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Sample records for layer-by-layer covalent attachment

  1. Amperometric glucose biosensor based on layer-by-layer covalent attachment of AMWNTs and IO(4)(-)-oxidized GOx.

    PubMed

    Sun, Yingying; Wang, Haiying; Sun, Changqing

    2008-09-15

    Multi-wall carbon nanotubes (MWNTs) functionalized with amino groups were prepared via silane treatment using 3-aminopropyltrimethoxysilane (APS) as a silane-coupling agent. The resultant amino terminated MWNTs (AMWNTs) were applied to construct glucose biosensors with IO(4)(-)-oxidized glucose oxidase (IO(4)(-)-oxidized GOx) through the layer-by-layer (LBL) covalent self-assembly method without any cross-linker. Scanning electron microscopy (SEM) indicated that the assembled AMWNTs were almost in a form of small bundles or single nanotubes, and the surface density increased uniformly with the number of GOx/AMWNTs bilayers. From the analysis of voltammetric signals, a linear increment of the coverage of GOx per bilayer was estimated. The resulting biosensor showed excellent catalytic activity towards the electroreduction of dissolved oxygen at low overvoltage, based on which glucose concentration was monitored conveniently. The enzyme electrode exhibited good electrocatalytic response towards the glucose and that response increased with the number of GOx/AMWNTs bilayers, suggesting that the analytical performance such as sensitivity and detection limit of the glucose biosensors could be tuned to the desired level by adjusting the number of deposited GOx/AMWNTs bilayers. The biosensor constructed with four bilayers of GOx/AMWNTs showed high sensitivity of 7.46 microA mM(-1)cm(-2) and the detection limit of 8.0 microM, with a fast response less than 10s. Because of relative low applied potential, the interference from other electro-oxidizable compounds was minimized, which improved the selectivity of the biosensors. Furthermore, the obtained enzyme electrodes also showed remarkable stability due to the covalent interaction between the GOx and AMWNTs.

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

    PubMed Central

    Gattás-Asfura, KM; Valdes, M; Celik, E; Stabler, CL

    2014-01-01

    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. 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.

  4. Covalent layer-by-layer functionalization of multiwalled carbon nanotubes by click chemistry.

    PubMed

    Zhang, Yu; He, Hongkun; Gao, Chao; Wu, Jiayan

    2009-05-19

    The covalent functionalization of multiwalled carbon nanotubes (MWNTs) by layer-by-layer (LbL) click chemistry is reported. The clickable polymers of poly(2-azidoethyl methacrylate) and poly(propargyl methacrylate) were synthesized at first by atom transfer radical polymerization (ATRP) of 2-azidoethyl methacrylate and reverse addition-fragmentation chain transfer (RAFT) polymerization of propargyl methacrylate, respectively. The two polymers were then alternately coated on alkyne-modified multiwalled carbon nanotubes using Cu(I)-catalyzed click reaction of Huisgen 1,3-dipolar cycloaddition between azides and alkynes. Thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) measurements confirm that the quantity and thickness of the clicked polymer shell on MWNTs can be well controlled by adjusting the cycles or numbers of click reaction and the polymer shell is uniform and even. X-ray photoelectron spectroscopy (XPS) and Fourier tranform infrared (FTIR) measurements showed that there were still a great amount of residual azido groups on the surfaces of the functionalized MWNTs after clicking three layers of polymers. Furthermore, alkyne-modified rhodamine B and monoalkyne-terminated polystyrene were subsequently used to functionalize the clickable polymer grafted MWNTs, giving rise to fluorescent carbon nanotubes (CNTs) and CNT-based polystyrene brushes, respectively. It demonstrates that the residual azido groups on the surfaces of MWNTs are available for further click reaction with various functional molecules.

  5. Layer by layer assembly of a biocatalytic packaging film: lactase covalently bound to low-density polyethylene.

    PubMed

    Wong, Dana E; Talbert, Joey N; Goddard, Julie M

    2013-06-01

    Active packaging is utilized to overcome limitations of traditional processing to enhance the health, safety, economics, and shelf life of foods. Active packaging employs active components to interact with food constituents to give a desired effect. Herein we describe the development of an active package in which lactase is covalently attached to low-density polyethylene (LDPE) for in-package production of lactose-free dairy products. The specific goal of this work is to increase the total protein content loading onto LDPE using layer by layer (LbL) deposition, alternating polyethylenimine, glutaraldehyde (GL), and lactase, to enhance the overall activity of covalently attached lactase. The films were successfully oxidized via ultraviolet light, functionalized with polyethylenimine and glutaraldehyde, and layered with immobilized purified lactase. The total protein content increased with each additional layer of conjugated lactase, the 5-layer sample reaching up to 1.3 μg/cm2 . However, the increase in total protein did not lend to an increase in overall lactase activity. Calculated apparent Km indicated the affinity of immobilized lactase to substrate remains unchanged when compared to free lactase. Calculated apparent turnover numbers (kcat ) showed with each layer of attached lactase, a decrease in substrate turnover was experienced when compared to free lactase; with a decrease from 128.43 to 4.76 s(-1) for a 5-layer conjugation. Our results indicate that while LbL attachment of lactase to LDPE successfully increases total protein mass of the bulk material, the adverse impact in enzyme efficiency may limit the application of LbL immobilization chemistry for bioactive packaging use. © 2013 Institute of Food Technologists®

  6. Covalent layer-by-layer assemblies of polyelectrolytes and homobifunctional spacers.

    PubMed

    El Haitami, Alae E; Thomann, Jean-Sébastien; Jierry, Loïc; Parat, Audrey; Voegel, Jean-Claude; Schaaf, Pierre; Senger, Bernard; Boulmedais, Fouzia; Frisch, Benoît

    2010-07-20

    The step-by-step buildup of organic films through physical or covalent bonds is usually performed by the alternating adsorption of two types of polymeric chains. Overcompensation of the interacting groups after each deposition step (e.g., charge overcompensation in the case of polyelectrolyte multilayers) allows the buildup process to proceed. This overcompensation is intimately linked to the polymeric nature of the interacting species. We report here another type of film architecture also based on step-by-step construction but involving the covalent bonding, through the Sharpless click reaction, between polyelectrolytes (i.e., polyanions) and neutral bifunctional molecules. The films are built by the Cu(I)-catalyzed click reaction of poly(acrylic acid) (PAA) functionalized with ethylene glycol (EG) arms, each ending with either an alkyne or an azide group, and bifunctionalized EG spacers ended with either alkyne or azide functions. We prove that these systems lead to the regular buildup of films that cover the whole substrate surface and whose roughness varies as the thickness of the film core. The effects of various parameters on film buildup are investigated. The grafting density of reactive moieties along the PAA chains has no influence on the thickness increment per bilayer. EG spacers bifunctionalized with alkyne groups reacting with PAA chains functionalized with azide arms give films that grow more rapidly than those obtained with azide-functionalized EG spacers and alkyne-functionalized PAA chains. The influence of the length of the EG arm (grafted on PAA) and of the EG spacer on the film buildup is also investigated: longer arms or longer spacers lead to larger thickness increments per bilayer, except for very large spacers of 50 EG units for which the thickness is the smallest probably because of size exclusion effects during the deposition.

  7. Covalent layer-by-layer grafting (LBLG) functionalized superhydrophobic stainless steel mesh for oil/water separation

    NASA Astrophysics Data System (ADS)

    Jiang, Bin; Zhang, Hongjie; Sun, Yongli; Zhang, Luhong; Xu, Lidong; Hao, Li; Yang, Huawei

    2017-06-01

    A superhydrophobic and superoleophilic stainless steel (SS) mesh for oil/water separation has been developed by using a novel, facile and inexpensive covalent layer-by-layer grafting (LBLG) method. Hierarchical micro/nanostructure surface was formed through grafting the (3-aminopropyl) triethoxysilane (SCA), polyethylenimine (PEI) and trimesoyl chloride (TMC) onto the mesh in sequence, accompanied with SiO2 nanoparticles subtly and firmly anchored in multilayers. Superhydrophobic characteristic was realized by self-assembly grafting of hydrophobic groups onto the surface. The as-prepared mesh exhibits excellent superhydrophobicity with a water contact angle of 159°. Moreover, with a low sliding angle of 4°, it shows the ;lotus effect; for self-cleaning. As for application evaluation, the as-prepared mesh can be used for large-scale separation of oil/water mixtures with a relatively high separation efficiency after 30 times reuse (99.88% for n-octane/water mixture) and a high intrusion pressure (3.58 kPa). More importantly, the mesh exhibited excellent stability in the case of vibration situation, long-term storage as well as saline corrosion conditions, and the compatible pH range was determined to be 1-13. In summary, this work provides a brand new method of modifying SS mesh in a covalent LBLG way, and makes it possible to introduce various functionalized groups onto the surface.

  8. Surface molecular imprinted layer-by-layer film attached to a porous membrane for selective filtration.

    PubMed

    Liu, Zhihua; Yi, Yu; Gauczinski, Jan; Xu, Huaping; Schönhoff, Monika; Zhang, Xi

    2011-10-04

    A surface molecular imprinted layer-by-layer (SMILbL) film was fabricated on a polyethersulfone (PES) porous membrane substrate for selective filtration of cations and anions. The LbL deposition procedure and the ultraviolet (UV) cross-linking of the modified membrane were monitored by attenuated total reflection-infrared (ATR-IR) spectra. The SMILbL-PES membrane with 4.5 bilayers of diazoresin (DAR)/poly(acrylic acid) complexed with 5,10,15,20-tetrakis(4-(trimethylammonio)-phenyl)-21H,23H-porphyrin tetratosylate (PAA-Por(4+)) effectively reduced the permeation velocity of Por(4+) after washing the Por(4+) template out. In comparison to a control film DAR/PAA-modified PES membrane (ConLbL-PES) in a dialysis experiment, the SMILbL-PES membrane exhibited better selectivity for permeation of 5,10,15,20-tetraphenyl-21H,23H-porphine-p,p',p″,p‴-tetrasulfonic acid tetrasodium hydrate (Por(4-)) against permeation of Por(4+). In pressure-driven transport experiments, the SMILbL-PES membrane showed a much longer blocking time for Por(4+) than for Por(4-), indicating the selective loading of Por(4+) into the SMILbL film. The surface charge of the SMILbL-PES membrane after Por(4+) loading was higher than that of other membranes, resulting in an enhanced rejection ability of the SMILbL-PES membrane to Por(4+) caused by Coulomb repulsion. A possible mechanism was proposed as follows. The binding sites generated through imprinting in the SMILbL-PES membrane enable loading of a larger amount of Por(4+). The stronger repulsion between Por(4+) and the SMILbL film may cause the main contribution to the selective rejection of Por(4+). It can be easily imagined that this concept can be extended to the construction of composite membranes from other imprinting systems. © 2011 American Chemical Society

  9. Adhesive layer-by-layer films of carboxymethylated cellulose nanofibril-dopamine covalent bioconjugates inspired by marine mussel threads.

    PubMed

    Karabulut, Erdem; Pettersson, Torbjörn; Ankerfors, Mikael; Wågberg, Lars

    2012-06-26

    The preparation of multifunctional films and coatings from sustainable, low-cost raw materials has attracted considerable interest during the past decade. In this respect, cellulose-based products possess great promise due not only to the availability of large amounts of cellulose in nature but also to the new classes of nanosized and well-characterized building blocks of cellulose being prepared from trees or annual plants. However, to fully utilize the inherent properties of these nanomaterials, facile and also sustainable preparation routes are needed. In this work, bioinspired hybrid conjugates of carboxymethylated cellulose nanofibrils (CNFC) and dopamine (DOPA) have been prepared and layer-by-layer (LbL) films of these modified nanofibrils have been built up in combination with a branched polyelectrolyte, polyethyleneimine (PEI), to obtain robust, adhesive, and wet-stable nanocoatings on solid surfaces. It is shown that the chemical functionalization of CNFCs with DOPA molecules alters their conventional properties both in liquid dispersion and at the interface and also influences the LbL film formation by reducing the electrostatic interaction. Although the CNFC-DOPA conjugates show a lower colloidal stability in aqueous dispersions due to charge suppression, it was possible to prepare the LbL films through the consecutive deposition of the building blocks. Adhesive forces between multilayer films prepared using chemically functionalized CNFCs and a silica probe are much stronger in the presence of Fe(3+) than those between a multilayer film prepared from unmodified nanofibrils and a silica probe. The present work demonstrates a facile way to prepare chemically functionalized cellulose nanofibrils whereby more extended applications can produce novel cellulose-based materials with different functionalities.

