scanning and moving the laser beam on the layer of powder. Thickness of the sintered layer varies from 0.74 to 1.55 mm, as the result of changing the laser processing conditions.

  5. Anti-fogging and anti-frosting behaviors of layer-by-layer assembled cellulose derivative thin film

    NASA Astrophysics Data System (ADS)

    Shibraen, Mahmoud H. M. A.; Yagoub, Hajo; Zhang, Xuejian; Xu, Jian; Yang, Shuguang

    2016-05-01

    Two cellulose derivatives, quaternized cellulose (QC) and carboxymethyl cellulose (CMC), were layer-by-layer (LbL) assembled to prepare a thin film. QC was also LbL assembled with two synthetic polyelectrolytes, poly(acrylic acid) (PAA) and poly(styrene sulfonate) (PSS), separately. The anti-fogging and anti-frosting properties of the assembled films were studied. QC/CMC thin film exhibits anti-fogging and anti-frosting behaviors, whereas QC/PAA and QC/PSS films do not have capacity for anti-fogging and anti-frosting. The anti-fogging and anti-frosting properties of QC/CMC film are attributed to that water molecules can be quickly adsorbed into the matrix of the film. The water adsorption of QC/CMC film was illustrated by the optical thickness increment.

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

    PubMed

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

    2016-12-01

    Controlled drug delivery systems are an encouraging solution to some drug disadvantages such as reduced solubility, deprived biodistribution, tissue damage, fast breakdown of the drug, cytotoxicity, or side effects. Self-ordered nanoporous anodic alumina is an auspicious material for drug delivery due to its biocompatibility, stability, and controllable pore geometry. Its use in drug delivery applications has been explored in several fields, including therapeutic devices for bone and dental tissue engineering, coronary stent implants, and carriers for transplanted cells. In this work, we have created and analyzed a stimuli-responsive drug delivery system based on layer-by-layer pH-responsive polyelectrolyte and nanoporous anodic alumina. The results demonstrate that it is possible to control the drug release using a polyelectrolyte multilayer coating that will act as a gate. PMID:27550052

  7. Layer-by-layer assembly of antibacterial coating on interbonded 3D fibrous scaffolds and its cytocompatibility assessment.

    PubMed

    Tang, Yanwei; Zhao, Yan; Wang, Hongxia; Gao, Yuan; Liu, Xin; Wang, Xungai; Lin, Tong

    2012-08-01

    Bonded fibrous matrices have shown great potential in tissue engineering because of their unique 3D structures and pore characteristics. For some applications, bacterial infections must be taken into account, and antibacterial function is highly desired. In this study, an antibacterial polymer, polyhexamethylene biguanide (PHMB), was applied onto the fiber surface of a bonded poly(ε-caprolactone) (PCL) fibrous matrix with the objective to achieve both strong antibacterial effect and good cell compatibility. The coatings were prepared by using an electrostatic layer-by-layer (LbL) assembly technique, which allowed the control of PHMB loading and coating uniformity on the fiber surface. The PHMB coating provided antibacterial activities, but had no toxicity on mammalian cells. This bonded PCL fibrous matrix with electrostatically self-assembled PHMB may provide a new antiinfective tissue scaffold for various biomedical applications. PMID:22581705

  8. Preparation of a novel composite nanofiber gel-encapsulated human placental extract through layer-by-layer self-assembly

    PubMed Central

    LIU, GUOHUI; CHEN, XI; ZHOU, WU; YANG, SHUHUA; YE, SHUNAN; CAO, FAQI; LIU, YI; XIONG, YUAN

    2016-01-01

    Aqueous human placenta extract (HPE) has been previously used to treat chronic soft tissue ulcer; however, the optimal dosage of HPE has yet to be elucidated. The present study investigated a novel nanofiber gel composed through layer-by-layer (LbL) self-assembly, in which HPE was encapsulated. IKVAV, RGD, RAD16 and FGL-PA were screened and combined to produce an optimal vehicle nanofiber gel through LbL assembly. Subsequently, the aqueous HPE was encapsulated into this nanofiber at the appropriate concentration, and the morphology, particle size, drug loading efficacy, encapsulation rate, release efficiency and structure validation were detected. The encapsulation efficiency of all three HPE samples was >90%, the nanofiber gel exhibited a slow releasing profile, and the structure of HPE encapsulated in the nanofiber gel was unvaried. In conclusion, this type of novel composite nanocapsules may offer a promising delivery system for HPE. PMID:27073463

  9. Ultraviolet protection cotton fabric achieved via layer-by-layer self-assembly of graphene oxide and chitosan

    NASA Astrophysics Data System (ADS)

    Tian, Mingwei; Hu, Xili; Qu, Lijun; Du, Minzhi; Zhu, Shifeng; Sun, Yaning; Han, Guangting

    2016-07-01

    Cotton fabrics with robust ultraviolet protective property can be facilely prepared by depositing graphene oxide (GO) and chitosan (CS) upon fabric substrate via the electrostatic layer-by-layer self-assembly approach. The structure and morphology of the resultant fabrics were characterized by SEM, AFM, FTIR, XPS and dyeing color depth (K/S value), and the ultraviolet (UV) blocking properties were also further investigated. As expected, the UV protection ability was evaluated with Ultraviolet Protection Factor (UPF), and the cotton fabrics deposited with GO and CS showed more than 40-fold increase with a UPF value of 452 than that of control cotton (UPF rating at 9.37). Moreover, the LbL deposited fabric showed excellent washing durability even after 10 times water laundering.

  10. Layer-by-layer engineering fluorescent polyelectrolyte coated mesoporous silica nanoparticles as pH-sensitive nanocarriers for controlled release

    NASA Astrophysics Data System (ADS)

    Du, Pengcheng; Zhao, Xubo; Zeng, Jin; Guo, Jinshan; Liu, Peng

    2015-08-01

    Fluorescent core/shell composite has been fabricated by the layer-by-layer (LbL) assembly of the fluorescein isothiocyanate modified chitosan (CS-FITC) and sodium alginate (AL) onto the carboxyl modified mesoporous silica nanoparticles (MSN-COOH), followed by PEGylation. It exhibits stability in high salt-concentration media and the pH responsive fluorescent feature can be used for cell imaging. Furthermore, the modified MSN cores can enhance the DOX loading capacity and the multifunctional polyelectrolyte shell can adjust the drug release upon the media pH, showing a low leakage quantity at the neutral environment but significantly enhanced release at lower pH media mimicking the tumor environments. Therefore, the biocompatible fluorescent polyelectrolyte coated mesoporous silica nanoparticles (MSN-LBL-PEG) offer promise for tumor therapy.

  11. Layer-by-layer polymer coated gold nanoparticles for topical delivery of imatinib mesylate to treat melanoma.

    PubMed

    Labala, Suman; Mandapalli, Praveen Kumar; Kurumaddali, Abhinav; Venuganti, Venkata Vamsi Krishna

    2015-03-01

    The aim of this study was to investigate the feasibility of using layer-by-layer polymer coated gold nanoparticles (AuNP) as a carrier for topical iontophoretic delivery of imatinib mesylate (IM). AuNP were prepared by the Turkevich method and were stabilized and functionalized using polyvinylpyrrolidone and polyethylene imine. The functionalized AuNP were then sequentially coated with anionic poly(styrenesulfonate) and cationic polyethylene imine and loaded with IM. The layer-by-layer polymer coated AuNP (LbL-AuNP) showed average particle size and zeta-potential of 98.5 ± 4.3 nm and 32.3 ± 1.3 mV respectively. After LbL coating of AuNP, the surface plasmon resonance wavelength shifted from 518 to 530 nm. The loading efficiency of IM in LbL-AuNP was found to be 28.3 ± 2.3%, which was greatest for any small molecule loaded in AuNP. In vitro skin penetration studies in excised porcine ear skin showed that iontophoresis (0.47 mA/cm(2)) application enhanced the skin penetration of IM loaded AuNP by 6.2-fold compared to passive application. Tape stripping studies showed that iontophoresis of IM loaded LbL-AuNP retained 7.8- and 4.9-fold greater IM in stratum corneum and viable skin respectively compared with iontophoresis of free IM. LbL-AuNP were taken up rapidly (15 min) by B16F10 murine melanoma cells. Furthermore, IM loaded LbL-AuNP significantly (p < 0.001) decreased B16F10 cell viability compared to free IM. We have shown for the first time that IM can be delivered by topical application using LbL coated gold nanoparticles to treat melanoma. PMID:25587849

  12. An effective combination of electrodeposition and layer-by-layer assembly to construct composite films with luminescence switching behavior.

    PubMed

    Gao, Wenmei; Ma, Hongwei; Zheng, Daming; Dong, Zhaojun; Wu, Lixin; Bi, Lihua

    2015-09-01

    This article presents a combination strategy of electrodeposition and a layer-by-layer assembly to fabricate functional composite films with luminescence switching behavior. Firstly, a novel green luminescence film consisting of 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HOPTS) was first obtained on ITO by a facile electrodeposition method. Then, the multilayer films containing different layers of tungstophosphate K12.5Na1.5[NaP5W30O110]·15H2O (P5W30) were further fabricated on the green luminescence film to form the composite films [(HOPTS)50/(PDDA/P5W30)n] (n = 10, film 1; n = 27, film 2; n = 57, film 3). Cyclic voltammetry and fluorescence spectroscopy were used to characterize the electrochemical activity of P5W30 and the luminescence property of HOPTS in the composite films, respectively. Lastly, in situ UV-Vis spectroelectrochemical and fluorescence spectroelectrochemical measurements were applied to investigate the luminescence switching behaviors of the composite films controlled by the electrochromism component of P5W30 upon electrochemical modulation. In summary, the investigation results revealed that the electrodeposition method is convenient and rapid, and thus-prepared composite films showed improved luminescence switching performance in terms of switching process, activation cycles, coloration efficiency, and bleached-state transparency as well as good stability, wide voltage range and good reversibility. Therefore, the present study offers a new fabrication route for the multifunctional composite films through an effective combination of electrodeposition and layer-by-layer assembly technique. PMID:26219637

  13. Layer-by-layer charging in non-volatile memory devices using embedded sub-2 nm platinum nanoparticles

    SciTech Connect

    Ramalingam, Balavinayagam; Zheng, Haisheng; Gangopadhyay, Shubhra

    2014-04-07

    In this work, we demonstrate multi-level operation of a non-volatile memory metal oxide semiconductor capacitor by controlled layer-by-layer charging of platinum nanoparticle (PtNP) floating gate devices with defined gate voltage bias ranges. The device consists of two layers of ultra-fine, sub-2 nm PtNPs integrated between Al{sub 2}O{sub 3} tunneling and separation layers. PtNP size and interparticle distance were varied to control the particle self-capacitance and associated Coulomb charging energy. Likewise, the tunneling layer thicknesses were also varied to control electron tunneling to the first and second PtNP layers. The final device configuration with optimal charging behavior and multi-level programming was attained with a 3 nm Al{sub 2}O{sub 3} initial tunneling layer, initial PtNP layer with particle size 0.54 ± 0.12 nm and interparticle distance 4.65 ± 2.09 nm, 3 nm Al{sub 2}O{sub 3} layer to separate the PtNP layers, and second particle layer with 1.11 ± 0.28 nm PtNP size and interparticle distance 2.75 ± 1.05 nm. In this device, the memory window of the first PtNP layer saturated over a programming bias range of 7 V to 14 V, after which the second PtNP layer starts charging, exhibiting a multi-step memory window with layer-by-layer charging.

  14. A resonance enhancement of the phase relaxation in the electron spin echo of nitroxide covalently attached to cytochrome c

    NASA Astrophysics Data System (ADS)

    Hilczer, W.; Goslar, J.; Gramza, M.; Hoffmann, S. K.; Blicharski, W.; Osyczka, A.; Turyna, B.; Froncisz, W.

    1995-12-01

    The spin lattice T1 and phase memory TM relaxation times were measured by an electron spin echo technique for the nitroxide spin label attached covalently to horse heart cytochrome c below 80 K for oxidized (Fe 3+) and reduced (Fe 2+) samples. T1 decreases on heating and below 10 K is governed by the direct relaxation process for the reduced sample. The spin-lattice relaxation is enhanced by a cross-relaxation to Fe 3+ in an oxidized sample. In the TM temperature dependence an unusual deep minimum appears at about 25 K. This resonance type effect which vanishes completely for the reduced sample is due to a coupling to the Fe 3+ spins. The spin-lattice relaxation rate of Fe 3+ is comparable to the TM of nitroxide at low temperature producing a minimum in TM when the Ti value corresponds to the spin packet width of excited spins.

  15. A method for the second-site screening of K-Ras in the presence of a covalently attached first-site ligand

    PubMed Central

    Sun, Qi; Phan, Jason; Friberg, Anders R.; Camper, DeMarco V.; Olejniczak, Edward T.; Fesik, Stephen W.

    2015-01-01

    K-Ras is a well-validated cancer target but is considered to be “undruggable” due to the lack of suitable binding pockets. We previously discovered small molecules that bind weakly to K-Ras but wanted to improve their binding affinities by identifying ligands that bind near our initial hits that we could link together. Here we describe an approach for identifying second site ligands that uses a cysteine residue to covalently attach a compound for tight binding to the first site pocket followed by a fragment screen for binding to a second site. This approach could be very useful for targeting Ras and other challenging drug targets. PMID:25087006

  16. Covalent attachment of Anderson-type polyoxometalates to single-walled carbon nanotubes gives enhanced performance electrodes for lithium ion batteries.

    PubMed

    Ji, Yuanchun; Hu, Jun; Huang, Lujiang; Chen, Wei; Streb, Carsten; Song, Yu-Fei

    2015-04-20

    Single-walled carbon nanotubes (SWNTs) covalently functionalized with redox-active organo-modified polyoxometalate (POM) clusters have been synthesized and employed as electrode materials in lithium ion batteries. The Anderson cluster [MnMo6 O24 ](9-) is functionalized with Tris (NH2 C(CH2 OH)3 ) moieties, giving the new organic-inorganic hybrid [N(nC4 H9 )4 ]3 [MnMo6 O18 {(OCH2 )3 CNH2 }2 ]. The compound is then covalently attached to carboxylic acid-functionalized SWNTs by amide bond formation and the stability of this nanocomposite is confirmed by various spectroscopic methods. Electrochemical analyses show that the nanocomposite displays improved performance as an anode material in lithium ion batteries compared with the individual components, that is, SWNTs and/or Anderson clusters. High discharge capacities of up to 932 mAh g(-1) at a current density of 0.5 mA cm(-2) can be observed, together with high long-term cycling stability and decreased electrochemical impedance. Chemisorption of the POM cluster on the SWNTs is shown to give better electrode performance than the purely physisorbed analogues. PMID:25765945

  17. Effect of ionic liquid on the native and denatured state of a protein covalently attached to a probe: Solvation dynamics study

    NASA Astrophysics Data System (ADS)

    Chowdhury, Rajdeep; Mojumdar, Supratik Sen; Chattoraj, Shyamtanu; Bhattacharyya, Kankan

    2012-08-01

    Effect of a room temperature ionic liquid (RTIL, [pmim][Br]) on the solvation dynamics of a probe covalently attached to a protein (human serum albumin (HSA)) has been studied using femtosecond up-conversion. For this study, a solvation probe, 7-diethylamino-3-(4-maleimidophenyl)-4-methylcoumarin (CPM) has been covalently attached to the lone cysteine group (cys-34) of the protein HSA. Addition of 1.5 M RTIL or 6 M GdnHCl causes a red shift of the emission maxima of CPM bound to HSA by 3 nm and 12 nm, respectively. The average solvation time ⟨τs⟩ decreases from 650 ps (in native HSA) to 260 ps (˜2.5 times) in the presence of 1.5 M RTIL and to 60 ps (˜11 times) in the presence of 6 M GdnHCl. This is ascribed to unfolding of the protein by RTIL or GdnHCl and therefore making the probe CPM more exposed. When 1.5 M RTIL is added to the protein denatured by 6 M GdnHCl in advance, a further ˜5 nm red shift along with further ˜2 fold faster solvent relaxation (⟨τ⟩ ˜30 ps) is observed. Our previous fluorescence correlation spectroscopy study [D. K. Sasmal, T. Mondal, S. Sen Mojumdar, A. Choudhury, R. Banerjee, and K. Bhattacharyya, J. Phys. Chem. B 115, 13075 (2011), 10.1021/jp207829y] suggests that addition of RTIL to the protein denatured by 6 M GdnHCl causes a reduction in hydrodynamic radius (rh). It is demonstrated that in the presence of RTIL and GdnHCl, though the protein is structurally more compact, the local environment of CPM is very different from that in the native state.

  18. The use of plasma-activated covalent attachment of early domains of tropoelastin to enhance vascular compatibility of surfaces.

    PubMed

    Hiob, Matti A; Wise, Steven G; Kondyurin, Alexey; Waterhouse, Anna; Bilek, Marcela M; Ng, Martin K C; Weiss, Anthony S

    2013-10-01

    All current metallic vascular prostheses, including stents, exhibit suboptimal biocompatibility. Improving the re-endothelialization and reducing the thrombogenicity of these devices would substantially improve their clinical efficacy. Tropoelastin (TE), the soluble precursor of elastin, mediates favorable endothelial cell interactions while having low thrombogenicity. Here we show that constructs of TE corresponding to the first 10 ("N10") and first 18 ("N18") N-terminal domains of the molecule facilitate endothelial cell attachment and proliferation equivalent to the performance of full-length TE. This N-terminal ability contrasts with the known role of the C-terminus of TE in facilitating cell attachment, particularly of fibroblasts. When immobilized on a plasma-activated coating ("PAC"), N10 and N18 retained their bioactivity and endothelial cell interactive properties, demonstrating attachment and proliferation equivalent to full-length TE. In whole blood assays, both N10 and N18 maintained the low thrombogenicity of PAC. Furthermore, these N-terminal constructs displayed far greater resistance to protease degradation by blood serine proteases kallikrein and thrombin than did full-length TE. When immobilized onto a PAC surface, these shorter constructs form a modified metal interface to establish a platform technology for biologically compatible, implantable cardiovascular devices. PMID:23863453

  19. Extension of Light-Harvesting Ability of Photosynthetic Light-Harvesting Complex 2 (LH2) through Ultrafast Energy Transfer from Covalently Attached Artificial Chromophores.

    PubMed

    Yoneda, Yusuke; Noji, Tomoyasu; Katayama, Tetsuro; Mizutani, Naoto; Komori, Daisuke; Nango, Mamoru; Miyasaka, Hiroshi; Itoh, Shigeru; Nagasawa, Yutaka; Dewa, Takehisa

    2015-10-14

    Introducing appropriate artificial components into natural biological systems could enrich the original functionality. To expand the available wavelength range of photosynthetic bacterial light-harvesting complex 2 (LH2 from Rhodopseudomonas acidophila 10050), artificial fluorescent dye (Alexa Fluor 647: A647) was covalently attached to N- and C-terminal Lys residues in LH2 α-polypeptides with a molar ratio of A647/LH2 ≃ 9/1. Fluorescence and transient absorption spectroscopies revealed that intracomplex energy transfer from A647 to intrinsic chromophores of LH2 (B850) occurs in a multiexponential manner, with time constants varying from 440 fs to 23 ps through direct and B800-mediated indirect pathways. Kinetic analyses suggested that B800 chromophores mediate faster energy transfer, and the mechanism was interpretable in terms of Förster theory. This study demonstrates that a simple attachment of external chromophores with a flexible linkage can enhance the light harvesting activity of LH2 without affecting inherent functions of energy transfer, and can achieve energy transfer in the subpicosecond range. Addition of external chromophores, thus, represents a useful methodology for construction of advanced hybrid light-harvesting systems that afford solar energy in the broad spectrum. PMID:26403467

  20. Bioinspired Titanium Drug Eluting Platforms Based on a Poly-β-cyclodextrin-Chitosan Layer-by-Layer Self-Assembly Targeting Infections.

    PubMed

    Pérez-Anes, Alexandra; Gargouri, Myriem; Laure, William; Van Den Berghe, Hélène; Courcot, Elisabeth; Sobocinski, Jonathan; Tabary, Nicolas; Chai, Feng; Blach, Jean-François; Addad, Ahmed; Woisel, Patrice; Douroumis, Dennis; Martel, Bernard; Blanchemain, Nicolas; Lyskawa, Joël

    2015-06-17

    In the field of implantable titanium-based biomaterials, infections and inflammations are the most common forms of postoperative complications. The controlled local delivery of therapeutics from implants through polyelectrolyte multilayers (PEMs) has recently emerged as a versatile technique that has shown great promise in the transformation of a classical medical implant into a drug delivery system. Herein, we report the design and the elaboration of new biodegradable multidrug-eluting titanium platforms based on a polyelectrolyte multilayer bioactive coating that target infections. These systems were built up in mild conditions according to the layer-by-layer (L-b-L) assembly and incorporate two biocompatible polysaccharides held together through electrostatic interactions. A synthetic, negatively charged β-cyclodextrin-based polymer (PCD), well-known for forming stable and reversible complexes with hydrophobic therapeutic agents, was exploited as a multidrug reservoir, and chitosan (CHT), a naturally occurring, positively charged polyelectrolyte, was used as a barrier for controlling the drug delivery rate. These polyelectrolyte multilayer films were strongly attached to the titanium surface through a bioinspired polydopamine (PDA) film acting as an adhesive first layer and promoting the robust anchorage of PEMs onto the biomaterials. Prior to the multilayer film deposition, the interactions between both oppositely charged polyelectrolytes, as well the multilayer growth, were monitored by employing surface plasmon resonance (SPR). Several PEMs integrating 5, 10, and 15 bilayers were engineered using the dip coating strategy, and the polyelectrolyte surface densities were estimated by colorimetric titrations and gravimetric analyses. The morphologies of these multilayer systems, as well as their naturally occurring degradation in a physiological medium, were investigated by scanning electron microscopy (SEM), and their thicknesses were measured by means of

  1. Silica nanoparticles for the layer-by-layer assembly of fully electro-active cytochrome c multilayers

    PubMed Central

    2011-01-01

    Background For bioanalytical systems sensitivity and biomolecule activity are critical issues. The immobilization of proteins into multilayer systems by the layer-by-layer deposition has become one of the favorite methods with this respect. Moreover, the combination of nanoparticles with biomolecules on electrodes is a matter of particular interest since several examples with high activities and direct electron transfer have been found. Our study describes the investigation on silica nanoparticles and the redox protein cytochrome c for the construction of electro-active multilayer architectures, and the electron transfer within such systems. The novelty of this work is the construction of such artificial architectures with a non-conducting building block. Furthermore a detailed study of the size influence of silica nanoparticles is performed with regard to formation and electrochemical behavior of these systems. Results We report on interprotein electron transfer (IET) reaction cascades of cytochrome c (cyt c) immobilized by the use of modified silica nanoparticles (SiNPs) to act as an artificial matrix. The layer-by-layer deposition technique has been used for the formation of silica particles/cytochrome c multilayer assemblies on electrodes. The silica particles are characterized by dynamic light scattering (DLS), Fourier transformed infrared spectroscopy (FT-IR), Zeta-potential and transmission electron microscopy (TEM). The modified particles have been studied with respect to act as an artificial network for cytochrome c and to allow efficient interprotein electron transfer reactions. We demonstrate that it is possible to form electro-active assemblies with these non-conducting particles. The electrochemical response is increasing linearly with the number of layers deposited, reaching a cyt c surface concentration of about 80 pmol/cm2 with a 5 layer architecture. The interprotein electron transfer through the layer system and the influence of particle size are

  2. Antifouling and Antibacterial Multifunctional Polyzwitterion/Enzyme Coating on Silicone Catheter Material Prepared by Electrostatic Layer-by-Layer Assembly.

    PubMed

    Vaterrodt, Anne; Thallinger, Barbara; Daumann, Kevin; Koch, Dereck; Guebitz, Georg M; Ulbricht, Mathias

    2016-02-01

    The formation of bacterial biofilms on indwelling medical devices generally causes high risks for adverse complications such as catheter-associated urinary tract infections. In this work, a strategy for synthesizing innovative coatings of poly(dimethylsiloxane) (PDMS) catheter material, using layer-by-layer assembly with three novel functional polymeric building blocks, is reported, i.e., an antifouling copolymer with zwitterionic and quaternary ammonium side groups, a contact biocidal derivative of that polymer with octyl groups, and the antibacterial hydrogen peroxide (H2O2) producing enzyme cellobiose dehydrogenase (CDH). CDH oxidizes oligosaccharides by transferring electrons to oxygen, resulting in the production of H2O2. The design and synthesis of random copolymers which combine segments that have antifouling properties by zwitterionic groups and can be used for electrostatically driven layer-by-layer (LbL) assembly at the same time were based on the atom-transfer radical polymerization of dimethylaminoethyl methacrylate and subsequent partial sulfobetainization with 1,3-propane sultone followed by quaternization with methyl iodide only or octyl bromide and thereafter methyl iodide. The alternating multilayer systems were formed by consecutive adsorption of the novel polycations with up to 50% zwitterionic groups and of poly(styrenesulfonate) as the polyanion. Due to its negative charge, enzyme CDH was also firmly embedded as a polyanionic layer in the multilayer system. This LbL coating procedure was first performed on prefunctionalized silicon wafers and studied in detail with ellipsometry as well as contact angle (CA) and zetapotential (ZP) measurements before it was transferred to prefunctionalized PDMS and analyzed by CA and ZP measurements as well as atomic force microscopy. The coatings comprising six layers were stable and yielded a more neutral and hydrophilic surface than did PDMS, the polycation with 50% zwitterionic groups having the largest

  3. Layer-by-layer paper-stacking nanofibrous membranes to deliver adipose-derived stem cells for bone regeneration

    PubMed Central

    Wan, Wenbing; Zhang, Shiwen; Ge, Liangpeng; Li, Qingtao; Fang, Xingxing; Yuan, Quan; Zhong, Wen; Ouyang, Jun; Xing, Malcolm

    2015-01-01

    Bone tissue engineering through seeding of stem cells in three-dimensional scaffolds has greatly improved bone regeneration technology, which historically has been a constant challenge. In this study, we researched the use of adipose-derived stem cell (ADSC)-laden layer-by-layer paper-stacking polycaprolactone/gelatin electrospinning nanofibrous membranes for bone regeneration. Using this novel paper-stacking method makes oxygen distribution, nutrition, and waste transportation work more efficiently. ADSCs can also secrete multiple growth factors required for osteogenesis. After the characterization of ADSC surface markers CD29, CD90, and CD49d using flow cytometry, we seeded ADSCs on the membranes and found cells differentiated, with significant expression of the osteogenic-related proteins osteopontin, osteocalcin, and osteoprotegerin. During 4 weeks in vitro, the ADSCs cultured on the paper-stacking membranes in the osteogenic medium exhibited the highest osteogenic-related gene expressions. In vivo, the paper-stacking scaffolds were implanted into the rat calvarial defects (5 mm diameter, one defect per parietal bone) for 12 weeks. Investigating with microcomputer tomography, the ADSC-laden paper-stacking membranes showed the most significant bone reconstruction, and from a morphological perspective, this group occupied 90% of the surface area of the defect, produced the highest bone regeneration volume, and showed the highest bone mineral density of 823.06 mg/cm3. From hematoxylin and eosin and Masson staining, the new bone tissue was most evident in the ADSC-laden scaffold group. Using quantitative polymerase chain reaction analysis from collected tissues, we found that the ADSC-laden paper-stacking membrane group presented the highest osteogenic-related gene expressions of osteocalcin, osteopontin, osteoprotegerin, bone sialoprotein, runt-related transcription factor 2, and osterix (two to three times higher than the control group, and 1.5 times higher than

  4. Synthesis of antireflective silica coatings through the synergy of polypeptide layer-by-layer assemblies and biomineralization

    NASA Astrophysics Data System (ADS)

    Lee, Yung-Lun; Lin, Ting-Xuan; Hsu, Feng-Ming; Jan, Jeng-Shiung

    2016-01-01

    We report a versatile approach to synthesize silica coatings with antireflective (AR) characteristics through the combination of a layer-by-layer (LbL) assembly technique and biomineralization. LbL assembled decanoyl-modified poly(l-lysine)/poly(l-glutamic acid) (PLL-g-Dec/PLGA) multilayer films were used as templates for silica mineralization, followed by calcination. The specific deposition of silica onto the LbL polypeptide assemblies through amine-catalyzed polycondensation resulted in silica coatings that exhibited the transcription of the nano-/microstructured polypeptide films and their film thickness and porosity can be tuned by varying the number of bilayers, degree of substitution, and PLL molecular weight. AR silica coatings exhibiting more than 6% increase in transmittance in the near UV/visible spectral range can be obtained at an optimized refractive index, thickness, and surface roughness. The abrasion test showed that the silica coatings exhibited sufficient structural durability due to continuous silica nanostructures and low surface roughness. This study demonstrated that nanostructured thin films can be synthesized for AR coatings using the synergy between the LbL assembly technique and biomineralization.We report a versatile approach to synthesize silica coatings with antireflective (AR) characteristics through the combination of a layer-by-layer (LbL) assembly technique and biomineralization. LbL assembled decanoyl-modified poly(l-lysine)/poly(l-glutamic acid) (PLL-g-Dec/PLGA) multilayer films were used as templates for silica mineralization, followed by calcination. The specific deposition of silica onto the LbL polypeptide assemblies through amine-catalyzed polycondensation resulted in silica coatings that exhibited the transcription of the nano-/microstructured polypeptide films and their film thickness and porosity can be tuned by varying the number of bilayers, degree of substitution, and PLL molecular weight. AR silica coatings exhibiting

  5. PREVENTION OF POLYURETHANE OXIDATIVE DEGRADATION WITH PHENOLIC-ANTIOXIDANTS COVALENTLY ATTACHED TO THE HARD SEGMENTS: STRUCTURE FUNCTION RELATIONSHIPS

    PubMed Central

    Stachelek, Stanley J; Alferiev, Ivan; Ueda, Masako; Eckels, Edward C.; Gleason, Kevin T.; Levy, Robert J

    2010-01-01

    Oxidative degradation of the polyurethane elastomeric (PU) components greatly reduces the efficacy of PU containing cardiovascular devices. Covalently appending the phenol-based antioxidant, 4-substituted 2,6-di-tert-butylphenol (DBP), to PU hard segments effectively reduced oxidative degradation of the PU in vivo and in vitro in prior studies by our group. In these experiments we analyze the contribution of the tethering molecule to the antioxidant capabilities of the DBP modified PU. Bromoalkylation chemistry was used to link DBP to the hard segment of the polyether polyurethane, Tecothane, via our original linker (PU-DBP), or variants containing side chains with 1 (PU-C-DBP) or 3 (PU-3C-DBP) carbons. Two additional DBP variants were fabricated in which the DBP group was appended to the alkyl chain via an oxygen atom (PU-O-DBP) or an amide linkage in the middle of the tether (PU-NHCO-DBP). All DBP variant films and unmodified control films were subject to oxidative degradation via 15 day immersion in a solution of 20% H2O2 + 0.1 M CoCl2. At the end of the oxidation protocol films were analyzed for the presence of oxidation related endpoints via scanning electron microscopy, contact angle measurements and Fourier transformation infrared spectroscopy (FTIR). All DBP containing variants resisted oxidation damage significantly better than the unmodified control PU. SEM analysis of oxidized PU-C-DBP and PU-O-DBP showed evidence of surface cracking consistent with oxidative degradation of the PU surfaces. Similarly there was a trend in increased ether cross-linking, a marker for oxidative degradation, in PU-C-DBP and PU-NHCO-DBP films. Consistent with these FTIR results, both PU-C-DBP and PU-NHCO-DBP had significant reductions in measured surface hydrophobicity as a result of oxidation. These data show for the first time that the choice of linker molecule significantly affects the efficiency of the linked phenolic antioxidant. PMID:20306526

  6. The Effect of Layer-by-Layer Assembly Coating on the Proliferation and Differentiation of Neural Stem Cells.

    PubMed

    Li, Wenyan; Guan, Teng; Zhang, Xiaosha; Wang, Ziyuan; Wang, Meng; Zhong, Wen; Feng, Hua; Xing, Malcolm; Kong, Jiming

    2015-02-11

    Nanocoating of a single-cell with biocompatible materials creates a defined microenvironment for cell differentiation and proliferation, as well as a model for studies in cell biology. In addition, the acidic environment in the tissue of stroke victims necessitates drug release upon pH stimuli. Here, we report the encapsulation of single neural stem cells (NSCs) using a layer-by-layer (LbL) self-assembly technique with polyelectrolytes gelatin and alginate. Analysis of the NSCs showed that the LbL encapsulation would not affect the viability, proliferation, or differentiation of the cells. When insulin-like growth factor-1 (IGF-1) was loaded on the coating material alginate, its release from alginate into the medium presented in a time-dependent and pH-dependent way. IGF-1 significantly enhanced the proliferation of the encapsulated NSCs, demonstrating a drug-carrier function of the LbL single-cell nanocoating. It provided a potential treatment strategy for nervous system disorders such as stroke. PMID:25347385

  7. Sensing skin for strain monitoring made of PC-CNT conductive polymer nanocomposite sprayed layer by layer.

    PubMed

    Robert, Colin; Feller, Jean François; Castro, Mickaël

    2012-07-25

    Sensing skins about 1.5 μm thick made of 40 nanolayers of conductive polymer nanocomposites (CPC) were sprayed layer by layer (sLbL) directly on a PET woven textile to demonstrate their versatility to monitor the deformation of a flexible, rigid and rough substrate such as a commercial boat sail. CPC sensing skins were developed by structuring a 3D carbon nanotubes network into three kinds of amorphous thermoplastic matrices (PMMA, aPS, PC). Adjustable parameters such as the thickness (number of sprayed layers) and the initial resistance of CPC transducers (CNT content relatively to percolation threshold) enabled to tailor both sensitivity and stability of the piezo-resistive responses, so that it was possible to monitor the strain evolution in the elastic domain and damage accumulation over this limit. Polymer matrices were selected after calculation of their χ Flory-Huggins parameters to evaluate their interactions with the PET substrate and solvent of dispersion, and after the comparison of their stress/strain characteristics, particularly their elastic limit. PC-1%CNT was found to be the best candidate satisfying both chemical and physical criteria. Finally, the exponential evolution of the piezo-resistive response of CPC sensing skins on a wide range of deformation (until breakage at ε = 27%), was well fitted with a model based on quantum tunnelling conduction inducing an exponential evolution of resistance with variations of CNT/CNT junction gap from 0.5 to 0.625 nm. PMID:22704247

  8. Selective layer-by-layer self-assembly on patterned porous films modulated by Cassie-Wenzel transition.

    PubMed

    Ke, Bei-Bei; Wan, Ling-Shu; Li, Yang; Xu, Ming-Yao; Xu, Zhi-Kang

    2011-03-21

    We describe a robust and facile approach to the selective modification of patterned porous films via layer-by-layer (LBL) self-assembly. Positively charged honeycomb-patterned films were prepared from polystyrene-block-poly(N,N-dimethyl-aminoethyl methacrylate) (PS-b-PDMAEMA) and a PS/PDMAEMA blend by the breath figure method followed by surface quaternization. Alginate and chitosan were alternately deposited on the films via LBL self-assembly. The assembly on the PS-b-PDMAEMA film exhibits two stages with different growth rates, as elucidated by water contact angles, fluorescence microscopy, and quartz crystal microbalance results. The assembly can be controlled on the top surface or across all surfaces of the film by changing the number of deposition cycles. We confirm that there exists a Cassie-Wenzel transition with an increase in deposition cycles, which is responsible for the tunable assembly. For the PS/PDMAEMA film, the pores can be completely wetted and the polyelectrolytes selectively assemble inside the pores, instead of on the top surface. The controllable selective assembly forms unique hierarchical structures and opens a new route for surface modification of patterned porous films. PMID:21221432

  9. Biological and immunotoxicity evaluation of antimicrobial peptide-loaded coatings using a layer-by-layer process on titanium

    PubMed Central

    Shi, Jue; Liu, Yu; Wang, Ying; Zhang, Jing; Zhao, Shifang; Yang, Guoli

    2015-01-01

    The prevention and control of peri-implantitis is a challenge in dental implant surgery. Dental implants with sustained antimicrobial coating are an ideal way of preventing peri-implantitis. This study reports development of a non- immunotoxicity multilayered coating on a titanium surface that had sustained antimicrobial activity and limited early biofilm formation. In this study, the broad spectrum AMP, Tet213, was linked to collagen IV through sulfo-SMPB and has been renamed as AMPCol. The multilayer AMPCol coatings were assembled on smooth titanium surfaces using a LBL technique. Using XPS, AFM, contact angle analysis, and QCM, layer-by-layer accumulation of coating thickness was measured and increased surface wetting compared to controls was confirmed. Non-cytotoxicity to HaCaT and low erythrocyte hemolysis by the AMPCol coatings was observed. In vivo immunotoxicity assays showed IP administration of AMPCol did not effect serum immunoglobulin levels. This coating with controlled release of AMP decreased the growth of both a Gram-positive aerobe (Staphylococcus aureus) and a Gram-negative anaerobe (Porphyromonas gingivalis) up to one month. Early S. aureus biofilm formation was inhibited by the coating. The excellent long-term sustained antimicrobial activity of this multilayer coating is a potential method for preventing peri-implantitis through coated on the neck of implants before surgery. PMID:26548760

  10. Controllable preparation of multishelled NiO hollow nanospheres via layer-by-layer self-assembly for supercapacitor application

    NASA Astrophysics Data System (ADS)

    Yang, Zeheng; Xu, Feifei; Zhang, Weixin; Mei, Zhousheng; Pei, Bo; Zhu, Xiao

    2014-01-01

    In this work, we demonstrate a facile layer-by-layer (LBL) self-assembly method for controllable preparation of single-, double-, and triple-shelled NiO hollow nanospheres by calcining Ni(OH)2/C precursors formed at different stage. It is observed that the external nanoflakes of the NiO hollow nanospheres are inherited from the Ni(OH)2 precursors organized on the surface of carbon spheres via a self-assembly growth process and the inner shells result from the formation of different Ni(OH)2 layers within the carbon spheres during different preparation cycles. Supercapacitive performance of the three types of NiO hollow nanospheres as active electrode materials has been evaluated by cyclic voltammetry (CV) and galvanostatic charge-discharge. The results indicate that double-shelled NiO hollow nanosphere sample with largest surface area (92.99 m2 g-1) exhibits the best electrochemical properties among the three NiO hollow nanosphere samples. It delivers a high capacitance of 612.5 F g-1 at 0.5 A g-1 and demonstrates a superior long-term cyclic stability, with over 90% specific capacitance retention after 1000 charge-discharge cycles. This excellent performance is ascribed to the short diffusion path and large surface area of the unique hollow structure with nanoflake building blocks for bulk accessibility of faradaic reaction.

  11. Layer-by-Layer Fabrication of High-Performance Polyamide/ZIF-8 Nanocomposite Membrane for Nanofiltration Applications.

    PubMed

    Wang, Luying; Fang, Manquan; Liu, Jing; He, Jing; Li, Jiding; Lei, Jiandu

    2015-11-01

    The conventional blending fabrication for thin-film nanocomposite (TFN) membranes is to disperse porous fillers in aqueous/organic phases prior to interfacial polymerization, and the aggregation of fillers may lead to the significant decrease in membrane performance. To overcome this limitation, we proposed a novel layer-by-layer (LBL) fabrication to prepare a polyamide (PA)/ZIF-8 nanocomposite membrane with a multilayer structure: a porous substrate, a ZIF-8 interlayer, and a PA coating layer. The PA/ZIF-8 (LBL) membrane for nanofiltration applications was prepared by growing an interlayer of ZIF-8 nanoparticles on an ultrafiltration membrane through in situ growth and then coating it with an ultrathin PA layer through interfacial polymerization. The obtained PA/ZIF-8 (LBL) membrane exhibited both better permeance and selectivity than did the conventional PA/ZIF-8 TFN membrane because of the ZIF-8 in situ growth producing a ZIF-8 interlayer with more ZIF-8 nanoparticles but fewer aggregates. Compared with the pure PA membrane (the flux of 11.2 kg/m(2)/h and rejection of 99.6%) for dye removal, the obtained PA/ZIF-8 (LBL) membranes achieved a significant improvement in membrane permeance and selectivity. (Flux was up to 27.1 kg/m(2)/h, and the rejection reaches 99.8%.) This LBL fabrication is a promising methodology for other polymer nanocomposite membranes simultaneously having high permeance and good selectivity. PMID:26485228

  12. Optical and electronic properties of layer-by-layer and composite polyaniline-cadmium selenide quantum dot films

    NASA Astrophysics Data System (ADS)

    Ayub, Ambreen; Shakoor, Abdul; Elahi, Asmat; Rizvi, Tasneem Zahra

    2015-08-01

    Two organic-inorganic hybrid films of intrinsically conducting polymer; polyaniline and cadmium selenide quantum dots were prepared. One by layer-by-layer deposition of polyaniline and cadmium selenide films on PEDOT-PSS/ITO coated glass substrate (ITO/PEDOT-PSS/PANI/CdSe) and other by depositing polyaniline-cadmium selenide quantum dots composite film on the same substrate (ITO/PEDOT-PSS/PANI-CdSe) using spin coating technique. Pure polyaniline, cadmium selenide quantum dots and their composites thus obtained were characterized using X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and UV/VIS/NIR absorption spectroscopy. The surface morphologies were studied by Scanning Electron Microscopy (SEM). The diode performance parameters were compared and contrasted for the two devices obtained by different deposition routes. J-V characteristics of these devices showed a rectifying contact with Al metal, however with variation in performance parameters like barrier height, ideality factor and reverse saturation current the ITO/PEDOT-PSS/PANI-CdSe/Al device exhibited better diode performance as compared to ITO/PEDOT-PSS/PANI/CdSe/Al device.

  13. Intracellular interactions of electrostatically mediated layer-by-layer assembled polyelectrolytes based sorafenib nanoparticles in oral cancer cells.

    PubMed

    Poojari, Radhika; Kini, Sudarshan; Srivastava, Rohit; Panda, Dulal

    2016-07-01

    In this paper, we report the preparation of LbL-nanoSraf (100-300nm) comprising of layer-by-layer (LbL) assembled polyelectrolytes dextran-sulfate/poly-l-arginine, with a multikinase inhibitor sorafenib (Sraf) encapsulated calcium carbonate (CaCO3) nanoparticles for oral cancer therapy in vitro. The zeta potential of LbL-nanoSraf exhibited a negative charge of the polyanionic dextran sulfate, which alternated with a positive charge of polycationic poly-l-arginine indicating a successful LbL assembly of the two polyelectrolyte bilayers on the CaCO3 nanoparticles. The LbL-nanoSraf exhibited an encapsulation efficiency of 61±4%. The LbL-nanoSraf was characterized using field-emission gun scanning electron microscopy, X-ray powder diffraction, atomic force microscopy and confocal laser scanning microscopy. Confocal laser scanning microscopy, flow cytometry and transmission electron microscopic investigations showed the internalization of LbL-nanoSraf in human oral cancer (KB) cells. The LbL-nanoSraf exhibited more potent antiproliferative, apoptotic and antimigratory activities in KB cells than the free drug Sraf. The findings could promote the application of nano-sized LbL assembled polyelectrolytes for the delivery of Raf-kinase inhibitors and provide mechanistic insights for oral cancer therapy. PMID:26998875

  14. Mechanically durable, superomniphobic coatings prepared by layer-by-layer technique for self-cleaning and anti-smudge.

    PubMed

    Brown, Philip S; Bhushan, Bharat

    2015-10-15

    Superomniphobic surfaces are of interest for anti-fouling, self-cleaning, anti-smudge and low-drag applications. Many bioinspired surfaces developed previously are of limited use due to a lack of mechanical durability. From a previously developed technique, an adapted layer-by-layer approach involving charged species with electrostatic interactions between layers is combined with an uncharged fluorosilane layer to result in a durable, superomniphobic coating. This technique can provide the flexibility needed to improve adhesion to the substrate with the addition of a low surface tension coating at the air interface. In this work, polyelectrolyte binder, SiO2 nanoparticles, and fluorosilane layers are deposited, providing the combination of surface roughness and low surface tension to result in a superomniphobic coating with droplets of liquids with surface tensions from 72 to 21 mN m(-1) displaying contact angles exceeding 155° with low tilt angles. The durability of these coatings was examined through the use of micro- and macrowear experiments. These coatings currently display levels of transparency acceptable for automotive applications. Fabrication via this novel combination of techniques results in durable, superomniphobic coatings displaying improved performance compared to existing work where either the durability or the repellency is compromised. PMID:26133277

  15. Antiwetting Fabric Produced by a Combination of Layer-by-Layer Assembly and Electrophoretic Deposition of Hydrophobic Nanoparticles.

    PubMed

    Joung, Young Soo; Buie, Cullen R

    2015-09-16

    This work describes a nanoparticle coating method to produce durable antiwetting polyester fabric. Electrophoretic deposition is used for fast modification of polyester fabric with silica nanoparticles embedded in polymeric networks for high durability coatings. Typically, electrophoretic deposition (EPD) is utilized on electrically conductive substrates due to its dependence on an applied electrical field. EPD on nonconductive materials has been attempted but are limited by weak adhesion, cracks, and other irregularities. To resolve these issues, we coat polyester fabric with thin polymer layers using electrostatic self-assembly (layer-by-layer self-assembly). Next, silica nanoparticles are uniformly dispersed on the polymer layers. Finally, polymerically stabilized silica nanoparticles are deposited by EPD on the fabric, followed by heat treatment. The modified fabric shows high static contact angle and low contact angle hysteresis, while keeping its original color, flexibility, and air permeability. During a skin fiction resistance test, the hydrophobicity of the coating layer was maintained over 500 h. Furthermore, we also show that this approach facilitates patterned regions of wettability by modifying the electric field in EPD. PMID:26312560

  16. Incorporation of basic fibroblast growth factor by a layer-by-layer assembly technique to produce bioactive substrates.

    PubMed

    Ma, Lie; Zhou, Jie; Gao, Changyou; Shen, Jiacong

    2007-10-01

    Basic fibroblast growth factor (bFGF) was immobilized onto quartz slides and collagen films by assembly with chondroitin sulfate (CS) in a layer-by-layer (LBL) manner. First, the LBL-deposition process on the amino-silanized quartz slides was monitored by UV-vis spectroscopy and water contact angle measurement. By substituting the normal bFGF with rhodamine-labeled one (Rd-bFGF), a linear increase of the absorbance versus bilayer number was recorded. The water contact angle oscillated between the odd CS and the even bFGF layers, demonstrating the alternating change of the surface chemistry. Scanning force microscopy (SFM) revealed that the surface topography was altered slightly after multilayer assembly. In vitro incubation of the CS/bFGF multilayers in PBS showed that approximately 30% of the incorporated bFGF was released within 8 days. In vitro cell culture found that the fibroblasts showed star-like morphology with plenty of pseudopods on the bFGF-incorporated collagen film after cultured for 1 day, and the collagen films assembled with bFGF possess improved bioactivity than that of the virgin one and the bFGF control. Since the immobilized growth factors can maximally retain their bioactivity, the LBL assembly would be a potential approach to construct a bioactive substrate for biomedical applications. PMID:17385225

  17. Layer-by-layer construction of protein architectures through avidin-biotin and lectin-sugar interactions for biosensor applications.

    PubMed

    Takahashi, Shigehiro; Sato, Katsuhiko; Anzai, Jun-ichi

    2012-02-01

    In this review, the preparation and properties of protein architectures constructed by layer-by-layer (LbL) deposition through avidin-biotin and concanavalin A (Con A)-sugar interactions are discussed in relation to their use for optical and electrochemical biosensors. LbL films can be constructed through the alternate deposition of avidin and biotin-labeled enzymes on the surfaces of optical probes and electrodes. The enzymes retain their catalytic activity, resulting in the formation of optical and electrochemical biosensors. Alternatively, Con A can be used to construct enzyme-containing LbL films and microcapsules using sugar-labeled enzymes. Some enzymes such as glucose oxidase and horseradish peroxidase can be used for this purpose without labeling with sugar, because these enzymes contain intrinsic hydrocarbon chains on their molecular surfaces. The Con A/enzyme LbL architectures were successfully used to develop biosensors sensitive to specific substrates of the enzyme. In addition, Con A-based films can be used for the optical and electrochemical detection of sugars. PMID:21866404

  18. Layer-by-layer coated lipid-polymer hybrid nanoparticles designed for use in anticancer drug delivery.

    PubMed

    Ramasamy, Thiruganesh; Tran, Tuan Hiep; Choi, Ju Yeon; Cho, Hyuk Jun; Kim, Jeong Hwan; Yong, Chul Soon; Choi, Han-Gon; Kim, Jong Oh

    2014-02-15

    Polyelectrolyte multilayers created via sequential adsorption of complimentary materials may be useful in the delivery of small molecules such as anti-cancer drugs. In this study, layer-by-layer (LbL) nanoarchitectures were prepared by step-wise deposition of naturally derived chitosan and hyaluronic acid on negatively charged hybrid solid lipid nanoparticles (SLNs). A doxorubicin/dextran sulfate complex was incorporated into the SLNs. This resulted in the production of spherical nanoparticles ∼ 265 nm in diameter, with a zeta potential of approximately -12 mV. The nanoparticles were physically stable and exhibited controlled doxorubicin (DOX) release kinetics. Further pharmacokinetic manipulations revealed that in comparison with both free DOX and uncoated DOX-loaded SLNs, LbL-functionalized SLNs remarkably enhanced the circulation half-life and decreased the elimination rate of the drug. Cumulatively, our results suggest that this novel LbL-coated system, with a pH-responsive shell and molecularly targeted entities, has the potential to act as a vehicle to deliver medication to targeted tumor regions. PMID:24507332

  19. Water-based preparation of highly oleophobic thin films through aggregation of nanoparticles using layer-by-layer treatment

    NASA Astrophysics Data System (ADS)

    Nishizawa, Shingo; Shiratori, Seimei

    2012-12-01

    The layer-by-layer (LBL) adsorption technique has potential for controlling the surface wettability. In this study, we controlled surface wettability between "superhydrophobic and oleophobic" and "hydrophobic and oleophilic" by LBL process on TiO2 nanoparticle with hydrophobic polymer and hydrophilic polymer. From the cast coating with LBL process on TiO2 nanoparticle, the surface showed "superhydophobic and oleophobic" when the top surface was hydrophobic polymer, on the other hand, the surface showed "hydrophobic and oleophilic" when the top surface was hydrophilic polymer. The LBL process also affected to the structure of TiO2 nanoparticle/polymer composite, and TiO2 nanoparticle were aggregated with polymers in LBL process. In the condition of the aggregated diameter of TiO2 nanoparticle/polymer composite around 10 μm in solution, the oleohobicity of spray coated film was enhanced with its hierarchical structure (static contact angles of rapeseed oil of 150° and hexadecane of 145°) "Superhydrophobic and high oleophobic" surfaces generated from all water-based dispersions are expected for application in technologies that need to avoid organic solvents.

  20. Surface modulation of complex stiffness via layer-by-layer assembly as a facile strategy for selective cell adhesion.

    PubMed

    Chang, Hao; Zhang, He; Hu, Mi; Chen, Xia-chao; Ren, Ke-feng; Wang, Jin-lei; Ji, Jian

    2015-02-01

    In-stent restenosis and thrombosis are the main severe problems that occur after the percutaneous vascular intervention. The competition between endothelial cells (ECs) and smooth muscle cells (SMCs) plays a key role during these pathological changes. The regulation of this competition offers new opportunities to design biomaterials in the cardiovascular fields. Bioactive molecules have been typically employed to increase EC adhesion and thereafter to enhance EC competitiveness; however, this method is associated with limitations from the point of view of practical and industrial applications. Herein, we present an approach to enhance EC competitiveness over that of SMC through the selective EC adhesion, which is achieved by modulating a complex surface stiffness based on the technique of layer-by-layer (LbL) assembly. This complex stiffness can be achieved by regulating the thickness of multilayer films coordinating with a rigid underlying substrate. The selective cell adhesion is attributed to changes in the complex surface stiffness and a different intrinsic property between ECs and SMCs. This study provides a facile and broadly applicable approach for the purpose of the enhancement of EC competitiveness over that of SMC, which has great potential for the development of cell-based functional biomaterials in the cardiovascular field. PMID:26218126

  1. Preparation of very thin superconducting films of Y-Ba-Cu-O by a layer-by-layer resistive evaporation

    NASA Astrophysics Data System (ADS)

    Azoulay, Jacob; Goldschmidt, Dan; Brener, R.

    1989-10-01

    We report here on 1/4 -μm-thick superconducting Y-Ba-Cu-O films, produced by a sequential layer-by-layer deposition of Cu, BaF2, and YF3, utilizing solely resistive evaporation from tungsten boats onto SrTiO3 substrates. The films are composed primarily of quasioriented elongated grains and have, on the average, the correct stoichiometry. A transition onset at 75 K and width of ˜25 K have been observed in these films. The shape of the current-voltage curve indicates that Josephson-coupled weak links limit the transport in these films. However, the magnitude of critical current (3000 A/cm2 at ˜10 K) is larger than that found in bulk ceramic superconductors. The origin of weak links in these films is probably in the regions of contact between the elongated grains. The relatively large critical current density, as compared to regular bulk ceramic superconductors, is presumably related to the quasioriented nature of the film.

  2. Ultrathin Nanotube/Nanowire Electrodes by Spin-Spray Layer-by-Layer Assembly: A Concept for Transparent Energy Storage.

    PubMed

    Gittleson, Forrest S; Hwang, Daniel; Ryu, Won-Hee; Hashmi, Sara M; Hwang, Jonathan; Goh, Tenghooi; Taylor, André D

    2015-10-27

    Fully integrated transparent devices require versatile architectures for energy storage, yet typical battery electrodes are thick (20-100 μm) and composed of optically absorbent materials. Reducing the length scale of active materials, assembling them with a controllable method and minimizing electrode thickness should bring transparent batteries closer to reality. In this work, the rapid and controllable spin-spray layer-by-layer (SSLbL) method is used to generate high quality networks of 1D nanomaterials: single-walled carbon nanotubes (SWNT) and vanadium pentoxide (V2O5) nanowires for anode and cathode electrodes, respectively. These ultrathin films, deposited with ∼2 nm/bilayer precision are transparent when deposited on a transparent substrate (>87% transmittance) and electrochemically active in Li-ion cells. SSLbL-assembled ultrathin SWNT anodes and V2O5 cathodes exhibit reversible lithiation capacities of 23 and 7 μAh/cm(2), respectively at a current density of 5 μA/cm(2). When these electrodes are combined in a full cell, they retain ∼5 μAh/cm(2) capacity over 100 cycles, equivalent to the prelithiation capacity of the limiting V2O5 cathode. The SSLbL technique employed here to generate functional thin films is uniquely suited to the generation of transparent electrodes and offers a compelling path to realize the potential of fully integrated transparent devices. PMID:26344174

  3. Rapid electrostatics-assisted layer-by-layer assembly of near-infrared-active colloidal photonic crystals.

    PubMed

    Askar, Khalid; Leo, Sin-Yen; Xu, Can; Liu, Danielle; Jiang, Peng

    2016-11-15

    Here we report a rapid and scalable bottom-up technique for layer-by-layer (LBL) assembling near-infrared-active colloidal photonic crystals consisting of large (⩾1μm) silica microspheres. By combining a new electrostatics-assisted colloidal transferring approach with spontaneous colloidal crystallization at an air/water interface, we have demonstrated that the crystal transfer speed of traditional Langmuir-Blodgett-based colloidal assembly technologies can be enhanced by nearly 2 orders of magnitude. Importantly, the crystalline quality of the resultant photonic crystals is not compromised by this rapid colloidal assembly approach. They exhibit thickness-dependent near-infrared stop bands and well-defined Fabry-Perot fringes in the specular transmission and reflection spectra, which match well with the theoretical calculations using a scalar-wave approximation model and Fabry-Perot analysis. This simple yet scalable bottom-up technology can significantly improve the throughput in assembling large-area, multilayer colloidal crystals, which are of great technological importance in a variety of optical and non-optical applications ranging from all-optical integrated circuits to tissue engineering. PMID:27494632

  4. The inactivation of Staphylococcus aureus biofilms using low-power argon plasma in a layer-by-layer approach

    PubMed Central

    Traba, Christian; Liang, Jun F.

    2014-01-01

    The direct application of low power argon plasma for the decontamination of pre-formed Staphylococcus aureus biofilms on various surfaces was examined. Distinct chemical/physical properties of reactive species found in argon plasmas generated at different wattages all demonstrated very potent but very different anti-biofilm mechanisms of action. An in depth analysis of results showed that: (1) the different reactive species produced in each plasma demonstrated specific antibacterial and/or anti-biofilm activity, and 2) the commonly associated etching effect could be manipulated and even controlled, depending on experimental conditions. Under optimal experimental parameters, bacterial cells in S. aureus biofilms were killed (>99.9%) by plasmas within 10 min of exposure and no bacteria nor biofilm re-growth from argon discharge gas treated biofilms was observed for 150 h. The decontamination ability of plasmas for the treatment of biofilm related contaminations on various materials was confirmed and an entirely novel layer-by-layer decontamination approach was designed and examined. PMID:25569189

  5. Synthesis of antireflective silica coatings through the synergy of polypeptide layer-by-layer assemblies and biomineralization.

    PubMed

    Lee, Yung-Lun; Lin, Ting-Xuan; Hsu, Feng-Ming; Jan, Jeng-Shiung

    2016-01-28

    We report a versatile approach to synthesize silica coatings with antireflective (AR) characteristics through the combination of a layer-by-layer (LbL) assembly technique and biomineralization. LbL assembled decanoyl-modified poly(l-lysine)/poly(l-glutamic acid) (PLL-g-Dec/PLGA) multilayer films were used as templates for silica mineralization, followed by calcination. The specific deposition of silica onto the LbL polypeptide assemblies through amine-catalyzed polycondensation resulted in silica coatings that exhibited the transcription of the nano-/microstructured polypeptide films and their film thickness and porosity can be tuned by varying the number of bilayers, degree of substitution, and PLL molecular weight. AR silica coatings exhibiting more than 6% increase in transmittance in the near UV/visible spectral range can be obtained at an optimized refractive index, thickness, and surface roughness. The abrasion test showed that the silica coatings exhibited sufficient structural durability due to continuous silica nanostructures and low surface roughness. This study demonstrated that nanostructured thin films can be synthesized for AR coatings using the synergy between the LbL assembly technique and biomineralization. PMID:26752150

  6. Fabrication of hybrid graphene oxide/polyelectrolyte capsules by means of layer-by-layer assembly on erythrocyte cell templates

    PubMed Central

    Irigoyen, Joseba; Politakos, Nikolaos; Diamanti, Eleftheria; Rojas, Elena; Marradi, Marco; Ledezma, Raquel; Arizmendi, Layza; Rodríguez, J Alberto; Ziolo, Ronald F

    2015-01-01

    Summary A novel and facile method was developed to produce hybrid graphene oxide (GO)–polyelectrolyte (PE) capsules using erythrocyte cells as templates. The capsules are easily produced through the layer-by-layer technique using alternating polyelectrolyte layers and GO sheets. The amount of GO and therefore its coverage in the resulting capsules can be tuned by adjusting the concentration of the GO dispersion during the assembly. The capsules retain the approximate shape and size of the erythrocyte template after the latter is totally removed by oxidation with NaOCl in water. The PE/GO capsules maintain their integrity and can be placed or located on other surfaces such as in a device. When the capsules are dried in air, they collapse to form a film that is approximately twice the thickness of the capsule membrane. AFM images in the present study suggest a film thickness of approx. 30 nm for the capsules in the collapsed state implying a thickness of approx. 15 nm for the layers in the collapsed capsule membrane. The polyelectrolytes used in the present study were polyallylamine hydrochloride (PAH) and polystyrenesulfonate sodium salt (PSS). Capsules where characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light scattering (DLS) and Raman microscopy, the constituent layers by zeta potential and GO by TEM, XRD, and Raman and FTIR spectroscopies. PMID:26734521

  7. Layer-by-Layer Deposition with Polymers Containing Nitrilotriacetate, A Convenient Route to Fabricate Metal- and Protein-Binding Films.

    PubMed

    Wijeratne, Salinda; Liu, Weijing; Dong, Jinlan; Ning, Wenjing; Ratnayake, Nishanka Dilini; Walker, Kevin D; Bruening, Merlin L

    2016-04-27

    This paper describes a convenient synthesis of nitrilotriacetate (NTA)-containing polymers and subsequent layer-by-layer adsorption of these polymers on flat surfaces and in membrane pores. The resulting films form NTA-metal-ion complexes and capture 2-3 mmol of metal ions per mL of film. Moreover, these coatings bind multilayers of polyhistidine-tagged proteins through association with NTA-metal-ion complexes. Inclusion of acrylic acid repeat units in NTA-containing copolymers promotes swelling to increase protein binding in films on Au-coated wafers. Adsorption of NTA-containing films in porous nylon membranes gives materials that capture ∼46 mg of His-tagged ubiquitin per mL. However, the binding capacity decreases with the protein molecular weight. Due to the high affinity of NTA for metal ions, the modified membranes show modest leaching of Ni(2+) in binding and rinsing buffers. Adsorption of NTA-containing polymers is a simple method to create metal- and protein-binding films and may, with future enhancement of stability, facilitate development of disposable membranes that rapidly purify tagged proteins. PMID:27042860

  8. Amperometric glucose biosensor based on layer-by-layer films of microperoxidase-11 and liposome-encapsulated glucose oxidase.

    PubMed

    Graça, J S; de Oliveira, R F; de Moraes, M L; Ferreira, M

    2014-04-01

    An important step in several bioanalytical applications is the immobilization of biomolecules. Accordingly, this procedure must be carefully chosen to preserve their biological structure and fully explore their properties. For this purpose, we combined the versatility of the layer-by-layer (LbL) method for the immobilization of biomolecules with the protective behavior of liposome-encapsulated systems to fabricate a novel amperometric glucose biosensor. To obtain the biosensing unit, an LbL film of the H2O2 catalyst polypeptide microperoxidase-11 (MP-11) was assembled onto an indium-tin oxide (ITO) electrode followed by the deposition of a liposome-encapsulated glucose oxidase (GOx) layer. The biosensor response toward glucose detection showed a sensitivity of 0.91±0.09 (μA/cm2)/mM and a limit of detection (LOD) of 8.6±1.1 μM, demonstrating an improved performance compared to similar biosensors with a single phospholipid-liposome or even containing a non-encapsulated GOx layer. Finally, glucose detection was also performed in a zero-lactose milk sample to demonstrate the potential of the biosensor for food analysis. PMID:24491835

  9. Biological and immunotoxicity evaluation of antimicrobial peptide-loaded coatings using a layer-by-layer process on titanium

    NASA Astrophysics Data System (ADS)

    Shi, Jue; Liu, Yu; Wang, Ying; Zhang, Jing; Zhao, Shifang; Yang, Guoli

    2015-11-01

    The prevention and control of peri-implantitis is a challenge in dental implant surgery. Dental implants with sustained antimicrobial coating are an ideal way of preventing peri-implantitis. This study reports development of a non- immunotoxicity multilayered coating on a titanium surface that had sustained antimicrobial activity and limited early biofilm formation. In this study, the broad spectrum AMP, Tet213, was linked to collagen IV through sulfo-SMPB and has been renamed as AMPCol. The multilayer AMPCol coatings were assembled on smooth titanium surfaces using a LBL technique. Using XPS, AFM, contact angle analysis, and QCM, layer-by-layer accumulation of coating thickness was measured and increased surface wetting compared to controls was confirmed. Non-cytotoxicity to HaCaT and low erythrocyte hemolysis by the AMPCol coatings was observed. In vivo immunotoxicity assays showed IP administration of AMPCol did not effect serum immunoglobulin levels. This coating with controlled release of AMP decreased the growth of both a Gram-positive aerobe (Staphylococcus aureus) and a Gram-negative anaerobe (Porphyromonas gingivalis) up to one month. Early S. aureus biofilm formation was inhibited by the coating. The excellent long-term sustained antimicrobial activity of this multilayer coating is a potential method for preventing peri-implantitis through coated on the neck of implants before surgery.

  10. Thickness dependence of curvature, strain, and response time in ionic electroactive polymer actuators fabricated via layer-by-layer assembly

    NASA Astrophysics Data System (ADS)

    Montazami, Reza; Liu, Sheng; Liu, Yang; Wang, Dong; Zhang, Qiming; Heflin, James R.

    2011-05-01

    Ionic electroactive polymer (IEAP) actuators containing porous conductive network composites (CNCs) and ionic liquids can result in high strain and fast response times. Incorporation of spherical gold nanoparticles in the CNC enhances conductivity and porosity, while maintaining relatively small thickness. This leads to improved mechanical strain and bending curvature of the actuators. We have employed the layer-by-layer self-assembly technique to fabricate a CNC with enhanced curvature (0.43 mm-1) and large net intrinsic strain (6.1%). The results demonstrate that curvature and net strain of IEAP actuators due to motion of the anions increase linearly with the thickness of the CNC as a result of the increased volume in which the anions can be stored. In addition, after subtracting the curvature of a bare Nafion actuator without a CNC, it is found that the net intrinsic strain of the CNC layer is independent of thickness for the range of 20-80 nm, indicating that the entire CNC volume contributes equivalently to the actuator motion. Furthermore, the response time of the actuator due to anion motion is independent of CNC thickness, suggesting that traversal through the Nafion membrane is the limiting factor in the anion motion.

  11. Improvement of the surface wettability of silicone hydrogel contact lenses via layer-by-layer self-assembly technique.

    PubMed

    Lin, Chien-Hong; Cho, Hsien-Lung; Yeh, Yi-Hsing; Yang, Ming-Chien

    2015-12-01

    The surface wettability and anti-protein adsorption of a silicone-based hydrogel that was synthesized by a block copolymer of polydimethylsiloxane (PDMS) and poly (ethylene glycol) methacrylate (PEGMA) was improved via polyelectrolyte multilayer (PEM) immobilization. Polysaccharide PEMs of chitosan (CS, as a positive-charged agent) and hyaluronic acid (HA, as a negative-charged and anti-adhesive agent) were successfully assembled on the PDMS-PU-PEGMA silicone hydrogel in a layer-by-layer (LBL) self-assembly manner. Atomic force microscopy (AFM) and dyeing data verified the progressive buildup of the PEM silicone hydrogel. The results showed that the contact angle of the silicone hydrogel decreased with an increase in the number of PEM grafting layers. Furthermore, after immobilizing five layers of CS/HA, the protein adsorption decreased from 78 ± 11 to 26 ± 4 μg/cm(2) for HSA and from 55 ± 10 to 20 ± 4 μg/cm(2) for lysozymes. This indicates that CS/HA PEM-immobilized silicone hydrogels can resist protein adsorption. Furthermore, these hydrogels were non-cytotoxic according to an in vitro L929 fibroblast assay. Overall, the results demonstrated that the modified silicone hydrogels exhibited hydrophilicity and anti-protein adsorption, as well as relatively high oxygen permeability and optical transparency. Therefore, they would be applicable as a contact lens material. PMID:26519935

  12. Improved and targeted delivery of bioactive molecules to cells with magnetic layer-by-layer assembled microcapsules

    NASA Astrophysics Data System (ADS)

    Pavlov, Anton M.; Gabriel, Samantha A.; Sukhorukov, Gleb B.; Gould, David J.

    2015-05-01

    Despite our increasing knowledge of cell biology and the recognition of an increasing repertoire of druggable intracellular therapeutic targets, there remain a limited number of approaches to deliver bioactive molecules to cells and even fewer that enable targeted delivery. Layer-by-layer (LbL) microcapsules are assembled using alternate layers of oppositely charged molecules and are potential cell delivery vehicles for applications in nanomedicine. There are a wide variety of charged molecules that can be included in the microcapsule structure including metal nanoparticles that introduce physical attributes. Delivery of bioactive molecules to cells with LbL microcapsules has recently been demonstrated, so in this study we explore the delivery of bioactive molecules (luciferase enzyme and plasmid DNA) to cells using biodegradable microcapsules containing a layer of magnetite nanoparticles. Interestingly, significantly improved intracellular luciferase enzyme activity (25 fold) and increased transfection efficiency with plasmid DNA (3.4 fold) was observed with magnetic microcapsules. The use of a neodymium magnet enabled efficient targeting of magnetic microcapsules which further improved the delivery efficiency of the cargoes as a consequence of increased microcapsule concentration at the magnetic site. Microcapsules were well tolerated by cells in these experiments and only displayed signs of toxicity at a capsule : cell ratio of 100 : 1 and with extended exposure. These studies illustrate how multi-functionalization of LbL microcapsules can improve and target delivery of bioactive molecules to cells.