  10. 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

    2016-03-10

    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

  11. Innovation in Layer-by-Layer Assembly.

    PubMed

    Richardson, Joseph J; Cui, Jiwei; Björnmalm, Mattias; Braunger, Julia A; Ejima, Hirotaka; Caruso, Frank

    2016-12-14

    Methods for depositing thin films are important in generating functional materials for diverse applications in a wide variety of fields. Over the last half-century, the layer-by-layer assembly of nanoscale films has received intense and growing interest. This has been fueled by innovation in the available materials and assembly technologies, as well as the film-characterization techniques. In this Review, we explore, discuss, and detail innovation in layer-by-layer assembly in terms of past and present developments, and we highlight how these might guide future advances. A particular focus is on conventional and early developments that have only recently regained interest in the layer-by-layer assembly field. We then review unconventional assemblies and approaches that have been gaining popularity, which include inorganic/organic hybrid materials, cells and tissues, and the use of stereocomplexation, patterning, and dip-pen lithography, to name a few. A relatively recent development is the use of layer-by-layer assembly materials and techniques to assemble films in a single continuous step. We name this "quasi"-layer-by-layer assembly and discuss the impacts and innovations surrounding this approach. Finally, the application of characterization methods to monitor and evaluate layer-by-layer assembly is discussed, as innovation in this area is often overlooked but is essential for development of the field. While we intend for this Review to be easily accessible and act as a guide to researchers new to layer-by-layer assembly, we also believe it will provide insight to current researchers in the field and help guide future developments and innovation.

  12. 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.

  13. Covalent attachment of lactase to low-density polyethylene films.

    PubMed

    Goddard, J M; Talbert, J N; Hotchkiss, J H

    2007-01-01

    Polymer films to which bioactive compounds such as enzymes are covalently attached offer potential for in-package processing of food. Beta-galactosidase (lactase) was covalently attached to surface-functionalized low-density polyethylene films. A two-step wet chemical functionalization introduced 15.7 nmol/cm2 primary amines to the film surface. Contact angle, dye assays, X-ray photoelectron spectroscopy, and appropriate protein assays were used to characterize changes in film surface chemistry after each step in the process of attachment. Glutaraldehyde was used to covalently attach lactase to the surface at a density of 6.0 microg protein per cm2 via reductive amination. The bond between the covalently attached lactase and the functionalized polyethylene withstood heat treatment in the presence of an ionic denaturant with 74% enzyme retention, suggesting that migration of the enzyme into the food product would be unlikely. The resulting polyethylene had an enzyme activity of 0.020 lactase units (LU)/cm2 (approximately 4500 LU/g). These data suggest that enzymes that may have applications in foods can be covalently attached to inert polymer surfaces, retain significant activity, and thus have potential as a nonmigratory active packaging materials.

  14. Burning Graphene Layer-by-Layer

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    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.

  15. 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

  16. Dextran coatings for aggregation control of layer-by-layer assembled polyelectrolyte microcapsules.

    PubMed

    Usov, Denys; Sukhorukov, Gleb B

    2010-08-03

    We propose dextran and dextran polyaldehyde (DPA) coatings for modification of layer-by-layer (LbL) assembled polyelectrolyte microcapsules which provide stability against aggregation in 0.75 M aqueous solutions of mono- and bivalent ions (Na(+), Cl(-), Ca(2+), HPO(4)(2-)). The microcapsules were prepared of three bilayers of poly(4-styrenesulfonate) (PSS) and poly(allylamine) (PAH). Dextran and its derivatives were attached to amino-terminated surface of the microcapsules via three types of chemical bonds of subsequently increasing strength: (1) hydrogen bonds, (2) hydrolyzable covalent cross-links resulting from aldehydes and primary amines coupling, and (3) nonhydrolyzable covalent C-N single bonds of secondary amines. Attachment of the DPA materials via the latter two types of bonds resulted in strengthening the capsules' walls which preserved a fraction of the microcapsules from disintegration upon electrostatic swelling in 0.1 M NaOH. The non-disintegrated fraction of the DPA-coated microcapsules restored their initial size after pH was decreased back to neutral. The microcapsules coated with the original dextran immobilized via hydrogen bonds and the bare microcapsules were fully dissolved under the alkaline conditions. The preserved fraction of the microcapsules was higher for the DPA materials with higher contents of the aldehyde groups and after conversion of the hydrolyzable covalent cross-links to the nonhydrolyzable secondary amines via reduction with NaBH(4). The higher contents of the aldehyde groups and the reduction led to the lower limiting swelling degree of the DPA-coated microcapsules at alkaline pH. The proposed coatings can be used for colloid stabilization of polyelectrolyte microcapsules in aqueous medium, encapsulation of pH-insensitive macromolecules at the postpreparation stage, and pH-triggered release of encapsulated material.

  17. Layer-by-layer dielectric breakdown of hexagonal boron nitride.

    PubMed

    Hattori, Yoshiaki; Taniguchi, Takashi; Watanabe, Kenji; Nagashio, Kosuke

    2015-01-27

    Hexagonal boron nitride (BN) is widely used as a substrate and gate insulator for two-dimensional (2D) electronic devices. The studies on insulating properties and electrical reliability of BN itself, however, are quite limited. Here, we report a systematic investigation of the dielectric breakdown characteristics of BN using conductive atomic force microscopy. The electric field strength was found to be ∼ 12 MV/cm, which is comparable to that of conventional SiO2 oxides because of the covalent bonding nature of BN. After the hard dielectric breakdown, the BN fractured like a flower into equilateral triangle fragments. However, when the applied voltage was terminated precisely in the middle of the dielectric breakdown, the formation of a hole that did not penetrate to the bottom metal electrode was clearly observed. Subsequent I-V measurements of the hole indicated that the BN layer remaining in the hole was still electrically inactive. On the basis of these observations, layer-by-layer breakdown was confirmed for BN with regard to both physical fracture and electrical breakdown. Moreover, statistical analysis of the breakdown voltages using a Weibull plot suggested the anisotropic formation of defects. These results are unique to layered materials and unlike the behavior observed for conventional 3D amorphous oxides.

  18. Strategies to balance covalent and non-covalent biomolecule attachment within collagen-GAG biomaterials

    PubMed Central

    Pence, Jacquelyn C.; Gonnerman, Emily A.; Bailey, Ryan C.; Harley, Brendan A.C.

    2014-01-01

    Strategies to integrate instructive biomolecular signals into a biomaterial are becoming increasingly complex and bioinspired. While a large majority of reports still use repeated treatments with soluble factors, this approach can be prohibitively costly and difficult to translate in vivo for applications where spatial control over signal presentation is necessary. Recent efforts have explored the use of covalent immobilization of biomolecules to the biomaterial, via both bulk (ubiquitous) as well as spatially-selective light-based crosslinking, as a means to both enhance stability and bioactivity. However, little is known about how processing conditions during immobilization impact the degree of unintended non-covalent interactions, or fouling, that takes place between the biomaterial and the biomolecule of interest. Here we demonstrate the impact of processing conditions for bulk carbodiimide (EDC) and photolithography-based benzophenone (BP) crosslinking on specific attachment vs. fouling of a model protein (Concanavalin A, ConA) within collagen-glycosaminoglycan (CG) scaffolds. Collagen source significantly impacts the selectivity of biomolecule immobilization. EDC crosslinking intensity and ligand concentration significantly impacted selective immobilization. For benzophenone photoimmobilization we observed that increased UV exposure time leads to increased ConA immobilization. Immobilization efficiency for both EDC and BP strategies was maximal at physiological pH. Increasing ligand concentration during immobilization process led to enhanced immobilization for EDC chemistry, no impact on BP immobilization, but significant increases in non-specific fouling. Given recent efforts to covalently immobilize biomolecules to a biomaterial surface to enhance bioactivity, improved understanding of the impact of crosslinking conditions on selective attachment versus non-specific fouling will inform the design of instructive biomaterials for applications across tissue

  19. Strategies to balance covalent and non-covalent biomolecule attachment within collagen-GAG biomaterials.

    PubMed

    Pence, Jacquelyn C; Gonnerman, Emily A; Bailey, Ryan C; Harley, Brendan A C

    2014-09-01

    Strategies to integrate instructive biomolecular signals into a biomaterial are becoming increasingly complex and bioinspired. While a large majority of reports still use repeated treatments with soluble factors, this approach can be prohibitively costly and difficult to translate in vivo for applications where spatial control over signal presentation is necessary. Recent efforts have explored the use of covalent immobilization of biomolecules to the biomaterial, via both bulk (ubiquitous) as well as spatially-selective light-based crosslinking, as a means to both enhance stability and bioactivity. However, little is known about how processing conditions during immobilization impact the degree of unintended non-covalent interactions, or fouling, that takes place between the biomaterial and the biomolecule of interest. Here we demonstrate the impact of processing conditions for bulk carbodiimide (EDC) and photolithography-based benzophenone (BP) crosslinking on specific attachment vs. fouling of a model protein (Concanavalin A, ConA) within collagen-glycosaminoglycan (CG) scaffolds. Collagen source significantly impacts the selectivity of biomolecule immobilization. EDC crosslinking intensity and ligand concentration significantly impacted selective immobilization. For benzophenone photoimmobilization we observed that increased UV exposure time leads to increased ConA immobilization. Immobilization efficiency for both EDC and BP strategies was maximal at physiological pH. Increasing ligand concentration during immobilization process led to enhanced immobilization for EDC chemistry, no impact on BP immobilization, but significant increases in non-specific fouling. Given recent efforts to covalently immobilize biomolecules to a biomaterial surface to enhance bioactivity, improved understanding of the impact of crosslinking conditions on selective attachment versus non-specific fouling will inform the design of instructive biomaterials for applications across tissue

  20. Covalent Attachment of Ferrocene to Silicon Microwire Arrays.

    PubMed

    Kang, Onkar S; Bruce, Jared P; Herbert, David E; Freund, Michael S

    2015-12-09

    A fully integrated, freestanding device for photoelectrochemical fuel generation will likely require covalent attachment of catalysts to the surface of the photoelectrodes. Ferrocene has been utilized in the past as a model system for molecular catalyst integration on planar silicon; however, the surface structure of high-aspect ratio silicon microwires envisioned for a potential device presents potential challenges with respect to stability, characterization, and mass transport. Attachment of vinylferrocene to Cl-terminated surfaces of silicon microwires was performed thermally. By varying the reaction time, solutions of vinylferrocene in di-n-butyl ether were employed to control the extent of functionalization. X-ray photoelectron spectroscopy (XPS) and electrochemistry were used to estimate the density and surface coverage of the silicon microwire arrays with ferrocenyl groups, which could be controllably varied from 1.23 × 10(-11) to 4.60 × 10(-10) mol cm(-2) or 1 to 30% of a monolayer. Subsequent backfill of the remaining Si-Cl sites with methyl groups produced ferrocenyl-terminated surfaces that showed unchanged cyclic volammograms following two months in air, under ambient conditions, and repeated electrochemical cycling.

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

    USDA-ARS?s Scientific Manuscript database

    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 ...

  2. 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

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

    PubMed

    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/cm(2). 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/cm(2)) than on surfaces with a higher concentration of FGF-2 (120 ng/cm(2)).