  13. A comparative study of two different approaches for the incorporation of silver nanoparticles into layer-by-layer films

    PubMed Central

    2014-01-01

    In this work, a comparative study about the incorporation of silver nanoparticles (AgNPs) into thin films is presented using two alternative methods, the in situ synthesis process and the layer-by-layer embedding deposition technique. The influence of several parameters such as color of the films, thickness evolution, thermal post-treatment, or distribution of the AgNPs along the coatings has been studied. Thermal post-treatment was used to induce the formation of hydrogel-like AgNPs-loaded thin films. Cross-sectional transmission electron microscopy micrographs, atomic force microscopy images, and UV-vis spectra reveal significant differences in the size and distribution of the AgNPs into the films as well as the maximal absorbance and wavelength position of the localized surface plasmon resonance absorption bands before and after thermal post-treatment. This work contributes for a better understanding of these two approaches for the incorporation of AgNPs into thin films using wet chemistry. PMID:24982607

  14. Layer-by-layer carbon nanotube bio-templates for in situ monitoring of the metabolic activity of nitrifying bacteria

    NASA Astrophysics Data System (ADS)

    Loh, Kenneth J.; Guest, Jeremy S.; Ho, Genevieve; Lynch, Jerome P.; Love, Nancy G.

    2009-03-01

    Despite the wide variety of effective disinfection and wastewater treatment techniques for removing organic and inorganic wastes, pollutants such as nitrogen remain in wastewater effluents. If left untreated, these nitrogenous wastes can adversely impact the environment by promoting the overgrowth of aquatic plants, depleting dissolved oxygen, and causing eutrophication. Although nitrification/denitrification processes are employed during advanced wastewater treatment, effective and efficient operation of these facilities require information of the pH, dissolved oxygen content, among many other parameters, of the wastewater effluent. In this preliminary study, a biocompatible CNT-based nanocomposite is proposed and validated for monitoring the biological metabolic activity of nitrifying bacteria in wastewater effluent environments (i.e., to monitor the nitrification process). Using carbon nanotubes and a pH-sensitive conductive polymer (i.e., poly(aniline) emeraldine base), a layer-by-layer fabrication technique is employed to fabricate a novel thin film pH sensor that changes its electrical properties in response to variations in ambient pH environments. Laboratory studies are conducted to evaluate the proposed nanocomposite's biocompatibility with wastewater effluent environments and its pH sensing performance.

  15. Reagentless biosensor based on layer-by-layer assembly of functional multiwall carbon nanotubes and enzyme-mediator biocomposite*

    PubMed Central

    Zhou, Xing-hua; Xi, Feng-na; Zhang, Yi-ming; Lin, Xian-fu

    2011-01-01

    A simple and controllable layer-by-layer (LBL) assembly method was proposed for the construction of reagentless biosensors based on electrostatic interaction between functional multiwall carbon nanotubes (MWNTs) and enzyme-mediator biocomposites. The carboxylated MWNTs were wrapped with polycations poly(allylamine hydrochloride) (PAH) and the resulting PAH-MWNTs were well dispersed and positively charged. As a water-soluble dye methylene blue (MB) could mix well with horseradish peroxidase (HRP) to form a biocompatible and negatively-charged HRP-MB biocomposite. A (PAH-MWNTs/HRP-MB)n bionanomultilayer was then prepared by electrostatic LBL assembly of PAH-MWNTs and HRP-MB on a polyelectrolyte precursor film-modified Au electrode. Due to the excellent biocompatibility of HRP-MB biocomposite and the uniform LBL assembly, the immobilized HRP could retain its natural bioactivity and MB could efficiently shuttle electrons between HRP and the electrode. The incorporation of MWNTs in the bionanomultilayer enhanced the surface coverage concentration of the electroactive enzyme and increased the catalytic current response of the electrode. The proposed biosensor displayed a fast response (2 s) to hydrogen peroxide with a low detection limit of 2.0×10−7 mol/L (S/N=3). This work provided a versatile platform in the further development of reagentless biosensors. PMID:21634040

  16. A Stimuli-Responsive Biosensor of Glucose on Layer-by-Layer Films Assembled through Specific Lectin-Glycoenzyme Recognition.

    PubMed

    Yao, Huiqin; Gan, Qianqian; Peng, Juan; Huang, Shan; Zhu, Meilin; Shi, Keren

    2016-01-01

    The research on intelligent bioelectrocatalysis based on stimuli-responsive materials or interfaces is of great significance for biosensors and other bioelectronic devices. In the present work, lectin protein concanavalin A (Con A) and glycoenzyme glucose oxidase (GOD) were assembled into {Con A/GOD}n layer-by-layer (LbL) films by taking advantage of the biospecific lectin-glycoenzyme affinity between them. These film electrodes possess stimuli-responsive properties toward electroactive probes such as ferrocenedicarboxylic acid (Fc(COOH)₂) by modulating the surrounding pH. The CV peak currents of Fc(COOH)₂ were quite large at pH 4.0 but significantly suppressed at pH 8.0, demonstrating reversible stimuli-responsive on-off behavior. The mechanism of stimuli-responsive property of the films was explored by comparative experiments and attributed to the different electrostatic interaction between the films and the probes at different pH. This stimuli-responsive films could be used to realize active/inactive electrocatalytic oxidation of glucose by GOD in the films and mediated by Fc(COOH)₂ in solution, which may establish a foundation for fabricating novel stimuli-responsive electrochemical biosensors based on bioelectrocatalysis with immobilized enzymes. PMID:27104542

  17. Layer-by-layer assembled films of multi-walled carbon nanotubes with chitosan and cellulose nanocrystals.

    PubMed

    Trigueiro, João Paulo Campos; Silva, Glaura Goulart; Pereira, Fabiano Vargas; Lavall, Rodrigo Lassarote

    2014-10-15

    Chitosan solutions and cellulose nanocrystal suspensions were used to produce highly stable aqueous dispersions of multi-walled carbon nanotubes (MWCNTs). The different MWCNT dispersions, presenting positive and negative charges, were used to prepare multilayered hybrid thin films through electrostatic layer-by-layer (LBL) self-assembly. The MWCNTs are well dispersed and homogeneously distributed on each layer of chitosan and cellulose nanocrystals of the films. The nanotubes are densely packed in each multilayer, forming a random network. The surface of the LBL film exhibited a uniform and relatively smooth surface with a mean roughness value of ∼5.8±0.4nm. Electrochemical characterization revealed a decrease in two orders of magnitude in the film resistance as the number of bilayers increased from 5 to 20, which is a consequence of an increase in the amount of conductive material (MWCNT). The thin films with up to 20 bilayers exhibited transmittance higher than 90% in the visible range. The results presented in this work demonstrate the viability of the LBL technique for the deposition of active materials using the biopolymer pair chitosan/cellulose nanocrystals. The obtained films can be employed for the design of transparent and biocompatible carbon nanostructured based electrodes. PMID:25086396

  18. Layer-by-layer assembly of multifunctional porous N-doped carbon nanotube hybrid architectures for flexible conductors and beyond.

    PubMed

    Zhao, Songfang; Gao, Yongju; Li, Jinhui; Zhang, Guoping; Zhi, Chunyi; Deng, Libo; Sun, Rong; Wong, Ching-Ping

    2015-04-01

    Coassemble diverse functional nanomaterials with carbon nanotubes (CNTs) to form three-dimensional (3D) porous CNTs hybrid architectures (CHAs) are potentially desirable for applications in energy storage, flexible conductors, and catalysis, because of diverse functionalities and synergistic effects in the CHAs. Herein, we report a scalable strategy to incorporate various functional nanomaterials with N-doped CNTs (N-CNTs) into such 3D porous CHAs on the polyurethane (PU) sponge skeletons via layer-by-layer (LbL) assembly. To investigate their properties and applications, the specific CHAs based on N-CNTs and Ag nanoparticles (NPs), denoted as PU-(N-CNTs/Ag NPs)n, are developed. The unique binary structure enables these specific CHAs conductors to possess reliable mechanical and electrical performance under various elastic deformations as well as excellent hydrophilicity. Moreover, they are employed as strain-gauge sensor and heterogeneous catalyst, respectively. The sensor could detect continuous signal, static signal, and pulse signal with superior sustainability and reversibility, indicating an important branch of electromechanical devices. Furthermore, the synergistic effects among N-CNTs, Ag NPs, and porous structure endow the CHAs with excellent performance in catalysis. We have a great expectation that LbL assembly can afford a universal route for incorporating diverse functional materials into one structure. PMID:25749434

  19. A Stimuli-Responsive Biosensor of Glucose on Layer-by-Layer Films Assembled through Specific Lectin-Glycoenzyme Recognition

    PubMed Central

    Yao, Huiqin; Gan, Qianqian; Peng, Juan; Huang, Shan; Zhu, Meilin; Shi, Keren

    2016-01-01

    The research on intelligent bioelectrocatalysis based on stimuli-responsive materials or interfaces is of great significance for biosensors and other bioelectronic devices. In the present work, lectin protein concanavalin A (Con A) and glycoenzyme glucose oxidase (GOD) were assembled into {Con A/GOD}n layer-by-layer (LbL) films by taking advantage of the biospecific lectin-glycoenzyme affinity between them. These film electrodes possess stimuli-responsive properties toward electroactive probes such as ferrocenedicarboxylic acid (Fc(COOH)2) by modulating the surrounding pH. The CV peak currents of Fc(COOH)2 were quite large at pH 4.0 but significantly suppressed at pH 8.0, demonstrating reversible stimuli-responsive on-off behavior. The mechanism of stimuli-responsive property of the films was explored by comparative experiments and attributed to the different electrostatic interaction between the films and the probes at different pH. This stimuli-responsive films could be used to realize active/inactive electrocatalytic oxidation of glucose by GOD in the films and mediated by Fc(COOH)2 in solution, which may establish a foundation for fabricating novel stimuli-responsive electrochemical biosensors based on bioelectrocatalysis with immobilized enzymes. PMID:27104542

  20. Layer-by-layer modification of high surface curvature nanoparticles with weak polyelectrolytes using a multiphase solvent precipitation process.

    PubMed

    Nagaraja, Ashvin T; You, Yil-Hwan; Choi, Jeong-Wan; Hwang, Jin-Ha; Meissner, Kenith E; McShane, Michael J

    2016-03-15

    The layer-by-layer modification of ≈5 nm mercaptocarboxylic acid stabilized gold nanoparticles was studied in an effort to illustrate effective means to overcome practical issues in handling and performing surface modification of such extremely small materials. To accomplish this, each layer deposition cycle was separated into a multi-step process wherein solution pH was controlled in two distinct phases of polyelectrolyte adsorption and centrifugation. Additionally, a solvent precipitation step was introduced to make processing more amenable by concentrating the sample and exchanging solution pH before ultracentrifugation. The pH-dependent assembly on gold nanoparticles was assessed after each layer deposition cycle by monitoring the plasmon peak absorbance location, surface charge, and the percentage of nanoparticles recovered. The selection of solution pH during the adsorption phase was found to be a critical parameter to enhance particle recovery and maximize surface charge when coating with weak polyelectrolytes. One bilayer was deposited with a high yield and the modified particles exhibited enhanced colloidal stability across a broad pH range and increased ionic strength. These findings support the adoption of this multi-step processing approach as an effective and generalizable approach to improve stability of high surface curvature particles. PMID:26771506

  1. Enzymatic Catalysis Combining the Breath Figures and Layer-by-Layer Techniques: Toward the Design of Microreactors.

    PubMed

    De León, A S; Garnier, T; Jierry, L; Boulmedais, F; Muñoz-Bonilla, A; Rodríguez-Hernández, J

    2015-06-10

    Herein, we report the fabrication of microstructured porous surfaces with controlled enzymatic activity by combining the breath figures and the layer-by-layer techniques. Two different types of porous surfaces were designed based on fluorinated and carboxylated copolymers in combination with PS, using poly(2,3,4,5,6-pentafluorostyrene)-b-polystyrene (PS5F31-b-PS21) and polystyrene-b-poly(acrylic acid) (PS19-b-PAA10) block copolymers, respectively. For comparative purposes, flat surfaces having similar chemistry were obtained by spin-coating. Poly(sodium 4-styrenesulfonate)/poly(allylamine hydrochloride) (PSS/PAH) multilayers incorporating alkaline phosphatase (ALP) were built on these porous surfaces to localize the enzyme both inside and outside of the pores using PS/PS5F31-b-PS21 surfaces and only inside the pores on PS/PS19-b-PAA10 surfaces. A higher catalytic activity of ALP (about three times) was obtained with porous surfaces compared to the flat ones. The catalysis happens specifically inside the holes of PS/PS19-b-PAA10surfaces, where ALP is located. This opens the route for applications in microreactors. PMID:25984795

  2. Analysis of layer-by-layer thin-film oxide growth using RHEED and Atomic Force Microscopy

    NASA Astrophysics Data System (ADS)

    Adler, Eli; Sullivan, M. C.; Gutierrez-Llorente, Araceli; Joress, H.; Woll, A.; Brock, J. D.

    2015-03-01

    Reflection high energy electron diffraction (RHEED) is commonly used as an in situ analysis tool for layer-by-layer thin-film growth. Atomic force microscopy is an equally common ex situ tool for analysis of the film surface, providing visual evidence of the surface morphology. During growth, the RHEED intensity oscillates as the film surface changes in roughness. It is often assumed that the maxima of the RHEED oscillations signify a complete layer, however, the oscillations in oxide systems can be misleading. Thus, using only the RHEED maxima is insufficient. X-ray reflectivity can also be used to analyze growth, as the intensity oscillates in phase with the smoothness of the surface. Using x-ray reflectivity to determine the thin film layer deposition, we grew three films where the x-ray and RHEED oscillations were nearly exactly out of phase and halted deposition at different points in the growth. Pre-growth and post-growth AFM images emphasize the fact that the maxima in RHEED are not a justification for determining layer completion. Work conducted at the Cornell High Energy Synchrotron Source (CHESS) supported by NSF Awards DMR-1332208 and DMR-0936384 and the Cornell Center for Materials Research Shared Facilities are supported through DMR-1120296.

  3. Stabilization of starch-based microgel-lysozyme complexes using a layer-by-layer assembly technique.

    PubMed

    Zhang, Bao; Pan, Yi; Chen, Hanqing; Liu, Tengfei; Tao, Han; Tian, Yaoqi

    2017-01-01

    The layer-by-layer assembly of polyelectrolyte multilayers of chitosan (CS) and carboxymethyl starch (CMS) on soft and porous pH- and ionic strength-response microgels was determined by confocal laser scanning microscopy (CLSM) and zeta potential measurements. In vitro release of lysozyme from the stabilized microgels under simulated gastric and intestinal fluids was also investigated. The distribution of CS in the microgels was identified by CLSM, and the optimal molecular weight of CS was 100kDa, which could only be absorbed on the microgel surface. The CS was used as the first layer, while the CMS was used as the second layer, and the zeta potential revealed that the optimal weight ratios of CS and CMS to microgels in the complexes were 0.1 and 0.06, respectively. The in vitro release experiments suggested that the stabilized double-layer microgel complexes could potentially be applied as a carrier system to prevent early release in the stomach to target intestinal delivery. PMID:27507468

  4. Advanced fibroblast proliferation inhibition for biocompatible coating by electrostatic layer-by-layer assemblies of heparin and chitosan derivatives.

    PubMed

    Follmann, Heveline D M; Naves, Alliny F; Martins, Alessandro F; Félix, Olivier; Decher, Gero; Muniz, Edvani C; Silva, Rafael

    2016-07-15

    Heparin and different chitosan derivatives were applied to produce stable electrostatic layer-by-layer assemblies and further used as coating technique to inhibit natural inflammatory response to implants. Heparin was assembled with chitosan and N-methylated chitosan derivatives, namely N,N-dimethyl chitosan (DMC) and N,N,N-trimethyl chitosan (TMC), by dipping method. DMC and TMC (chitosan derivatives) were synthesized and characterized before LbL assembly. Ellipsometry, quartz crystal microbalance (QCM-D), and contact angle were used to demonstrate the deposition of polyelectrolyte multilayers onto silicon wafers using polyelectrolyte solutions with different ionic strength. The biological properties of these films were evaluated by cell culture assays using NIH/3T3 fibroblast cells. LbL assemblies of Heparin and chitosan derivatives showed to be biocompatible, and at the same time they strongly hinder the proliferation speed of fibroblasts up to 40-fold factors. Therefore, the multilayers prepared from heparin and chitosan derivatives have good features to be used as an alternative coating treatment for biomedical implants with reduced body rejection properties. PMID:27089015

  5. Layer-by-Layer assembled growth factor reservoirs for steering the response of 3T3-cells.

    PubMed

    Naves, Alliny F; Motay, Marvin; Mérindol, Rémi; Davi, Christiane P; Felix, Olivier; Catalani, Luiz H; Decher, Gero

    2016-03-01

    Layer-by-Layer (LbL) assemblies of heparin (Hep) and chitosan (Chi) were prepared for use as reservoirs for acidic and basic fibroblast growth factors (aFGFs and bFGFs, respectively). The effects of the architecture and composition of the reservoirs on the viability and proliferation of NIH-3T3 fibroblast cells were studied under starvation conditions. The reservoir stability was monitored by ellipsometry. The aFGF and bFGF loadings were determined using a dissipation-enhanced quartz crystal microbalance (QCM-D). Stability and release assays were performed in a phosphate buffer at physiological conditions. The results demonstrated that the amount of aFGF and bFGF loaded into and released from LbL reservoirs composed of 3 and 6 layer pairs could be controlled. Cell culture assays in low serum culture medium (LSCM) demonstrated that incorporating very small amounts of aFGF and bFGF into the (Hep/Chi)n multilayers significantly improved the proliferation of the NIH-3T3 fibroblasts. The cells did not proliferate on (Hep/Chi)n assemblies prepared in the absence of FGF under identical conditions. The LbL reservoirs were highly effective for the long-term storage (up to 9 months) of aFGF and bFGF. This work demonstrates the potential of LbL reservoirs for use as biomaterial coatings. PMID:26700236

  6. Novel Polymer Nanocomposites Resulted from Melt Processing of Polystyrene-Based Substrates Coated with Layer-by-Layer Assemblies

    NASA Astrophysics Data System (ADS)

    Soltani, Iman; Spontak, Richard J.

    The novel polymer nanocomposites (PNCs) prepared through two steps of coating polystyrene-based substrates with layer-by-layer (LBL) deposition of montmorillonite and alternative polyelectrolyte layers of polyethyleneimine and polyethylene terephthalate ionomer, followed by their cyclic melt pressing, demonstrated particular morphologies. Transmission electron microscopy images at high magnification scales showed the occurrence of swollen intercalation and flocculated exfoliations of clay platelets, down to a few nanometer thickness, inside and sometimes out of LBL assemblies crushed portions. In fact, intercalation and exfoliation of clay platelets, established in LBL assemblies, increased by shear applied through their repetitive melt pressing. Additionally, x-ray diffractometry traces confirmed the aforementioned increase in clay intercalation. These high aspect ratio LBL assemblies portions formed highly tortuous labyrinths, which may work as scavenging centers to promote barrier properties of the PNCs against transport of gases like oxygen and carbon dioxide. It is despite spontaneously low interaction between hydrophobic styrenic groups and almost hydrophilic natural clay and moderate efficiency of cyclic pressing for providing intensive shear stress on samples.

  7. Layer-by-layer assembly of graphene oxide nanosheets on polyamide membranes for durable reverse-osmosis applications.

    PubMed

    Choi, Wansuk; Choi, Jungkyu; Bang, Joona; Lee, Jung-Hyun

    2013-12-11

    Improving membrane durability associated with fouling and chlorine resistance remains one of the major challenges in desalination membrane technology. Here, we demonstrate that attractive features of graphene oxide (GO) nanosheets such as high hydrophilicity, chemical robustness, and ultrafast water permeation can be harnessed for a dual-action barrier coating layer that enhances resistance to both fouling and chlorine-induced degradation of polyamide (PA) thin-film composite (TFC) membranes while preserving their separation performance. GO multilayers were coated on the PA-TFC membrane surfaces via layer-by-layer (LbL) deposition of oppositely charged GO nanosheets. Consequently, it was shown that the conformal GO coating layer can increase the surface hydrophilicity and reduce the surface roughness, leading to the significantly improved antifouling performance against a protein foulant. It was also demonstrated that the chemically inert nature of GO nanosheets enables the GO coating layer to act as a chlorine barrier for the underlying PA membrane, resulting in a profound suppression of the membrane degradation in salt rejection upon chlorine exposure. PMID:24219033

  8. Comparative study of layer-by-layer deposition techniques for poly(sodium phosphate) and poly(allylamine hydrochloride)

    PubMed Central

    2013-01-01

    An inorganic short chain polymer, poly(sodium phosphate), PSP, together with poly(allylamine hydrochloride), PAH, is used to fabricate layer-by-layer (LbL) films. The thickness, roughness, contact angle, and optical transmittance of these films are studied depending on three parameters: the precursor solution concentrations (10-3 and 10-4 M), the number of bilayers deposited (20, 40, 60, 80, and 100 bilayers), and the specific technique used for the LbL fabrication (dipping or spraying). In most cases of this experimental study, the roughness of the nanofilms increases with the number of bilayers. This contradicts the basic observations made in standard LbL assemblies where the roughness decreases for thicker coatings. In fact, a wide range of thickness and roughness was achieved by means of adjusting the three parameters mentioned above. For instance, a roughness of 1.23 or 205 nm root mean square was measured for 100 bilayer coatings. Contact angles close to 0 were observed. Moreover, high optical transmittance is also reported, above 90%, for 80 bilayer films fabricated with the 10-4 M solutions. Therefore, these multilayer structures can be used to obtain transparent superhydrophilic surfaces. PMID:24359137

  9. Pushing the Limits: 3D Layer-by-Layer-Assembled Composites for Cathodes with 160 C Discharge Rates.

    PubMed

    Mo, Runwei; Tung, Siu On; Lei, Zhengyu; Zhao, Guangyu; Sun, Kening; Kotov, Nicholas A

    2015-05-26

    Deficiencies of cathode materials severely limit cycling performance and discharge rates of Li batteries. The key problem is that cathode materials must combine multiple properties: high lithium ion intercalation capacity, electrical/ionic conductivity, porosity, and mechanical toughness. Some materials revealed promising characteristics in a subset of these properties, but attaining the entire set of often contrarian characteristics requires new methods of materials engineering. In this paper, we report high surface area 3D composite from reduced graphene oxide loaded with LiFePO4 (LFP) nanoparticles made by layer-by-layer assembly (LBL). High electrical conductivity of the LBL composite is combined with high ionic conductivity, toughness, and low impedance. As a result of such materials properties, reversible lithium storage capacity and Coulombic efficiency were as high as 148 mA h g(-1) and 99%, respectively, after 100 cycles at 1 C. Moreover, these composites enabled unusually high reversible charge-discharge rates up to 160 C with a storage capacity of 56 mA h g(-1), exceeding those of known LFP-based cathodes, some of them by several times while retaining high content of active cathode material. The study demonstrates that LBL-assembled composites enable resolution of difficult materials engineering tasks. PMID:25910177

  10. Design and in vitro evaluation of layer by layer siRNA nanovectors targeting breast tumor initiating cells.

    PubMed

    Jaganathan, Hamsa; Mitra, Sucharita; Srinivasan, Srimeenakshi; Dave, Bhuvanesh; Godin, Biana

    2014-01-01

    Efficient therapeutics and early detection has helped to increase breast cancer survival rates over the years. However, the recurrence of breast cancer remains to be a problem and this may be due to the presence of a small population of cells, called tumor initiating cells (TICs). Breast TICs are resistant to drugs, difficult to detect, and exhibit high self-renewal capabilities. In this study, layer by layer (LBL) small interfering RNA (siRNA) nanovectors (SNVs) were designed to target breast TICs. SNVs were fabricated using alternating layers of poly-L-lysine and siRNA molecules on gold (Au) nanoparticle (NP) surfaces. The stability, cell uptake, and release profile for SNVs were examined. In addition, SNVs reduced TIC-related STAT3 expression levels, CD44+/CD24-/EpCAM+ surface marker levels and the number of mammospheres formed compared to the standard transfection agent. The data from this study show, for the first time, that SNVs in LBL assembly effectively delivers STAT3 siRNA and inhibit the growth of breast TICs in vitro. PMID:24694753

  11. The inactivation of Staphylococcus aureus biofilms using low-power argon plasma in a layer-by-layer approach.

    PubMed

    Traba, Christian; Liang, Jun F

    2015-01-01

    The direct application of low power argon plasma for the decontamination of pre-formed Staphylococcus aureus biofilms on various surfaces was examined. Distinct chemical/physical properties of reactive species found in argon plasmas generated at different wattages all demonstrated very potent but very different anti-biofilm mechanisms of action. An in-depth analysis of the results showed that: (1) the different reactive species produced in each plasma demonstrated specific antibacterial and/or anti-biofilm activity; and (2) the commonly associated etching effect could be manipulated and even controlled, depending on the experimental conditions. Under optimal experimental parameters, bacterial cells in S. aureus biofilms were killed (> 99.9%) by plasmas within 10 min of exposure and no bacteria nor biofilm regrowth from argon discharge gas treated biofilms was observed for 150 h. The decontamination ability of plasmas for the treatment of biofilm related contaminations on various materials was confirmed and an entirely novel layer-by-layer decontamination approach was designed and examined. PMID:25569189

  12. Label-free electrochemical aptasensor constructed by layer-by-layer technology for sensitive and selective detection of cancer cells.

    PubMed

    Wang, Tianshu; Liu, Jiyang; Gu, Xiaoxiao; Li, Dan; Wang, Jin; Wang, Erkang

    2015-07-01

    Here, a cytosensor was constructed with ferrocene-appended poly(allylamine hydrochloride) (Fc-PAH) functionalized graphene (Fc-PAH-G), poly(sodium-p-styrenesulfonate) (PSS) and aptamer (AS1411) by layer-by-layer assembly technology. The hybrid nanocomposite Fc-PAH-G not only brings probes on the electrode and also promotes electron transfer between the probes and the substrate electrode. Meanwhile, LBL technology provides more effective probes to enhance amplified signal for improving the sensitivity of the detection. While AS1411 forming G-quardruplex structure and binding cancer cells, the current response of the sensing electrode decreased due to the insulating properties of cellular membrane. Differential pulse voltammetry (DPV) was performed to investigate the electrochemical detection of HeLa cells attributing to its sensitivity of the current signal change. The as-prepared aptasensor showed a high sensitivity and good stability, a widely detection range from 10 to 10(6) cells/mL with a detection limit as low as 10 cells/mL for the detection of cancer cells. PMID:26043089

  13. Preparation and characterization of an anionic dye-polycation molecular films by electrostatic layer-by-layer adsorption process

    NASA Astrophysics Data System (ADS)

    Dey, D.; Hussain, S. A.; Nath, R. K.; Bhattacharjee, D.

    2008-07-01

    This communication reports the formation and characterization of self-assembled films of a low molecular weight anionic dye amaranth and polycation poly(allylamine hydrochloride) (PAH) by electrostatic alternating layer-by-layer (LBL) adsorption. It was observed that there was almost no material loss occurred during adsorption process. The UV-vis absorption and fluorescence spectra of amaranth solution reveal that with the increase in amaranth concentration in solution, the aggregated species starts to dominate over the monomeric species. New aggregated band at 600 nm was observed in amaranth-PAH mixture solution absorption spectrum. A new broad low intense band at the longer wavelength region, in the amaranth-PAH mixture solution fluorescence spectrum was observed due to the closer association of amaranth molecule while tagged into the polymer backbone of PAH and consequent formation of aggregates. The broad band system in the 650-750 nm region in the fluorescence spectra of different layered LBL films changes in intensity distribution among various bands within itself, with changing layer number and at 10 bilayer LBL films the longer wavelength band at 710 nm becomes prominent. Existence of dimeric or higher order n-meric species in the LBL films was confirmed by excitation spectroscopic studies. Almost 45 min was required to complete the interaction between amaranth and PAH molecules in the one-bilayer LBL film.

  14. Encapsulation of glucose oxidase microparticles within a nanoscale layer-by-layer film: immobilization and biosensor applications.

    PubMed

    Trau, Dieter; Renneberg, Reinhard

    2003-10-15

    We report on an immobilization strategy utilizing layer-by-layer encapsulated microparticles of enzymes within a nanoscale polyelectrolyte film. Encapsulation of glucose oxidase (GOD) microparticles was achieved by the sequential adsorption of oppositely charged polyelectrolytes onto the GOD biocrystal surface. The polyelectrolyte system polyallylamine/polystyrene sulfonate was used under high salt conditions to preserve the solid state of the highly water soluble GOD biocrystals during the encapsulation process. The resulting polymer multilayer capsule of about 15 nm wall thickness is permeable for small molecules (glucose), but non-permeable for macromolecules thus preventing the enzyme from leakage and at the same time shielding it from the outer environment e.g., from protease or microbial activity. Decrease of the buffer salt concentration leads to the dissolution of the enzyme under formation of mu-bioreactors. The spherical mu-bioreactors are bearing an extremely high loading of biocompound per volume. Encapsulated GOD was subsequently used to construct a biosensor by nanoengineered immobilisation of mu-bioreactor capsules onto an electrode surface. The presented approach demonstrates a general method to encapsulate highly soluble solid biomaterials and an immobilization strategy with the potential to create highly active thin and stable films of biomaterial. PMID:12941565

  15. Carbon nanotubes supported cerium dioxide and platinum nanohybrids: Layer-by-layer synthesis and enhanced electrocatalytic activity for methanol oxidation

    NASA Astrophysics Data System (ADS)

    Lou, Xinyuan; Chen, Jiayi; Wang, Mengdi; Gu, Jialei; Wu, Ping; Sun, Dongmei; Tang, Yawen

    2015-08-01

    We successfully synthesize carbon nanotubes (CNTs) supported cerium dioxide and platinum (Pt/CeO2/CNTs) nanohybrids via layer-by-layer assembly. The composition, morphology and structure of the as-prepared Pt/CeO2/CNTs nanohybrids are characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectrometer (EDX), selected-area electron diffraction (SAED), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and inductively coupled plasma atomic emission spectrometry (ICP-AES). By comparison of the electrocatalytic properties of the Pt/CeO2/CNTs with the Pt/CNTs, we systematically investigate the promotion effect of CeO2 on the Pt/CeO2/CNTs catalysts towards methanol oxidation. It is found that the introduction of CeO2 not only enhances the electrocatalytic activity and stability of the Pt/CeO2/CNTs catalyst for methanol oxidation but also minimizes the CO poisoning, probably accounting for the good oxygen carrying capacity of CeO2 and its high stability in acidic solution.

  16. Long-term stability at high temperatures for birefringence in PAZO/PAH layer-by-layer films.

    PubMed

    Ferreira, Quirina; Ribeiro, Paulo A; Oliveira, Osvaldo N; Raposo, Maria

    2012-03-01

    Optical memories with long-term stability at high temperatures have long been pursued in azopolymers with photoinduced birefringence. In this study, we show that the residual birefringence in layer-by-layer (LbL) films made with poly[1-[4-(3-carboxy-4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) alternated with poly(allylamine hydrochloride) (PAH) can be tuned by varying the extent of electrostatic interactions with film fabrication at different pHs for PAH. The dynamics of both writing and relaxation processes could be explained with a two-stage mechanism involving the orientation of the chromophores per se and the chain movement. Upon calculating the activation energies for these processes, we demonstrate semiquantitatively that reduced electrostatic interactions in films prepared at higher pH, for which PAH is less charged, are responsible for the longer stability at high temperatures. This is attributed to orientation of PAZO chromophores via cooperative aggregation, where the presence of counterions hindered relaxation. PMID:22335565

  17. Layer-by-layer assembly of versatile nanoarchitectures with diverse dimensionality: a new perspective for rational construction of multilayer assemblies.

    PubMed

    Xiao, Fang-Xing; Pagliaro, Mario; Xu, Yi-Jun; Liu, Bin

    2016-05-31

    Over the past few decades, layer-by-layer (LbL) assembly of multilayer thin films has garnered considerable interest on account of its ability to modulate nanometer control over film thickness and its extensive choice of usable materials for coating planar and particulate substrates, thus allowing for the fabrication of responsive and functional thin films for their potential applications in a myriad of fields. Herein, we provide elaborate information on the current developments of LbL assembly techniques including different properties, molecular interactions, and assembly methods associated with this promising bottom-up strategy. In particular, we highlight the principle for rational design and fabrication of a large variety of multilayer thin film systems including multi-dimensional capsules or spatially hierarchical nanostructures based on the LbL assembly technique. Moreover, we discuss how to judiciously choose the building block pairs when exerting the LbL assembly buildup which enables the engineering of multilayer thin films with tailor-made physicochemical properties. Furthermore, versatile applications of the diverse LbL-assembled nanomaterials are itemized and elucidated in light of specific technological fields. Finally, we provide a brief perspective and potential future challenges of the LbL assembly technology. It is anticipated that our current review could provide a wealth of guided information on the LbL assembly technique and furnish firm grounds for rational design of LbL assembled multilayer assemblies toward tangible applications. PMID:27003471

  18. Layer-by-layer coating of textile with two oppositely charged cyclodextrin polyelectrolytes for extended drug delivery.

    PubMed

    Junthip, Jatupol; Tabary, Nicolas; Chai, Feng; Leclercq, Laurent; Maton, Mickael; Cazaux, Frederic; Neut, Christel; Paccou, Laurent; Guinet, Yannick; Staelens, Jean-Noel; Bria, Marc; Landy, David; Hédoux, Alain; Blanchemain, Nicolas; Martel, Bernard

    2016-06-01

    The coating of a nonwoven textile by polyelectrolyte multilayer film (PEM) issued from cationic and anionic β-cyclodextrin (βCD) polyelectrolytes according to the layer-by-layer (LbL) technique was successfully attempted. The tert-butyl benzoic acid (TBBA) was used as drug model to evaluate the loading capacity and sustained release properties of this PEM system. The build-up of the multilayer assembly was monitored in situ by optical waveguide lightmode spectroscopy (OWLS) on the one hand, and was assessed by gravimetry on the other hand when applied onto the textile substrate. In parallel, the complexation study of TBBA with both CD polyelectrolytes was also investigated by nuclear magnetic resonance (NMR) and isothermal titration calorimetry (ITC). The influence of thermal crosslinking of the multilayered coating on its stability and on TBBA release kinetics in phosphate buffered saline (PBS) at 37°C was studied. Finally, biological and microbiological tests were performed to investigate the cytocompatibility and the intrisic antibacterial activity of multilayer assemblies. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 1408-1424, 2016. PMID:26833891

  19. Layer-by-Layer Approach to (2+1)D Photonic Crystal Superlattice with Enhanced Crystalline Integrity.

    PubMed

    Zhang, Lijing; Xiong, Zhuo; Shan, Liang; Zheng, Lu; Wei, Tongbo; Yan, Qingfeng

    2015-10-01

    Large-area polystyrene (PS) colloidal monolayers with high mechanical strength are created by a combination of the air/water interface self-assembly and the solvent vapor annealing technique. Layer-by-layer (LBL) stacking of these colloidal monolayers leads to the formation of (2+1)D photonic crystal superlattice with enhanced crystalline integrity. By manipulating the diameter of PS spheres and the repetition period of the colloidal monolayers, flexible control in structure and stop band position of the (2+1)D photonic crystal superlattice has been realized, which may afford new opportunities for engineering photonic bandgap materials. Furthermore, an enhancement of 97.3% on light output power of a GaN-based light emitting diode is demonstrated when such a (2+1)D photonic crystal superlattice employed as a back reflector. The performance enhancement is attributed to the photonic bandgap enhancement and good angle-independence of the (2+1)D photonic crystal superlattice. PMID:26179658

  20. Layer-by-layer immobilized catalase on electrospun nanofibrous mats protects against oxidative stress induced by hydrogen peroxide.

    PubMed

    Huang, Rong; Deng, Hongbing; Cai, Tongjian; Zhan, Yingfei; Wang, Xiankai; Chen, Xuanxuan; Ji, Ailing; Lil, Xueyong

    2014-07-01

    Catalase, a kind of redox enzyme and generally recognized as an efficient agent for protecting cells against hydrogen peroxide (H2O2)-induced cytotoxicity. The immobilization of catalase was accomplished by depositing the positively charged chitosan and the negatively charged catalase on electrospun cellulose nanofibrous mats through electrospining and layer-by-layer (LBL) techniques. The morphology obtained from Field emission scanning electron microscopy (FE-SEM) indicated that more orderly arranged three-dimension (3D) structure and roughness formed with increasing the number of coating bilayers. Besides, the enzyme-immobilized nanofibrous mats were found with high enzyme loading and activity, moreover, X-ray photoelectron spectroscopy (XPS) results further demonstrated the successful immobilization of chitosan and catalase on cellulose nanofibers support. Furthermore, we evaluated the cytotoxicity induced by hydrogen peroxide in the Human umbilical vascular endothelial cells with or without pretreatment of nanofibrous mats by MTT assay, LDH activity and Flow cytometric evaluation, and confirmed the pronounced hydrogen peroxide-induced toxicity, but pretreatment of immobilized catalase reduced the cytotoxicity and protected cells against hydrogen peroxide-induced cytotoxic effects which were further demonstrated by scanning electron microscopy (SEM) and Transmission Electron Microscopy (TEM) images. The data pointed toward a role of catalase-immobilized nanofibrous mats in protecting cells against hydrogen peroxide-induced cellular damage and their potential application in biomedical field. PMID:24804555

  1. Layer-by-layer assembly of electroactive dye/inorganic matrix film and its application as sensor for ascorbic acid.

    PubMed

    Kong, Xianggui; Shi, Wenying; Zhao, Jingwen; Wei, Min; Duan, Xue

    2011-07-15

    A novel inorganic-organic composite ultrathin film was fabricated by layer-by-layer assembly of naphthol green B (NGB) and layered double hydroxides (LDHs) nanoplatelets, which shows remarkable electrocatalytic behavior for oxidation of ascorbic acid. LDHs nanoplatelets were prepared using a method involving separate nucleation and aging steps (particle size: 25±5 nm; aspect ratio: 2-4) and used as building blocks for alternate deposition with NGB on indium tin oxide (ITO) substrates. UV-vis absorption spectroscopy and XRD display regular and uniform growth of the NGB/LDHs ultrathin film with extremely c-orientation of LDHs nanoplatelets (ab plane of microcrystals parallel to substrates). A continuous and uniform surface morphology was observed by SEM and AFM image. The film modified electrode displays a couple of well-defined reversible redox peaks attributed to Fe(2+)/Fe(3+) in NGB (ΔE(p)=68 mV and I(a)/I(c)=1.1). Moreover, the modified electrode shows a high electrocatalytic activity towards ascorbic acid in the range 1.2-55.2 μM with a detection limit of 0.51 μM (S/N=3). The Michaelis-Menten constant was calculated to be K(M)(app)=67.5 μM. PMID:21645731

  2. Silica nanoparticles and polyethyleneimine (PEI)-mediated functionalization: a new method of PEI covalent attachment for siRNA delivery applications.

    PubMed

    Buchman, Yekaterina Kapilov; Lellouche, Emmanuel; Zigdon, Sally; Bechor, Moshe; Michaeli, Shulamit; Lellouche, Jean-Paul

    2013-12-18

    Small-interfering RNA (siRNA) is a synthetic double-stranded RNA that consists of approximately 21 nucleotides (nts). It induces degradation of target mRNAs in a sequence-specific manner by the RNA interference (RNAi) mechanism. Thus, siRNAs offer a potential strategy for silencing mutated or defective genes that cause a variety of human diseases. The main obstacles of harnessing siRNAs as drugs are their inefficient delivery to cells and off-target effect making clinical applications very challenging. To address these issues, researchers have studied a variety of nanocarrier systems for siRNA delivery. This study presents the design, fabrication, and full characterization of innovative polyethyleneimine (PEI)-decorated polycationic 34.2 ± 4.2 nm silica (SiO2) NPs for siRNA-mediated gene silencing. More specifically, a new means of introduction (covalent mode of attachment) of the polycationic 25 kDa PEI polymer onto the SiO2 NP surface has been developed that makes use of an effective electrophilic double Michäel acceptor, divinyl sulfone (DVS). The resulting novel SiO2-PEI nanoparticles (SPEI NPs) have been fully characterized using a wide range of analytical, spectroscopic, and microscopic methods (TEM, DLS, ζ potential, elemental analysis (EA), XPS, TGA, and FTIR). Disclosing quite low cytotoxicity due to this unique mode of PEI covalent grafting, SPEI NPs/siRNA polyplexes have been successfully tested for the induction of gene silencing using dual-reporter luciferase transfected human osteosarcoma U2OS cells. The corresponding gene silencing data showed a clear correlation between PEI/siRNA ratios, siRNA concentration(s), and the level of gene silencing. Moreover, these SPEI NPs have been demonstrated to be thermodynamically stable with an ability to efficiently bind siRNAs and induce silencing for at least a one-year-long storage. PMID:24180511

  3. Insight in layer-by-layer assembly of cysteamine and L-cysteine on the copper surface by electrochemistry and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Song, Ping; Shen, Shu; Li, Chuan-Chuan; Guo, Xiao-Yu; Wen, Ying; Yang, Hai-Feng

    2015-02-01

    In this work, we examined the relationship between the anticorrosion behavior and the structure of the cysteamine/L-cysteine layer-by-layer coating on the copper surface via the self-assembled monolayers (SAMs) technique with electrochemistry and surface-enhanced Raman scattering (SERS) spectroscopy. SERS results elucidated the layer-by-layer adsorption mechanism of cysteamine/L-cysteine at the copper surface. Electrochemical investigations explored the inhibition behavior of cysteamine/L-cysteine for copper from corrosion with a high protection efficiency of 91.4%.

  4. Nickel-phendione complex covalently attached onto carbon nanotube/cross linked glucose dehydrogenase as bioanode for glucose/oxygen compartment-less biofuel cell

    NASA Astrophysics Data System (ADS)

    Korani, Aazam; Salimi, Abdollah; Hadadzadeh, Hasan

    2015-05-01

    Here, [Ni(phendion) (phen)]Cl2 complex, (phendion and phen are 1,10-phenanthroline-5,6-dione and 5-amino-1, 10-phenanthrolin) covalently attached onto carboxyl functionalized multi walls carbon nanotube modified glassy carbon electrode (GCE/MWCNTs-COOH) using solid phase interactions and combinatorial approaches.The attached [Ni(phendion) (phen)]Cl2 complex displays a surface controlled electrode process and it acts as an effective redox mediator for electrocatalytic oxidation of dihydronicotinamide adenine dinucleotide (NADH) at reduced overpotentials. With co-immobilization of glucose dehydrogenase enzyme (GDH) by crosslinking an effective biocatalyst for glucose oxidation designed. The onset potential and current density are -0.1 V versus Ag/AgCl electrode and 0.550 mA cm-2, which indicate the applicability of the proposed system as an efficient bioanode for biofuel cell (BFC) design. A GCE/MWCNTs modified with electrodeposited gold nanoparticles (AuNPs) as a platform for immobilization of bilirubin oxidase (BOD) and the prepared GCE/MWCNTs/AuNPs/BOD biocathode exhibits an onset potential of 0.56 V versus Ag/AgCl. The performance of the fabricated bioanode and biocathode in a membraneless enzyme based glucose/O2 biofuel cell is evaluated. The open circuit voltage of the cell and maximum current density are 520 mV and 0.233 mA cm-2, respectively, while maximum power density of 40 μWcm-2 achieves at voltage of 280 mV with stable output power after 24 h continues operation.

  5. Influence of Growth Characteristics of Induced Pluripotent Stem Cells on Their Uptake Efficiency for Layer-by-Layer Microcarriers.

    PubMed

    Reibetanz, Uta; Hübner, Denise; Jung, Matthias; Liebert, Uwe Gerd; Claus, Claudia

    2016-07-26

    Induced pluripotent stem cells (iPSCs) have the ability to differentiate into any specialized somatic cell type, which makes them an attractive tool for a wide variety of scientific approaches, including regenerative medicine. However, their pluripotent state and their growth in compact colonies render them difficult to access and, therefore, restrict delivery of specific agents for cell manipulation. Thus, our investigation focus was set on the evaluation of the capability of layer-by-layer (LbL) designed microcarriers to serve as a potential drug delivery system to iPSCs, as they offer several appealing advantages. Most notably, these carriers allow for the transport of active agents in a protected environment and for a rather specific delivery through surface modifications. As we could show, charge and mode of LbL carrier application as well as the size of the iPSC colonies determine the interaction with and the uptake rate by iPSCs. None of the examined conditions had an influence on iPSC colony properties such as colony morphology and size or maintenance of pluripotent properties. An overall interaction rate of LbL carriers with iPSCs of up to 20% was achieved. Those data emphasize the applicability of LbL carriers for stem cell research. Additionally, the potential use of LbL carriers as a promising delivery tool for iPSCs was contrasted to viral particles and liposomes. The identified differences among those delivery tools have substantiated our major conclusion that LbL carrier uptake rate is influenced by characteristic features of the iPSC colonies (most notably colony size) in addition to their surface charges. PMID:27362252

  6. Enhancement of dopamine sensing by layer-by-layer assembly of PVI-dmeOs and Nafion on carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Cui, Hui-Fang; Cui, Yu-Han; Sun, Yu-Long; Zhang, Kuan; Zhang, Wei-De

    2010-05-01

    In this study, carbon nanotubes (CNTs) were modified to further improve their performance in electrochemical sensing of dopamine (DA) levels. After a redox polymer, poly(vinylimidazole) complexed with Os(4, 4'-dimethyl- 2, 2-bipyridine)2Cl (termed PVI-dmeOs) was electrodeposited on multi-wall CNTs (MWCNTs), Nafion and PVI-dmeOs films were successfully layer-by-layer (LBL) assembled on the hydrophilic surface of the as-prepared PVI-dmeOs/CNTs nanocomposites through electrostatic interactions. The LBL assembly was proved by scanning electron microscopy (SEM), electrochemistry and UV-vis spectroscopy measurements. LBL assembly of Nafion/PVI-dmeOs films on CNTs significantly enhanced their linear sweep voltammetry (LSV) response sensitivity to DA, with a maximum enhancement for three Nafion/PVI-dmeOs film-modified MWCNTs. The LSV peak current density of (Nafion/PV I-dmeOs)3/CNT electrodes in response to 10 and 50 µM DA solutions was about 7.3 and 3.9 times those for bare CNTs. At the (Nafion/PV I-dmeOs)3/CNT electrodes, the limit of detection (LOD) (signal-to-noise ratio: 3) was 0.05 µM DA, the linear range was 0.1-10 µM DA (with a linear regression coefficient of 0.97) and the DA-sensing sensitivity was 8.15 µA cm - 2 µM - 1. The newly fabricated (Nafion/PV I-dmeOs)3/CNT electrodes may be developed as an ideal biosensor for direct and in situ measurement of DA levels.

  7. Functionalised nanoscale coatings using layer-by-layer assembly for imparting antibacterial properties to polylactide-co-glycolide surfaces.

    PubMed

    Gentile, Piergiorgio; Frongia, Maria E; Cardellach, Mar; Miller, Cheryl A; Stafford, Graham P; Leggett, Graham J; Hatton, Paul V

    2015-07-01

    In order to achieve high local biological activity and reduce the risk of side effects of antibiotics in the treatment of periodontal and bone infections, a localised and temporally controlled delivery system is desirable. The aim of this research was to develop a functionalised and resorbable surface to contact soft tissues to improve the antibacterial behaviour during the first week after its implantation in the treatment of periodontal and bone infections. Solvent-cast poly(d,l-lactide-co-glycolide acid) (PLGA) films were aminolysed and then modified by Layer-by-Layer technique to obtain a nano-layered coating using poly(sodium4-styrenesulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) as polyelectrolytes. The water-soluble antibiotic, metronidazole (MET), was incorporated from the ninth layer. Infrared spectroscopy showed that the PSS and PAH absorption bands increased with the layer number. The contact angle values had a regular alternate behaviour from the ninth layer. X-ray Photoelectron Spectroscopy evidenced two distinct peaks, N1s and S2p, indicating PAH and PSS had been introduced. Atomic Force Microscopy showed the presence of polyelectrolytes on the surface with a measured roughness about 10nm after 20 layers' deposition. The drug release was monitored by Ultraviolet-visible spectroscopy showing 80% loaded-drug delivery in 14 days. Finally, the biocompatibility was evaluated in vitro with L929 mouse fibroblasts and the antibacterial properties were demonstrated successfully against the keystone periodontal bacteria Porphyromonas gingivalis, which has an influence on implant failure, without compromising in vitro biocompatibility. In this study, PLGA was successfully modified to obtain a localised and temporally controlled drug delivery system, demonstrating the potential value of LbL as a coating technology for the manufacture of medical devices with advanced functional properties. PMID:25871538

  8. Dynamics of creation photoinduced birefringence on (PAH/PAZO)n layer-by-layer films: Analysis of consecutive cycles

    NASA Astrophysics Data System (ADS)

    Timóteo, Ana Rita Monteiro; Ribeiro, Jorge H. F.; Ribeiro, Paulo A.; Raposo, Maria

    2016-01-01

    Reproducibility and reliability of data is an important subject in the development of organic devices for photonics applications. This work reports the analysis of successive photoinduced birefringence creation curves in layer-by-layer films of poly(allylamine hydrochloride) (PAH) and poly{1-(4-(3-carboxy-4-hydroxyphenylazo) benzenesulfonamido)-1,2-ethanediyl, sodium salt} (PAZO) with different number of bilayers. The birefringence creation or writing curves are described by two processes: a faster one referring the contribution of trans-cis-trans photoisomerization cycles to the birefringence; and a slower one associated to the contribution of motion of the polymer chain to the birefringence. As the number of write-erase cycles increases, the characteristic times of these processes decreases, respectively, to values of 18 and 212 s independently of the number of bilayers of films while for the magnitudes the fast process prevailed relatively to the slow, by 70% against 30%. The observed behavior is explained by the thermal treatment given by the laser beam in the irradiated area with increase of free volume which contributes for the chromophore mobility. This conclusion was achieved by measuring the surface temperature during and after irradiation and analyzing by optical microscopy the film surface where an increase of holes and aggregation as a result of irradiation was observed. Infrared spectra of films after and before irradiation showed changes in the Cdbnd C absorbance indicating aggregation of azobenzene groups while changes in the protonated and deprotonated carboxylic acid groups are consistent with ionization degree diminishing which is explained by the removal of water molecules by heating caused by laser. The results presented in this paper indicates that an increase in the number of write-erase cycles contributes to reliable and reproducible birefringence characteristics of PAH/PAZO films - a good new from point of view of possible applications.

  9. Improving ice nucleation activity of zein film through layer-by-layer deposition of extracellular ice nucleators.

    PubMed

    Shi, Ke; Yu, Hailong; Lee, Tung-Ching; Huang, Qingrong

    2013-11-13

    Zein protein has been of scientific interest in the development of biodegradable functional food packaging. This study aimed at developing a novel zein-based biopolymer film with ice nucleation activity through layer-by-layer deposition of biogenic ice nucleators, that is, extracellular ice nucleators (ECINs) isolated from Erwinia herbicola , onto zein film surface. The adsorption behaviors and mechanisms were investigated using quartz crystal microbalance with dissipation monitoring (QCM-D). On unmodified zein surface, the highest ECINs adsorption occurred at pH 5.0; on UV/ozone treated zein surface followed by deposition of poly(diallyldimethylammonium chloride) (PDADMAC) layer, the optimum condition for ECINs adsorption occurred at pH 7.0 and I 0.05 M, where the amount of ECINs adsorbed was also higher than that on unmodified zein surface. QCM-D analyses further revealed a two-step adsorption process on unmodified zein surfaces, compared to a one-step adsorption process on PDADMAC-modified zein surface. Also, significantly, in order to quantify the ice nucleation activity of ECINs-coated zein films, an empirical method was developed to correlate the number of ice nucleators with the ice nucleation temperature measured by differential scanning calorimetry. Calculated using this empirical method, the highest ice nucleation activity of ECINs on ECINs-modified zein film reached 64.1 units/mm(2), which was able to elevate the ice nucleation temperature of distilled water from -15.5 °C to -7.3 °C. PMID:24106783

  10. Fabrication of graphene thin films based on layer-by-layer self-assembly of functionalized graphene nanosheets.

    PubMed

    Park, Je Seob; Cho, Sung Min; Kim, Woo-Jae; Park, Juhyun; Yoo, Pil J

    2011-02-01

    In this study, we present a facile means of fabricating graphene thin films via layer-by-layer (LbL) assembly of charged graphene nanosheets (GS) based on electrostatic interactions. To this end, graphite oxide (GO) obtained from graphite powder using Hummers method is chemically reduced to carboxylic acid-functionalized GS and amine-functionalized GS to perform an alternate LbL deposition between oppositely charged GSs. Specifically, for successful preparation of positively charged GS, GOs are treated with an intermediate acyl-chlorination reaction by thionyl chloride and a subsequent amidation reaction in pyridine, whereby a stable GO dispersibility can be maintained within the polar reaction solvent. As a result, without the aid of additional hybridization with charged nanomaterials or polyelectrolytes, the oppositely charged graphene nanosheets can be electrostatically assembled to form graphene thin films in an aqueous environment, while obtaining controllability over film thickness and transparency. Finally, the electrical property of the assembled graphene thin films can be enhanced through a thermal treatment process. Notably, the introduction of chloride functions during the acyl-chlorination reaction provides the p-doping effect for the assembled graphene thin films, yielding a sheet resistance of 1.4 kΩ/sq with a light transmittance of 80% after thermal treatment. Since the proposed method allows for large-scale production as well as elaborate manipulation of the physical properties of the graphene thin films, it can be potentially utilized in various applications, such as transparent electrodes, flexible displays and highly sensitive biosensors. PMID:21207942

  11. Electrochemical layer-by-layer approach to fabricate mechanically stable platinum black microelectrodes using a mussel-inspired polydopamine adhesive

    NASA Astrophysics Data System (ADS)

    Kim, Raeyoung; Nam, Yoonkey

    2015-04-01

    Objective. Platinum black (PtBK) has long been used for microelectrode fabrication owing to its high recording performance of neural signals. The porous structure of PtBK enlarges the surface area and lowers the impedance, which results in background noise reduction. However, the brittleness of PtBK has been a problem in practice. In this work, we report mechanically stable PtBK microelectrodes using a bioinspired adhesive film, polydopamine (pDA), while maintaining the low impedance of PtBK. Approach. The pDA layer was incorporated into the PtBK structure through electrochemical layer-by-layer deposition. Varying the number of layers and the order of materials, multi-layered pDA-PtBK hybrids were fabricated and the electrical properties, both impedance and charge injection limit, were evaluated. Main results. Multilayered pDA-PtBK hybrids had electrical impedances as low as PtBK controls and charge injection limit twice larger than controls. For the 30 min-ultrasonication agitation test, impedance levels rarely changed for some of the pDA-PtBK hybrids indicating that the pDA improved the mechanical property of the PtBK structures. The pDA-PtBK hybrid microelectrodes readily recorded neural signals of cultured hippocampal neurons, where background noise levels and signal-to-noise were 2.43 ∼ 3.23 μVrms and 28.4 ∼ 69.1, respectively. Significance. The developed pDA-PtBK hybrid microelectrodes are expected to be applicable to neural sensors for neural prosthetic studies.

  12. Oxidation-reduction dynamics in layer-by-layer self-assembled redox polyelectrolyte multilayer modified electrodes.

    PubMed

    Tagliazucchi, M; Grumelli, D; Bonazzola, C; Calvo, E J

    2006-06-01

    The oxidation-reduction dynamics of layer-by-layer (LbL) self-assembled redox polyelectrolyte multilayer films on electrodes has been studied by cyclic voltammetry, chrono-amperometry, electrochemical quartz crystal microbalance (EQCM), ellipsometry, and Fourier transform reflection-absorption infrared spectroscopy (FT-IRRAS). Thin layer electrochemistry with fast electron transfer at the underlying metal-film interface and charge propagation by electron hopping between adjacent redox sites in the finite thin film has been observed. An almost ideal cyclic voltammetry for a fixed number of redox sites in the thin surface film suggests that the multilayer can be fully oxidized and reduced in the time scale of the experiment (RT/vF > or = 0.05 sec). The electron hopping diffusion coefficient 3 x 10(-10) cm2 s(-1) was obtained from the chronoamperometric current transient and the ellipsometric thickness. Both cyclic voltammetry and potential step yield a surface osmium bipyridyl redox concentration of gamma Os = 4 x 10(-10) mol x cm(-2) for (PAH-Os)5(PVS)4 film. Exchange of ions and solvent occur simultaneously to the charge injection as revealed by the EQCM mass change and the ellipsometric thickness change. From the end-to-end mass-to-charge linear relationship, the molar mass of the ionic and neutral species exchanged largely exceeds the molar mass of any ions or solvent which suggests an important flux of solvent during redox switching. An initial "break in" effect is observed for the first oxidation-reduction cycles when a newly self-assembled film equilibrates with the electrolyte as charge is injected during the electrochemical perturbation. PMID:17025077

  13. Facile construction of multicompartment multienzyme system through layer-by-layer self-assembly and biomimetic mineralization.

    PubMed

    Shi, Jiafu; Zhang, Lei; Jiang, Zhongyi

    2011-03-01

    In nature, some organelles such as mitochondria and chloroplasts possess multicompartment structure, which render powerful and versatile performance in cascade conversion, selective separation, and energy transfer. In this study, mitochondria-inspired hybrid double membrane microcapsules (HDMMCs) were prepared through synergy between biomimetic mineralization and layer-by-layer (LbL) self-assembly using double templating strategy. The organic inner membrane was acquired via LbL self-assembly of oxidized alginate (o-alginate) and protamine on the CaCO(3) template, the silica template layer was then formed onto the inner membrane through biomimetic silicification using protamine as inducer and silicate as precursor, the organic-inorganic hybrid outer membrane was acquired via biomimetic mineralization of titanium precursor. After the CaCO(3) template and the silica template are removed subsequently, multicompartment microcapsules with microscale lumen and nanoscale intermembrane space were obtained. The double membrane structure of the HDMMCs was verified by high resolution scanning electron microscopy (HRSEM), and the superior mechanical stability of HDMMCs was demonstrated by osmotic pressure experiment and fluorescence microscopy. A multienzyme system was constructed by following this protocol: the first enzyme was encapsulated in the lumen of the HDMMCs, whereas the second enzyme was encapsulated in the intermembrane space. Compared to encapsulated multienzyme in single-compartment microcapsules (SCMCs) or in free form in aqueous solution, enzymatic activity, selectivity, and recycling stability of HDMMCs-enabled multienzyme system were significantly improved. Because of the inherent gentle and generic feature, the present study can be utilized to create a variety of compartment structures for the potential applications in chemical/biological catalysis and separation, drug/gene delivery systems, and biosensors. PMID:21348442

  14. Transparent conductors from layer-by-layer assembled SWNT films: importance of mechanical properties and a new figure of merit.

    PubMed

    Shim, Bong Sup; Zhu, Jian; Jan, Edward; Critchley, Kevin; Kotov, Nicholas A

    2010-07-27

    New transparent conductors (TCs) capable of replacing traditional indium tin oxide (ITO) are much needed for displays, sensors, solar cells, smart energy-saving windows, and flexible electronics. Technical requirements of TCs include not only high electrical conductivity and transparency but also environmental stability and mechanical property which are often overlooked in the research environment. Single-walled carbon nanotube (SWNT) coatings have been suggested as alternative TC materials but typically lack sufficient wear resistance compared to ITO. Balancing conductance, transparency, durability, and flexibility is a formidable challenge, which leads us to the introduction of a new TC figure of merit, PiTC, incorporating all these qualities. Maximization of PiTC to that of ITO or better can be suggested as an initial research goal. Fine tuning of SWNT layer-by-layer (LBL) polymeric nanocomposite structures makes possible integration of all the necessary properties. The produced TC demonstrated resistivity of 86 Omega/sq with 80.2% optical transmittance combined with tensile modulus, strength, and toughness of the film of 12.3+/-3.4 GPa, 218+/-13 MPa, and 8+/-1.7 J/g, respectively. A new transparent capping layer to conserve these properties in the hostile environment with matching or better strength, toughness, and transparency parameters was also demonstrated. Due to application demands, bending performance of TC made by LBL was of special interest and exceeded that of ITO by at least 100 times. Cumulative figure of merit PiTC for the produced coatings was 0.15 Omega(-1), whereas the conventional ITO showed PiTC<0.07 Omega(-1). With overall electrical and optical performance comparable to ITO and exceptional mechanical properties, the described coatings can provide an excellent alternative to ITO or other nanowire- and nanotube-based TC specifically in flexible electronics, displays, and sensors. PMID:20552974

  15. Polymer/Perovskite-type nanoparticle multilayers with multielectric properties prepared from ligand addition-induced layer-by-layer assembly.

    PubMed

    Kim, Younghoon; Kook, Kyungyun; Hwang, Sun Kak; Park, Cheolmin; Cho, Jinhan

    2014-03-25

    We introduce an adsorption mechanism for a layer-by-layer (LbL) assembly (i.e., a ligand addition-induced LbL assembly) and demonstrate that the (polymer/perovskite nanoparticle (NP))n nanocomposite films based on the ligand addition LbL exhibit ferroelectric and resistive switching properties. Oleic acid (OA)-stabilized BaTiO3 NPs (OA-BTO NPs) with a size of approximately 8 nm were LbL-assembled with amine-functionalized dendrimers (NH2-dendrimers) using the high affinity between NH2 moieties and Ti ions. The ferroelectric properties of the (NH2-dendrimer/OA-BTO NP)n multilayers were generated by the Ti disorder in the OA-BTO NP unit cell despite the use of sub-10 nm OA-BTO NPs (i.e., OA-BTO NPs), which are near the critical size for ferroelectric properties. Additionally, the (NH2-dendrimer/OA-BTO NP)n multilayers sandwiched between the bottom (platinum) and top (silver or tungsten) electrodes exhibited a resistive switching memory at a relatively low operating voltage below 2 V with a switching speed of approximately 100 ns and an ON/OFF current ratio of approximately 10(4). Furthermore, the ferroelectric and resistive switching properties could be further improved by controlling the bilayer number (n). We believe that our approach can provide a basis for designing and exploiting multifunctional memory electronics based on a variety of perovskite NPs with ferroelectric properties. PMID:24571293

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

    PubMed

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

    2015-05-27

    The layer-by-layer (LbL) assembled multilayer has been widely used as good barrier film or capsule due to the advantages of its flexible tailoring of film permeability and compactness. Although many specific systems have been proposed for film design, developing a versatile strategy to control film compactness remains a challenge. We introduced the simple mechanical energy of a high gravity field to the LbL assembly process to tailor the multilayer permeability through adjusting film compactness. By taking poly(diallyldimethylammonium chloride) (PDDA) and poly{1-4[4-(3-carboxy-4-hydroxyphenylazo)benzenesulfonamido]-1,2-ethanediyl sodium salt} (PAzo) as a model system, we investigated the LbL assembly process under a high gravity field. The results showed that the high gravity field introduced effectively accelerated the multilayer deposition process by 20-fold compared with conventional dipping assembly; the adsorption rate was positively dependent on the rotating speed of the high gravity equipment and the concentration of the building block solutions. More interestingly, the film compactness of the PDDA/PAzo multilayer prepared under the high gravity field increased remarkably with the growing rotational speed of the high gravity equipment, as demonstrated through comparisons of surface morphology, cyclic voltammetry curves, and photoisomerization kinetics of PDDA/PAzo multilayers fabricated through the conventional dipping method and through LbL assembly under a high gravity field, respectively. In this way, we have introduced a simple and versatile external form of mechanical energy into the LbL assembling process to improve film compactness, which should be useful for further applications in controlled ion permeability, anticorrosion, and drug loading. PMID:25951984

  17. Bio-Inspired Aquaporinz Containing Double-Skinned Forward Osmosis Membrane Synthesized through Layer-by-Layer Assembly

    PubMed Central

    Wang, Shuzheng; Cai, Jin; Ding, Wande; Xu, Zhinan; Wang, Zhining

    2015-01-01

    We demonstrated a novel AquaporinZ (AqpZ)-incorporated double-skinned forward osmosis (FO) membrane by layer-by-layer (LbL) assembly strategy. Positively charged poly(ethyleneimine) (PEI) and negatively charged poly(sodium 4-styrenesulfonate) (PSS) were alternately deposited on both the top and bottom surfaces of a hydrolyzed polyacrylonitrile (H-PAN) substrate. Subsequently, an AqpZ-embedded 1,2-dioleloyl-sn-glycero-3-phosphocholine (DOPC)/1,2-dioleoyl-3-trimethylammonium- propane (chloride salt) (DOTAP) supported lipid bilayer (SLB) was formed on PSS-terminated (T-PSS) membrane via vesicle rupture method. The morphology and structure of the biomimetic membranes were characterized by in situ atomic force microscopy (AFM), scanning electron microscope (SEM), Fourier transform infrared spectrometer using the attenuated total reflection technique (ATR-FTIR), and contact angle. Moreover, the FO performance of the resultant membrane was measured by using 2 M MgCl2 solution as draw solution and deionized (DI) water as feed solution, respectively. The membrane with a protein-to-lipid weight ratio (P/L) of 1/50 exhibits 13.2 L/m2h water flux and 3.2 g/m2h reversed flux by using FO mode, as well as 15.6 L/m2h water flux and 3.4 L/m2h reversed flux for PRO mode (the draw solution is placed against the active layer). It was also shown that the SLB layer of the double-skinned FO membrane can increase the surface hydrophilicity and reduce the surface roughness, which leads to an improved anti-fouling performance against humic acid foulant. The current work introduced a new method of fabricating high performance biomimetic FO membrane by combining AqpZ and a double-skinned structure based on LbL assembly. PMID:26266426

  18. Dynamics of layer-by-layer growth of a polyelectrolyte multilayer studied in situ using attenuated total reflectance infrared spectroscopy.

    PubMed

    Owusu-Nkwantabisah, Silas; Gammana, Madhira; Tripp, Carl P

    2014-10-01

    Attenuated total reflectance infrared spectroscopy (ATR-IR) was used to study the dynamic layer-by-layer (LBL) growth of a sodium polyacrylate (NaPA)/poly(diallydimethylammonium) chloride (PDADMAC) multilayer on TiO2 particles. Molecular weights (Mw) used were 30 and 60 kDa for NaPA and 8.5 and 150 kDa for PDADMAC. IR spectra were recorded in situ as a function of time and were used to obtain the dynamic mass adsorbed and bound fraction of the polymers during each deposition step. For 30 kDa NaPA layers, the dynamics of adsorption show an initial rapid rise in mass followed by a slow increase toward a plateau value upon LBL with 150 kDa PDADMAC. In contrast, the 60 kDa NaPA layers achieve a plateau quickly and do not show a slow increase toward a plateau. In the case of LBL with 150 kDa PDADMAC, the dynamics of the bound fraction of polymer per layer suggest that polymer diffusion and conformational rearrangement occur for the layers of 30 kDa NaPA but not for the 60 kDa NaPA layers. Furthermore, PDADMAC adsorption profiles show that there is no diffusion of the PDADMAC layers and that PDADMAC flattens onto the underlying layer. A linear growth in the mass adsorbed per layer was observed for 150 kDa PDADMAC with both molecular weights of NaPA. In the case of 8.5 kDa PDADMAC, smaller growth increments and the desorption of underlying layers were observed. This work demonstrates the use of ATR-IR in obtaining the dynamics of LBL multilayer formation. Furthermore, it provides an example in which polymer diffusion during LBL film formation does not lead to exponential growth. PMID:25203136

  19. Layer-by-layer TiO(2)/WO(3) thin films as efficient photocatalytic self-cleaning surfaces.

    PubMed

    Patrocinio, Antonio Otavio T; Paula, Leonardo F; Paniago, Roberto M; Freitag, Janna; Bahnemann, Detlef W

    2014-10-01

    New TiO2/WO3 films were produced by the layer-by-layer (LbL) technique and successfully applied as self-cleaning photocatalytic surfaces. The films were deposited on fluorine doped tin oxide (FTO) glass substrates from the respective metal oxide nanoparticles obtained by the sol-gel method. Thirty alternative immersions in pH = 2 TiO2 and pH = 10 WO3 sols resulted in ca. 400 nm thick films that exhibited a W(VI)/Ti(IV) molar ratio of 0.5, as determined by X-ray photoelectron spectroscopy. Scanning electron microscopy, along with atomic force images, showed that the resulting layers are constituted by aggregates of very small nanoparticles (<20 nm) and exhibited nanoporous and homogeneous morphology. The electronic and optical properties of the films were investigated by UV-vis spectrophotometry and ultraviolet photoelectron spectroscopy. The films behave as nanoscale heterojunctions, and the presence of WO3 nanoparticles caused a decrease in the optical band gap of the bilayers compared to that of pure LbL TiO2 films. The TiO2/WO3 thin films exhibited high hydrophilicity, which is enhanced after exposition to UV light, and they can efficiently oxidize gaseous acetaldehyde under UV(A) irradiation. Photonic efficiencies of ξ = 1.5% were determined for films constituted by 30 TiO2/WO3 bilayers in the presence of 1 ppm of acetaldehyde, which are ∼2 times higher than those observed for pure LbL TiO2 films. Therefore, these films can act as efficient and cost-effective layers for self-cleaning, antifogging applications. PMID:25216058

  20. Chemical improvement of chitosan-modified beads for the immobilization of Enterococcus faecium DBFIQ E36 L-arabinose isomerase through multipoint covalent attachment approach.