  4. The potential of cashew gum functionalization as building blocks for layer-by-layer films.

    PubMed

    Leite, Álvaro J; Costa, Rui R; Costa, Ana M S; Maciel, Jeanny S; Costa, José F G; de Paula, Regina C M; Mano, João F

    2017-10-15

    Cashew gum (CG), an exudate polysaccharide from Anacardium occidentale trees, was carboxymethylated (CGCm) and oxidized (CGO). These derivatives were characterized by FTIR and zeta potential measurements confirming the success of carboxymethylation and oxidation reactions. Nanostructured multilayered films were then produced through layer-by-layer (LbL) assembly in conjugation with chitosan via electrostatic interactions or Schiff bases covalent bonds. The films were analyzed by QCM-D and AFM. CG functionalization increased the film thickness, with the highest thickness being achieved for the lowest oxidation degree. The roughest surface was obtained for the CGO with the highest oxidation degree due to the predominance of covalent Schiff bases. This work shows that nanostructured films can be assembled and stabilized by covalent bonds in alternative to the conventional electrostatic ones. Moreover, the functionalization of CG can increase its feasibility in multilayers films, widening its potential in biomedical, food industry, or environmental applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. 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.

  6. Electrochemical-coupling layer-by-layer (ECC-LbL) assembly.

    PubMed

    Li, Mao; Ishihara, Shinsuke; Akada, Misaho; Liao, Meiyong; Sang, Liwen; Hill, Jonathan P; Krishnan, Venkata; Ma, Yuguang; Ariga, Katsuhiko

    2011-05-18

    Electrochemical-coupling layer-by-layer (ECC-LbL) assembly is introduced as a novel fabrication methodology for preparing layered thin films. This method allows us to covalently immobilize functional units (e.g., porphyrin, fullerene, and fluorene) into thin films having desired thicknesses and designable sequences for both homo- and heteroassemblies while ensuring efficient layer-to-layer electronic interactions. Films were prepared using a conventional electrochemical setup by a simple and inexpensive process from which various layering sequences can be obtained, and the photovoltaic functions of a prototype p/n heterojunction device were demonstrated. © 2011 American Chemical Society

  7. Nanoengineering Catalyst Supports via Layer-by Layer Surface Functionalization

    SciTech Connect

    Yan, Wenfu; Mahurin, Shannon Mark; Overbury, Steven {Steve} H; Dai, Sheng

    2006-01-01

    Recent progress in the layer-by-layer surface modification of oxides for the preparation of highly active and stable gold nanocatalysts is briefly reviewed. Through a layer-by-layer surface modification approach, the surfaces of various catalyst supports including both porous and nonporous silica materials and TiO{sub 2} nanoparticles were modified with monolayers or multilayers of distinct metal oxide ultra-thin films. The surface-modified materials were used as supports for Au nanoparticles, resulting in highly active nanocatalysts for low-temperature CO oxidation. Good stability against sintering under high-temperature treatment was achieved for a number of the Au catalysts through surface modification of the support material. The surface modification of supports can be a viable route to control both the composition and structure of support and nanoparticle interfaces, thereby tailoring the stability and activity of the supported catalyst systems.

  8. DNA visualization in single molecule studies carried out with optical tweezers: Covalent versus non-covalent attachment of fluorophores.

    PubMed

    Suei, Sandy; Raudsepp, Allan; Kent, Lisa M; Keen, Stephen A J; Filichev, Vyacheslav V; Williams, Martin A K

    2015-10-16

    In this study, we investigated the use of the covalent attachment of fluorescent dyes to double-stranded DNA (dsDNA) stretched between particles using optical tweezers (OT) and compared the mechanical properties of the covalently-functionalized chain to that of unmodified DNA and to DNA bound to a previously uncharacterized groove-binder, SYBR-gold. Modified DNA species were obtained by covalently linking azide-functionalized organic fluorophores onto the backbone of DNA chains via the alkyne moieties of modified bases that were incorporated during PCR. These DNA molecules were then constructed into dumbbells by attaching polystyrene particles to the respective chain ends via biotin or digoxigenin handles that had been pre-attached to the PCR primers which formed the ends of the synthesized molecule. Using the optical tweezers, the DNA was stretched by separating the two optically trapped polystyrene particles. Displacements of the particles were measured in 3D using an interpolation-based normalized cross-correlation method and force-extension curves were calculated and fitted to the worm-like chain model to parameterize the mechanical properties of the DNA. Results showed that both the contour and persistence length of the covalently-modified dsDNAs were indistinguishable from that of the unmodified dsDNA, whereas SYBR-gold binding perturbed the contour length of the chain in a force-dependent manner. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. 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. Copyright © 2015 Elsevier Inc. All rights reserved.

  10. 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.

  11. 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.

  12. Layer-by-layer assembly of ferrocene-modified linear polyethylenimine redox polymer films.

    PubMed

    DeLuca, Jared L; Hickey, David P; Bamper, Daniel A; Glatzhofer, Daniel T; Johnson, Matthew B; Schmidtke, David W

    2013-07-22

    Herein, both electrostatic and covalent layer-by-layer assembly were used for the construction of multicomposite thin films using a ferrocene-modified linear poly(ethylenimine) redox polymer (Fc-C6-LPEI) as the cationic polyelectrolye, and poly(acrylic acid) (PAA), poly(glutamic acid) (PGA), or glucose oxidase (GOX) as the negative polyelectrolyte. The assembly of the multilayer films was characterized by cyclic voltammetry (CV), UV/Vis spectroscopy, and ellipsometry with the enzymatic response of the films containing GOX being characterized via constant potential amperometry. CV measurements suggested that the successful buildup of multilayer films was dependent upon the nature of the anionic polyelectrolyte used. Electrostatic assembly of films composed of Fc-C6-LPEI and either PAA or PGA produced large oxidation peak current densities of 630 and 670 μA cm(-2), respectively, during cyclic voltammetry. Increased measured absorbance by UV/Vis spectroscopy and increased measured film thicknesses (400-600 nm) by ellipsometry provided additional evidence of successful film formation. In contrast, the films incorporating GOX that were electrostatically assembled surprisingly produced significantly lower electrochemical responses (12 μA cm(-2)), low absorbance values, and reduced film thicknesses (~15 nm), and glucose electro-oxidation current densities less than 1 μA cm(-2), which all suggested unstable or minimal film formation. Subsequently, we developed a covalent layer-by-layer approach to fabricate films of Fc-C6-LPEI/GOX by covalently linking the amine groups of Fc-C6-LPEI to the aldehyde groups of periodate-oxidized glucose oxidase. Covalent assembly of the Fc-C6-LPEI/GOX films produced oxidation peak current densities during cyclic voltammetry of 40 μA cm(-2) and glucose electro-oxidation current densities of 220 μA cm(-2). These films also showed an increase in their thicknesses (~140 nm) relative to the electrostatic GOX films. For the films containing

  13. Electrostatic layer-by-layer construction of fibrous TMV biofilms.

    PubMed

    Tiu, Brylee David B; Kernan, Daniel L; Tiu, Sicily B; Wen, Amy M; Zheng, Yi; Pokorski, Jonathan K; Advincula, Rigoberto C; Steinmetz, Nicole F

    2017-01-26

    As nature's choice in designing complex architectures, the bottom-up assembly of nanoscale building blocks offers unique solutions in achieving more complex and smaller morphologies with wide-ranging applications in medicine, energy, and materials science as compared to top-down manufacturing. In this work, we employ charged tobacco mosaic virus (TMV-wt and TMV-lys) nanoparticles in constructing multilayered fibrous networks via electrostatic layer-by-layer (LbL) deposition. In neutral aqueous media, TMV-wt assumes an anionic surface charge. TMV-wt was paired with a genetically engineered TMV-lys variant that displays a corona of lysine side chains on its solvent-exposed surface. The electrostatic interaction between TMV-wt and TMV-lys nanoparticles became the driving force in the highly controlled buildup of the multilayer TMV constructs. Since the resulting morphology closely resembles the 3-dimensional fibrous network of an extracellular matrix (ECM), the capability of the TMV assemblies to support the adhesion of NIH-3T3 fibroblast cells was investigated, demonstrating potential utility in regenerative medicine. Lastly, the layer-by-layer deposition was extended to release the TMV scaffolds as free-standing biomembranes. To demonstrate potential application in drug delivery or vaccine technology, cargo-functionalized TMV biofilms were programmed.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. The Chemistry and Biochemistry of Heme c: Functional Bases for Covalent Attachment

    PubMed Central

    Bowman, Sarah E. J.; Bren, Kara L.

    2009-01-01

    A discussion of the literature concerning the synthesis, function, and activity of heme c-containing proteins is presented. Comparison of the properties of heme c, which is covalently bound to protein, is made to heme b, which is bound noncovalently. A question of interest is why nature uses biochemically expensive heme c in many proteins when its properties are expected to be similar to heme b. Considering the effects of covalent heme attachment on heme conformation and on the proximal histidine interaction with iron, it is proposed that heme attachment influences both heme reduction potential and ligand-iron interactions. PMID:19030605

  20. Cell behavior on gallium nitride surfaces: peptide affinity attachment versus covalent functionalization.

    PubMed

    Foster, Corey M; Collazo, Ramon; Sitar, Zlatko; Ivanisevic, Albena

    2013-07-02

    Gallium nitride is a wide band gap semiconductor that demonstrates a unique set of optical and electrical properties as well as aqueous stability and biocompatibility. This combination of properties makes gallium nitride a strong candidate for use in chemical and biological applications such as sensors and neural interfaces. Molecular modification can be used to enhance the functionality and properties of the gallium nitride surface. Here, gallium nitride surfaces were functionalized with a PC12 cell adhesion promoting peptide using covalent and affinity driven attachment methods. The covalent scheme proceeded by Grignard reaction and olefin metathesis while the affinity driven scheme utilized the recognition peptide isolated through phage display. This study shows that the method of attaching the adhesion peptide influences PC12 cell adhesion and differentiation as measured by cell density and morphological analysis. Covalent attachment promoted monolayer and dispersed cell adhesion while affinity driven attachment promoted multilayer cell agglomeration. Higher cell density was observed on surfaces modified using the recognition peptide. The results suggest that the covalent and affinity driven attachment methods are both suitable for promoting PC12 cell adhesion to the gallium nitride surface, though each method may be preferentially suited for distinct applications.

  1. The covalent attachment of polyamines to proteins in plant mitochondria.

    PubMed

    Votyakova, T V; Wallace, H M; Dunbar, B; Wilson, S B

    1999-02-01

    Plant mitochondria from both potato and mung bean incorporated radioactivity into acid insoluble material when incubated with labelled polyamines (spermine, spermidine and putrescine). Extensive washing of mitochondrial precipitates with trichloroacetic acid and the excess of cold polyamine failed to remove bound radioactivity. Addition of nonradioactive polyamine stopped further incorporation of radioactivity but did not release radioactivity already bound. The radioactivity is incorporated into the membrane fraction. The labelling process has all the features of an enzymatic reaction: it is long lasting with distinctive kinetics peculiar to each polyamine, it is temperature dependent and is affected by N-ethylmaleimide. The latter inhibits the incorporation of putrescine but stimulates the incorporation of spermine and spermidine. Treatment of prelabelled mitochondria with pepsin releases bound radioactivity thus indicating protein to be the ligand for the attachment of polyamines. HPLC of mitochondrial hydrolysates revealed that the radioactivity bound to mitochondria is polyamines; traces of acetyl polyamines were also found in some samples. On autoradiograms of SDS/PAGE gels several radioactive bands of proteins were detected. Protein sequencing of labelled spots from a 2D gel gave a sequence which was 60% identical to catalase. We suggest that the attachment of polyamines to mitochondrial proteins occurs cotranslationally possibly via transglutaminases.

  2. Dynamics of Polyelectrolyte Chains within Layer-by-Layer Assemblies

    NASA Astrophysics Data System (ADS)

    Sukhishvili, Svetlana

    2015-03-01

    Layer-by-layer (LbL) assembly of charged polymers/nanoparticles finds diverse industrial applications ranging from NIR reflective heat-reduction to multi-stage drug delivery. Internal layering of film components lies at the heart of their performance. I will discuss experiments aimed to unravel relationships between center-of-mass diffusion of polyelectrolyte (PE) chains within LbL films, PE molecular characteristics, environmental conditions (salt concentration), and film structure. Upon film annealing in salt solutions, chain diffusion is highly anisotropic (as probed by fluorescence recovery after photobleaching and neutron reflectometry), and is strongly coupled with film structure. For layered LbL films, PE diffusion in the direction parallel to the substrate reveals quasi-Rouse scaling with molecular weight (D ~ M-1) , even for long chains, suggesting that chains disentangle upon adsorption. Finally, I will discuss quantitative aspects of salt-induced PE chain diffusion in directions parallel and perpendicular to the substrate, and their consequences for persistent layering within LbL films. This work was supported by the National Science Foundation under Award DMR-0906474.