    PubMed

    Manzo, Ricardo M; de Sousa, Marylane; Fenoglio, Cecilia L; Gonçalves, Luciana Rocha Barro; Mammarella, Enrique J

    2015-10-01

    D-tagatose is produced from D-galactose by the enzyme L-arabinose isomerase (L-AI) in a commercially viable bioprocess. An active and stable biocatalyst was obtained by modifying chitosan gel structure through reaction with TNBS, D-fructose or DMF, among others. This led to a significant improvement in L-AI immobilization via multipoint covalent attachment approach. Synthetized derivatives were compared with commercial supports such as Eupergit(®) C250L and glyoxal-agarose. The best chitosan derivative for L-AI immobilization was achieved by reacting 4 % (w/v) D-fructose with 3 % (w/v) chitosan at 50 °C for 4 h. When compared to the free enzyme, the glutaraldehyde-activated chitosan biocatalyst showed an apparent activity of 88.4 U g (gel) (-1) with a 211-fold stabilization factor while the glyoxal-agarose biocatalyst gave an apparent activity of 161.8 U g (gel) (-1) with an 85-fold stabilization factor. Hence, chitosan derivatives were comparable to commercial resins, thus becoming a viable low-cost strategy to obtain high active L-AI insolubilized derivatives. PMID:26254040

  1. When is one layer complete? Using simultaneous in-situ RHEED and x-ray reflectivity to map layer-by-layer thin-film oxide growth

    NASA Astrophysics Data System (ADS)

    Sullivan, M. C.; Ward, M. J.; Joress, H.; Gutierrez-Llorente, A.; White, A. E.; Woll, A.; Brock, J. D.

    2014-03-01

    The most popular tool for characterizing in situ layer-by-layer growth is Reflection High-Energy Electron Diffraction (RHEED). X-ray reflectivity can also be used to study layer-by-layer growth, as long as the incident angle of the x-rays is far from a Bragg peak. During layer-by-layer homoepitaxial growth, both the RHEED intensity and the reflected x-ray intensity will oscillate, and each complete oscillation indicates the addition of one layer of material. However, it is well documented, but not well understood, that the maxima in the RHEED intensity oscillations do not necessarily occur at the completion of a layer. In contrast, the maxima in the x-ray intensity oscillations do occur at the completion of a layer, thus the RHEED and x-ray oscillations are rarely in phase. We present our results on simultaneous in situ x-ray reflectivity and RHEED during layer-by-layer growth of SrTiO3 and discuss how to determine the completion of a layer for RHEED oscillations independent of the phase of the RHEED oscillation. Supported by DOE Office of Basic Energy Sciences Award DE-SC0001086, CHESS is supported by the NSF & NIH/NIGMS via NSF award DMR-0936384.

  2. Flame retardant polymer-clay nanocoatings on cotton textile substrates using a newly developed, continuous layer-by-layer deposition process

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cotton’s exceptional softness, breathability, and absorbency have made it America’s best selling textile fiber; however, cotton textiles are generally more combustible than most synthetic fabrics. In this study, a continuous layer-by-layer self-assembly technique was used to deposit polymer-clay nan...

  3. Fabricating Electrochromic Thin Films Based on Metallo-Polymers Using Layer-by-Layer Self-Assembly: An Attractive Laboratory Experiment

    ERIC Educational Resources Information Center

    Schott, Marco; Beck, Matthias; Winkler, Franziska; Lorrmann, Henning; Kurth, Dirk G.

    2015-01-01

    Metallo-supramolecular polyelectrolytes (MEPE) based on iron(II)-acetate and 1,4-bis(2,2':6',2?-terpyridin-4'-yl)benzene are assembled by layer-by-layer deposition on transparent electrode surfaces. When a potential is applied, the color of the film can be switched from blue to transparent. Due to the strong absorption and the fast switching…

  4. Layer-by-layer electrodeposition of redox polymers and enzymes on screen-printed carbon electrodes for the preparation of reagentless biosensors.

    PubMed

    Gao, Qiang; Yang, Xiurong

    2004-01-01

    Layer-by-layer electrodeposition of redox polymer/enzyme composition films on screen-printed carbon electrodes for fabrication of reagentless enzyme biosensors has been proposed and the resulting films were found to be very stable and rigid. PMID:14737317

  5. Optical coherence tomography (OCT) in hereditary retinal degenerations: Layer-by-layer analyses in normal and diseased retinas

    NASA Astrophysics Data System (ADS)

    Huang, Yijun

    OCT is a new technique for non-invasive, non-contact, cross-sectional imaging of biological tissues with micrometer longitudinal resolution. As it applies to the field of ophthalmology, OCT can delineate retinal sublayers based on their backscattering characteristics, and permit quantitative measurement of the structure of retina in vivo. This dissertation intended to clarify the basis of the OCT signals and whether this procedure has potential for diagnosis and monitoring of human retinal degenerative diseases. Key to this goal are quantitation of OCT signal features and accurate, layer-by-layer correlation of these features with underlying retinal microanatomy. In normal and degenerate avian and swine retinas, OCT signal features were quantified using custom computer programs, and were correlated with cryosections of unfixed retinas obtained at the same retinal location. The results suggested a definable and quantifiable relationship between OCT signal components and retinal microanatomy. The correlation in the outer retina indicated that the OCT posterior highly reflective band, or the outer- retina-choroid complex (ORCC), is attributable to the photoreceptor layer, RPE, and anterior choroid. Further evidence of OCT signal origin was provided by the rd chicken and the rhodopsin P347L mutant transgenic swine. In these animals where photoreceptors had degenerated, OCT abnormalities were observed at the level of and vitreal to the ORCC, consistent with the hypothesis that photoreceptors contribute to the ORCC. Studies of quantitative OCT analysis in man were also performed. In selected hereditary retinal degenerative diseases in which there was regional difference in retinal function, frequently observed OCT abnormalities that were associated with visual dysfunction were reduced OCT thickness, reduced ORCC thickness, increased reflectivity posterior to ORCC, and abnormal OCT signal lamination. These preliminary results suggested that OCT abnormalities at the level

  6. Ultrathin films of functional polyelectrolytes on flat surfaces and colloidal particles using the layer-by-layer deposition technique

    NASA Astrophysics Data System (ADS)

    Park, Mi-Kyoung

    Layer-by-layer (LbL) self-assembly techniques have been used to prepare ultrathin polymer films with controlled thicknesses and compositions. The technique is based on the alternate adsorption of oppositely charged polyelectrolyte layers on substrates. This dissertation details the investigation of ultrathin films with functional polyelectrolytes coated on flat substrates and colloidal particles. Several systems were investigated including: liquid crystal (LC) photoalignment layers, photo-crosslinkable permselective membranes, luminescent hollow-shell particles, and conducting polymer colloidal particles. The multilayer films of an azo-polymer and a polycation were utilized to control azimuthal alignment of liquid crystals. Irradiation of a hybrid LC cell with linearly polarized light resulted in in-plane homogeneous LC alignment, which is dependent on the thickness, and irradiation time. The director of the LC molecules was found to be perpendicular to the polarization plane and can be reoriented. The photocross-linkable multilayer membranes comprising poly(acrylic acid) and poly(allyamine hydrochloride) modified with benzophenone groups have been prepared. It was demonstrated that the permeability of the multilayer films can be controlled by the number of layers as well as the UV irradiation time. Furthermore, a "smart" pH-switchable membrane was produced by adjusting the pH of the dipping solution while maintaining stability throughout the cross-linked structure. The membrane showed pH-sensitive permselectivity, that is, the film was permeable to the cationic molecules, but impermeable to the anionic molecules at pH 10 and vise versa at pH 3. Luminescent core-shell particles and hollow capsules were prepared by the LbL deposition of polystyrenesulfonate (PSS) and a water-soluble ionene precursor polymer containing fluorene units (PI) onto spherical colloid particles. Subsequent cross-linking of the PI in the multilayer shell formed luminescent conjugated oligo

  7. Adsorption of cobalt ferrite nanoparticles within layer-by-layer films: a kinetic study carried out using quartz crystal microbalance.

    PubMed

    Alcantara, Gustavo B; Paterno, Leonardo G; Afonso, André S; Faria, Ronaldo C; Pereira-da-Silva, Marcelo A; Morais, Paulo C; Soler, Maria A G

    2011-12-28

    The paper reports on the successful use of the quartz crystal microbalance technique to assess accurate kinetics and equilibrium parameters regarding the investigation of in situ adsorption of nanosized cobalt ferrite particles (CoFe(2)O(4)--10.5 nm-diameter) onto two different surfaces. Firstly, a single layer of nanoparticles was deposited onto the surface provided by the gold-coated quartz resonator functionalized with sodium 3-mercapto propanesulfonate (3-MPS). Secondly, the layer-by-layer (LbL) technique was used to build multilayers in which the CoFe(2)O(4) nanoparticle-based layer alternates with the sodium sulfonated polystyrene (PSS) layer. The adsorption experiments were conducted by modulating the number of adsorbed CoFe(2)O(4)/PSS bilayers (n) and/or by changing the CoFe(2)O(4) nanoparticle concentration while suspended as a stable colloidal dispersion. Adsorption of CoFe(2)O(4) nanoparticles onto the 3-MPS-functionalized surface follows perfectly a first order kinetic process in a wide range (two orders of magnitude) of nanoparticle concentrations. These data were used to assess the equilibrium constant and the adsorption free energy. Alternatively, the Langmuir adsorption constant was obtained while analyzing the isotherm data at the equilibrium. Adsorption of CoFe(2)O(4) nanoparticles while growing multilayers of CoFe(2)O(4)/PSS was conducted using colloidal suspensions with CoFe(2)O(4) concentration in the range of 10(-8) to 10(-6) (moles of cobalt ferrite per litre) and for different numbers of cycles n = 1, 3, 5, and 10. We found the adsorption of CoFe(2)O(4) nanoparticles within the CoFe(2)O(4)/PSS bilayers perfectly following a first order kinetic process, with the characteristic rate constant growing with the increase of CoFe(2)O(4) nanoparticle concentration and decreasing with the rise of the number of LbL cycles (n). Additionally, atomic force microscopy was employed for assessing the LbL film roughness and thickness. We found the film

  8. Label-free electrochemical IgE aptasensor based on covalent attachment of aptamer onto multiwalled carbon nanotubes/ionic liquid/chitosan nanocomposite modified electrode.

    PubMed

    Khezrian, Somayeh; Salimi, Abdollah; Teymourian, Hazhir; Hallaj, Rahman

    2013-05-15

    A simple, sensitive and label-free aptamer-based biosensor for the detection of human immunoglobulin E (IgE) is developed using the electrochemical transduction method. A special immobilization interface consisting of multiwalled carbon nanotubes/ionic liquid/chitosan nanocomposite (MWCNTs/IL/Chit) is utilized to improve the conductivity and performance characteristics of the biosensor as well as to increase the loading amount of aptamer DNA sequence. A 5'-amino-terminated aptamer is covalently attached onto MWCNTs/IL/Chit modified glassy carbon (GC) electrode via a linker of glutaraldehyde (GA). Methylene blue (MB) is used as an electrochemical indicator which is intercalated into the aptamer through the specific interaction with its guanine bases. In the absence of IgE, MB bound to the aptamer produces a strong differential pulse voltammetric (DPV) signal. But when IgE exists, the intercalated MB releases from the aptamer, resulting an obviously decreased DPV signal. This phenomenon can be applied for human IgE detection. The peak current of MB linearly decreases with the concentration of IgE over a range of 0.5-30 nM with a detection limit of 37 pM. By using Bovine serum albumin (BSA) and lysozyme, the excellent specificity of this sensing system for the detection of IgE is also demonstrated. Finally, the proposed aptasensor is successfully used to IgE analysis in human serum sample. The obtained result is well agreed with the value obtained by the standard ELISA method. The herein described approach is expected to promote the exploitation of aptamer-based biosensors for protein assays in biochemical and biomedical studies. PMID:23313881

  9. Monitoring the Switching of Single BSA-ATTO 488 Molecules Covalently End-Attached to a pH-Responsive PAA Brush.

    PubMed

    Akkilic, Namik; Molenaar, Robert; Claessens, Mireille M A E; Blum, Christian; de Vos, Wiebe M

    2016-09-01

    We describe a novel combination of a responsive polymer brush and a fluorescently labeled biomolecule, where the position of the biomolecule can be switched from inside to outside the brush and vice versa by a change in pH. For this, we grafted ultrathin, amino-terminated poly(acrylic acid) brushes to glass and silicon substrates. Individual bovine serum albumin (BSA) molecules labeled with fluorophore ATTO 488 were covalently end-attached to the polymers in this brush using a bis-N-succinimidyl-(pentaethylene glycol) linker. We investigated the dry layer properties of the brush-protein ensemble, and it is swelling behavior using spectroscopic ellipsometry. Total internal reflection fluorescence (TIRF) microscopy enabled us to study the distance-dependent switching of the fluorescently labeled protein molecules. The fluorescence emission from the labeled proteins ceased (out-state) when the polymer chains stretched away from the interface under basic pH conditions, and fluorescence recurred (in-state) when the chains collapsed under acidic conditions. Moreover, TIRF allowed us to study the fluorescence switching behavior of fluorescently labeled BSA molecules down to the single-molecule level, and we demonstrate that this switching is fast but that the exact intensity during the in-state is the result of a more random process. Control experiments verify that the switching behavior is directly correlated to the responsive behavior of the polymer brush. We propose this system as a platform for switchable sensor applications but also as a method to study the swelling and collapse of individual polymer chains in a responsive polymer brush. PMID:27525503

  10. Synthesis, structure and electrochemical properties of novel Li-Co-Mn-O epitaxial thin-film electrode using layer-by-layer deposition process

    NASA Astrophysics Data System (ADS)

    Lim, Jaemin; Lee, Soyeon; Suzuki, Kota; Kim, KyungSu; Kim, Sangryun; Taminato, Sou; Hirayama, Masaaki; Oshima, Yoshifumi; Takayanagi, Kunio; Kanno, Ryoji

    2015-04-01

    A novel epitaxial thin-film electrode for lithium batteries, with a composition of Li0.92Co0.65Mn1.35O4 and a cubic spinel structure, is fabricated on a SrTiO3(111) single-crystal substrate. Fabrication is carried out by layer-by-layer pulsed laser deposition of LiCoO2 with a layered rock-salt structure and LiMn2O4 with a spinel structure. The electrode is found to exhibit unique disordering of the lithium (8a) and transition-metal (16d) sites, leading to a higher rate capability and cycle retention ratio than those for a thin-film electrode with the same composition prepared by a conventional single-step deposition process. The proposed layer-by-layer deposition method allows an expanded range of compositional and structural variations for lithium battery electrode materials.

  11. The shape dependence of core shell and hollow titania nanoparticles on coating thickness during layer-by-layer and sol gel synthesis

    NASA Astrophysics Data System (ADS)

    Nelson, Kimberly; Deng, Yulin

    2006-07-01

    Titania core-shell and hollow nanoparticles with different aspect ratios were synthesized using layer-by-layer assembly and sol-gel nanocoating methods with cellulose nanowhiskers as the template. During growth of the coating layer, the shape of the nanoparticles did not maintain the shape of the high aspect ratio template, as previously assumed. The shape of the coated particles is a function of the coating thickness. It is suggested that the overall particle shape and aspect ratio of the nanoparticles are tunable by choosing an appropriate template and coating thickness in layer-by-layer or sol-gel templating synthesis. The nanorods and hollow titania particles synthesized by these methods were characterized by transmission electron microscopy, scanning electron microscopy and x-ray diffraction.

  12. Electrochemical and spectroelectrochemical behavior of the TCNQ(0/)(-) couple on a glassy carbon electrode. Layer-by-layer nucleation and growth.

    PubMed

    Gómez, L; Rodríguez-Amaro, R

    2006-08-15

    On the basis of the electrochemical results obtained for thin films of 7,7,8,8- tetracyanoquinodimethane (TCNQ) on a glassy carbon electrode, the reduction and oxidation of the [TCNQ](0/)(-) couple in KCl aqueous media occurs via a mechanism involving layer-by-layer nucleation and growth. In situ recorded UV-visible spectroelectrochemical data allow two different crystal structures for the oxidized form of TCNQ to be discriminated. PMID:16893249

  13. The single NqrB and NqrC subunits in the Na(+)-translocating NADH: quinone oxidoreductase (Na(+)-NQR) from Vibrio cholerae each carry one covalently attached FMN.

    PubMed

    Casutt, Marco S; Schlosser, Andreas; Buckel, Wolfgang; Steuber, Julia

    2012-10-01

    The Na(+)-translocating NADH:quinone oxidoreductase (Na(+)-NQR) is the prototype of a novel class of flavoproteins carrying a riboflavin phosphate bound to serine or threonine by a phosphodiester bond to the ribityl side chain. This membrane-bound, respiratory complex also contains one non-covalently bound FAD, one non-covalently bound riboflavin, ubiquinone-8 and a [2Fe-2S] cluster. Here, we report the quantitative analysis of the full set of flavin cofactors in the Na(+)-NQR and characterize the mode of linkage of the riboflavin phosphate to the membrane-bound NqrB and NqrC subunits. Release of the flavin by β-elimination and analysis of the cofactor demonstrates that the phosphate group is attached at the 5'-position of the ribityl as in authentic FMN and that the Na(+)-NQR contains approximately 1.7mol covalently bound FMN per mol non-covalently bound FAD. Therefore, each of the single NqrB and NqrC subunits in the Na(+)-NQR carries a single FMN. Elimination of the phosphodiester bond yields a dehydro-2-aminobutyrate residue, which is modified with β-mercaptoethanol by Michael addition. Proteolytic digestion followed by mass determination of peptide fragments reveals exclusive modification of threonine residues, which carry FMN in the native enzyme. The described reactions allow quantification and localization of the covalently attached FMNs in the Na(+)-NQR and in related proteins belonging to the Rhodobacter nitrogen fixation (RNF) family of enzymes. This article is part of a Special Issue entitled: 17th European Bioenergetics Conference (EBEC 2012). PMID:22366169

  14. Covalent Chemistry beyond Molecules.

    PubMed

    Jiang, Juncong; Zhao, Yingbo; Yaghi, Omar M

    2016-03-16

    Linking molecular building units by covalent bonds to make crystalline extended structures has given rise to metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), thus bringing the precision and versatility of covalent chemistry beyond discrete molecules to extended structures. The key advance in this regard has been the development of strategies to overcome the "crystallization problem", which is usually encountered when attempting to link molecular building units into covalent solids. Currently, numerous MOFs and COFs are made as crystalline materials in which the large size of the constituent units provides for open frameworks. The molecular units thus reticulated become part of a new environment where they have (a) lower degrees of freedom because they are fixed into position within the framework; (b) well-defined spatial arrangements where their properties are influenced by the intricacies of the pores; and (c) ordered patterns onto which functional groups can be covalently attached to produce chemical complexity. The notion of covalent chemistry beyond molecules is further strengthened by the fact that covalent reactions can be carried out on such frameworks, with full retention of their crystallinity and porosity. MOFs are exemplars of how this chemistry has led to porosity with designed metrics and functionality, chemically-rich sequences of information within their frameworks, and well-defined mesoscopic constructs in which nanoMOFs enclose inorganic nanocrystals and give them new levels of spatial definition, stability, and functionality. PMID:26863450

  15. Interrogating chemical variation via layer-by-layer SERS during biofouling and cleaning of nanofiltration membranes with further investigations into cleaning efficiency.

    PubMed

    Cui, Li; Chen, Pengyu; Zhang, Bifeng; Zhang, Dayi; Li, Junyi; Martin, Francis L; Zhang, Kaisong

    2015-12-15

    Periodic chemical cleaning is an essential step to maintain nanofiltration (NF) membrane performance and mitigate biofouling, a major impediment in high-quality water reclamation from wastewater effluent. To target the important issue of how to clean and control biofouling more efficiently, this study developed surface-enhanced Raman spectroscopy (SERS) as a layer-by-layer tool to interrogate the chemical variations during both biofouling and cleaning processes. The fact that SERS only reveals information on the surface composition of biofouling directly exposed to cleaning reagents makes it ideal for evaluating cleaning processes and efficiency. SERS features were highly distinct and consistent with different biofouling stages (bacterial adhesion, rapid growth, mature and aged biofilm). Cleaning was performed on two levels of biofouling after 18 h (rapid growth of biofilm) and 48 h (aged biofilm) development. An opposing profile of SERS bands between biofouling and cleaning was observed and this suggests a layer-by-layer cleaning mode. In addition, further dynamic biochemical and infrastructural changes were demonstrated to occur in the more severe 48-h biofouling, resulting in the easier removal of sessile cells from the NF membrane. Biofouling substance-dependent cleaning efficiency was also evaluated using the surfactant sodium dodecyl sulfate (SDS). SDS appeared more efficient in cleaning lipid than polysaccharide and DNA. Protein and DNA were the predominant residual substances (irreversible fouling) on NF membrane leading to permanent flux loss. The chemical information revealed by layer-by-layer SERS will lend new insights into the optimization of cleaning reagents and protocols for practical membrane processes. PMID:26433006

  16. Recent developments in the layer-by-layer assembly of polyaniline and carbon nanomaterials for energy storage and sensing applications. From synthetic aspects to structural and functional characterization

    NASA Astrophysics Data System (ADS)

    Marmisollé, Waldemar A.; Azzaroni, Omar

    2016-05-01

    The construction of hybrid polymer-inorganic nanoarchitectures for electrochemical purposes based on the layer-by-layer assembly of conducting polymers and carbon nanomaterials has become increasingly popular over the last decade. This explosion of interest is primarily related to the increasing mastery in the design of supramolecular constructs using simple wet chemical approaches. Concomitantly, this continuous research activity paved the way to the rapid development of nanocomposites or ``nanoblends'' readily integrable into energy storage and sensing devices. In this sense, the layer-by-layer (LbL) assembly technique has allowed us to access three-dimensional (3D) multicomponent carbon-based network nanoarchitectures displaying addressable electrical, electrochemical and transport properties in which conducting polymers, such as polyaniline, and carbon nanomaterials, such as carbon nanotubes or nanographene, play unique roles without disrupting their inherent functions - complementary entities coexisting in harmony. Over the last few years the level of functional sophistication reached by LbL-assembled carbon-based 3D network nanoarchitectures, and the level of knowledge related to how to design, fabricate and optimize the properties of these 3D nanoconstructs have advanced enormously. This feature article presents and discusses not only the recent advances but also the emerging challenges in complex hybrid nanoarchitectures that result from the layer-by-layer assembly of polyaniline, a quintessential conducting polymer, and diverse carbon nanomaterials. This is a rapidly developing research area, and this work attempts to provide an overview of the diverse 3D network nanoarchitectures prepared up to now. The importance of materials processing and LbL integration is explored within each section and while the overall emphasis is on energy storage and sensing applications, the most widely-used synthetic strategies and characterization methods for ``nanoblend

  17. Recent developments in the layer-by-layer assembly of polyaniline and carbon nanomaterials for energy storage and sensing applications. From synthetic aspects to structural and functional characterization.

    PubMed

    Marmisollé, Waldemar A; Azzaroni, Omar

    2016-05-21

    The construction of hybrid polymer-inorganic nanoarchitectures for electrochemical purposes based on the layer-by-layer assembly of conducting polymers and carbon nanomaterials has become increasingly popular over the last decade. This explosion of interest is primarily related to the increasing mastery in the design of supramolecular constructs using simple wet chemical approaches. Concomitantly, this continuous research activity paved the way to the rapid development of nanocomposites or "nanoblends" readily integrable into energy storage and sensing devices. In this sense, the layer-by-layer (LbL) assembly technique has allowed us to access three-dimensional (3D) multicomponent carbon-based network nanoarchitectures displaying addressable electrical, electrochemical and transport properties in which conducting polymers, such as polyaniline, and carbon nanomaterials, such as carbon nanotubes or nanographene, play unique roles without disrupting their inherent functions - complementary entities coexisting in harmony. Over the last few years the level of functional sophistication reached by LbL-assembled carbon-based 3D network nanoarchitectures, and the level of knowledge related to how to design, fabricate and optimize the properties of these 3D nanoconstructs have advanced enormously. This feature article presents and discusses not only the recent advances but also the emerging challenges in complex hybrid nanoarchitectures that result from the layer-by-layer assembly of polyaniline, a quintessential conducting polymer, and diverse carbon nanomaterials. This is a rapidly developing research area, and this work attempts to provide an overview of the diverse 3D network nanoarchitectures prepared up to now. The importance of materials processing and LbL integration is explored within each section and while the overall emphasis is on energy storage and sensing applications, the most widely-used synthetic strategies and characterization methods for "nanoblend

  18. Sonication-assisted drug encapsulation in layer-by-layer self-assembled gelatin-poly (styrenesulfonate) polyelectrolyte nanocapsules: process optimization.

    PubMed

    Pandey, Abhijeet P; Singh, Saurabh S; Patil, Ganesh B; Patil, Pravin O; Bhavsar, Chetan J; Deshmukh, Prashant K

    2015-01-01

    We report the development of Layer-by-Layer (LbL) polyelectrolyte self-assembled nanocrystalline drug-delivery platform using two experimental factors, namely the number of coatings and temperature during deposition with three varying levels. The optimized formulation (Fopt) was assessed for zeta potential and particle size using Fourier Transform Infrared Spectroscopy (FT-IR), Differential Scanning Calorimetry (DSC), and Scanning Electron Microscopy (SEM). Charge reversal along with an increase in particle size confirmed coating of polyelectrolyte on drug nanocrystals. The FT-IR study revealed no signs of incompatibility or change in formulation property during preformulation and stability study. This fact was further supported by DSC results. PMID:24684490

  19. Promoting the selection and maintenance of fetal liver stem/progenitor cell colonies by layer-by-layer polypeptide tethered supported lipid bilayer.

    PubMed

    Lee, I-Chi; Liu, Yung-Chiang; Tsai, Hsuan-Ang; Shen, Chia-Ning; Chang, Ying-Chih

    2014-12-10

    In this study, we designed and constructed a series of layer-by-layer polypeptide adsorbed supported lipid bilayer (SLB) films as a novel and label-free platform for the isolation and maintenance of rare populated stem cells. In particular, four alternative layers of anionic poly-l-glutamic acid and cationic poly-l-lysine were sequentially deposited on an anionic SLB. We found that the fetal liver stem/progenitor cells from the primary culture were selected and formed colonies on all layer-by-layer polypeptide adsorbed SLB surfaces, regardless of the number of alternative layers and the net charges on those layers. Interestingly, these isolated stem/progenitor cells formed colonies which were maintained for an 8 day observation period. Quartz crystal microbalance with dissipation measurements showed that all SLB-polypeptide films were protein resistant with serum levels significantly lower than those on the polypeptide multilayer films without an underlying SLB. We suggest the fluidic SLB promotes selective binding while minimizing the cell-surface interaction due to its nonfouling nature, thus limiting stem cell colonies from spreading. PMID:25243588

  20. Bioinspired, roughness-induced, water and oil super-philic and super-phobic coatings prepared by adaptable layer-by-layer technique

    NASA Astrophysics Data System (ADS)

    Brown, Philip S.; Bhushan, Bharat

    2015-09-01

    Coatings with specific surface wetting properties are of interest for anti-fouling, anti-fogging, anti-icing, self-cleaning, anti-smudge, and oil-water separation applications. Many previous bioinspired surfaces are of limited use due to a lack of mechanical durability. Here, a layer-by-layer technique is utilized to create coatings with four combinations of water and oil repellency and affinity. An adapted layer-by-layer approach is tailored to yield specific surface properties, resulting in a durable, functional coating. This technique provides necessary flexibility to improve substrate adhesion combined with desirable surface chemistry. Polyelectrolyte binder, SiO2 nanoparticles, and silane or fluorosurfactant layers are deposited, combining surface roughness and necessary chemistry to result in four different coatings: superhydrophilic/superoleophilic, superhydrophobic/superoleophilic, superhydrophobic/superoleophobic, and superhydrophilic/superoleophobic. The superoleophobic coatings display hexadecane contact angles >150° with tilt angles <5°, whilst the superhydrophobic coatings display water contact angles >160° with tilt angles <2°. One coating combines both oleophobic and hydrophobic properties, whilst others mix and match oil and water repellency and affinity. Coating durability was examined through the use of micro/macrowear experiments. These coatings display transparency acceptable for some applications. Fabrication via this novel combination of techniques results in durable, functional coatings displaying improved performance compared to existing work where either durability or functionality is compromised.

  1. Bioinspired, roughness-induced, water and oil super-philic and super-phobic coatings prepared by adaptable layer-by-layer technique.

    PubMed

    Brown, Philip S; Bhushan, Bharat

    2015-01-01

    Coatings with specific surface wetting properties are of interest for anti-fouling, anti-fogging, anti-icing, self-cleaning, anti-smudge, and oil-water separation applications. Many previous bioinspired surfaces are of limited use due to a lack of mechanical durability. Here, a layer-by-layer technique is utilized to create coatings with four combinations of water and oil repellency and affinity. An adapted layer-by-layer approach is tailored to yield specific surface properties, resulting in a durable, functional coating. This technique provides necessary flexibility to improve substrate adhesion combined with desirable surface chemistry. Polyelectrolyte binder, SiO2 nanoparticles, and silane or fluorosurfactant layers are deposited, combining surface roughness and necessary chemistry to result in four different coatings: superhydrophilic/superoleophilic, superhydrophobic/superoleophilic, superhydrophobic/superoleophobic, and superhydrophilic/superoleophobic. The superoleophobic coatings display hexadecane contact angles >150° with tilt angles <5°, whilst the superhydrophobic coatings display water contact angles >160° with tilt angles <2°. One coating combines both oleophobic and hydrophobic properties, whilst others mix and match oil and water repellency and affinity. Coating durability was examined through the use of micro/macrowear experiments. These coatings display transparency acceptable for some applications. Fabrication via this novel combination of techniques results in durable, functional coatings displaying improved performance compared to existing work where either durability or functionality is compromised. PMID:26353971

  2. Layer-by-layer assembly synthesis of ZnO/SnO{sub 2} composite nanowire arrays as high-performance anode for lithium-ion batteries

    SciTech Connect

    Wang, Jiazheng; Du, Ning; Zhang, Hui; Yu, Jingxue; Yang, Deren

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer SnO{sub 2} nanoparticles was deposited on ZnO nanoarrays through layer-by-layer assembly. Black-Right-Pointing-Pointer The composite nanowire arrays show improved performance as anode for Li-ion battery. Black-Right-Pointing-Pointer Improved performance was attributed to the combining advantages of each ingredient. -- Abstract: A layer-by-layer approach has been developed to synthesize ZnO/SnO{sub 2} composite nanowire arrays on copper substrate. ZnO nanowire arrays have been first prepared on copper substrate through seed-assisted method, and then, the surface of ZnO nanowires have been modified by the polyelectrolyte. After oxidation-reduction reaction, SnO{sub 2} layer has been deposited onto the surface of ZnO nanowires. The as-synthesized ZnO/SnO{sub 2} composite nanowire arrays have been applied as anode for lithium-ion batteries, which show high reversible capacity and good cycling stability compared to pure ZnO nanowire arrays and SnO{sub 2} nanoparticles. It is believed that the improved performance may be attributed to the high capacity of SnO{sub 2} and the good cycling stability of the array structure on current collector.

  3. Surface immobilization of a tetra-ruthenium substituted polyoxometalate water oxidation catalyst through the employment of conducting polypyrrole and the layer-by-layer (LBL) technique.

    PubMed

    Anwar, Nargis; Sartorel, Andrea; Yaqub, Mustansara; Wearen, Kevin; Laffir, Fathima; Armstrong, Gordon; Dickinson, Calum; Bonchio, Marcella; McCormac, Timothy

    2014-06-11

    A tetra Ru-substituted polyoxometalate Na10[{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2] (Ru4POM) has been successfully immobilised onto glassy carbon electrodes and indium tin oxide (ITO) coated glass slides through the employment of a conducting polypyrrole matrix and the layer-by-layer (LBL) technique. The resulting Ru4POM doped polypyrrole films showed stable redox behavior associated with the Ru centres within the Ru4POM, whereas, the POM's tungsten-oxo redox centres were not accessible. The films showed pH dependent redox behavior within the pH range 2-5 whilst exhibiting excellent stability towards redox cycling. The layer-by-layer assembly was constructed onto poly(diallyldimethylammonium chloride) (PDDA) modified carbon electrodes by alternate depositions of Ru4POM and a Ru(II) metallodendrimer. The resulting Ru4POM assemblies showed stable redox behavior for the redox processes associated with Ru4POM in the pH range 2-5. The charge transfer resistance of the LBL films was calculated through AC-Impedance. Surface characterization of both the polymer and LBL Ru4POM films was carried out using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Initial investigations into the ability of the Ru4POM LBL films to electrocatalytically oxidise water at pH 7 have also been conducted. PMID:24758586

  4. Peptide isolated from Cry1Ab16 toxin present in Bacillus thuringiensis: Synthesis and morphology data for layer-by-layer films studied by atomic force microscopy.