  3. 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

  4. 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

  5. Layer-by-layer microcapsules templated on erythrocyte ghost carriers.

    PubMed

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

    2011-08-30

    This work reports the fabrication of layer-by-layer (LbL) microcapsules that provide a simple mean for controlling the burst and subsequent release of bioactive agents. Red blood cell (RBC) ghosts were loaded with fluorescently labeled dextran and lysozyme as model compounds via hypotonic dialysis with an encapsulation efficiency of 27-31%. It is demonstrated that these vesicles maintain their shape and integrity and that a uniform distribution of the encapsulated agents within these carriers is achieved. The loaded vesicles were then successfully coated with the biocompatible polyelectrolytes, poly-L-arginine hydrochloride and dextran sulfate. It is demonstrated that the release profiles of the encapsulated molecules can be regulated over a wide range by adjusting the number of polyelectrolyte layers. In addition, the LbL shell also protects the RBC ghost from decomposition thereby potentially preserving the bioactivity of encapsulated drugs or proteins. These microcapsules, consisting of an RBC ghost coated with a polyelectrolyte multilayer, provide a simple mean for the preparation of loaded LbL microcapsules eliminating the core dissolution and post-loading of bioactive agents, which are required for conventional LbL microcapsules.

  6. 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.

  7. Polyelectrolyte Layer-by-Layer Assembly on Organic Electrochemical Transistors.

    PubMed

    Pappa, Anna-Maria; Inal, Sahika; Roy, Kirsty; Zhang, Yi; Pitsalidis, Charalampos; Hama, Adel; Pas, Jolien; Malliaras, George G; Owens, Roisin M

    2017-03-29

    Oppositely charged polyelectrolyte multilayers (PEMs) were built up in a layer-by-layer (LbL) assembly on top of the conducting polymer channel of an organic electrochemical transistor (OECT), aiming to combine the advantages of well-established PEMs with a high performance electronic transducer. The multilayered film is a model system to investigate the impact of biofunctionalization on the operation of OECTs comprising a poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) film as the electrically active layer. Understanding the mechanism of ion injection into the channel that is in direct contact with charged polymer films provides useful insights for novel biosensing applications such as nucleic acid sensing. Moreover, LbL is demonstrated to be a versatile electrode modification tool enabling tailored surface features in terms of thickness, softness, roughness, and charge. LbL assemblies built up on top of conducting polymers will aid the design of new bioelectronic platforms for drug delivery, tissue engineering, and medical diagnostics.

  8. Layer-by-layer assemblies for antibacterial applications.

    PubMed

    Zhu, Xiaoying; Jun Loh, Xian

    2015-12-01

    The adhesion and proliferation of bacteria on various artificial surfaces affects the functionality of these specific interfaces. To overcome the problems caused by bacterial growth on these surfaces, various antibacterial coatings were developed. In this review, we summarized most of the antibacterial surfaces prepared by the Layer-by-Layer (LbL) assembly approach and classified these LbL films based on their antibacterial mechanisms. In the first group, the bactericidal LbL assemblies which incorporate various biocides including heavy metals, antibiotics, cationic molecules, antimicrobial peptides and enzymes are able to kill surrounding or contacted bacteria. In the second group, we focused on the physical aspects of film surfaces. Bacterial adhesion resistant LbL films have been fabricated to adjust the substrate surface properties such as surface free energy (or wettability), roughness, and surface charge which may affect the adhesion of bacteria. Furthermore, as an enhancement in the antibacterial efficiency, multifunctional LbL assemblies combining both bactericidal and adhesion resistant functionalities were discussed. The advantages and limitations of these antibacterial LbL assemblies were summarized and subsequently directions for future development were proposed.

  9. Layer-by-Layer Assemblies for Cancer Treatment and Diagnosis.

    PubMed

    Liu, Xi Qiu; Picart, Catherine

    2016-02-10

    The layer-by-layer (LbL) technique was introduced in the early 1990s. 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. Recent progress in the applications of LbL assemblies in the field of cancer therapy, diagnosis, and fundamental biological study are highlighted here. The potential of LbL-based systems as drug carriers is 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 behavior in vitro. The advantages of LbL systems, important challenges that need to be overcome, and future perspectives in clinical practice are then highlighted.

  10. 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

  11. Layer by layer etching of LaAlSiOx

    NASA Astrophysics Data System (ADS)

    Hayashi, Hisataka

    2016-09-01

    In order to fabricate a gate transistor with high-k oxide materials, removal of high-k oxide films after gate electrode etching is necessary for the formation of ohmic contacts on source and drain regions. It is crucial that the removal process of high-k oxide film by dry etching is highly selective to and low in damage to the Si substrate in order to avoid the degradation of device performances. Sasaki et al. have achieved a high LaAlSiOx-to-Si selectivity of 6.7 using C4F8/Ar/H2 plasma. In the LaAlSiOx etching process using C4F8/Ar/H2 plasma, H2 plays a role in breaking the metal-oxygen bond to enhance etching of LaAlSiOx. Based on this result, the process was decomposed into two steps: a surface modification step using H2 plasma to break the metal-oxygen bond, and a removal step using C4F8/Ar plasma. A sequential layer by layer etching could realize low damage etching, similar to atomic layer etching. Therefore, a sequential LaAlSiOx etching process using a H2 surface modification step followed by a removal step using C4F8/Ar plasma is investigated. Experiments were carried out on 300 mm diameter wafers using the 100/13.56 MHz dual frequency superimposed capacitively coupled plasma reactor. The etching gases were H2 and C4F8/Ar for each step, respectively. Plasma process conditions were 100 MHz power of 1000 W (plasma generation), 13.56MHz power varied from 0 W to 300W (ion energy control). The substrate temperature was 40 °C. 15nm thick LaAlSiOx blanket film was used for evaluation of the etched amount. Film thickness was measured by X-ray fluorescent analysis thickness meter before and after plasma exposure. The etched amount of LaAlSiOx by the C4F8/Ar plasma step doubled with H2 modification. It is confirmed that when the C4F8/Ar plasma treatment time is sufficient to remove the surface modification layer, a self-limiting reaction is realized. Furthermore, it is confirmed that the etched amount per step can be controlled by control of the ion energy of H2

  12. Reversible covalent attachment of C[sub 60] to a polymer support

    SciTech Connect

    Guhr, K.I.; Greaves, M.D.; Rotello, V.M. )

    1994-06-29

    We have developed a method for the covalent attachment of fullerenes to a polymer support through an apparent Diels-Alder cycloaddition. This addition has been shown to be readily reversible, allowing recovery of C[sub 60] upon heating of the resin. Further optimization and characterization of these polymers is being pursued. Additionally, their application to the nonchromatographic purification of fullerenes is currently under study and will be reported in due course. 19 refs., 1 fig.

  13. Covalent attachment of actin filaments to Tween 80 coated polystyrene beads for cargo transportation.

    PubMed

    Kaur, Harsimran; Das, Tapan; Kumar, Rajesh; Ajore, Ram; Bharadwaj, Lalit M

    2008-04-01

    In this manuscript, a new strategy has been reported for circumscribed covalent attachment of barbed and pointed ends of actin filaments to polystyrene beads. A comparative study of attachment of actin filaments to polystyrene beads was performed by blocking functionally active sites on polystyrene beads with nonionic detergents such as Tween 20, Tween 80 and polyethylene glycol (PEG). Effective blocking of active sites was obtained with Tween 80 at 0.1% concentration. Attachment of single bundle of actin filament to bead was assessed by rotational motion of bead tailed actin in front and lateral view. Velocity of actin filaments attached to different size of beads in in-vitro motility assay was calculated to ascertain their attachments. Velocity of actin attached to 1.0 and 3.0 microm polystyrene beads was reduced to 3.0-4.0 and 0.0-1.0 microm/s, respectively as compared to free actin velocity of 4.0-6.0 microm/s. Single point attachment of actin filaments to different size of beads was assessed by decrease in sliding velocity. Present study provides insight into the actin-myosin based molecular motor systems for drug delivery and biosensors applications.

  14. Layer-by-Layer polyelectrolyte assemblies for encapsulation and release of active compounds.

    PubMed

    Guzmán, Eduardo; Mateos-Maroto, Ana; Ruano, Marta; Ortega, Francisco; Rubio, Ramón G

    2017-04-20

    Soft assemblies obtained following the Layer-by-Layer (LbL) approach are accounted among the most interesting systems for designing biomaterials and drug delivery platforms. This is due to the extraordinary versatility and flexibility offered by the LbL method, allowing for the fabrication of supramolecular multifunctional materials using a wide range of building blocks through different types of interactions (electrostatic, hydrogen bonds, acid-base or coordination interactions, or even covalent bonds). This provides the bases for the building of materials with different sizes, shapes, compositions and morphologies, gathering important possibilities for tuning and controlling the physico-chemical properties of the assembled materials with precision in the nanometer scale, and consequently creating important perspective for the application of these multifunctional materials as cargo systems in many areas of technological interest. This review studies different physico - chemical aspects associated with the assembly of supramolecular materials by the LbL method, paying special attention to the description of these aspects playing a central role in the application of these materials as cargo platforms for encapsulation and release of active compounds. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. 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

  16. 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.

  17. 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.

  18. Carbon Nanotubes Covalently Attached to Functionalized Surfaces Directly through the Carbon Cage.

    PubMed

    Williams, Mackenzie G; Gao, Fei; BenDhiab, Ibtihel; Teplyakov, Andrew

    2017-02-07

    The covalent attachment of nonfunctionalized and carboxylic acid-functionalized carbon nanotubes to amine-terminated organic monolayers on gold and silicon surfaces is investigated. It is well established that the condensation reaction between a carboxylic acid and an amine is a viable method to anchor carbon nanotubes to solid substrates. The work presented here shows that the presence of the carboxylic group on the nanotube is not required for attachment to occur, as direct attachment via the substrate amine and the nanotube cage can take place. Scanning and transmission electron microscopy and atomic force microscopy confirm the presence of carbon nanotubes in intimate contact with the surface. X-ray photoelectron spectroscopy is utilized to compare the surface chemistry of the functionalized and nonfunctionalized carbon nanotubes and is supported by a computational investigation. Ion fragments attributed to the direct attachment between the surface and carbon nanotube cage are detected by time-of-flight secondary ion mass spectrometry. The overall attachment scheme is evaluated and can be further used on multiple carbonaceous materials attached to solid substrates.

  19. Covalent attachment of heme to the protein moiety in an insect E75 nitric oxide sensor

    PubMed Central

    Aicart-Ramos, Clara; Valhondo-Falcón, Margarita; Ortiz de Montellano, Paul R.; Rodriguez-Crespo, Ignacio

    2012-01-01

    We have recombinantly expressed and purified the ligand binding domains (LBDs) of four insect nuclear receptors of the E75 family. The Drosophila melanogaster and Bombyx mori nuclear receptors were purified as ferric hemoproteins with Soret maxima at 424 nm, whereas their ferrous form had a Soret maximum at 425 nm that responds to ·NO and CO binding. In contrast, the purified LBD of Oncopeltus fasciatus displayed a Soret maximum at 415 nm for the ferric protein that shifted to 425 nm in its ferrous state. Binding of ·NO to the heme moiety of D. melanogaster and B. mori E75 LBD resulted in the appearance of a peak at 385 nm, whereas this peak appeared at 416 nm in the case of the O. fasciatus hemoprotein, resembling the behaviour displayed by its human homolog Rev-erbβ. HPLC analysis revealed that, unlike the D. melanogaster and B. mori counterparts, the heme group of O. fasciatus is covalently attached to the protein through the side-chains of two amino acids. The large sequence homology with O. fasciatus E75 led us to clone and express the LBD of Blattella germanica, which established that its spectral properties closely resemble those of O. fasciatus and that it also has the heme group covalently bound to the protein. Hence, ·NO/CO regulation of the transcriptional activity of these nuclear receptors might be differently controlled among various insect species. In addition, covalent heme binding provides strong evidence that at least some of these nuclear receptors function as diatomic gas sensors rather than heme sensors. Finally, our findings expand the classes of hemoproteins in which the heme group is normally covalently attached to the polypeptide chain. PMID:22946928

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

    PubMed

    Gao, Peng; Liao, Zhi; 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.

  1. 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

  2. Amperometric detection of catechol using tyrosinase modified electrodes enhanced by the layer-by-layer assembly of gold nanocubes and polyelectrolytes.

    PubMed

    Karim, Md Nurul; Lee, Ji Eun; Lee, Hye Jin

    2014-11-15

    A novel amperometric biosensor for catechol was developed using the layer-by-layer (LbL) self-assembly of positively charged hexadecyltrimethylammonium stabilized gold nanocubes (AuNCs), negatively charged poly(sodium 4-styrenesulfonate) and tyrosinase on a screen printed carbon electrode (SPCE). A carboxylic acid terminated alkanethiol assembled on electrochemically deposited Au nanoparticles on a SPCE was used as a platform for LbL assembly. Each SPCE sensor surface was terminated with tyrosinase and the electrocatalytic response due to the tyrosinase reaction with catechol was measured using cyclic voltammetry and square wave voltammetry (SWV). The effect of introducing AuNCs into the LbL assembly to further enhance the catechol detection performance was then investigated by comparing the SWV results to those from biosensors created using both the tyrosinase modified LbL assembly in the absence of NCs and the covalent attachment of tyrosinase. A wide dynamic range from 10nM to 80 µM of catechol with an excellent sensitivity of 13.72 A/M and a detection limit of 0.4 nM were both achieved alongside a good selectivity and reproducibility for the AuNC-modified electrodes. As a demonstration, the optimized biosensor design was applied to determine catechol concentrations in tea samples.

  3. Covalent attachment of mechanoresponsive luminescent micelles to glasses and polymers in aqueous conditions.

    PubMed

    Sagara, Yoshimitsu; Komatsu, Toru; Ueno, Tasuku; Hanaoka, Kenjiro; Kato, Takashi; Nagano, Tetsuo

    2014-03-19

    Covalent attachment of mechanoresponsive luminescent organic or organometallic compounds to other materials is a promising approach to develop a wide variety of mechanoresponsive luminescent materials. Here, we report covalently linkable mechanoresponsive micelles that change their photoluminescence from yellow to green in response to mechanical stimulation under aqueous conditions. These micelles are composed of a dumbbell-shaped amphiphilic pyrene derivative having amine groups at the peripheral positions of its dendrons. Using a well-established cross-linker, the micelles were covalently linked via their peripheral amine groups to the surface of glass beads, polylactic acid (PLA) beads, and living cells under aqueous conditions. Vortexing of glass beads bearing the micelles in a glass vial filled with water caused a photoluminescence color change from yellow to green. PLA beads bearing the micelles showed no change in photoluminescence color under the same conditions. We ascribe this result to the lower density and stiffness of the PLA beads, because the color of the PLA beads changed on vortexing in the presence of bare glass beads. HeLa cells and HL-60 cells bearing the micelles showed no obvious photoluminescence color change under vortexing. The structure, photophysical properties, and mechanism of photoluminescence color change of the micellar assemblies were examined.

  4. Fluorescence of covalently attached pyrene as a general RNA folding probe

    PubMed Central

    Smalley, Mary K.; Silverman, Scott K.

    2006-01-01

    Fluorescence techniques are commonly and powerfully applied to monitor biomolecular folding. In a limited fashion, the fluorescence emission intensity of covalently attached pyrene has been used as a reporter of RNA conformational changes. Here, we pursue two goals: we examine the relationship between tether identity and fluorescence response, and we determine the general utility of pyrene fluorescence to monitor RNA folding. The P4–P6 domain of the Tetrahymena group I intron RNA was systematically modified at multiple nucleotide positions with pyrene derivatives that provide a range of tether lengths and compositions between the RNA and chromophore. Certain tethers typically lead to a superior fluorescence signal upon RNA folding, as demonstrated by equilibrium titrations with Mg2+. In addition, useful fluorescence responses were obtained with pyrene placed at several nucleotide positions dispersed throughout P4–P6. This suggests that monitoring of tertiary folding by fluorescence of covalently attached pyrene will be generally applicable to structured RNA molecules. PMID:16401611

  5. Spray-assisted layer-by-layer assembly on hyaluronic acid scaffolds for skin tissue engineering.

    PubMed

    Monteiro, Isa P; Shukla, Anita; Marques, Alexandra P; Reis, Rui L; Hammond, Paula T

    2015-01-01

    Tissue engineering approaches for the development of a single epidermal-dermal scaffold to treat full-thickness skin defects have been limited by difficulties in the fabrication of a bilayer scaffold combining the specific properties of the epidermis and the dermis. Here we present an innovative approach to developing a scaffold that holds promise for skin tissue engineering. We utilize the spray-assisted layer-by-layer assembly technique to deposit a polyelectrolyte multilayer film composed of hyaluronic acid and poly-L-lysine (the epidermal component) on a porous hyaluronic acid scaffold (the dermal component), in a rapid and controlled manner. The multilayer film promotes cell adhesion, contributing to regeneration of the epidermal barrier functions of skin. While human keratinocytes attached and proliferated on the coated porous scaffolds, they did not invade the porous dermal component, thus leaving room for seeding of relevant fibroblast cell types in this scaffold. This scaffold therefore holds promise for co-culture of different cells, which may be useful for treatment of full-thickness skin defects as well as other tissue engineering applications. © 2014 Wiley Periodicals, Inc.

  6. 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.

  7. Electrochemical properties of multilayer film assembled by layer-by-layer adsorption of redox polymer

    NASA Astrophysics Data System (ADS)

    Sun, Tao; Zheng, Haitao; Liu, Shiyang; Liu, Pu; Zhou, Jingli; Suye, Shin-ichiro

    2009-07-01

    A redox polymer, poly(ethylenimine)ferrocene (PEI-Fc) was prepared by attaching electroactive ferrocene groups to the backbone of a water soluble, biocompatible polyelectrolyte, poly(ethylenimine), and multilayer film composed of polystyrenesulfonate sodium (PSS) and PEI-Fc was prepared by alternate layer-by-layer (LBL) self-assembly adsorption technique based on the electrostatic force between the opposite charges carried by these two polymers. UV-Vis spectra was used to monitor the LBL process, and the thickness and immobilization amount of each layer were characterized by quartz crystal microbalance (QCM), which showed the formation of nano-scale multilayer structure and linear mass increase dependent on the alternate adsorption cycles. The electrochemical properties of the PEI-Fc/PSS multilayer film modified gold electrode were investigated by cyclic voltammetry. It was observed clearly that the electrochemical properties of this multilayer film were strongly dependent on the layer number and the ferrocene content in PEI-Fc. The electrochemical kinetic was analyzed based on a general model for surface process, and the experimental data fitted well with that evaluated from the above model. This redox polymer showed potential for the construction of reagentless biosensor.

  8. 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.

  9. Layer-by-Layer Bioprinting of Stem Cells for Retinal Tissue Regeneration

    DTIC Science & Technology

    2015-10-01

    AWARD NUMBER: W81XWH-14-1-0522 TITLE: Layer-by-Layer Bioprinting of Stem Cells for Retinal Tissue Regeneration PRINCIPAL INVESTIGATOR...TITLE AND SUBTITLE Layer-by-Layer Bioprinting of Stem Cells for Retinal Tissue Regeneration 5a. CONTRACT NUMBER 5b. GRANT NUMBER W81XWH-14-1-0522 5c...bioprinting process using stem cells for retinal tissue regeneration. The LBL nature of the bioprinting process matches nicely with the native

  10. Layer-by-Layer Bioprinting of Stem Cells for Retinal Tissue Regeneration

    DTIC Science & Technology

    2016-12-01

    AWARD NUMBER: W81XWH-14-1-0522 TITLE: Layer-by-Layer Bioprinting of Stem Cells for Retinal Tissue Regeneration PRINCIPAL INVESTIGATOR...4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Layer-by-Layer Bioprinting of Stem Cells for Retinal Tissue Regeneration 5b. GRANT NUMBER 5c. PROGRAM...stem cells for retinal tissue regeneration. The LBL nature of the bioprinting process matches nicely with the native, multilaminar anatomy of the

  11. Heterogeneous electron-transfer kinetics for PQQ covalently attached to aminoalkanethiol monolayers on gold.

    PubMed

    Park, Wonchoul; Ahmed, Jalal; Kim, Sunghyun

    2009-01-01

    Pyrroloquinoline quinone (PQQ) was covalently attached to a gold electrode surface via the self-assembled monolayers of aminoalkanethiols (NH2)(CH2)nSH) with different alkyl chain lengths (n=2, 6, 8, and 11). The voltammetric behaviors of PQQ-SAMs both at full and at partial monolayers were examined. It was found that the redox response of PQQ became more reversible with increasing dilution by alkanethiols owing to the less lateral interaction between PQQ heads. Voltammograms were transformed from quasi-reversibility to irreversibility as the alkyl chain spacer became longer. The electron tunneling barrier constant (beta) and distance dependence of the long range electron-transfer parameters have been studied in acidic solution using cyclic voltammetry. A logarithmic dependence of the heterogeneous electron-transfer rate constant on the alkyl chain length was found for full and partial PQQ monolayers. The beta value was close to 1.0 per CH2 unit regardless of dilution effect.

  12. Antimicrobial peptide coatings for hydroxyapatite: electrostatic and covalent attachment of antimicrobial peptides to surfaces.

    PubMed

    Townsend, Leigh; Williams, Richard L; Anuforom, Olachi; Berwick, Matthew R; Halstead, Fenella; Hughes, Erik; Stamboulis, Artemis; Oppenheim, Beryl; Gough, Julie; Grover, Liam; Scott, Robert A H; Webber, Mark; Peacock, Anna F A; Belli, Antonio; Logan, Ann; de Cogan, Felicity

    2017-01-01

    The interface between implanted devices and their host tissue is complex and is often optimized for maximal integration and cell adhesion. However, this also gives a surface suitable for bacterial colonization. We have developed a novel method of modifying the surface at the material-tissue interface with an antimicrobial peptide (AMP) coating to allow cell attachment while inhibiting bacterial colonization. The technology reported here is a dual AMP coating. The dual coating consists of AMPs covalently bonded to the hydroxyapatite surface, followed by deposition of electrostatically bound AMPs. The dual approach gives an efficacious coating which is stable for over 12 months and can prevent colonization of the surface by both Gram-positive and Gram-negative bacteria.

  13. 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

  14. 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

  15. 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

  16. Stable, covalent attachment of laminin to microposts improves the contractility of mouse neonatal cardiomyocytes.

    PubMed

    Ribeiro, Alexandre J S; Zaleta-Rivera, Kathia; Ashley, Euan A; Pruitt, Beth L

    2014-09-10

    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

  17. Covalent attachment of nanoparticles to copolymer surfaces to control structure-property relationships

    NASA Astrophysics Data System (ADS)

    McConnell, Marla D.

    Interest in functional nanoparticles has increased in recent years, because their small size gives them unique properties. Surface assembly of nanoparticles is particularly appealing, because it can create surfaces with tunable wetting and optical properties. This thesis presents a novel method for the covalent assembly of silica nanoparticles on random copolymer films via covalent bonding, and the subsequent analysis of the wetting and optical properties of these functionalized surfaces. First, the kinetics of the covalent attachment of amine-modified silica nanoparticles to poly(styrene-ran-acrylic acid) were investigated. The surface swelling of the copolymer films upon exposure to reaction solvents was studied with in situ AFM. The films' surface roughness controlled the nanoparticle attachment kinetics, as well as the final nanoparticle coverage. For particle diameters on the order of the roughness features, 70% surface coverage was achieved, while particles with diameters much larger than the surface features reached only 30% coverage. The wetting properties of the nanoparticle surfaces were investigated as a function of particle coverage and diameter. At low coverages of small particles, the surfaces exhibited Wenzel-type wetting behavior. At high particle coverages, the surfaces showed Cassie-type wetting. Finally, the particles were observed to sink into the polymer film with increasing reaction time. This sinking, as well as the magnitude of the contact angles achieved at high particle coverages, led to the hypothesis that polymer chains wet onto the surface of the silica particles. Core-shell Janus particles were prepared by electrostatic assembly of gold nanoparticles on the unprotected surfaces of the silica particles. The plasmon resonance absorption of the gold particles underwent a red shift upon formation of closely-packed networks on the silica particle surfaces. By applying gold, chromium, and gold:palladium coatings to the Janus particles and

  18. Direct electrochemistry of Phanerochaete chrysosporium cellobiose dehydrogenase covalently attached onto gold nanoparticle modified solid gold electrodes.