    PubMed

    Plácido, Alexandra; de Oliveira Farias, Emanuel Airton; Marani, Mariela M; Gomes Vasconcelos, Andreanne; Leite, José R S A; Delerue-Matos, Cristina

    2016-09-01

    The peptide PcL342-354C was obtained from the Cry1Ab16 toxin present in Bacillus thuringiensis ("Computational Modeling Deduced Three Dimensional Structure of Cry1Ab16 Toxin from B. thuringiensis AC11" (Kashyap, 2012) [1]). In this data article, we report the synthesis and characterization of the PcL342-354C peptide by MALDI-TOF/TOF mass spectrometry. In addition, the preparation of layer-by-layer films is shown based on interspersion of this peptide with both polyethylenimine (PEI) and poly(sodium 4-styrenesulfonate) (PSS), self-assembled on ITO (indium tin oxide) electrodes. The morphology of the ITO/PEI/PSS/PcL342-354C film was analyzed using atomic force microscopy (AFM). We also evaluated the effect of the number of bilayers in ITO/PEI/(PSS/PcL342-354C) n on the morphology of the film using AFM amplitude images. Further details about this study were published elsewhere, "Layer-by-layer films containing peptides of the Cry1Ab16 toxin from B. thuringiensis for potential biotechnological applications," (Plácido et al., 2016) [2]. PMID:27294178

  5. The fabrication of nanocomposite thin films with TiO2 nanoparticles by the layer-by-layer deposition method for multifunctional cotton fabrics.

    PubMed

    Ugur, Sule S; Sariişik, Merih; Aktaş, A Hakan

    2010-08-13

    A multilayer nanocomposite film composed of anatase TiO(2) nanoparticles was fabricated on cationically modified woven cotton fabrics by the layer-by-layer molecular self-assembly technique. For cationic surface charge, cotton fabrics were pre-treated with 2,3-epoxypropyltrimethylammonium chloride (EP3MAC) by a pad-batch method. Attenuated total reflectance Fourier transform infrared spectroscopy (FTIR), x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to verify the presence of deposited nanolayers. Photocatalytic activities of the nanocomposite films were evaluated through the degradation of red wine pollutant. Nano-TiO(2) deposition enhanced the protection of cotton fabrics against UV radiation in comparison with the untreated cotton fabrics. Air permeability and whiteness value analysis was performed on the fabrics before and after the treatment with TiO(2) nanoparticles by the layer-by-layer deposition method. Tensile strength tests of the warp and weft yarns were performed to evaluate the effect of solution pH value changes during the alternate dipping procedures. For the first time the durability of the effect of the self-assembled multilayer films on the cotton fabric functional properties was analyzed after 10 and 20 washing cycles at 40 degrees C for 30 min. PMID:20647626

  6. Bioinspired, roughness-induced, water and oil super-philic and super-phobic coatings prepared by adaptable layer-by-layer technique

    PubMed Central

    Brown, Philip S.; Bhushan, Bharat

    2015-01-01

    Coatings with specific surface wetting properties are of interest for anti-fouling, anti-fogging, anti-icing, self-cleaning, anti-smudge, and oil-water separation applications. Many previous bioinspired surfaces are of limited use due to a lack of mechanical durability. Here, a layer-by-layer technique is utilized to create coatings with four combinations of water and oil repellency and affinity. An adapted layer-by-layer approach is tailored to yield specific surface properties, resulting in a durable, functional coating. This technique provides necessary flexibility to improve substrate adhesion combined with desirable surface chemistry. Polyelectrolyte binder, SiO2 nanoparticles, and silane or fluorosurfactant layers are deposited, combining surface roughness and necessary chemistry to result in four different coatings: superhydrophilic/superoleophilic, superhydrophobic/superoleophilic, superhydrophobic/superoleophobic, and superhydrophilic/superoleophobic. The superoleophobic coatings display hexadecane contact angles >150° with tilt angles <5°, whilst the superhydrophobic coatings display water contact angles >160° with tilt angles <2°. One coating combines both oleophobic and hydrophobic properties, whilst others mix and match oil and water repellency and affinity. Coating durability was examined through the use of micro/macrowear experiments. These coatings display transparency acceptable for some applications. Fabrication via this novel combination of techniques results in durable, functional coatings displaying improved performance compared to existing work where either durability or functionality is compromised. PMID:26353971

  7. The fabrication of nanocomposite thin films with TiO2 nanoparticles by the layer-by-layer deposition method for multifunctional cotton fabrics

    NASA Astrophysics Data System (ADS)

    Ugur, Şule S.; Sariişik, Merih; Hakan Aktaş, A.

    2010-08-01

    A multilayer nanocomposite film composed of anatase TiO2 nanoparticles was fabricated on cationically modified woven cotton fabrics by the layer-by-layer molecular self-assembly technique. For cationic surface charge, cotton fabrics were pre-treated with 2,3-epoxypropyltrimethylammonium chloride (EP3MAC) by a pad-batch method. Attenuated total reflectance Fourier transform infrared spectroscopy (FTIR), x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to verify the presence of deposited nanolayers. Photocatalytic activities of the nanocomposite films were evaluated through the degradation of red wine pollutant. Nano-TiO2 deposition enhanced the protection of cotton fabrics against UV radiation in comparison with the untreated cotton fabrics. Air permeability and whiteness value analysis was performed on the fabrics before and after the treatment with TiO2 nanoparticles by the layer-by-layer deposition method. Tensile strength tests of the warp and weft yarns were performed to evaluate the effect of solution pH value changes during the alternate dipping procedures. For the first time the durability of the effect of the self-assembled multilayer films on the cotton fabric functional properties was analyzed after 10 and 20 washing cycles at 40 °C for 30 min.

  8. Capillary Flow Layer-by-Layer: A Microfluidic Platform for the High-Throughput Assembly and Screening of Nanolayered Film Libraries

    PubMed Central

    2015-01-01

    Layer-by-layer (LbL) assembly is a powerful tool with increasing real world applications in energy, biomaterials, active surfaces, and membranes; however, the current state of the art requires individual sample construction using large quantities of material. Here we describe a technique using capillary flow within a microfluidic device to drive high-throughput assembly of LbL film libraries. This capillary flow layer-by-layer (CF-LbL) method significantly reduces material waste, improves quality control, and expands the potential applications of LbL into new research spaces. The method can be operated as a simple lab benchtop apparatus or combined with liquid-handling robotics to extend the library size. Here we describe and demonstrate the technique and establish its ability to recreate and expand on the known literature for film growth and morphology. We use the same platform to assay biological properties such as cell adhesion and proliferation and ultimately provide an example of the use of this approach to identify LbL films for surface-based DNA transfection of commonly used cell types. PMID:24836460

  9. Ultrafast atomic layer-by-layer oxygen vacancy-exchange diffusion in double-perovskite LnBaCo2O5.5+δ thin films.

    PubMed

    Bao, Shanyong; Ma, Chunrui; Chen, Garry; Xu, Xing; Enriquez, Erik; Chen, Chonglin; Zhang, Yamei; Bettis, Jerry L; Whangbo, Myung-Hwan; Dong, Chuang; Zhang, Qingyu

    2014-01-01

    Surface exchange and oxygen vacancy diffusion dynamics were studied in double-perovskites LnBaCo2O5.5+δ (LnBCO) single-crystalline thin films (Ln = Er, Pr; -0.5 < δ < 0.5) by carefully monitoring the resistance changes under a switching flow of oxidizing gas (O2) and reducing gas (H2) in the temperature range of 250 ~ 800 °C. A giant resistance change ΔR by three to four orders of magnitude in less than 0.1 s was found with a fast oscillation behavior in the resistance change rates in the ΔR vs. t plots, suggesting that the oxygen vacancy exchange diffusion with oxygen/hydrogen atoms in the LnBCO thin films is taking the layer by layer oxygen-vacancy-exchange mechanism. The first principles density functional theory calculations indicate that hydrogen atoms are present in LnBCO as bound to oxygen forming O-H bonds. This unprecedented oscillation phenomenon provides the first direct experimental evidence of the layer by layer oxygen vacancy exchange diffusion mechanism. PMID:24751601

  10. Development and characterization of a layer by layer ultrasound assisted spray deposition process for thin polymer films

    NASA Astrophysics Data System (ADS)

    Balakrishnan, Anandh

    An Ultrasound assisted Atomization (UA) system has been developed and investigated to synthesize ˜20microm polyurethane thin films with uniform, repeatable thickness and microstructure. The UA system comprised a 20 kHz atomizer probe mounted on 750 W/cm2 transducer, a heated glass chamber and a rotating substrate. The rationale for the work has been built through a careful Design of Experiments (DoE) that sought to answer questions regarding the process-microstructure relationships from both the spray and material points of view. The independent variables chosen were the polymer solution weight percentage (0.2%, 2%, and 4%), power amplitude (energy) percentage supplied to the nozzle (23%, 29%, 37%, and 46%),the temperature of deposition (45°C, 80°C) and flow rate (50microL/min, 150microL/min). The research questions focused on influence of the process parameters on the microstructure and properties of the film. One of the problems involved fixing the trajectory of the spray and also making use of the droplet surfaces created by the spray. To achieve this, a simple air-draft attachment was devised and the influence of the same was evaluated through process and film characterization experiments. A mechanism for the draft has been schematically provided. The use of such a draft to fabricate thin polymer films via ultrasound atomization has not been achieved before and represents a 'first step' in advancing this ultrasound technology. The primary findings of the work were that the film microstructure and properties were heavily influenced by the flow rate, energy of atomization, and test temperature. In addition, the droplet diameters seemed to be readily amenable to change for the 0.2 and 2% solutions and the use of the air-draft made the process feasible, repeatable and accurate. For the 4% solutions, viscosity seemed to stabilize the liquid solution film at the tip requiring larger energies of atomization. In all, relative to the 0.2% films the fracture strengths

  11. Layer-by-layer immobilization of quaternized carboxymethyl chitosan/organic rectorite and alginate onto nanofibrous mats and their antibacterial application.

    PubMed

    Jiang, Linbin; Lu, Yuan; Liu, Xingyun; Tu, Hu; Zhang, Jianwei; Shi, Xiaowen; Deng, Hongbing; Du, Yumin

    2015-05-01

    Quaternized carboxymethyl chitosan (QCM-chitosan) and organic rectorite (OREC) immobilized nanofibrous mats are fabricated via layer-by-layer (LBL) technique in a self-assembly manner. The negatively charged cellulose nanofibrous mats hydrolyzed from electrospun cellulose acetate (CEL) mats are alternately modified with the positively charged QCM-chitosan and OREC intercalated composites and the negatively charged sodium alginate (ALG) via LBL technique. The morphology and antibacterial activity of the resultant mats are studied by changing the number of deposition bilayers, the compositions of dipping solutions and outermost layer. X-ray photoelectron spectroscopy results imply that QCM-chitosan and OREC are coated on cellulose mats. Besides, wide angle X-ray diffraction and small angle X-ray diffraction are applied to investigate the crystalline of the composite mats and the interlayer distance of OREC, respectively. The antibacterial activity of the mats increases with the incorporation of OREC into LBL films. PMID:25659718

  12. Dynamics of the layer-by-layer assembly of a poly(acrylic acid)-lanthanide complex colloid and poly(diallyldimethyl ammonium).

    PubMed

    Xu, Jiali; Wang, Zhiliang; Wen, Lingang; Zhou, Xianju; Xu, Jian; Yang, Shuguang

    2016-01-21

    Poly(acrylic acid) (PAA) and lanthanide (Ln) ions, such as Ce(3+), Eu(3+), and Tb(3+), were prepared as dispersed complex colloidal particles through three different protocols with rigorous control of the pH value and mixing ratio. The negatively charged PAA-Ln complex particles were layer-by-layer (LbL) assembled with positively charged poly(diallyldimethyl ammonium) (PDDA) to prepare a thin film. The film thickness growth is much quicker than PDDA/PAA film. Due to the incorporation of Ln(3+) ions, the film exhibits fluorescence. During LbL assembly, PDDA-PAA association based on electrostatic force and PAA-Ce association based on coordination are in competition, which leads to the LbL assembly of PDDA and PAA-Ln complex colloidal particles being a complicated dynamic process. PMID:26549538

  13. Nanostructured composite films of ceria nanoparticles with anti-UV and scratch protection properties constructed using a layer-by-layer strategy

    NASA Astrophysics Data System (ADS)

    Zhang, Songsong; Li, Jie; Guo, Xianpeng; Liu, Lianhe; Wei, Hao; Zhang, Yingwei

    2016-09-01

    Rare earth cerium oxide (ceria) nanoparticles have attracted extensive research attention due to their advantageous anti-UV and anti-scratch properties. However, a general and facile method for the fabrication of composite films using ceria and possessing these advantages is still lacking. Here, we report the fabrication of multilayers of ceria and polymeric species poly(styrene sulfonate) (PSS) and poly(diallyl-dimethyl ammonium) (PDDA) via the layer-by-layer deposition strategy. The thickness of the multilayers increased linearly with the number of bilayers, indicating accurate control of the film structure in the nanoscopic range. The constructed multilayers were transparent in the visible spectral region and at the same time presented anti-UV properties. In addition, the multilayers also presented scratch protection properties.

  14. Titanium modified with layer-by-layer sol-gel tantalum oxide and an organodiphosphonic acid: a coating for hydroxyapatite growth.

    PubMed

    Arnould, C; Volcke, C; Lamarque, C; Thiry, P A; Delhalle, J; Mekhalif, Z

    2009-08-15

    Titanium and its alloys are widely used in surgical implants due to their appropriate properties like corrosion resistance, biocompatibility, and load bearing. Unfortunately when metals are used for orthopedic and dental implants there is the possibility of loosening over a long period of time. Surface modification is a good way to counter this problem. A thin tantalum oxide layer obtained by layer-by-layer (LBL) sol-gel deposition on top of a titanium surface is expected to improve biocorrosion resistance in the body fluid, biocompatibility, and radio-opacity. This elaboration step is followed by a modification of the tantalum oxide surface with an organodiphosphonic acid self-assembled monolayer, capable of chemically binding to the oxide surface, and also improving hydroxyapatite growth. The different steps of this proposed process are characterized by surfaces techniques like contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). PMID:19481760

  15. Construction and evaluation of nitric oxide generating vascular graft material loaded with organoselenium catalyst via layer-by-layer self-assembly.

    PubMed

    An, Jun; Chen, SiYuan; Gao, JingChen; Zhang, Xu; Wang, YuanYuan; Li, YanDong; Mikhalovsky, Sergey; Kong, DeLing; Wang, ShuFang

    2015-08-01

    A new biomimetic material for artificial blood vessel with in situ catalytic generation of nitric oxide (NO) was prepared in this study. Organoselenium immobilized polyethyleneimine as NO donor catalyst and sodium alginate were alternately loaded onto the surface of electrospun polycaprolactone matrix via electrostatic layer-by-layer self-assembly. This material revealed significant NO generation when contacting NO donor S-nitrosoglutathione (GSNO). Adhesion and spreading of smooth muscle cells were inhibited on this material in the presence of GSNO, while proliferation of endothelial cells was promoted. In vitro platelet adhesion and arteriovenous shunt experiments demonstrated good antithrombotic properties of this material, with inhibited platelet activation and aggregation, and prevention of acute thrombosis. This study may provide a new method of improving cellular function and antithrombotic property of vascular grafts. PMID:26014212

  16. Wavefunction engineering: From quantum wells to near-infrared type-II colloidal quantum dots synthesized by layer-by-layer colloidal epitaxy.

    PubMed

    Li, J Jack; Tsay, James M; Michalet, Xavier; Weiss, Shimon

    2005-11-15

    We review the concept and the evolution of bandgap and wavefunction engineering, the seminal contributions of Dr. Chemla to the understanding of the rich phenomena displayed in epitaxially grown quantum confined systems, and demonstrate the application of these concepts to the colloidal synthesis of high quality type-II CdTe/CdSe quantum dots using successive ion layer adsorption and reaction chemistry. Transmission electron microscopy reveals that CdTe/CdSe can be synthesized layer by layer, yielding particles of narrow size distribution. Photoluminescence emission and excitation spectra reveal discrete type-II transitions, which correspond to energy lower than the type-I bandgap. The increase in the spatial separation between photoexcited electrons and holes as a function of successive addition of CdSe monolayers was monitored by photoluminescence lifetime measurements. Systematic increase in lifetimes demonstrates the high level of wavefunction engineering and control in these systems. PMID:22865949

  17. Narrow growth window for stoichiometric, layer-by-layer growth of LaAlO3 thin films using pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Golalikhani, M.; Lei, Q. Y.; Wolak, M. A.; Davidson, B. A.; Xi, X. X.

    2016-06-01

    We study the structure and surface morphology of the 100 nm homoepitaxial LaAlO3 films grown by pulsed laser deposition in a broad range of growth parameters. We show that there is a narrow window of growth conditions in which the stoichiometric, bulk-like structure is obtained while maintaining a 2-dimensional (2D) layer-by-layer growth mode. In our system, these optimum growth conditions are 100 mTorr background pressure with laser energy density 1.5-2 J/cm2. The sensitivity to growth conditions of the stoichiometry and structure of LaAlO3 films can have a crucial role in the 2-D electron gas formed at the LaAlO3/SrTiO3 interface.

  18. Fabrication of N-doped TiO2 coatings on nanoporous Si nanopillar arrays through biomimetic layer by layer mineralization.

    PubMed

    Yan, Yong; Wang, Dong; Schaaf, Peter

    2014-06-14

    Si/N-doped TiO2 core/shell nanopillar arrays with a nanoporous structure are fabricated through a simple protein-mediated TiO2 deposition process. The Si nanopillar arrays are used as templates and alternatively immersed in aqueous solutions of catalytic molecules (protamine, PA) and the titania precursor (titanium(iv) bis(ammonium lactato)dihydroxide, Ti-BALDH) for the layer by layer mineralization of a PA/TiO2 coating. After a subsequent calcination, a N-doped TiO2 layer is formed, and its thickness could be controlled by varying the cycles of deposition. Moreover, the nanoporous structure of the Si nanopillars strongly affects the formation of the TiO2 layer. The obtained Si/TiO2 nanocomposites show significantly improved solar absorption compared with commercially purchased TiO2 nanoparticles. PMID:24754039

  19. A study on the interactions of cationic porphyrin with nano clay platelets in Layer-by-Layer (LbL) self assembled films

    NASA Astrophysics Data System (ADS)

    Bhattacharjee, J.; Banik, Soma; Hussain, S. A.; Bhattacharjee, D.

    2015-07-01

    In the present communication, interaction of tetracationic porphyrin, 5,10,15,10-tetrakis (1-methyl-4-pyrindino) porphyrin tetra (p-toluenesulfonate) (TMPyP) with anionic nano clay platelets laponite has been studied in aqueous clay dispersion and Layer-by-Layer (LbL) self assembled film. Electrostatic adsorption of TMPyP molecules on clay platelets resulted in the flattenening of meso-substituent groups which led to the development of a new adsorbed band in the UV-vis absorption spectra. J-band was also formed due to overlapped organizations of organo-clay hybrid molecules in the LbL film leading to J-aggregates. Atomic force microscopic (AFM) studies gave visual evidence of this favoured organization in the monolayer LbL film.

  20. Multilayered gold/silica nanoparticulate bilayer devices using layer-by-layer self organisation for flexible bending and pressure sensing applications

    SciTech Connect

    Shah Alam, Md.; Mohammed, Waleed S.; Dutta, Joydeep

    2014-02-17

    A pressure and bending sensor was fabricated using multilayer thin films fabricated on a flexible substrate based on layer-by-layer self-organization of 18 nm gold nanoparticles separated by a dielectric layer of 30 nm silica nanoparticles. 50, 75, and 100 gold-silica bi-layered films were deposited and the device characteristics were studied. A threshold voltage was required for electron conduction which increases from 2.4 V for 50 bi-layers to 3.3 V for 100 bi-layers. Upon bending of the device up to about 52°, the threshold voltage and slope of the I-V curves change linearly. Electrical characterization of the multilayer films was carried out under ambient conditions with different pressures and bending angles in the direct current mode. This study demonstrates that the developed multilayer thin films can be used as pressure as well as bending sensing applications.

  1. Layer-by-layer assembly of luminescent ultrathin films by Mg-Al-Eu LDHs nanosheets and organic ligand with high transparency

    NASA Astrophysics Data System (ADS)

    Zhang, Wenjun; Li, Yanlin; Fan, Hongxian

    2016-01-01

    We fabricated a kind of luminescent ordered multilayer transparent ultrathin films (OMTFs) based on inorganic rare earth doped layered double hydroxides (Mg-Al-Eu LDHs) nanosheets and the organic ligand 2-thenoyltrifluoroacetone (TTA) via layer-by-layer assembly method. At the same time, Polyvinyl Alcohol (PVA) aqueous solution was used as intermediate linkers. UV-visible absorption spectroscopy, X-ray diffraction, fluorescence spectroscopy and scanning electron microscopy were introduced to investigate the structure and properties of these films. Surprisingly, the uniformity and the fluorescence emission intensity of OMTFs which utilized polyvinyl Alcohol (PVA) as intermediate linkers are significantly enhanced compared with that of OMTFs without PVA. Herein, it was found that the fluorescence emission intensity of this kind of ultrathin film with PVA displays a monotonic increase as the number of deposition cycles increasing, and further the films which are highly transparent, uniform and ultrathin have potential applications in the optical display devices.

  2. Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery

    PubMed Central

    Xu, Wanxing; Li, Xianfeng; Cao, Jingyu; Zhang, Hongzhang; Zhang, Huamin

    2014-01-01

    In this work we presented a general strategy for the fabrication of membranes with well-defined ions transport channels through solvent-responsive layer-by-layer assembly (SR-LBL). Multilayered poly (diallyldimethylammonium chloride) (PDDA) and poly (acrylic acid) (PAA) complexes were first introduced on the inner pore wall and the surface of sulfonated poly (ether ether ketone)/poly (ether sulfone) (PES/SPEEK) nanofiltration membranes to form ions transport channels with tuned radius. This type of membranes are highly efficient for the separators of batteries especially vanadium flow batteries (VFBs): the VFBs assembled with prepared membranes exhibit an outstanding performance in a wide current density range, which is much higher than that assembled with commercial Nafion 115 membranes. This idea could inspire the development of membranes for other flow battery systems, as well as create further progress in similar areas such as fuel cells, electro-dialysis, chlor-alkali cells, water electrolysis and so on. PMID:24500376

  3. Selective transport of ions and molecules across layer-by-layer assembled membranes of polyelectrolytes, p-sulfonato-calix[n]arenes and Prussian Blue-type complex salts.

    PubMed

    Tieke, Bernd; Toutianoush, Ali; Jin, Wanqin

    2005-11-30

    Our recent studies in the field of ultrathin membranes prepared upon layer-by-layer assembly of various polyionic compounds such as polyelectrolytes, calixarenes and polyelectrolytes, and metal hexacyanoferrate salts such as Prussian Blue are reviewed. It is demonstrated that polyelectrolyte multilayers can be used (a) as nanofiltration and reverse osmosis membranes suitable for water softening and seawater desalination and (b) as molecular sieves and ion sieves for size-selective separation of neutral and charged aromatic compounds. Furthermore, hybrid membranes of p-sulfonato-calixarenes and cationic polyelectrolytes showing specific host-guest interactions with permeating ions are described. The membranes exhibit high selectivities for distinct metal ions. Finally, it is demonstrated that purely inorganic membranes of Prussian Blue (PB) and analogues can be prepared upon multiple sequential adsorption of transition metal cations and hexacyanoferrate anions. Due to the porous lattice of PB, the membranes are useful as ion filters able to separate cesium from sodium ions, for example. PMID:16091277

  4. Dynamic layer-by-layer self-assembly of multi-walled carbon nanotubes on quartz wool for on-line separation of lysozyme in egg white.

    PubMed

    Du, Zhuo; Zhang, Suling; Zhou, Chanyuan; Liu, Miao; Li, Gongke

    2012-05-30

    The multi-walled carbon nanotubes (MWNTs) coated quartz wool (MWNTs/QW) prepared by dynamic layer-by-layer self-assembly was used as solid-phase extraction (SPE) absorbent for on-line separation and preconcentration of lysozyme in egg white. The coating procedures were performed continuously in a flow system operated by a set of sequential injection devices. The quartz wool was placed in a microcolumn forming a loose packing to guarantee the minimized flow impedance and the intimate contact between proteins and absorbent surface. Various parameters affecting SPE efficiency including the volume, pH, ionic strength and flow rate of sample and eluent were systematically studied. The feasibility of the proposed method was validated by successfully applied to the separation of lysozyme in egg white. PMID:22608421

  5. Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery

    NASA Astrophysics Data System (ADS)

    Xu, Wanxing; Li, Xianfeng; Cao, Jingyu; Zhang, Hongzhang; Zhang, Huamin

    2014-02-01

    In this work we presented a general strategy for the fabrication of membranes with well-defined ions transport channels through solvent-responsive layer-by-layer assembly (SR-LBL). Multilayered poly (diallyldimethylammonium chloride) (PDDA) and poly (acrylic acid) (PAA) complexes were first introduced on the inner pore wall and the surface of sulfonated poly (ether ether ketone)/poly (ether sulfone) (PES/SPEEK) nanofiltration membranes to form ions transport channels with tuned radius. This type of membranes are highly efficient for the separators of batteries especially vanadium flow batteries (VFBs): the VFBs assembled with prepared membranes exhibit an outstanding performance in a wide current density range, which is much higher than that assembled with commercial Nafion 115 membranes. This idea could inspire the development of membranes for other flow battery systems, as well as create further progress in similar areas such as fuel cells, electro-dialysis, chlor-alkali cells, water electrolysis and so on.

  6. Layer-By-Layer Assembled Hybrid Film of Carbon Nanotubes/Iron Oxide Nanocrystals for Reagentless Electrochemical Detection of H2O2

    SciTech Connect

    Miao, Yuqing; Wang, Hua; Shao, Yuyan; Tang, Zhiwen; Wang, Jun; Lin, Yuehe

    2009-04-01

    A new approach to construct a reagentless H2O2 electrochemical sensor is described. Iron oxide magnetic nanocystals (IOMNs), as peroxidase mimetics, were employed to assemble a multilayer structure layer by layer. Polythionin was electrodeposited onto the glassy carbon electrode surface to introduce amino groups. Carboxyl functionalized multi-walled carbon nanotubes, amino functionalized IOMNs, and thionin monomers were anchored onto a polythionin-functionalized GC surface in order by carbodiimide or glutaraldehyde chemistry. The resulting multilayer construction with three layers of IOMNs and thionin mediator exhibits excellent electrochemical response to the reduction of H2O2, whereas such a modified electrode with one layer construction only yields a slight response to H2O2 of the same concentration. The tethered MWCNs enlarge the amount of immobilized IOMNs and effectively shuttle electrons between the electrode and the thionin.

  7. Effect of Layer-by-Layer (LbL) Encapsulation of Nano-Emulsified Fish Oil on Their Digestibility Ex Vivo and Skin Permeability In Vitro

    PubMed Central

    Jung, Eun Young; Hong, Ki Bae; Son, Heung Soo; Suh, Hyung Joo; Park, Yooheon

    2016-01-01

    Omega-3 rich fish oils are extremely labile, thus requiring control of oxidation and off flavor development. A recently proposed emulsification method, layer-by-layer (LbL) deposition, was found to be a plausible method to enhance the characteristics of bioactive ingredients, especially lipids. The present work was designed to test the possibility of enhancing the uptake and utilization of omega-3 fatty acids present in fish oil. The bioavailability of nano-emulsified fish oil was monitored in terms of intestinal absorption as well as skin permeability by using the everted intestinal sac model and Franz cell model. The skin permeability and intestinal absorption characteristics was significantly improved by LbL emulsification with lecithin/chitosan/low methoxypectin. Multilayer encapsulation along with nano-emulsification can be a useful method to deliver biologically active lipids and related components, such as fish oil. The protective effect of this tool from lipid oxidation still needs to be verified. PMID:27390723

  8. Layer by layer growth of BaTiO 3 thin films with extremely smooth surfaces by laser molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Wang, H. S.; Ma, K.; Cui, D. F.; Peng, Z. Q.; Zhou, Y. L.; Lu, H. B.; Chen, Z. H.; Li, L.; Yang, G. Z.

    1997-05-01

    Using pure ozone-assisted laser molecular beam epitaxy, we have grown c-axis-oriented single crystal BaTiO 3 thin films on SrTiO 3 substrates at temperatures ( Ts) of 400-750°C and under ambient gas pressures of 5 × 10 -5 to 1 × 10 -1 Pa, respectively. Stripy reflection high-energy electron diffraction (RHEED) patterns and regular RHEED intensity oscillations reveal the smooth surface and layer-by-layer epitaxial growth of the films. Scanning electron microscopy analysis shows that the films are free of pinholes, grain boundaries and outgrowths on the surface. In addition, we found a strong dependence of the film lattice constant c on Ts, which might be related to the strain in the film.

  9. In vivo evaluation of bone-bonding ability of RGD-coated porous implant using layer-by-layer electrostatic self-assembly.

    PubMed

    Yang, Guo-Li; He, Fu-Ming; Yang, Xiao-Feng; Wang, Xiao-Xiang; Zhao, Shi-Fang

    2009-07-01

    RGD has been demonstrated to improve implant osseointegration. However, few studies are known about an effect of RGD coating on a bone-bonding ability of screw-shaped porous implant. The aim of this study was to investigate the effect of RGD coating using the layer-by-layer self-assembly technique on the bone-bonding ability of porous implant. 60 implants of 10 mm in length (30 control and 30 RGD-coated) were inserted into femurs of 30 rabbits and 30 implants of 8 mm in length (15 control and 15 RGD-coated) were inserted into tibias of 15 rabbits. At 4, 8, and 12 weeks post-implantation, femurs and tibias were retrieved and prepared for removal torque tests (RTQ) and histomorphometric evaluation, respectively. No differences were found in the RTQ values between two implants at 4 weeks (p = 0.932). There were statistical significances in the RTQ values at 8 and 12 weeks (p = 0.002, 0.001, respectively). New bone was formed on both implant surfaces. The bone-implant contact pattern appeared to produce a broad-based direct contact in both implants. The RGD-coated implants showed a significantly greater BIC in the threads inside the cortical bone compared with the control implants at 4, 8, and 12 weeks (p = 0.024, 0.041, 0.022, respectively). No differences were found in the bone area within the same threads between two implants at 4 weeks (p = 0.806) whereas differences were found at 8 and 12 weeks (p = 0.009, 0.031, respectively). It was concluded that RGD coating using the layer-by-layer self-assembly technique has a positive effect on the bone-bonding ability of porous implant. PMID:18491389

  10. A method of layer-by-layer gold nanoparticle hybridization in a quartz crystal microbalance DNA sensing system used to detect dengue virus

    NASA Astrophysics Data System (ADS)

    Chen, Sz-Hau; Chuang, Yao-Chen; Lu, Yi-Chen; Lin, Hsiu-Chao; Yang, Yun-Liang; Lin, Chih-Sheng

    2009-05-01

    Dengue virus (DENV) is nowadays the most important arthropod-spread virus affecting humans existing in more than 100 countries worldwide. A rapid and sensitive detection method for the early diagnosis of infectious dengue virus urgently needs to be developed. In the present study, a circulating-flow quartz crystal microbalance (QCM) biosensing method combining oligonucleotide-functionalized gold nanoparticles (i.e. AuNP probes) used to detect DENV has been established. In the DNA-QCM method, two kinds of specific AuNP probes were linked by the target sequences onto the QCM chip to amplify the detection signal, i.e. oscillatory frequency change (ΔF) of the QCM sensor. The target sequences amplified from the DENV genome act as a bridge for the layer-by-layer AuNP probes' hybridization in the method. Besides being amplifiers of the detection signal, the specific AuNP probes used in the DNA-QCM method also play the role of verifiers to specifically recognize their target sequences in the detection. The effect of four AuNP sizes on the layer-by-layer hybridization has been evaluated and it is found that 13 nm AuNPs collocated with 13 nm AuNPs showed the best hybridization efficiency. According to the nanoparticle application, the DNA-QCM biosensing method was able to detect dengue viral RNA in virus-contaminated serum as plaque titers being 2 PFU ml-1 and a linear correlation (R2 = 0.987) of ΔF versus virus titration from 2 × 100 to 2 × 106 PFU ml-1 was found. The sensitivity and specificity of the present DNA-QCM method with nanoparticle technology showed it to be comparable to the fluorescent real-time PCR methods. Moreover, the method described herein was shown to not require expensive equipment, was label-free and highly sensitive.

  11. The coat protein of the yeast double-stranded RNA virus L-A attaches covalently to the cap structure of eukaryotic mRNA.

    PubMed Central

    Blanc, A; Goyer, C; Sonenberg, N

    1992-01-01

    The eukaryotic mRNA 5' cap structure m7GpppX (where X is any nucleotide) interacts with a number of cellular proteins. Several of these proteins were studied in mammalian, yeast, and drosophila cells and found to be involved in translation initiation. Here we describe a novel cap-binding protein, the coat protein of L-A, a double-stranded RNA virus that is persistently maintained in many Saccharomyces cerevisiae strains. The results also suggest that the coat protein of a related double-stranded RNA virus (L-BC) is likewise a cap-binding protein. Strikingly, in contrast to the cellular cap-binding proteins, the interaction between the L-A virus coat protein and the cap structure is through a covalent bond. Images PMID:1630453

  12. Identification of cysteine-644 as the covalent site of attachment of dexamethasone 21-mesylate to murine glucocorticoid receptors in WEHI-7 cells

    SciTech Connect

    Smith, L.I.; Bodwell, J.E.; Mendel, D.B.; Ciardelli, T.; North, W.G.; Munck, A.

    1988-05-17

    Dexamethasone 21-mesylate is a highly specific synthetic glucocorticoid derivative that binds covalently to glucocorticoid receptors via sulfhydryl groups. The authors have identified the amino acid that reacts with the dexamethasone 21-mesylate by using enzymatic digestion and microsequencing for radiolabel. Nonactivated glucocorticoid receptors obtained from labeling intact WEHI-7 mouse thymoma cells with (/sup 3/H)dexamethasone 21-mesylate were immunopurified and analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. Trypsin digestion followed by reversed-phase high-performance liquid chromatography (reversed-phase HPLC) produced a single (/sup 3/H)dexamethasone 21-mesylate labeled peptide. Automated Edman degradation of this peptide revealed that the (/sup 3/H)dexamethasone 21-mesylate was located at position 5 from the amino terminus. Dual-isotope labeling studies with (/sup 3/H)dexamethasone 21-mesylate and (/sup 35/S)methionine demonstrated that this peptide contained methionine. Staphylococcus aureus V8 protease digestion of (/sup 3/H)dexamethasone 21-mesylate labeled steroid-binding subunits generated a different radiolabeled peptide containing label at position 7 from the amino terminus. On the basis of the published amino acid sequence of the murine glucocorticoid receptor, their data clearly identify cysteine-644 as the single residue in the steroid-binding domain that covalently binds dexamethasone 21-mesylate. They have confirmed this finding by demonstrating that a synthetic peptide representing the amino acid sequence 640-650 of the murine glucocorticoid receptor behaves in an identical manner on reversed-phase HPLC as the trypsin-generated peptide from intact cells.