    PubMed

    Matsumura, Hirotoshi; Ortiz, Roberto; Ludwig, Roland; Igarashi, Kiyohiko; Samejima, Masahiro; Gorton, Lo

    2012-07-24

    Achieving efficient electrochemical communication between redox enzymes and various electrode materials is one of the main challenges in bioelectrochemistry and is of great importance for developing electronic applications. Cellobiose dehydrogenase (CDH) is an extracellular flavocytochrome composed of a catalytic FAD containing dehydrogenase domain (DH(CDH)), a heme b containing cytochrome domain (CYT(CDH)), and a flexible linker region connecting the two domains. Efficient direct electron transfer (DET) of CDH from the basidiomycete Phanerochaete chrysosporium (PcCDH) covalently attached to mixed self-assembled monolayer (SAM) modified gold nanoparticle (AuNP) electrode is presented. The thiols used were as follows: 4-aminothiophenol (4-ATP), 4-mercaptobenzoic acid (4-MBA), 4-mercaptophenol (4-MP), 11-mercapto-1-undecanamine (MUNH(2)), 11-mercapto-1-undecanoic acid (MUCOOH), and 11-mercapto-1-undecanol (MUOH). A covalent linkage between PcCDH and 4-ATP or MUNH(2) in the mixed SAMs was formed using glutaraldehyde as cross-linker. The covalent immobilization and the surface coverage of PcCDH were confirmed with surface plasmon resonance (SPR). To improve current density, AuNPs were cast on the top of polycrystalline gold electrodes. For all the immobilized PcCDH modified AuNPs electrodes, cyclic voltammetry exhibited clear electrochemical responses of the CYT(CDH) with fast electron transfer (ET) rates in the absence of substrate (lactose), and the formal potential was evaluated to be +162 mV vs NHE at pH 4.50. The standard ET rate constant (k(s)) was estimated for the first time for CDH and was found to be 52.1, 59.8, 112, and 154 s(-1) for 4-ATP/4-MBA, 4-ATP/4-MP, MUNH(2)/MUCOOH, and MUNH(2)/MUOH modified electrodes, respectively. At all the mixed SAM modified AuNP electrodes, PcCDH showed DET only via the CYT(CDH). No DET communication between the DH(CDH) domain and the electrode was found. The current density for lactose oxidation was remarkably increased by

  19. Multilayer nanostructured porphyrin arrays constructed by layer-by-layer self-assembly.

    PubMed

    Smith, Arthur R G; Ruggles, Jeremy L; Yu, Aimin; Gentle, Ian R

    2009-09-01

    UV-vis absorption, atomic force microscopy (AFM), contact angle, and X-ray reflectivity experiments were performed on thin films deposited on crystalline silicon substrates as alternating layers of a porphyrin with anionic functionality, tetra-5,10,15,20-(4-sulfonatophenyl)porphine (TSPP) or the metalated version, Cu(II)TSPP, and the cationic polyelectrolyte, poly(diallyldimethylammonium chloride) (PDDA). The films were made by dipping in alternating aqueous solutions containing film components (layer-by-layer deposition). Modeling of the X-ray reflectivity data revealed differences in the films' thickness depending on the method of film deposition. An unusual decrease in film thickness after each polyelectrolyte dip was also observed for films using TSSP. UV-vis measurements revealed that a similar amount of TSSP was included within films despite the method of formation. UV-vis measurements also revealed the presence of free-base, H-aggregate, and J-aggregate forms of the porphyrin after TSPP dipping, and the subsequent disappearance of the J-aggregate after dipping in the PDDA solution. A model of film formation was proposed on the basis of the concept of two different types of porphyrin aggregates being present after dipping in porphyrin solution. A layer of porphyrin molecules initially attach to the Si surface such that the planar molecules are arranged side by side as H-aggregates with an excess of J-aggregated material on top. The J-aggregate is then removed and replaced by a layer of PDDA. A change in contact angle of 14 degrees was observed between porphyrin and polyelectrolyte layers due to the more hydrophobic nature of the polymer. The presence of the J-aggregate was confirmed in AFM images obtained from the porphyrin layer. Exposure of the films to solutions of alternating pHs of 10 and 1.8 resulted in reproducible switching of the UV-vis spectra, indicating a possible sensing application.

  20. Covalent attachment of diamondoid phosphonic acid dichlorides to tungsten oxide surfaces.

    PubMed

    Li, Fei Hua; Fabbri, Jason D; Yurchenko, Raisa I; Mileshkin, Alexander N; Hohman, J Nathan; Yan, Hao; Yuan, Hongyuan; Tran, Ich C; Willey, Trevor M; Bagge-Hansen, Michael; Dahl, Jeremy E P; Carlson, Robert M K; Fokin, Andrey A; Schreiner, Peter R; Shen, Zhi-Xun; Melosh, Nicolas A

    2013-08-06

    Diamondoids (nanometer-sized diamond-like hydrocarbons) are a novel class of carbon nanomaterials that exhibit negative electron affinity (NEA) and strong electron-phonon scattering. Surface-bound diamondoid monolayers exhibit monochromatic photoemission, a unique property that makes them ideal electron sources for electron-beam lithography and high-resolution electron microscopy. However, these applications are limited by the stability of the chemical bonding of diamondoids on surfaces. Here we demonstrate the stable covalent attachment of diamantane phosphonic dichloride on tungsten/tungsten oxide surfaces. X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy revealed that diamondoid-functionalized tungsten oxide films were stable up to 300-350 °C, a substantial improvement over conventional diamondoid thiolate monolayers on gold, which dissociate at 100-200 °C. Extreme ultraviolet (EUV) light stimulated photoemission from these diamondoid phosphonate monolayers exhibited a characteristic monochromatic NEA peak with 0.2 eV full width at half-maximum (fwhm) at room temperature, showing that the unique monochromatization property of diamondoids remained intact after attachment. Our results demonstrate that phosphonic dichloride functionality is a promising approach for forming stable diamondoid monolayers for elevated temperature and high-current applications such as electron emission and coatings in micro/nano electromechanical systems (MEMS/NEMS).

  1. Prokaryotic ubiquitin-like protein remains intrinsically disordered when covalently attached to proteasomal target proteins.

    PubMed

    Barandun, Jonas; Damberger, Fred F; Delley, Cyrille L; Laederach, Juerg; Allain, Frédéric H T; Weber-Ban, Eilika

    2017-02-01

    The post-translational modification pathway referred to as pupylation marks proteins for proteasomal degradation in Mycobacterium tuberculosis and other actinobacteria by covalently attaching the small protein Pup (prokaryotic ubiquitin-like protein) to target lysine residues. In contrast to the functionally analogous eukaryotic ubiquitin, Pup is intrinsically disordered in its free form. Its unfolded state allows Pup to adopt different structures upon interaction with different binding partners like the Pup ligase PafA and the proteasomal ATPase Mpa. While the disordered behavior of free Pup has been well characterized, it remained unknown whether Pup adopts a distinct structure when attached to a substrate. Using a combination of NMR experiments and biochemical analysis we demonstrate that Pup remains unstructured when ligated to two well-established pupylation substrates targeted for proteasomal degradation in Mycobacterium tuberculosis, malonyl transacylase (FabD) and ketopantoyl hydroxylmethyltransferase (PanB). Isotopically labeled Pup was linked to FabD and PanB by in vitro pupylation to generate homogeneously pupylated substrates suitable for NMR analysis. The single target lysine of PanB was identified by a combination of mass spectroscopy and mutational analysis. Chemical shift comparison between Pup in its free form and ligated to substrate reveals intrinsic disorder of Pup in the conjugate. When linked to the proteasomal substrates FabD and PanB, Pup is unstructured and retains the ability to interact with its different binding partners. This suggests that it is not the conformation of Pup attached to these two substrates which determines their delivery to the proteasome, but the availability of the degradation complex and the depupylase.

  2. 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.

  3. 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

  4. 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

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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, ...

  7. 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…

  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. A novel bioelectrochemical sensing platform based on covalently attachment of cobalt phthalocyanine to graphene oxide.

    PubMed

    Hosseini, Hadi; Mahyari, Mojtaba; Bagheri, Akbar; Shaabani, Ahmad

    2014-02-15

    Graphene oxide-cobalt phthalocyanine (GO-PcCo) hybrid material as a new electrocatalyst was synthesized and used successfully to fabrication of new biosensor for the electrooxidation of l-cysteine (CSH) in aqueous media. Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) images revealed that cobalt phthalocyanine is covalently attachment on graphene oxide sheets as single layers GO-PcCo. Cyclic voltammetric studies showed that the GO-PcCo/glassy carbon electrode (GO-PcCo/GCE) improves electrochemical behavior of CSH oxidation, as compared to the GO and PcCo. In addition, the results indicated that GO and PcCo have a synergic effect in the electrooxidation of CSH. The catalytic oxidation responses were studied and the reaction mechanisms were discussed. The electrocatalytic behavior is further developed as a new detection scheme for CSH by chronoamperometry method and under optimized conditions, excellent analytical features, including high sensitivity and selectivity, low detection limit and satisfactory dynamic range, were achieved.

  10. 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.

  11. 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.

  12. 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.

  13. Polysaccharide-based polyelectrolytes hollow microcapsules constructed by layer-by-layer technique.

    PubMed

    Zhang, Yifeng; Chen, Cong; Wang, Jianguo; Zhang, Lina

    2013-07-25

    Two water-soluble polysaccharide derivatives, carboxymethylated and quarternized glucans (CMGP and QGP) were synthesized for the first time from water-insoluble polysaccharides (GP) extracted from Ganoderma lucidum. Hollow microspheres were constructed using electrostatic layer-by-layer (LbL) deposition of the CMGP and QGP polyelectrolytes onto colloidal ZnO particles followed by the core decomposition with an acid solution. The structures of the multilayered CMGP/QGP microspheres were investigated by transmission electron microscopy (TEM), zeta potential and dynamic light scattering (DLS). The results revealed that the multilayer thickness increased regularly from 48 to 145 nm as the number of deposited CMGP/QGP layers was increased from two to seven, and the mean increment of thickness was ∼25 nm per layer, reflecting the high regularity of the layer-by-layer assembly. This work provided an easy method to construct hollow microcapsules with biocompatibility and controlled dimensions.

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    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.

  15. 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.

  16. Layer-by-layer etching of LaAlSiO x

    NASA Astrophysics Data System (ADS)

    Omura, Mitsuhiro; Furumoto, Kazuhito; Matsuda, Kazuhisa; Sasaki, Toshiyuki; Sakai, Itsuko; Hayashi, Hisataka

    2017-06-01

    Layer-by-layer etching of LaAlSiO x using surface modification and selective removal steps was investigated. Selective removal of the LaAlSiO x layer modified by H2 plasma treatment was achieved by bias-power-adjusted C4F8/Ar plasma treatment. Self-limiting etching of LaAlSiO x with respect to the C4F8/Ar plasma step time was realized by initializing the chamber condition using O2 plasma. It was possible to control the saturation etching depth by changing the ion energy of the H2 plasma treatment. The repeatability of the self-limiting etching was confirmed, and the etching depth per cycle was about 0.6 nm. Layer-by-layer etching of LaAlSiO x was thus successfully realized using a three-step sequential process employing H2, C4F8/Ar and O2 plasmas.

  17. Layer-by-Layer Encapsulation of Probiotics for Delivery to the Microbiome.

    PubMed

    Anselmo, Aaron C; McHugh, Kevin J; Webster, Jamie; Langer, Robert; Jaklenec, Ana

    2016-11-01

    The gastrointestinal (GI) microbiome is widely investigated for its role in many diseases. However, technologies designed for microbiome delivery are lacking. Here, a layer-by-layer (LbL) approach is reported for probiotic encapsulation to protect probiotics against GI tract insults and improve their adhesion and growth on the intestines. These advantages translate to significantly enhanced survival of LbL-probiotics in vivo.

  18. 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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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

    2016-01-06

    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.

  20. Layer-by-layer epitaxial thin films of the pyrochlore Tb2Ti2O7

    NASA Astrophysics Data System (ADS)

    Bovo, Laura; Rouleau, Christopher M.; Prabhakaran, Dharmalingam; Bramwell, Steven T.

    2017-02-01

    Layer-by-layer epitaxial growth of the pyrochlore magnet Tb2Ti2O7 on the isostructural substrate Y2Ti2O7 results in high-quality single crystal films of up to 60 nm thickness. Substrate-induced strain is shown to act as a strong and controlled perturbation to the exotic magnetism of Tb2Ti2O7, opening up the general prospect of strain-engineering the diverse magnetic and electrical properties of pyrochlore oxides.

  1. "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.

  2. Layer-by-layer epitaxial thin films of the pyrochlore Tb2Ti2O7.

    PubMed

    Bovo, Laura; Rouleau, Christopher M; Prabhakaran, Dharmalingam; Bramwell, Steven T

    2017-02-03

    Layer-by-layer epitaxial growth of the pyrochlore magnet Tb2Ti2O7 on the isostructural substrate Y2Ti2O7 results in high-quality single crystal films of up to 60 nm thickness. Substrate-induced strain is shown to act as a strong and controlled perturbation to the exotic magnetism of Tb2Ti2O7, opening up the general prospect of strain-engineering the diverse magnetic and electrical properties of pyrochlore oxides.

  3. Freestanding films of crosslinked gold nanoparticles prepared via layer-by-layer spin-coating.

    PubMed

    Schlicke, Hendrik; Schröder, Jan H; Trebbin, Martin; Petrov, Alexey; Ijeh, Michael; Weller, Horst; Vossmeyer, Tobias

    2011-07-29

    A new, extremely efficient method for the fabrication of films comprised of gold nanoparticles (GNPs) crosslinked by organic dithiols is presented in this paper. The method is based on layer-by-layer spin-coating of both components, GNPs and crosslinker, and enables the deposition of films several tens of nanometers in thickness within a few minutes. X-ray diffraction and conductance measurements reveal the proper adjustment concentration of the crosslinker solution of the critical is in order to prevent the destabilization and coalescence of particles. UV/vis spectroscopy, atomic force microscopy, and conductivity measurements indicate that films prepared via layer-by-layer spin-coating are of comparable quality to coatings prepared via laborious layer-by-layer self-assembly using immersion baths. Because spin-coated films are not bound chemically to the substrate, they can be lifted-off by alkaline underetching and transferred onto 3d-electrodes to produce electrically addressable, freely suspended films. Comparative measurements of the sheet resistances indicate that the transfer process does not compromise the film quality.

  4. Freestanding films of crosslinked gold nanoparticles prepared via layer-by-layer spin-coating

    NASA Astrophysics Data System (ADS)

    Schlicke, Hendrik; Schröder, Jan H.; Trebbin, Martin; Petrov, Alexey; Ijeh, Michael; Weller, Horst; Vossmeyer, Tobias

    2011-07-01

    A new, extremely efficient method for the fabrication of films comprised of gold nanoparticles (GNPs) crosslinked by organic dithiols is presented in this paper. The method is based on layer-by-layer spin-coating of both components, GNPs and crosslinker, and enables the deposition of films several tens of nanometers in thickness within a few minutes. X-ray diffraction and conductance measurements reveal the proper adjustment concentration of the crosslinker solution of the critical is in order to prevent the destabilization and coalescence of particles. UV/vis spectroscopy, atomic force microscopy, and conductivity measurements indicate that films prepared via layer-by-layer spin-coating are of comparable quality to coatings prepared via laborious layer-by-layer self-assembly using immersion baths. Because spin-coated films are not bound chemically to the substrate, they can be lifted-off by alkaline underetching and transferred onto 3d-electrodes to produce electrically addressable, freely suspended films. Comparative measurements of the sheet resistances indicate that the transfer process does not compromise the film quality.

  5. Layer-by-layer self-assembled shells for drug delivery.

    PubMed

    Ariga, Katsuhiko; Lvov, Yuri M; Kawakami, Kohsaku; Ji, Qingmin; Hill, Jonathan P

    2011-08-14

    There are several requirements for the safe and effective delivery of therapeutic agents for human use. Direct injection of drugs may cause side effects due to their permeation to other, undiseased regions of the body so that concealment and targeting with appropriate materials is a critical consideration in the design of practical drug delivery systems. In particular, carriers with structures which can be flexibly controlled are more useful since functional structure units can be assembled in component-by-component and/or layer-by-layer fashion. In this review, we focus on preparation of layer-by-layer shells directed at drug delivery applications. After a description of the fundamentals of layer-by-layer (LbL) assembly, recent progress in the field of self-assembled microshells and nanoshells for drug delivery applications are summarized. In addition, concepts developed to solve current difficulties are also described. Encapsulation of insoluble drugs in nanoshells and their delivery can satisfy some of the demands of practical medical use. Thus, aqueous suspensions of insoluble drugs have been subjected to powerful ultrasonic treatment followed by sequential addition of polycations and polyanions to the particle solution leading to assembly of ultra-thin polyelectrolyte shells on the nano-sized drug particles. In another innovative example, stepwise release of drugs from LbL films of mesoporous capsules to the exterior in the absence of external stimuli was demonstrated. It can be regarded as stimuli-free auto-modulated material release.

  6. Layer-by-layer all-transfer-based organic solar cells.

    PubMed

    Kim, Jung Kyu; Kim, Wanjung; Wang, Dong Hwan; Lee, Haksoo; Cho, Sung M; Choi, Dae-Geun; Park, Jong Hyeok

    2013-04-30

    For the first time, we describe a novel cost- and time-effective vacuum-free process to fabricate bulk-heterojunction (BHJ) organic photovoltaics (OPVs) via layer-by-layer selective stamping transfer of all layers. By controlling the surface properties of polyurethane acrylate (PUA) stamping molds with ultraviolet (UV)-ozone (UVO) exposure, poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS), BHJ layer, and metal cathode were uniformly transferred layer by layer onto each of the bottom layers. Among several interfaces between each layer, we found that the interface between the active layer and metal cathode is a critical factor in obtaining conventional device-like efficiency. To enhance the interfacial connectivity between the BHJ layer and metal cathode and increase electron extraction from the BHJ layer, a titanium oxide (TiOx) interlayer was introduced. Cell performance was optimized by controlling the concentration of TiOx solution. The poly(3-hexylthiophene-2,5-diyl)/[6,6]-phenyl-C61-butyric acid methyl ester (P3HT/PC60BM) BHJ device fabricated by transferring PEDOT/PSS, TiOx/active layer, and Al cathode showed 2.01% power conversion efficiency. This efficiency is not comparable to those of conventional OPVs, but our approach shows the possibility of fabricating OPVs via the layer-by-layer transfer method for the first time.

  7. 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

  8. 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

  9. Linker-free covalent attachment of the extracellular matrix protein tropoelastin to a polymer surface for directed cell spreading.

    PubMed

    Bax, Daniel V; McKenzie, David R; Weiss, Anthony S; Bilek, Marcela M M

    2009-11-01

    Polymers are used for the fabrication of many prosthetic implants. It is desirable for these polymers to promote biological function by promoting the adhesion, differentiation and viability of cells. Here we have used plasma immersion ion implantation (PIII) treatment of polystyrene to modify the polymer surface, and so modulate the binding of the extracellular matrix protein tropoelastin. PIII treated, but not untreated polystyrene, bound tropoelastin in a sodium dodecyl sulfate (SDS)-resistant manner, consistent with previous enzyme-binding data that demonstrated the capability of these surfaces to covalently attach proteins without employing chemical linking molecules. Furthermore sulfo-NHS acetate (SNA) blocking of tropoelastin lysine side chains eliminated the SDS-resistant binding of tropoelastin to PIII-treated polystyrene. This implies tropoelastin is covalently attached to the PIII-treated surface via its lysine side chains. Cell spreading was only observed on tropoelastin coated, PIII-treated polystyrene surfaces, indicating that tropoelastin was more biologically active on the PIII-treated surface compared to the untreated surface. A contact mask was used to pattern the PIII treatment. Following tropoelastin attachment, cells spread preferentially on the PIII-treated sections of the polystyrene surface. This demonstrates that PIII treatment of polystyrene improves the polymer's tropoelastin binding properties, with advantages for tissue engineering and prosthetic design.

  10. 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.

  11. 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

  12. 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.

  13. Layer-by-layer nanostructured hybrid films of polyaniline and vanadium oxide.

    PubMed

    Ferreira, Marystela; Zucolotto, Valtencir; Huguenin, Fritz; Torresi, Roberto M; Oliveira, Osvaldo N

    2002-02-01

    Supramolecular structures of polyaniline (PANI) and vanadium oxide (V2O5) have been assembled via the electrostatic layer-by-layer (ELBL) technique. Strong ionic interactions and H-bonding impart unique features to the ELBL films, which are distinct from cast films obtained with the same materials. The interactions were manifested in UV-vis and Fourier transform infrared spectroscopy data. They are enhanced by the intimate contact between the components, as the films are molecularly thin, with 25 A per PANI/V2O5 bilayer.

  14. Graphene-based multilayers constructed from layer-by-layer self-assembly techniques.

    PubMed

    Yu, Bing; Liu, Xiaomian; Cong, Hailin; Yuan, Hua; Wang, Dong; Li, Zejing

    2014-02-01

    This paper reviews the recent research and development of graphene-based multilayers fabricated from layer-by-layer (LBL) self-assembly technique. Graphene multilayer films, due to their excellent performances and specific applications, have attracted widespread attention during recent decades. In this paper, the preparation and property of self-assembled graphene multilayer films are introduced. The application of different graphene multilayer films in transparent conducting films (TCFs), field effect transistors (FETs), lithium ion batteries (LIBs), supercapacitors, and solar cells are summarized and discussed. The perspectives for the future developments of self-assembled graphene multilayer films are proposed.

  15. 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.

  16. Recent progresses in layer-by-layer assembled biogenic capsules and their applications.

    PubMed

    Xuan, Mingjun; Zhao, Jie; Shao, Jingxin; Du, Cuiling; Cui, Wei; Duan, Li; Qi, Wei; Li, Junbai

    2017-02-01

    In this review, we summarize the recent progress made in the fabrication of pure natural materials such as biogenic capsules. Unlike polyelectrolyte capsules, biogenic capsules are primarily prepared with pure natural components using layer-by-layer (LbL) assembly on sacrificial templates. These capsules have been developed as smart materials for guest molecule encapsulation and delivery in the last two decades. With the extreme demands on biodegradability and biocompatibility, biogenic capsules exhibit unique properties that can be integrated with special ligands or conjugated functional groups for the design of intelligent platforms, significantly enriching their functions and applications. Copyright © 2016 Elsevier Inc. All rights reserved.

  17. Light-induced storage in layer-by-layer films of chitosan and an azo dye.

    PubMed

    dos Santos Júnior, D S; Bassi, A; Rodrigues Júnior, J J; Misoguti, L; Oliveira Júnior, O N; Mendonça, C R

    2003-01-01

    The buildup of layer-by-layer (LBL) films from chitosan and the azodye Ponceau-S (PS) was investigated under various experimental conditions, and the resulting films were used in optical storage experiments. The kinetics for the writing process in optical storage was faster for LBL films prepared at low pHs, probably because the films had a larger free volume for isomerization of the chromophores. The nanostructured nature of the LBL films also affected the crystallinity of chitosan, which was considerably decreased in this type of film as chitosan became protonated because of the electrostatic interactions between adjacent layers.

  18. 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.

  19. 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.

  20. 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.