  13. A Hydrogen-Evolving Ni(P2N2)2 Electrocatalyst Covalently Attached to a Glassy Carbon Electrode: Preparation, Characterization, and Catalysis. Comparisons With the Homogeneous Analog

    SciTech Connect

    Das, Atanu K.; Engelhard, Mark H.; Bullock, R. Morris; Roberts, John A.

    2014-07-07

    A hydrogen-evolving homogeneous Ni(P2N2)2 electrocatalyst with peripheral ester groups has been covalently attached to a 1,2,3-triazolyllithium-terminated glassy carbon electrode. The surface-confined complex is an electroctalyst for hydrogen evolution, showing onset of catalytic current at the same potential as the soluble parent complex. X-ray photoemission spectra show excellent agreement between the coupled and homogeneous species. Coverage approaches a dense monolayer. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. The XPS measurements were performed at EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

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

    NASA Astrophysics Data System (ADS)

    Prouty, Malcolm D.

    2007-12-01

    Layer-by-layer (LbL) self-assembly has demonstrated broad perspectives for encapsulating, and the controllable delivery, of drugs. The nano-scale polymer layers have the capability of material protection. Magnetic nanoparticles have great potential to be applied with LbL technology to achieve both "focusing" of the encapsulated drugs to a specific location followed by "switching" them on to release the encapsulated drugs. In this work, Phor21-betaCG(ala), dextran, and dexamethasone were used as model drugs. Encapsulation of these drugs with layer-by-layer self-assembly formed biolnano robotic capsules for controlled delivery and drug release. Silica nanoparticles coated with polyelectrolyte layers of sodium carboxymethyl cellulose (CMC) or gelatin B, along with an oppositely charged peptide drug (Phor2l-betaCG(ala)), were prepared using LbL self-assembly and confirmed using QCM and zeta potential measurements. The peptide drug was assembled as a component of the multilayer walls. The release kinetics of the embedded peptide were determined. Up to 18% of the embedded Phor21-betaCG(ala) was released from the CMC multilayers over a period of 28 hours. The release was based on physiological conditions, and an external control mechanism using magnetic nanoparticles needed to be developed. Magnetic permeability control experiments were setup by applying LbL self-assembly on MnCO3 micro-cores to fabricate polyelectrolyte microcapsules embedded with superparamagnetic gold coated cobalt (Co Au) nanoparticles. An alternating magnetic field was applied to the microcapsules to check for changes in permeability. Permeability experiments were achieved by adding fluorescein isothiocyanate (FITC) labeled dextran to the microcapsule solution. Before an alternating magnetic field was applied, the capsules remained impermeable to the FITC-dextran; however, after an alternating magnetic field was applied for 30 minutes, approximately 99% of the capsules were filled with FITC

  15. Transcutaneous iontophoretic delivery of STAT3 siRNA using layer-by-layer chitosan coated gold nanoparticles to treat melanoma.

    PubMed

    Labala, Suman; Jose, Anup; Venuganti, Venkata Vamsi Krishna

    2016-10-01

    Overexpression of signal transducer and activator of transcription 3 (STAT3) protein prevents apoptosis and enhances proliferation of melanocytes. The aim of this study was to investigate the feasibility of using layer-by-layer assembled gold nanoparticles (LbL-AuNP) as a carrier for iontophoretic delivery of STAT3 siRNA to treat melanoma. Chitosan coated AuNP (AuNP-CS) were prepared by direct reduction of HAuCl4 in the presence of chitosan. The AuNP-CS were then sequentially layered with siRNA and chitosan to form AuNP-CS/siRNA/CS. STAT3 siRNA replaced with scrambled siRNA or sodium alginate were used as controls. The average particle size and zeta-potential of the prepared LbL-AuNP were 150±10nm (PDI: 0.41±0.06) and 35±6mV, respectively. In vitro studies in B16F10 murine melanoma cells showed that AuNP-CS/siRNA/CS inhibited the cell growth by 49.0±0.6% and 66.0±0.2% at 0.25nM and 0.5nM STAT3 siRNA concentration, respectively. Fluorescence microscopy and flow cytometry studies showed a time dependent cell uptake of the LbL-AuNP up to 120min. Clathrin mediated endocytosis was found to be the predominant cell uptake mechanism for LbL-AuNP. STAT3 siRNA loaded LbL-AuNP reduced the STAT3 protein expression by 47.3% in B16F10 cells. Similarly, apoptosis assay showed 29% and 44% of early and late apoptotic events, respectively after treatment with STAT3 siRNA loaded LbL-AuNP. Confocal microscope and skin cryosections showed that application of 0.47mA/cm(2) of anodal iontophoresis enhanced the skin penetration of LbL-AuNP to reach viable epidermis. In conclusion, layer-by-layer chitosan coated AuNP can be developed as a carrier for iontophoretic delivery of STAT3 siRNA to treat melanoma. PMID:27318964

  16. Y{sub 2}O{sub 3}:Yb/Er nanotubes: Layer-by-layer assembly on carbon-nanotube templates and their upconversion luminescence properties

    SciTech Connect

    Huang, Weishi; Shen, Jianfeng; Wan, Lei; Chang, Yu; Ye, Mingxin

    2012-11-15

    Graphical abstract: Well-shaped Y{sub 2}O{sub 3}:Yb/Er nanotubes have been successfully synthesized on a large scale via layer-by-layer assembly on carbon nanotubes templates followed by a subsequent heat treatment process. The as-prepared Y{sub 2}O{sub 3}:Yb/Er nanotubes show a strong red emission corresponding to the {sup 4}F{sub 9/2}–{sup 4}I{sub 15/2} transition of the Er{sup 3+} ions under excitation at 980 nm. Display Omitted Highlights: ► Well-shaped Y{sub 2}O{sub 3}:Yb/Er nanotubes have been successfully synthesized. ► CNTs were used as templates for Y{sub 2}O{sub 3}:Yb/Er nanotubes. ► LBL assembly and calcination were used for preparation of Y{sub 2}O{sub 3}:Yb/Er nanotubes. ► The as-prepared Y{sub 2}O{sub 3}:Yb/Er nanotubes show a strong red emission. -- Abstract: Well-shaped Y{sub 2}O{sub 3}:Yb/Er nanotubes have been successfully synthesized on a large scale via layer-by-layer (LBL) assembly on carbon nanotubes (CNTs) templates followed by a subsequent heat treatment process. The crystal structure, element analysis, morphology and upconversion luminescence properties were characterized. XRD results demonstrate that the diffraction peaks of the samples calcinated at 800 °C or above can be indexed to the pure cubic phase of Y{sub 2}O{sub 3}. SEM images indicate that a large quantity of uniform and rough nanotubes with diameters of about 30–60 nm can be observed. The as-prepared Y{sub 2}O{sub 3}:Yb/Er nanotubes show a strong red emission corresponding to the {sup 4}F{sub 9/2}–{sup 4}I{sub 15/2} transition of the Er{sup 3+} ions under excitation at 980 nm, which have potential applications in such fields as nanoscale devices, molecular catalysts, nanobiotechnology, photonics and optoelectronics.

  17. Covalent attachment of aptamer onto nanocomposite as a high performance electrochemical sensing platform: Fabrication of an ultra-sensitive ibuprofen electrochemical aptasensor.

    PubMed

    Roushani, Mahmoud; Shahdost-Fard, Faezeh

    2016-11-01

    In the present study, we report a selective electrochemical aptasensor for the ultrasensitive detection of an anti-inflammatory drug, ibuprofen (IBP). The proposed system was achieved by the modification of a glassy carbon electrode (GCE) with multiwalled carbon nanotubes/ionic liquid/chitosan (MWCNTs/IL/Chit) nanocomposite and the covalent immobilization of the IBP specific aptamer (Apt) onto the modified electrode surface followed by methylene blue (MB) intercalated onto the Apt as the electrochemical redox marker. Upon the incubation of the IBP as a target in the proposed aptasensor, the peak current of MB decreases due to the formation of the Apt-IBP complex and the displacement of MB from the immobilized Apt onto the modified electrode surface. The nanocomposite not only increases the electrode surface area and accelerate the electron transfer kinetics but also it provides a highly stable matrix to enhance the loading amount of the Apt DNA sequence. Through differential pulse voltammetry (DPV) experiments, it was found that the proposed aptasensor could detect the IBP with a linear range (70pM up to 6μM) and the detection limit (LOD) as low as 20pM. The results showed that the aptasensor had good sensitivity, stability, reproducibility, and specificity to detect the IBP. The proposed aptasensor was successfully applied for measuring the IBP concentration in real samples. Based on our experiments we can say that the present method proposes new horizons for the development of other aptasensors for diagnostic application in biosensing. PMID:27524004

  18. Using in vitro selection to direct the covalent attachment of human immunodeficiency virus type 1 Rev protein to high-affinity RNA ligands.

    PubMed Central

    Jensen, K B; Atkinson, B L; Willis, M C; Koch, T H; Gold, L

    1995-01-01

    We have used an in vitro selection procedure called crosslinking SELEX (SELEX = systematic evolution of ligands by exponential enrichment) to identify RNA sequences that bind with high affinity and crosslink to the Rev protein from human immunodeficiency virus type 1 (HIV-1). A randomized RNA library substituted with the photoreactive chromophore 5-iodouracil was irradiated with monochromatic UV light in the presence of Rev. Those sequences with the ability to photocrosslink to Rev were partitioned from the rest of the RNA pool, amplified, and used for the next round of selection. Rounds of photocrosslinking selection were alternated with rounds of selection for RNA sequences with high affinity to Rev. This iterative, dual-selection method yielded RNA molecules with subnanomolar dissociation constants and high efficiency photocrosslinking to Rev. Some of the RNA molecules isolated by this procedure form a stable complex with Rev that is resistant to denaturing gel electrophoresis in the absence of UV irradiation. In vitro selection of nucleic acids by using modified nucleotides allows the isolation of nucleic acid molecules with potentially limitless chemical capacities to covalently attack a target molecule. Images Fig. 2 Fig. 3 Fig. 4 Fig. 5 PMID:8618873

  19. Spectroscopic and structural insights on molecular assembly consisting high potential zinc phthalocyanine photosensitizer attached to PyC60 through non-covalent interaction

    NASA Astrophysics Data System (ADS)

    Ray, Anamika; Santhosh, Kotni; Bhattacharya, Sumanta

    2015-01-01

    Efforts to improve the ease of self-assembly formation through non-covalent interaction has led to the development of zinc phthalocyanine (zinc-2,9,16,23-tetra-tert-butyl phthalocyanine, i.e., ZnPc) as a high potential photosensitizer molecule towards C60 pyrrolidine tris-acid ethyl ester (PyC60) in toluene and 1,2-dichlorobenzene (DCB). Steady state fluorescence experiment elicits efficient quenching of the fluorescence intensity of both H2- and ZnPc in presence of PyC60. The average value of binding constant for PyC60/H2-Pc and PyC60/ZnPc systems in toluene (DCB) are determined to be 9910 (13,460) and 12,710 (24,060) dm3 mol-1, respectively. Lifetime experiment yields ∼3 times larger magnitude of charge separated rate constant for the PyC60/ZnPc system compared to PyC60/H2-Pc in toluene. Photoinduced energy transfer between PyC60 and H2- (/ZnPc) has been evidenced with nanosecond laser photolysis method; transient absorption studies establish that energy transfer from TPyC60∗ to H2- and ZnPc occurs predominantly, as confirmed by the consecutive appearance of the triplet states of PyC60.

  20. Spectroscopic and structural insights on molecular assembly consisting high potential zinc phthalocyanine photosensitizer attached to PyC60 through non-covalent interaction.

    PubMed

    Ray, Anamika; Santhosh, Kotni; Bhattacharya, Sumanta

    2015-01-25

    Efforts to improve the ease of self-assembly formation through non-covalent interaction has led to the development of zinc phthalocyanine (zinc-2,9,16,23-tetra-tert-butyl phthalocyanine, i.e., ZnPc) as a high potential photosensitizer molecule towards C60 pyrrolidine tris-acid ethyl ester (PyC60) in toluene and 1,2-dichlorobenzene (DCB). Steady state fluorescence experiment elicits efficient quenching of the fluorescence intensity of both H2- and ZnPc in presence of PyC60. The average value of binding constant for PyC60/H2-Pc and PyC60/ZnPc systems in toluene (DCB) are determined to be 9910 (13,460) and 12,710 (24,060) dm(3) mol(-1), respectively. Lifetime experiment yields ∼3 times larger magnitude of charge separated rate constant for the PyC60/ZnPc system compared to PyC60/H2-Pc in toluene. Photoinduced energy transfer between PyC60 and H2- (/ZnPc) has been evidenced with nanosecond laser photolysis method; transient absorption studies establish that energy transfer from (T)PyC60(∗) to H2- and ZnPc occurs predominantly, as confirmed by the consecutive appearance of the triplet states of PyC60. PMID:25104284

  1. A Competition Assay to Identify Amyloidogenesis Inhibitors by Monitoring the Fluorescence Emitted by the Covalent Attachment of a Stilbene Derivative to Transthyretin

    PubMed Central

    Choi, Sungwook; Kelly, Jeffery W.

    2011-01-01

    Herein we demonstrate that competition between candidate kinetic stabilizer binding to transthyretin (TTR) and stilbene binding to and reaction with the same thyroxine sites within TTR can be utilized to discover potent and highly selective non-covalent TTR amyloidogenesis inhibitors. We report two stilbenes, S1 and S2, for use in distinct competition assays. Each bind selectively to TTR and then chemoselectively react to form an amide bond with the Lys-15 residue of TTR, creating a fluorescent conjugate. We used 28 TTR kinetic stabilizers exhibiting a known spectrum of plasma TTR binding selectivities and TTR amyloid fibril inhibition efficacies to validate the “TTR fluorescence conjugate competition assay”. The kinetic stabilizers competed with S1 for binding to recombinant TTR in buffer and with S2 for binding to endogenous levels of TTR in human blood serum. In both assay scenarios, we demonstrate that the lower the TTR-stilbene conjugate fluorescence after a 3 h competition, the greater the binding selectivity and potency of the candidate TTR kinetic stabilizer. These assays, particularly the assay utilizing S2 in human serum, replace two assays previously utilized to gather the same information. While not the focus of this manuscript, it is clear that the “TTR fluorescence conjugate competition assay” could be adapted for high throughput screening applications. PMID:21273081

  2. Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni(II).

    PubMed

    Das, Atanu K; Engelhard, Mark H; Lense, Sheri; Roberts, John A S; Bullock, R Morris

    2015-07-21

    Covalent tethering of P(Ph)2N(C6H4C≡CH)2 ligands (P(Ph)2N(C6H4C≡CH)2 = 1,5-di-(4-ethynylphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) to planar, azide-terminated glassy carbon electrode surfaces has been accomplished using a Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) coupling reaction, using a BH3←P protection-deprotection strategy. Deprotected, surface-confined ligands were metallated using [Ni(II)(MeCN)6](BF4)2. X-ray photoelectron spectroscopic measurements demonstrate that metallation introduced 1.3 equivalents Ni(II) per diphosphine onto the electrode surface. Exposure of the surface to a second diphosphine ligand, P(Ph)2N(Ph)2, resulted in the removal of Ni from the surface. Protection, coupling, deprotection, and metallation conditions were optimized using solution-phase model systems, with benzyl azide as a model for the azide-terminated carbon surface; these reactions generate a [Ni(II)(diphosphine)2](2+) complex. PMID:25811536

  3. Preparation of the antithrombotic and antimicrobial coating through layer-by-layer self-assembly of nattokinase-nanosilver complex and polyethylenimine.

    PubMed

    Wei, Xuetuan; Luo, Mingfang; Liu, Huizhou

    2014-04-01

    The bifunctional coating with antithrombotic and antimicrobial activity was developed using nattokinase (NK) and nanosilver (AgNPs). Firstly, the adsorption interactions between NK and AgNPs were confirmed, and the composite particles of NK-AgNPs were prepared by adsorption of NK with AgNPs. At 5FU/mL of NK concentration, the saturation adsorption capacity reached 24.35 FU/mg AgNPs with a high activity recovery of 97%, and adsorption by AgNPs also enhanced the heat stability and anticoagulant effect of NK. Based on the electrostatic force driven layer-by-layer self-assembly, the NK-AgNPs were further assembled with polyethylenimine (PEI) to form coating. UV-vis analysis showed that the self-assembly process was regular, and atom force microscopy analysis indicated that NK-AgNPs were uniformly embedded into the coating. The NK-AgNPs-PEI composite coating showed potent antithrombotic activity and antibacterial activity. This study developed a novel strategy to construct the bifunctional coating with antithrombotic and antimicrobial properties, and the coating material showed promising potential to be applied in the medical device. PMID:24534431

  4. Optical fiber sensors based on nanostructured coatings fabricated by means of the layer-by-layer electrostatic self-assembly method

    NASA Astrophysics Data System (ADS)

    Arregui, Francisco J.; Matías, Ignacio R.; Claus, Richard O.

    2007-07-01

    The Layer-by-Layer Electrostatic Self-Assembly (ESA) method has been successfully used for the design and fabrication of nanostructured materials. More specifically, this technique has been applied for the deposition of thin films on optical fibers with the purpose of fabricating different types of optical fiber sensors. In fact, optical fiber sensors for measuring humidity, temperature, pH, hydrogen peroxide, glucose, volatile organic compounds or even gluten have been already experimentally demonstrated. The versatility of this technique allows the deposition of these sensing coatings on flat substrates and complex geometries as well. For instance, nanoFabry-Perots and microgratings have been formed on cleaved ends of optical fibers (flat surfaces) and also sensing coatings have been built onto long period gratings (cylindrical shape), tapered fiber ends (conical shape), biconically tapered fibers or even the internal side of hollow core fibers. Among the different materials used for the construction of these sensing nanostructured coatings, diverse types such as polymers, inorganic semiconductors, colorimetric indicators, fluorescent dyes, quantum dots or even biological elements as enzymes can be found. This technique opens the door to the fabrication of new types of optical fiber sensors.

  5. Surface modification of poly(tetramethylene adipate-co-terephthalate) membrane via layer-by-layer assembly of chitosan and dextran sulfate polyelectrolyte multiplayer.

    PubMed

    Yu, Da-Guang; Jou, Chi-Hsiung; Lin, Wen-Ching; Yang, Ming-Chien

    2007-02-15

    The improvement of hydrophilicity and hemocompatibility of poly(tetramethylene adipate-co-terephthalate) (PTAT) membrane was developed via polyelectrolyte multilayers (PEMs) immobilization. The polysaccharide PEMs included chitosan (CS, as a positive-charged and antibacterial agent) and dextran sulfate (DS, as a negative-charged and anti-adhesive agent) were successfully prepared using the aminolyzed PTAT membrane in a layer-by-layer (LBL) self-assembly manner. The obtained results showed that the contact angle of as-modified PTAT membranes reached to the steady value after four bilayers of coating, hence suggesting that the full coverage was achieved. It could be found that the PTAT-PEMs membranes with DS as the outmost layer could resist the platelet adhesion and human plasma fibrinogen (HPF) adsorption, thereby prolonging effectively the blood coagulation times. According to L929 fibroblast cell growth inhibition index, the as-prepared PTAT membranes exhibited non-cytotoxic. Overall results demonstrated that such an easy, valid and shape-independent processing should be potential for surface modification of PTAT membrane in the application of hemodialysis devices. PMID:17174535

  6. Layer-by-layer assembled multilayer films of exfoliated layered double hydroxide and carboxymethyl-β-cyclodextrin for selective capacitive sensing of acephatemet.

    PubMed

    Gong, Jingming; Han, Xinmei; Zhu, Xiaolei; Guan, Zhangqiong

    2014-11-15

    Novel organic-inorganic hybrid ultrathin films were fabricated by alternate assembly of cationic exfoliated Mg-Al-layered double hydroxide (LDH) nanosheets and carboxymethyl-β-cyclodextrin (CMCD) as a polyanion onto a glassy carbon electrode (GCE) via a layer-by-layer (LBL) approach. The multilayer films were then characterized by means of X-ray powder diffraction (XRD), infrared spectroscopy (IR), and scanning electron microscopy (SEM). These films were found to possess a long range stacking order in the normal direction of the substrate with a continuous and uniform morphology. Its electrochemical performance was systematically investigated. Our results demonstrate that such a newly designed (LDH/CMCD)n multilayer film, combining the individual properties of CMCD (a high supramolecule recognition and enrichment capability) together with LDH nanosheets (a rigid inorganic matrix), can be applied to a sensitive, simple, and label-free capacitive detection of acephatemet (AM). Molecular docking calculations further disclose that the selective sensing behavior toward AM may be attributed to the specific binding ability of CMCD to AM. Under the optimized conditions, the capacitive change of AM was proportional to its concentration ranging from 0.001 to 0.10 μg mL(-1) and 0.1 to 0.8 μg mL(-1) with a detection limit 0.6 ng mL(-1) (S/N=3). Toward the goal for practical applications, this simple probe was further evaluated by monitoring AM in real samples. PMID:24912039

  7. Incorporating nanoporous polyaniline into layer-by-layer ionic liquid-carbon nanotube-graphene paper: towards freestanding flexible electrodes with improved supercapacitive performance

    NASA Astrophysics Data System (ADS)

    Sun, Yimin; Fang, Zheng; Wang, Chenxu; Zhou, Aijun; Duan, Hongwei

    2015-09-01

    The growing demand for lightweight and flexible supercapacitor devices necessitates innovation in electrode materials and electrode configuration. We have developed a new type of three-dimensional (3D) flexible nanohybrid electrode by incorporating nanoporous polyaniline (PANI) into layer-by-layer ionic liquid (IL) functionalized carbon nanotube (CNT)-graphene paper (GP), and explored its practical application as a freestanding flexible electrode in a supercapacitor. Our results have demonstrated that the surface modification of graphene nanosheets and CNTs by hydrophilic IL molecules makes graphene and CNTs well-dispersed in aqueous solution, and also improves the hydrophility of the assembled graphene-based paper. Furthermore, the integration of highly conductive one-dimensional (1D) CNTs with two-dimensional (2D) graphene nanosheets leads to 3D sandwich-structured nanohybrid paper with abundant interconnected pores, which is preferred for fast mass and electron transport kinetics. For in situ electropolymerization of PANI on paper electrodes, the IL functionalized CNT-GP (IL-CNT-GP) offers large surface area and interlayer spacing and the unique π surface of graphene and CNTs for efficient and stable loading of PANI. A key finding is that the structural integration of multiple components in this 3D freestanding flexible sheet electrode gives rise to a synergic effect, leading to a high capacitance of 725.6 F g-1 at a current density of 1 A g-1 and good cycling stability by retaining 90% of the initial specific capacitance after 5000 cycles.

  8. A new self-assembled layer-by-layer glucose biosensor based on chitosan biopolymer entrapped enzyme with nitrogen doped graphene.

    PubMed

    Barsan, Madalina M; David, Melinda; Florescu, Monica; Ţugulea, Laura; Brett, Christopher M A

    2014-10-01

    The layer-by-layer (LbL) technique has been used for the construction of a new enzyme biosensor. Multilayer films containing glucose oxidase, GOx, and nitrogen-doped graphene (NG) dispersed in the biocompatible positively-charged polymer chitosan (chit(+)(NG+GOx)), together with the negatively charged polymer poly(styrene sulfonate), PSS(-), were assembled by alternately immersing a gold electrode substrate in chit(+)(NG+GOx) and PSS(-) solutions. Gravimetric monitoring during LbL assembly by an electrochemical quartz microbalance enabled investigation of the adsorption mechanism and deposited mass for each monolayer. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the LbL modified electrodes, in order to establish the contribution of each monolayer to the overall electrochemical properties of the biosensor. The importance of NG in the biosensor architecture was evaluated by undertaking a comparative study without NG in the chit layer. The GOx biosensor's analytical properties were evaluated by fixed potential chronoamperometry and compared with similar reported biosensors. The biosensor operates at a low potential of -0.2V vs., Ag/AgCl, exhibiting a high sensitivity of 10.5 μA cm(-2) mM(-1), and a detection limit of 64 μM. This study shows a simple approach in developing new biosensor architectures, combining the advantages of nitrogen-doped graphene with the LbL technique for enzyme immobilization. PMID:24997303

  9. Layer-by-layer assembly of type I collagen and chondroitin sulfate on aminolyzed PU for potential cartilage tissue engineering application

    NASA Astrophysics Data System (ADS)

    He, Xianyun; Wang, Yingjun; Wu, Gang

    2012-10-01

    In this paper, a two-step method was used to synthesize a biodegradable polyurethane (PU) composed of L-lysine ethyl ester diisocyanate (LDI), poly(ɛ-caprolactone) diols (PCL-diol) and 1,4:3,6-dianhydro-D-sorbitol (isosorbide). Amino groups were introduced onto the surface of the PU membrane by an amination reacting with 1,3-propanediamine to produce polycationic substratum. And then, type I collagen (Col) and chondroitin sulfate (CS) were deposited alternately on the polycationic substratum through layer-by-layer (LBL) assembly technology. The FTIR and 1H NMR results showed that the polyurethane was successfully synthesized. Rhodamine B isothiocyanate (RBITC) fluorescence spectrum indicated that amino groups were successfully introduced onto the PU surface. The results of quartz-crystal microbalance (QCM) and RBITC-Col fluorescence spectroscopy monitoring the LBL assemble process presented that the Col/CS deposited alternately on the PU surface. X-ray photoelectron spectroscopy (XPS) results displayed that the CS deposited on the PU surface as well. The surface of the assembled PU became even smoother observed from the surface morphology by atomic force microscopy (AFM) imaging. The hydrophilicity of the PU membrane was greatly enhanced though the modification of LBL assembly. The PU modified with the adsorption of Col/CS may be a potential application for cartilage tissue engineering due to its created mimicking chondrogenic environment.

  10. Multilayer Films Electrodes Consisted of Cashew Gum and Polyaniline Assembled by the Layer-by-Layer Technique: Electrochemical Characterization and Its Use for Dopamine Determination

    PubMed Central

    Barros, Sergio Bitencourt Araújo; Leite, Cleide Maria da Silva; de Brito, Ana Cristina Facundo; Dos Santos Júnior, José Ribeiro; Zucolotto, Valtencir; Eiras, Carla

    2012-01-01

    We take advantage of polyelectrolyte feature exhibited by natural cashew gum (Anacardium occidentale L.) (CG), found in northeast Brazil, to employ it in the formation of electroactive nanocomposites prepared by layer-by-layer (LbL) technique. We used polyaniline unmodified (PANI) or modified with phosphonic acid (PA), PANI-PA as cationic polyelectrolyte. On the other hand, the CG or polyvinyl sulfonic (PVS) acids were used as anionic polyelectrolytes. The films were prepared with PANI or PANI-PA intercalated with CG or with PVS alternately resulting in four films with different sequences: PANI/CG PANI-PA/CG, PANI/PVS and PANI-PA/PVS, respectively. Analysis by cyclic voltammetry (CV) of the films showed that the presence of gum increases the stability of the films in acidic medium. The performance of the modified electrode of PANI-PA/CG was evaluated in electro analytical determination of dopamine (DA). The tests showed great sensitivity of the film for this analyte that was detected at 10−5 mol L−1. PMID:22505924

  11. Ultrastrong Freestanding Graphene Oxide Nanomembranes with Surface-Enhanced Raman Scattering Functionality by Solvent-Assisted Single-Component Layer-by-Layer Assembly.

    PubMed

    Xiong, Rui; Hu, Kesong; Zhang, Shuaidi; Lu, Canhui; Tsukruk, Vladimir V

    2016-07-26

    We report single-component ultrathin reduced graphene oxide (rGO) nanomembranes fabricated via nonconventional layer-by-layer assembly (LbL) of graphene oxide flakes, using organic solvent instead of water to provide strong complementary interactions and to ensure the uniform layered growth. This unique approach does not require regular polymeric from the assembly process or intermediate surface chemical modification. The resulting ultrastrong freestanding graphene oxide (rGO) LbL nanomembranes with a very low thickness of 3 nm (three GO monolayers) can be transferred over a large surface area across tens of square centimeters by using a facile surface-tension-assisted release technique. These uniform and ultrasmooth nanomembranes with high transparency (up to 93% at 550 nm) and high electrical conductivity (up to 3000 S/m) also exhibit outstanding mechanical strength of 0.5 GPa and a Young's modulus of 120 GPa, which are several times higher than that of other reported regular rGO films. Furthermore, up to 94 wt % of silver nanoplates can be sandwiched between 5 nm GO layers to construct a flexible freestanding protected noble metal monolayer with surface-enhanced Raman scattering properties. These flexible rGO/Ag/rGO nanomembranes can be transferred and conformally coat complex surfaces and show a cleaner Raman signature, enhanced wet stability, and lower oxidation compared to bare Ag nanostructures. PMID:27331853

  12. Hyaluronan/chitosan nanofilms assembled layer-by-layer and their antibacterial effect: A study using Staphylococcus aureus and Pseudomonas aeruginosa.

    PubMed

    Hernandez-Montelongo, J; Lucchesi, E G; Gonzalez, I; Macedo, W A A; Nascimento, V F; Moraes, A M; Beppu, M M; Cotta, M A

    2016-05-01

    In the last few years, chitosan-based coatings have been proposed as antibacterial surfaces for biomedical devices in order to prevent nosocomial infections. In that sense, this work reports the optimized synthesis of hyaluronan/chitosan (HA/CHI) nanofilms assembled layer-by-layer in order to maximize the antibacterial effect for two important human pathogenic bacteria, Staphylococcus aureus and Pseudomonas aeruginosa. In this assembly, HA forms a soft, highly hydrated, and nontoxic film, whereas CHI shows the antimicrobial characteristics. Our HA/CHI nanofilm synthesis optimization was based on changing pH values of the biopolymer stem-solutions and the consequent variation of their ionization degree. Furthermore, the surface density of primary amino groups, which are related to the antibacterial effect, was also enhanced by increasing the number of HA/CHI bilayers. The antibacterial effect of HA/CHI nanofilms was evaluated by the spread plate counting method for both bacteria. These results were correlated with the morphology of nanofilms (characterized using SEM and AFM), as well as with their chemical properties studied by UV-vis, Kelvin Probe Force microscopy and XPS spectroscopy. PMID:26896656

  13. Inkjet-assisted layer-by-layer printing of quantum dot/enzyme microarrays for highly sensitive detection of organophosphorous pesticides.

    PubMed

    Luan, Enxiao; Zheng, Zhaozhu; Li, Xinyu; Gu, Hongxi; Liu, Shaoqin

    2016-04-15

    We present a facile fabrication of layer-by-layer (LbL) microarrays of quantum dots (QDs) and acetylcholinesterase enzyme (AChE). The resulting arrays had several unique properties, such as low cost, high integration and excellent flexibility and time-saving. The presence of organophosphorous pesticides (OPs) can inhibit the AChE activity and thus changes the fluorescent intensity of QDs/AChE microscopic dot arrays. Therefore, the QDs/AChE microscopic dot arrays were used for the sensitive visual detection of OPs. Linear calibration for parathion and paraoxon was obtained in the range of 5-100 μg L(-1) under the optimized conditions with the limit of detection (LOD) of 10 μg L(-1). The arrays have been successfully used for detection of OPs in fruits and water real samples. The new array was validated by comparison with conventional high performance liquid chromatography-mass spectrometry (HPLC-MS). PMID:27016441

  14. Nano-Al{sub 2}O{sub 3} multilayer film deposition on cotton fabrics by layer-by-layer deposition method

    SciTech Connect

    Ugur, Sule S.; Sariisik, Merih; Aktas, A. Hakan

    2011-08-15

    Highlights: {yields} Cationic charges were created on the cotton fibre surfaces with 2,3-epoxypropyltrimethylammonium chloride. {yields} Al{sub 2}O{sub 3} nanoparticles were deposited on the cotton fabrics by layer-by-layer deposition. {yields} The fabrics deposited with the Al{sub 2}O{sub 3} nanoparticles exhibit better UV-protection and significant flame retardancy properties. {yields} The mechanical properties were improved after surface film deposition. -- Abstract: Al{sub 2}O{sub 3} nanoparticles were used for fabrication of multilayer nanocomposite film deposition on cationic cotton fabrics by electrostatic self-assembly to improve the mechanical, UV-protection and flame retardancy properties of cotton fabrics. Cotton fabric surface was modified with a chemical reaction to build-up cationic charge known as cationization. Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy, X-ray Photoelectron Spectroscopy and Scanning Electron Microscopy were used to verify the presence of deposited nanolayers. Air permeability, whiteness value, tensile strength, UV-transmittance and Limited Oxygen Index properties of cotton fabrics were analyzed before and after the treatment of Al{sub 2}O{sub 3} nanoparticles by electrostatic self-assemblies. It was proved that the flame retardancy, tensile strength and UV-transmittance of cotton fabrics can be improved by Al{sub 2}O{sub 3} nanoparticle additive through electrostatic self-assembly process.

  15. Layer-by-Layer Assembly of Multifunctional Flame Retardant Based on Brucite, 3-Aminopropyltriethoxysilane, and Alginate and Its Applications in Ethylene-Vinyl Acetate Resin.

    PubMed

    Wang, Yiliang; Yang, Xiaomei; Peng, Hui; Wang, Fang; Liu, Xiu; Yang, Yunguo; Hao, Jianwei

    2016-04-20

    An efficient and multifunctional brucite/3-aminopropyltriethoxysilane (APTES)/nickel alginate/APTES (B/A/Nia/A) hybrid flame retardant was fabricated via the layer-by-layer assembly technique with brucite, silane coupling agents, nickel chloride, and sodium alginate. The morphology, chemical composition, and structure of the hybrid flame retardant were characterized. The results confirmed the multilayer structure and indicated that the assembled driving forces were electrostatic interactions, dehydration condensation, hydrogen bonds, and coordination bonds. When used in ethylene-vinyl acetate (EVA) resin, the multifunctional flame retardant had better performance than brucite in improving the flame retardancy, smoke suppression, and mechanical properties. With 130 phr loading, the multifunctional flame retardant achieved a limiting oxygen index value of 32.3% and a UL 94 V-0 rating, whereas the brucite achieved only 31.1% and a V-2 rating, respectively. The peak heat release rate and total heat released decreased by 41.5% and 8.9%, respectively. The multifunctional flame retardant had an excellent performance in reducing the smoke, CO, and CO2 production rates. These improvements could be attributed to the catalyzing carbonization of nickel compounds and the formation of more protective char layers. Moreover, the elongation at break increased by 97.5%, which benefited from the improved compatibility and the sacrificial bonds in the nickel alginate. The mechanism of flame retardant, smoke suppression, and toughening is proposed. PMID:27002922

  16. Investigation of TiO2 Thin Film Growth by Layer-by-Layer Self-Assembly for Application to Optical Devices

    NASA Astrophysics Data System (ADS)

    Kyung, Kyu-Hong; Fujimoto, Kouji; Shiratori, Seimei; Kim, Jin-Ho; Kim, Sae-Hoon

    2010-04-01

    Recently, optical thin films fabricated using a water-based process have been strongly demanded. We fabricated TiO2 thin films consisting of poly(diallyl dimethyl ammonium chloride) (PDDA) and titanium(IV) bis(ammonium lactate) dihydroxide (TALH) for optical devices fabricated using layer-by-layer self-assembly. We report the effects of the pH and concentration of a solution, immersion time, and the amount of NaCl added to a solution on the thickness, morphology, surface roughness, and transmittance of fabricated thin films. The thickness, surface morphology, and transparency of (PDDA/TALH) thin films were determined by ellipsometry, field-emission scanning microscopy (FE-SEM), atomic force microscopy (AFM), and ultraviolet-visible (UV-vis) spectrometry. It was found that the thickness and surface morphology of (PDDA/TALH) multilayer films can be controlled by adjusting the TiO2 particle size of TALH solution. TiO2 particle size was controlled by adjusting the pH of TALH solution and the concentration of PDDA solution, and by adding NaCl to PDDA solution. It was found that we can increase deposition speed while maintaining optical quality by suppressing the surface roughness within 10 nm. These experimental results showed that the fabrication speed of thin films can be markedly increased, by approximately 6-fold.

  17. Determination of fluoroquinolone antibiotics through the fluorescent response of Eu(III) based nanoparticles fabricated by layer-by-layer technique.

    PubMed

    Davydov, Nikolay; Zairov, Rustem; Mustafina, Asiya; Syakayev, Viktor; Tatarinov, Dmitry; Mironov, Vladimir; Eremin, Sergei; Konovalov, Alexander; Mustafin, Marat

    2013-06-19

    The present work introduces the determination of fluoroquinolone antibiotics (FQs) in aqueous solutions through the fluorescent response of Eu(TTA)3 and [Eu(TTA)(3)1] (TTA(-) and 1 are thenoyltrifluoroacetonate and phosphine oxide derivative) complexes encapsulated into the polyelectrolyte capsules fabricated through layer-by-layer deposition of poly(sodium 4-styrenesulfonate) (PSS) and polyethyleneimine (PEI). The variation of luminescent core, polyelectrolyte deposition and concentration conditions reveals two modes of fluorescent response on FQs of diverse structure namely the sensitization and quenching of Eu(III) centered luminescence. The obtained regularities reveal the ternary complex formation and the ligand exchange occurring at the interface of polyelectrolyte coated [Eu(TTA)(3)1] based colloids as the reasons of the diverse fluorescent response of Eu(III) centered luminescence on FQs. The factors affecting the fluorescent response have been revealed, which are: the content of luminescent core, the mode of polyelectrolyte deposition, concentration and structure of FQs. The discrimination of moxifloxacin and lomefloxacin from levofloxacin, ofloxacin, difloxacin, perfloxacin through the quenching of Eu(III) luminescence in PSS-[Eu(TTA)(3)1] colloids has been revealed. PMID:23746410

  18. Drying and nondrying layer-by-layer assembly for the fabrication of sodium silicate/TiO2 nanoparticle composite films.

    PubMed

    Zhang, Lianbin; Liu, He; Zhao, Engui; Qiu, Lingying; Sun, Junqi; Shen, Jiacong

    2012-01-24

    Influences of drying and nondrying steps on structures of layer-by-layer (LbL) assembled sodium silicate/TiO(2) nanoparticles films (donated as silicate/TiO(2) films) have been systematically investigated. The nondrying LbL assembly produces highly porous silicate/TiO(2) films with large thickness. In contrast, the silicate/TiO(2) films fabricated with a drying step after each layer deposition are flat and thin without porous structures. In situ atomic force microscopy (AFM) measurements confirm that the sodium silicate and TiO(2) nanoparticles are deposited in their aggregated forms. A N(2) drying step can disintegrate the aggregated silicate and TiO(2) nanoparticles to produce thin silicate/TiO(2) films with compact structures. Without the drying steps, the aggregated silicate and TiO(2) nanoparticles are well retained, and their LbL assembly produces highly porous silicate/TiO(2) films of large thickness. The highly porous silicate/TiO(2) films are demonstrated to be useful as reusable film adsorbents for dye removal from wastewater because they can adsorb a large amount of cationic organic dyes and decompose them under UV irradiation. The present study is meaningful for exploring drying/nondrying steps for tailoring structure and functions of LbL assembled films. PMID:22185571

  19. A layer-by-layer ZnO nanoparticle-PbS quantum dot self-assembly platform for ultrafast interfacial electron injection.

    PubMed

    Eita, Mohamed; Usman, Anwar; El-Ballouli, Ala'a O; Alarousu, Erkki; Bakr, Osman M; Mohammed, Omar F

    2015-01-01

    Absorbent layers of semiconductor quantum dots (QDs) are now used as material platforms for low-cost, high-performance solar cells. The semiconductor metal oxide nanoparticles as an acceptor layer have become an integral part of the next generation solar cell. To achieve sufficient electron transfer and subsequently high conversion efficiency in these solar cells, however, energy-level alignment and interfacial contact between the donor and the acceptor units are needed. Here, the layer-by-layer (LbL) technique is used to assemble ZnO nanoparticles (NPs), providing adequate PbS QD uptake to achieve greater interfacial contact compared with traditional sputtering methods. Electron injection at the PbS QD and ZnO NP interface is investigated using broadband transient absorption spectroscopy with 120 femtosecond temporal resolution. The results indicate that electron injection from photoexcited PbS QDs to ZnO NPs occurs on a time scale of a few hundred femtoseconds. This observation is supported by the interfacial electronic-energy alignment between the donor and acceptor moieties. Finally, due to the combination of large interfacial contact and ultrafast electron injection, this proposed platform of assembled thin films holds promise for a variety of solar cell architectures and other settings that principally rely on interfacial contact, such as photocatalysis. PMID:25163799

  20. Stability and Morphology of Gold Nanoisland Arrays Generated from Layer-by-Layer Assembled Nanoparticle Multilayer Films: Effects of Heating Temperature and Particle Size

    PubMed Central

    Shon, Young-Seok; Aquino, Michael; Pham, ThienLoc V.; Rave, David; Ramirez, Michael; Lin, Kristopher; Vaccarello, Paul; Lopez, Gregory; Gredig, Thomas; Kwon, Chuhee

    2011-01-01

    This article reports the effects of heating temperature and composition of nanoparticle multilayer films on the morphology, stability, and optical property of gold nanoisland films prepared by nanoparticle self-assembly/heating method. First, nanoparticle-polymer multilayer films are prepared by the layer-by-layer assembly. Nanoparticle multilayer films are then heated at temperature ranging from 500 °C to 625 °C in air to induce an evaporation of organic matters from the films. During the heating process, the nanoparticles on the solid surface undergo coalescence, resulting in the formation of nanostructured gold island arrays. Characterization of nanoisland films using atomic force microscopy and UV-vis spectroscopy suggests that the morphology and stability of gold island films change when different heating temperatures are applied. Stable gold nanoisland thin film arrays can only be obtained after heat treatments at or above 575 °C. In addition, the results show that the use of nanoparticles with different sizes produces nanoisland films with different morphologies. Multilayer films containing smaller gold nanoparticles tend to produce more monodisperse and smaller island nanostructures. Other variables such as capping ligands around nanoparticles and molecular weight of polymer linkers are found to have only minimal effects on the structure of island films. The adsorption of streptavidin on the biotin-functionalized nanoisland films is studied for examining the biosensing capability of nanoisland arrays. PMID:21625329

  1. Enzyme and Mediator-coadsorbed Carbon Felt Electrode for Electrochemical Detection of Glucose Covered with Polymer Layers Based on Layer-by-Layer Technique.

    PubMed

    Yabuki, Soichi; Hirata, Yoshiki

    2015-01-01

    Glucose dehydrogenase (GlDH) and ferrocene were coadsorbed on a carbon felt (CF) sheet (5 × 10 mm, 2 mm thickness), which was used to construct an electrode for the electrochemical detection of glucose. A potential of +0.3 V vs. Ag/AgCl was applied on the base CF, and the current was measured. After the addition of glucose, the current increased and reached a steady state within 50 s. The current response was proportional to the glucose concentration up to 20 μM, with a lower detection limit of 1 μM. The surface of the CF electrode was covered by layers of polystyrene sulfonate and poly-L-lysine using layer-by-layer technique. Again the current response was proportional to glucose concentration up to 20 μM, with a lower detection limit of 2 μM. The oxidation current owing to electrochemical interferents such as L-ascorbate and acetaminophen was 1/8 times of the current observed on the unprotected electrode. In addition, the protection imparted stability to the electrode. Our work demonstrates that a GlDH/ferrocene CF electrode, protected with polystyrene sulfonate and poly-L-lysine, could be used for the electrochemical detection of glucose. PMID:26165293

  2. Electrochemical studies of biocatalytic anode of sulfonated graphene/ferritin/glucose oxidase layer-by-layer biocomposite films for mediated electron transfer.

    PubMed

    Inamuddin; Haque, Sufia Ul; Naushad, Mu

    2016-06-01

    In this study, a bioanode was developed by using layer-by-layer (LBL) assembly of sulfonated graphene (SG)/ferritin (Frt)/glucose oxidase (GOx). The SG/Frt biocomposite was used as an electron transfer elevator and mediator, respectively. Glucose oxidase (GOx) from Aspergillus niger was applied as a glucose oxidation biocatalyst. The electrocatalytic oxidation of glucose using GOx modified electrode increases with an increase in the concentration of glucose in the range of 10-50mM. The electrochemical measurements of the electrode was carried out by using cyclic voltammetry (CV) at different scan rates (20-100mVs(-1)) in 30mM of glucose solution prepared in 0.3M potassium ferrocyanide (K4Fe(CN)6) and linear sweep voltammetry (LSV). A saturation current density of 50±2mAcm(-2) at a scan rate of 100mVs(-1) for the oxidation of 30Mm glucose is achieved. PMID:27178792

  3. Layer-by-layer self-assembled osmium polymer-mediated laccase oxygen cathodes for biofuel cells: the role of hydrogen peroxide.

    PubMed

    Scodeller, Pablo; Carballo, Romina; Szamocki, Rafael; Levin, Laura; Forchiassin, Flavia; Calvo, Ernesto J

    2010-08-18

    High potential purified Trametes trogii laccase has been studied as a biocatalyst for oxygen cathodes composed of layer-by-layer self-assembled thin films by sequential immersion of mercaptopropane sulfonate-modified Au electrode surfaces in solutions containing laccase and osmium-complex bound to poly(allylamine), (PAH-Os). The polycation backbone carries the Os redox relay, and the polyanion is the enzyme adsorbed from a solution of a suitable pH so that the protein carries a net negative charge. Enzyme thin films were characterized by quartz crystal microbalance, ellipsometry, cyclic voltammetry, and oxygen reduction electrocatalysis under variable oxygen partial pressures with a rotating disk electrode. New kinetic evidence relevant to biofuel cells is presented on the detection of traces of H(2)O(2), intermediate in the O(2) reduction, with scanning electrochemical microscopy (SECM). Furthermore the inhibitory effect of peroxide on the biocatalytic current resulted in abnormal current dependence on the O(2) partial pressure and peak shape with hysteresis in the polarization curves under stagnant conditions, which is offset upon stirring with the RDE. The new kinetic evidence reported in the present work is very relevant for the operation of biofuel cells under stagnant conditions of O(2) mass transport. PMID:20698679

  4. Layer by layer assembly of ultrathin V₂O₅ anchored MWCNTs and graphene on textile fabrics for fabrication of high energy density flexible supercapacitor electrodes.

    PubMed

    Shakir, Imran; Ali, Zahid; Bae, Jihyun; Park, Jongjin; Kang, Dae Joon

    2014-04-21

    Among transition metal oxides, vanadium oxides have received relatively modest attention for supercapacitor applications. Yet, this material is abundant, relatively inexpensive and offer several oxidation states which can provide a broad range of redox reactions suitable for supercapacitor operation. Electrochemical supercapacitors based on nanostructured vanadium oxide (V₂O₅) suffer from relatively low energy densities as they have low surface area and poor electrical conductivities. To overcome these problems, we developed a layer by layer assembly (LBL) technique in which a graphene layer was alternatively inserted between MWCNT films coated with ultrathin (3 nm) V₂O₅. The insertion of a conductive spacer of graphene between the MWCNT films coated with V₂O₅ not only prevents agglomeration between the MWCNT films but also substantially enhances the specific capacitance by 67%, to as high as ∼2590 F g(-1). Furthermore, the LBL assembled multilayer supercapacitor electrodes exhibited an excellent cycling performance of >97%, capacitance retention over 5000 cycles and a high energy density of 96 W h kg(-1) at a power density of 800 W kg(-1). Our approach clearly offers an exciting opportunity for enhancing the device performance of metal oxide-based electrochemical supercapacitors suitable for next-generation flexible energy storage devices by employing a facile LBL assembly technique. PMID:24604248

  5. Layer-by-Layer Deposition of Organic-Inorganic Hybrid Multilayer on Microporous Polyethylene Separator to Enhance the Electrochemical Performance of Lithium-Ion Battery.

    PubMed

    Xu, Wuxia; Wang, Zhuyi; Shi, Liyi; Ma, Ying; Yuan, Shuai; Sun, Lining; Zhao, Yin; Zhang, Meihong; Zhu, Jiefang

    2015-09-23

    A simple layer-by-layer (LbL) self-assembly process of poly(acrylic acid) (PAA) and ZrO2 was applied to construct functional ultrathin multilayers on polyethylene (PE) separators without sacrificing the excellent porous structure of separators. Such PAA/ZrO2 LbL-modified PE separators possess good electrolyte wettability, excellent electrolyte uptake, high ionic conductivity and large Li(+) transference number. More importantly, the top layer of LbL self-assembly would affect the dissociation of electrolyte and the formation of solid electrolyte interphase (SEI) layer in half-cells. Compared with the pristine and (PAA/ZrO2)1PAA-modified PE separators, (PAA/ZrO2)3-modified PE separator shows a larger Li(+) transference number (0.6) and a faster tendency to form a stable SEI layer, endowing half-cells with excellent capacity retention at high C-rates and superior cycling performance. These fascinating characteristics will provide the LbL self-assembly with a promising method to improve the surface property of PE separators for high performance lithium-ion batteries. PMID:26336109

  6. Formation of layer-by-layer assembled titanate nanotubes filled coating on flexible polyurethane foam with improved flame retardant and smoke suppression properties.

    PubMed

    Pan, Haifeng; Wang, Wei; Pan, Ying; Song, Lei; Hu, Yuan; Liew, Kim Meow

    2015-01-14

    A fire blocking coating made from chitosan, titanate nanotubes and alginate was deposited on a flexible polyurethane (FPU) foam surface by a layer-by-layer assembly technique in an effort to reduce its flammability. First, titanate nanotubes were prepared by a hydrothermal method. And then the coating growth was carried out by alternately submerging FPU foams into chitosan solution, titanate nanotubes suspension and alginate solution. The mass gain of coating on the surface of FPU foams showed dependency on the concentration of titanate nanotubes suspension and the trilayers's number. Scanning electron microscopy indicated that titanate nanotubes were distributed well on the entire surface of FPU foam and showed a randomly oriented and entangled network structure. The cone calorimeter result indicated that the coated FPU foams showed reduction in the peak heat release rate (peak HRR), peak smoke production rate (peak SPR), total smoke release (TSR) and peak carbon monoxide (CO) production compared with those of the control FPU foam. Especially for the FPU foam with only 5.65 wt % mass gain, great reduction in peak HRR (70.2%), peak SPR (62.8%), TSR (40.9%) and peak CO production (63.5%) could be observed. Such a significant improvement in flame retardancy and the smoke suppression property for FPU foam could be attributed to the protective effect of titanate nanotubes network structure formed, including insulating barrier effect and adsorption effect. PMID:25496211

  7. Vitamin B12 Grafted Layer-by-Layer Liposomes Bearing HBsAg Facilitate Oral Immunization: Effect of Modulated Biomechanical Properties.

    PubMed

    Verma, Ashwni Kumar; Sharma, Shweta; Gupta, Pramod; Singodia, Deepak; Kansal, Shaswat; Sharma, Veena; Mishra, Prabhat Ranjan

    2016-07-01

    Adhesion forces of nanoparticulate materials toward biological membrane are crucial for designing a delivery system for therapeutic molecules and vaccines. The present study aims to investigate the impact of surface roughness of the nanoparticulate system in oral delivery of antigen and its targeting to toward intestinal antigen presenting cells. To evaluate this hypothesis, layer-by-layer coated liposomes (LBL-Lipo) were fabricated using sodium alginate and Vitamin B12 conjugated Chitosan (VitB12-Chi) as anionic and cationic polyelectrolyte, respectively. Change in surface roughness was observed on changes in pH from gastric to intestinal conditions attributed to increase and decrease in charge density on VitB12-Chi. Surface roughness was measured in terms of root-mean-square measured by topographical analysis using atomic force microscopy. LBL-Lipo were further characterized for their size, zeta potential, and release behavior to evaluate the potential for oral vaccine delivery. In vitro cell uptake in macrophage cells (J-744) shows about 2- and 3.1-fold increased uptake of rough LBL-Lipo over smooth LBL-Lipo at 37 °C (endocytosis) and 4 °C (endocytosis inhibition) indicating improved biological interaction. Further in vivo immunization study revealed that prototype formulations were able to produce 4.8- and 3.3-fold higher IgG and IgA levels in serum and feces, respectively, in comparison to smooth LBL-Lipo. PMID:27215337

  8. Layer-by-Layer Polyelectrolyte Assisted Growth of 2D Ultrathin MoS2 Nanosheets on Various 1D Carbons for Superior Li-Storage.

    PubMed

    Qu, Qunting; Qian, Feng; Yang, Siming; Gao, Tian; Liu, Weijie; Shao, Jie; Zheng, Honghe

    2016-01-20

    Transitional metal sulfide/carbon hybrids with well-defined structures could not only maximize the functional properties of each constituent but engender some unique synergistic effects, holding great promise for applications in Li-ion batteries and supercapacitors and for catalysis. Herein, a facile and versatile approach is developed to controllably grow 2D ultrathin MoS2 nanosheets with a large quantity of exposed edges onto various 1D carbons, including carbon nanotubes (CNTs), electrospun carbon nanofibers, and Te-nanowire-templated carbon nanofibers. The typical approach involves the employment of layer-by-layer (LBL) self-assembled polyelectrolyte, which controls spatially the uniform growth and orientation of ultrathin MoS2 nanosheets on these 1D carbons irrespective of their surface properties. Such unique structures of the as-prepared CNTs@MoS2 hybrid are significantly favorable for the fast diffusions of both Li-ions and electrons, satisfying the kinetic requirements of high-power lithium ion batteries. As a result, CNTs@MoS2 hybrids exhibit excellent electrochemical performances for lithium storage, including a high reversible capacity (1027 mAh g(-1)), high-rate capability (610 mAh g(-1) at 5 C), and excellent cycling stability (negligible capacity loss after 200 continuous cycles). PMID:26709711

  9. Papillaes-enhanced hydrophobicity of large-sized polytetrafluoroethylene-polyphenylene sulfite soft film prepared by layer-by-layer construction

    NASA Astrophysics Data System (ADS)

    Hou, Cheng Cheng; Wang, Wen Jun; Zhang, Yu; Guan, Zi Sheng

    2012-07-01

    Large-sized superhydrophobic soft film with hierarchical structures were prepared by combining papillaes on the polytetrafluoroethylene-polyphenylene sulfite (PTFE-PPS) surface via layer-by-layer construction on the glass substrate and heat treatment processes, therein, the papillaes were formed by 0.1 μm PTFE coated on the pollen grains. The water contact angles (CAs) and sliding angles (SAs) of the films are strongly dependent on the number density of the papillaes on the PTFE-PPS surface. A superhydrophobic surface with a water CA = 151.5° and SA = 4° was obtained when the number density was about 649 mm-2. The papillaes with micro/submicroscale structures play an important role in the formation of the superhydrophobic surface and can change Wenzel-type surface into Cassie-Baxter-type surface. The condensation of water vapor on the Cassie-Baxter-type PTFE-PPS film is much more difficult than that of on the Wenzel-type film. Our method may develop into a facile method to prepare large-sized soft film with low cost, which limited only by the size of the loading substrates.

  10. Layer-by-layer assembly of graphene oxide on polypropylene macroporous membranes via click chemistry to improve antibacterial and antifouling performance

    NASA Astrophysics Data System (ADS)

    Zhang, Zhen-Bei; Wu, Jing-Jing; Su, Yu; Zhou, Jin; Gao, Yong; Yu, Hai-Yin; Gu, Jia-Shan

    2015-03-01

    Polypropylene is an extensively used membrane material; yet, polypropylene membranes exhibit extremely poor resistance to protein fouling. To ameliorate this issue, graphene oxide (GO) nanosheets were used to modify macroporous polypropylene membrane (MPPM) via layer-by-layer assembly technique through click reaction. First, alkyne-terminated GO was prepared through esterification between carboxyl groups in GO and amide groups in propargylamine; azide-terminated GO was synthesized by the ring-opening reaction of epoxy groups in GO with sodium azide. Second, GO was introduced to the membrane by click chemistry. Characterizations of infrared spectra and X-ray photoelectron spectroscopy confirmed the modification. The sharply decreasing of static water contact angle indicated the improvement of the surface hydrophilicity for GO modified membrane. Introducing GO to the membrane results in a dramatic increase of water flux, improvements in the antifouling characteristics and antibacterial property for the membranes. The pure water flux through the 5-layered GO modified membrane is 1.82 times that through the unmodified one. The water flux restores to 43.0% for the unmodified membrane while to 79.8% for the modified membrane. The relative flux reduction decreases by 32.1% due to GO modification. The antibacterial property was also enhanced by two-thirds. These results demonstrate that the antifouling and antibacterial characteristics can be raised by tethering GO to the membrane surface.

  11. Characterization and nanoindentation testing of thin ZrO 2 films synthesized using layer-by-layer (LbL) deposited organic templates

    NASA Astrophysics Data System (ADS)

    Zlotnikov, I.; Gotman, I.; Gutmanas, E. Y.

    2008-12-01

    Thin organic LbL (layer-by-layer) films with negatively charged surface were used as templates for biomimetic deposition of ZrO 2 on Si wafers by hydrolysis of Zr(SO 4) 2 solution. The as-deposited ceramic layers were fully amorphous and were composed of the mixture of zirconia and zirconium sulfate. During transmission electron microscopy (TEM) examination, the amorphous ZrO 2 crystallized almost instantaneously to tetragonal (t) ZrO 2 under the electron beam. The ≤110 nm thick as-deposited layers were crack-free and adhered well to the LbL surface. Annealing at 500 °C led to complete crystallization of amorphous ZrO 2 to nanocrystalline t-ZrO 2. Further heating to 900 °C resulted in transformation to monoclinic ZrO 2, complete removal of sulfur and twofold shrinkage of the ceramic layer thickness. Both the nanohardness and elastic modulus of the deposited zirconia layers were significantly improved following the heat treatments.

  12. Preparation and layer-by-layer solution deposition of Cu(In,Ga)O2 nanoparticles with conversion to Cu(In,Ga)S2 films.

    PubMed

    Dressick, Walter J; Soto, Carissa M; Fontana, Jake; Baker, Colin C; Myers, Jason D; Frantz, Jesse A; Kim, Woohong

    2014-01-01

    We present a method of Cu(In,Ga)S2 (CIGS) thin film formation via conversion of layer-by-layer (LbL) assembled Cu-In-Ga oxide (CIGO) nanoparticles and polyelectrolytes. CIGO nanoparticles were created via a novel flame-spray pyrolysis method using metal nitrate precursors, subsequently coated with polyallylamine (PAH), and dispersed in aqueous solution. Multilayer films were assembled by alternately dipping quartz, Si, and/or Mo substrates into a solution of either polydopamine (PDA) or polystyrenesulfonate (PSS) and then in the CIGO-PAH dispersion to fabricate films as thick as 1-2 microns. PSS/CIGO-PAH films were found to be inadequate due to weak adhesion to the Si and Mo substrates, excessive particle diffusion during sulfurization, and mechanical softness ill-suited to further processing. PDA/CIGO-PAH films, in contrast, were more mechanically robust and more tolerant of high temperature processing. After LbL deposition, films were oxidized to remove polymer and sulfurized at high temperature under flowing hydrogen sulfide to convert CIGO to CIGS. Complete film conversion from the oxide to the sulfide is confirmed by X-ray diffraction characterization. PMID:24941104

  13. Morphology and Transport Properties of Novel Polymer Nanocomposites Resulted from Melt Processing of Polyvinylacetate Substrates Coated with Layer-by-Layer Assemblies

    NASA Astrophysics Data System (ADS)

    Soltani, Iman; Spontak, Richard J.

    Novel polymer nanocomposites (PNCs) were processed through layer-by-layer (LBL) deposition of clay and polyethylene terephthalate ionomer layers on polyvinylacetate (PVAc) substrates, followed by repetitive melt pressing of coated samples to crush LBL assemblies into the polymeric matrix. The increase in the clay content in resulted PNCs prepared through similar LBL coatings, relative to previously studied hydrophobic polystyrene-based nanocomposites, postulated superiority of PVAc, with relatively higher hydrophilicity, to interact with LBL assemblies. Also, these PNCs showed relatively good barrier improvement against transport of oxygen and carbon dioxide gases, proposing the scavenging effect of LBL assemblies crushed portions as highly tortuous labyrinths with high aspect ratios, comprising edge-edge flocculated exfoliated clay platelets, observed through transmission electron micrographs. However, combinative morphological investigations through optical microscopy, x-ray diffractometry, and transmission electron microscopy proposed low global dispersion of clay throughout polymeric matrix, conjecturing insufficient intensity of stress applied through cyclic melt pressing, and/or slight thermal degradation of samples via extended times of processing at high temperatures.

  14. Layer-by-layer hyaluronic acid/chitosan polyelectrolyte coated mesoporous silica nanoparticles as pH-responsive nanocontainers for optical bleaching of cellulose fabrics.

    PubMed

    Yilmaz, M Deniz

    2016-08-01

    Polyelectrolyte multilayer (PEM) films composed of two natural polysaccharides (hyaluronic acid and chitosan) were deposited through layer-by-layer (LbL) assembly on top of biocompatible mesoporous silica nanoparticles (MSNPs). Polyelectrolyte multilayer coated mesoporous silica nanoparticles (PEM-MSNPs) were characterized by using attenuated total reflection-fourier transform infrared spectroscopy (ATR-FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherms, UV-vis and fluorescence spectrophotometer. A commercially available and industrially used optical brightener, 4,4'-distyrylbiphenyl sulfonate sodium salt (CBSX) was loaded into nanocontainers (CBSX@PEM-MSNPs) to evaluate their use for the pH-sensitive release. The controlled release of CBSX from nanocontainers in response to pH is monitored by using UV-vis and fluorescence spectrophotometer in water and the almost 100% of encapsulated CBSX is released within 2h at pH 7. The increase in both whiteness and total color change at pH 7 on a cellulose fabric demonstrates the great potential of nanocontainers as pH-sensitive whitening agents for optical bleaching of cellulose fabrics. PMID:27112863

  15. Assembly of cell-laden hydrogel fiber into non-liquefied and liquefied 3D spiral constructs by perfusion-based layer-by-layer technique.

    PubMed

    Sher, Praveen; Oliveira, Sara M; Borges, João; Mano, João F

    2015-01-01

    In this work, three-dimensional (3D) self-sustaining, spiral-shaped constructs were produced through a combination of ionotropic gelation, to form cell-encapsulated alginate fibers, and a perfusion-based layer-by-layer (LbL) technique. Single fibers were assembled over cylindrical molds by reeling to form spiral shapes, both having different geometries and sizes. An uninterrupted nanometric multilayer coating produced by a perfusion-based LbL technique, using alginate and chitosan, generated stable 3D spiral-shaped macrostructures by gripping and affixing the threads together without using any crosslinking/binding agent. The chelation process altered the internal microenvironment of the 3D construct from the solid to the liquefied state while preserving the external geometry. L929 cell viability by MTS and dsDNA quantification favor liquefied 3D constructs more than non-liquefied ones. The proposed technique setup helps us to generate complex polyelectrolyte-based 3D constructs for tissue engineering applications and organ printing. PMID:25562702

  16. Dendrimer-carbon nanotube layer-by-layer film as an efficient host matrix for electrogeneration of PtCo electrocatalysts.

    PubMed

    Gasparotto, Luiz H S; Castelhano, André L B; Silva, Anielle C A; Dantas, Noelio O; Oliveira, Osvaldo N; Siqueira, José R

    2014-02-14

    In this paper we demonstrate that layer-by-layer (LbL) films of polyamidoamine (PAMAM) dendrimers and single-walled carbon nanotubes (SWCNTs) are efficient for controlling the morphology of electrogenerated cobalt (Co) and the platinum-cobalt (PtCo) alloy. While Co grew to the micrometer scale and poorly covered the ITO substrate, with the LbL matrix it was kept in the nanoscale regime and provided full substrate coverage. Pt-decorated Co nanoparticles were then generated by applying a single potential pulse in a solution containing simultaneously Co and Pt ions. Segregation of Pt and Co deposits was observed in field emission gun (FEG) images, but the PtCo alloy was probably formed to some extent according to X-ray diffraction analysis. The PtCo-LbL hybrid exhibited superior catalytic activity toward H2O2 reduction compared to the Pt-modified LbL film, which opens new prospects for applications in biosensing and fuel cells. PMID:24352729

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

    PubMed Central

    Han, Uiyoung; Seo, Younghye; Hong, Jinkee

    2016-01-01

    Layer by layer (lbl) assembled multilayer thin films are used in drug delivery systems with attractive advantages such as unlimited selection of building blocks and free modification of the film structure. In this paper, we report the fundamental properties of lbl films constructed from different substances such as PS-b-PAA amphiphilic block copolymer micelles (BCM) as nano-sized drug vehicles, 2D-shaped graphene oxide (GO), and branched polyethylenimine (bPEI). These films were fabricated by successive lbl assembly as a result of electrostatic interactions between the carboxyl group of BCM and amine group of functionalized GO or bPEI under various pH conditions. We also compared the thickness, roughness, morphology and degree of adsorption of the (bPEI/BCM) films to those in the (GO/BCM) films. The results showed significant difference because of the distinct pH dependence of each material. In addition, drug release rates of the GO/BCM film were more rapid those of the (bPEI/BCM) film in pH 7.4 and pH 2 PBS buffer solutions. In (bPEI/BCM/GO/BCM) film, the inserted GO layers into bPEI/BCM multilayer induced rapid drug release. We believe that these materials & pH dependent film properties allow developments in the control of coating techniques for biological and biomedical applications. PMID:27052827

  18. Visible-light-induced disruption of diselenide-containing layer-by-layer films: toward combination of chemotherapy and photodynamic therapy.

    PubMed

    Ren, Huifeng; Wu, Yaoting; Li, Yang; Cao, Wei; Sun, Zhiwei; Xu, Huaping; Zhang, Xi

    2013-12-01

    A photoresponsive polyelectrolyte multilayer film containing a diselenide functional group is fabricated using an unconventional layer-by-layer method. The polycation backbone is constructed through copolymerization of di-(1-hydroxylundecyl) diselenide and 1,4-bis(2-hydroxyethyl)piperazine with 2,4-diisocyanatotoluene. A common polyanion poly(styrene sulfonate) is selected as the polyanion. The obtained film can be gradually disrupted under the irradiation of mild visible light, and this process can be monitored with UV-vis spectroscopy. The residue of the film is estimated to be 17% after 5 h of irradiation. The intensity of the visible light can be as low as 50 mW cm⁻², which is even weaker than the sunlight. The cytotoxicity of the building blocks is evaluated in MTT assays using human hepatic cell line (L-02), and the results are satisfactory. Further tests show that cells can grow in a regular manner on this film, indicating good biocompatibility. In addition, the film can be used to achieve cargo loading and controlled release. Considering that light can not only trigger controlled release but also act as part of the therapy itself (photodynamic therapy), this system shows hope for further development into a platform for the combination of chemotherapy and photodynamic therapy, especially for applications concerning skin. PMID:23737377

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  20. Preparation and Layer-by-Layer Solution Deposition of Cu(In,Ga)O2 Nanoparticles with Conversion to Cu(In,Ga)S2 Films

    PubMed Central

    Dressick, Walter J.; Soto, Carissa M.; Fontana, Jake; Baker, Colin C.; Myers, Jason D.; Frantz, Jesse A.; Kim, Woohong

    2014-01-01

    We present a method of Cu(In,Ga)S2 (CIGS) thin film formation via conversion of layer-by-layer (LbL) assembled Cu-In-Ga oxide (CIGO) nanoparticles and polyelectrolytes. CIGO nanoparticles were created via a novel flame-spray pyrolysis method using metal nitrate precursors, subsequently coated with polyallylamine (PAH), and dispersed in aqueous solution. Multilayer films were assembled by alternately dipping quartz, Si, and/or Mo substrates into a solution of either polydopamine (PDA) or polystyrenesulfonate (PSS) and then in the CIGO-PAH dispersion to fabricate films as thick as 1–2 microns. PSS/CIGO-PAH films were found to be inadequate due to weak adhesion to the Si and Mo substrates, excessive particle diffusion during sulfurization, and mechanical softness ill-suited to further processing. PDA/CIGO-PAH films, in contrast, were more mechanically robust and more tolerant of high temperature processing. After LbL deposition, films were oxidized to remove polymer and sulfurized at high temperature under flowing hydrogen sulfide to convert CIGO to CIGS. Complete film conversion from the oxide to the sulfide is confirmed by X-ray diffraction characterization. PMID:24941104