  1. Pickering emulsion templated layer-by-layer assembly for making microcapsules.

    PubMed

    Li, Jian; Stöver, Harald D H

    2010-10-05

    Pickering emulsions stabilized by poly(sodium styrenesulfonate) (PSS) surface-modified LUDOX CL particles were used as templates for the layer-by-layer (LbL) deposition of polyelectrolytes and charged nanoparticles to form composite shells. The microcapsules resulting from repeated LbL coating with poly(diallyldimethylammonium chloride) (PDADMAC) and PSS had porous walls due to the loose arrangement of the original nanoparticle aggregates at the oil-water interface, leading to significant microcapsule rupture and low encapsulation efficiency. Microcapsules formed by coating with PDADMAC and anionic LUDOX HS nanoparticles led to dense walls and stronger microcapsules, suitable for microencapsulation of hydrophobic materials with a wide range of polarities.

  2. Surface-profile reconstruction of a liquid droplet based on layer-by-layer laser probing

    NASA Astrophysics Data System (ADS)

    Pavlov, I. N.; Raskovskaya, I. L.; Rinkevichyus, B. S.

    2017-07-01

    An experimental technique was developed for reconstructing the surface profile of a drop of liquid on a horizontal solid substrate using refractive images obtained by means of layer-by-layer laser probing. Examples of typical images obtained by vertical probing of drops of distilled water with a volume of 10-15 μL using a collimated laser beam are given. The inverse refraction problem is solved, and the global shape of the drop surface is restored. It is noted that, to restore the surface parameters of a microrelief, it is effective to use probing with a wide collimated beam.

  3. Layer-by-layer-assembled microfiltration membranes for biomolecule immobilization and enzymatic catalysis.

    PubMed

    Smuleac, V; Butterfield, D A; Bhattacharyya, D

    2006-11-21

    Multilayer assemblies of polyelectrolytes, for protein immobilization, have been created within the membrane pore domain. This approach was taken for two reasons: (1) the high internal membrane area can potentially increase the amount of immobilized protein, and (2) the use of convective flow allows uniform assembly of layers and eliminates diffusional limitations after immobilization. To build a stable assembly, the first polyelectrolyte layer was covalently attached to the membrane surface and inside the pore walls. Either poly(L-glutamic acid) (PLGA) or poly(L-lysine) (PLL) was used in this step. Subsequent deposition occurs by multiple electrostatic interactions between the adsorbing polyelectrolyte [poly(allylamine) hydrochloride (PAH) or poly(styrenesulfonate) (PSS)] and the oppositely charged layer. Three-layer membranes were created: PLL-PSS-PAH or PLGA-PAH-PSS, for an overall positive or negative charge, respectively. The overall charge on both the protein and membrane plays a substantial role in immobilization. When the protein and the membrane are oppositely charged, the amount immobilized and the stability within the polyelectrolyte assembly are significantly higher than for the case when both have similar charges. After protein incorporation in the multilayer assembly, the active site accessibility was comparable to that obtained in the homogeneous phase. This was tested by affinity interaction (avidin-biotin) and by carrying out two reactions (catalyzed by glucose oxidase and alkaline phosphatase). Besides simplicity and versatility, the ease of enzyme regeneration constitutes an additional benefit of this approach.

  4. Using the reactive dye method to covalently attach antibacterial compounds to cotton.

    USDA-ARS?s Scientific Manuscript database

    The antibacterial compounds used were sulfamethoxazole and trimethoprim. A version of the reactive dye method was used to react these two compounds chemically with the cotton fiber molecule. The two compounds were activated and then covalently bonded to cotton fabric, either separately or together...

  5. Mixed mosaic membranes prepared by layer-by-layer assembly for ionic separations.

    PubMed

    Rajesh, Sahadevan; Yan, Yu; Chang, Hsueh-Chia; Gao, Haifeng; Phillip, William A

    2014-12-23

    Charge mosaic membranes, which possess distinct cationic and anionic domains that traverse the membrane thickness, are capable of selectively separating dissolved salts from similarly sized neutral solutes. Here, the generation of charge mosaic membranes using facile layer-by-layer assembly methodologies is reported. Polymeric nanotubes with pore walls lined by positively charged polyethylenimine moieties or negatively charged poly(styrenesulfonate) moieties were prepared via layer-by-layer assembly using track-etched membranes as sacrificial templates. Subsequently, both types of nanotubes were deposited on a porous support in order to produce mixed mosaic membranes. Scanning electron microscopy demonstrates that the facile deposition techniques implemented result in nanotubes that are vertically aligned without overlap between adjacent elements. Furthermore, the nanotubes span the thickness of the mixed mosaic membranes. The effects of this unique nanostructure are reflected in the transport characteristics of the mixed mosaic membranes. The hydraulic permeability of the mixed mosaic membranes in piezodialysis operations was 8 L m(-2) h(-1) bar(-1). Importantly, solute rejection experiments demonstrate that the mixed mosaic membranes are more permeable to ionic solutes than similarly sized neutral molecules. In particular, negative rejection of sodium chloride is observed (i.e., the concentration of NaCl in the solution that permeates through a mixed mosaic membrane is higher than in the initial feed solution). These properties illustrate the ability of mixed mosaic membranes to permeate dissolved ions selectively without violating electroneutrality and suggest their utility in ionic separations.

  6. 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.

  7. Layer-by-layer click deposition of functional polymer coatings for combating marine biofouling.

    PubMed

    Yang, Wen Jing; Pranantyo, Dicky; Neoh, Koon-Gee; Kang, En-Tang; Teo, Serena Lay-Ming; Rittschof, Daniel

    2012-09-10

    "Click" chemistry-enabled layer-by-layer (LBL) deposition of multilayer functional polymer coatings provides an alternative approach to combating biofouling. Fouling-resistant azido-functionalized poly(ethylene glycol) methyl ether methacrylate-based polymer chains (azido-poly(PEGMA)) and antimicrobial alkynyl-functionalized 2-(methacryloyloxy)ethyl trimethyl ammonium chloride-based polymer chains (alkynyl-poly(META)) were click-assembled layer-by-layer via alkyne-azide 1,3-dipolar cycloaddition. The polymer multilayer coatings are resistant to bacterial adhesion and are bactericidal to marine Gram-negative Pseudomonas sp. NCIMB 2021 bacteria. Settlement of barnacle ( Amphibalanus (= Balanus ) amphitrite ) cyprids is greatly reduced on the multilayer polymer-functionalized substrates. As the number of the polymer layers increases, efficacy against bacterial fouling and settlement of barnacle cyprids increases. The LBL-functionalized surfaces exhibit low toxicity toward the barnacle cyprids and are stable upon prolonged exposure to seawater. LBL click deposition is thus an effective and potentially environmentally benign way to prepare antifouling coatings.

  8. Layer-by-layer assembly of patchy particles as a route to nontrivial structures

    NASA Astrophysics Data System (ADS)

    Patra, Niladri; Tkachenko, Alexei V.

    2017-08-01

    We propose a strategy for robust high-quality self-assembly of nontrivial periodic structures out of patchy particles and investigate it with Brownian dynamics simulations. Its first element is the use of specific patch-patch and shell-shell interactions between the particles, which can be implemented through differential functionalization of patched and shell regions with specific DNA strands. The other key element of our approach is the use of a layer-by-layer protocol that allows one to avoid the formation of undesired random aggregates. As an example, we design and self-assemble in silico a version of a double diamond lattice in which four particle types are arranged into bcc crystal made of four fcc sublattices. The lattice can be further converted to cubic diamond by selective removal of the particles of certain types. Our results demonstrate that by combining the directionality, selectivity of interactions, and the layer-by-layer protocol, a high-quality robust self-assembly can be achieved.

  9. 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.

  10. Zipper and layer-by-layer assemblies of artificial photosystems analyzed by combining optical and piezoelectric surface techniques.

    PubMed

    Porus, Mariya; Maroni, Plinio; Bhosale, Rajesh; Sakai, Naomi; Matile, Stefan; Borkovec, Michal

    2011-06-07

    Quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) were used to study zipper and layer-by-layer multilayer assemblies of artificial photosystems based on naphthalenediimides (NDIs) attached to an oligophenylethynyl (OPE-NDI) or p-oligophenyl (POP-NDI) backbone in dry and wet state. For the most interesting OPE-NDI zipper, one obtains for the dry film a monolayer thickness of 1.85 nm and a density of 1.58 g/cm(3), while the wet film has a larger monolayer thickness of 3.6 nm with a water content of 36%. The dry thickness of a monolayer in OPE-NDI zippers corresponds to about one-half of the length of the OPE scaffold in agreement with the proposed structure of the zipper. The low water content of the OPE-NDI films confirms their compact structure. The dry monolayer thickness of the POP-NDI films of 1.45 nm is smaller than that for the OPE-NDI films, which is probably related to a tilt of the POP scaffolds within the adsorbed layer. The POP-NDI films swell in water much more substantially, suggesting a much more open structure. These features are in excellent agreement with the better photophysical performance of the OPE-NDI assemblies when compared to the POP-NDI films.

  11. Photophysics and photochemistry of the UV filter kynurenine covalently attached to amino acids and to a model protein.

    PubMed

    Sherin, Peter S; Grilj, Jakob; Kopylova, Lyudmila V; Yanshole, Vadim V; Tsentalovich, Yuri P; Vauthey, Eric

    2010-09-16

    The photophysics and photochemistry of kynurenine (KN) covalently bound to the amino acids lysine, cysteine, and histidine, the antioxidant glutathione, and the protein lysozyme have been studied by optical spectroscopy with femto- and nanosecond time resolution. The fluorescence quantum yield of the adducts of KN to amino acids is approximately 2 times higher than that of the free KN in solution; KN attached to protein exhibits a 7-fold increase in the fluorescence quantum yield. The S(1) state dynamics of KN-modified lysozyme reveals a multiphasic decay with a broad dispersion of time constants from 1 ps to 2 ns. An increase of the triplet yield of KN bound to lysozyme is also observed; the triplet state undergoes fast intramolecular decay. The obtained results reveal an increase of the photochemical activity of KN after its covalent attachment to amino acids and proteins, which may contribute to the development of oxidative stress in the human lenses-the main causative factor for the cataract onset.

  12. Green coconut fiber: a novel carrier for the immobilization of commercial laccase by covalent attachment for textile dyes decolourization.

    PubMed

    Cristóvão, Raquel O; Silvério, Sara C; Tavares, Ana P M; Brígida, Ana Iraidy S; Loureiro, José M; Boaventura, Rui A R; Macedo, Eugénia A; Coelho, Maria Alice Z

    2012-09-01

    Commercial laccase formulation was immobilized on modified green coconut fiber silanized with 3-glycidoxypropyltrimethoxysilane, aiming to achieve a cheap and effective biocatalyst. Two different strategies were followed: one point (pH 7.0) and multipoint (pH 10.0) covalent attachment. The influence of immobilization time on enzymatic activity and the final reduction with sodium borohydride were evaluated. The highest activities were achieved after 2 h of contact time in all situations. Commercial laccase immobilized at pH 7.0 was found to have higher activity and higher affinity to the substrate. However, the immobilization by multipoint covalent attachment improved the biocatalyst thermal stability at 50 °C, when compared to soluble enzyme and to the immobilized enzyme at pH 7.0. The Schiff's bases reduction by sodium borohydride, in spite of causing a decrease in enzyme activity, showed to contribute to the increase of operational stability through bonds stabilization. Finally, these immobilized enzymes showed high efficiency in the continuous decolourization of reactive textile dyes. In the first cycle, the decolourization is mainly due to dyes adsorption on the support. However, when working in successive cycles, the adsorption capacity of the support decreases (saturation) and the enzymatic action increases, indicating the applicability of this biocatalyst for textile wastewater treatment.

  13. Combining the Physical Adsorption Approach and the Covalent Attachment Method to Prepare a Bifunctional Bioreactor

    PubMed Central

    Dong, Mengxing; Wu, Zhuofu; Lu, Ming; Wang, Zhi; Li, Zhengqiang

    2012-01-01

    Aminopropyl-functionalized SBA-15 mesoporous silica was used as a support to adsorb myoglobin. Then, in order to avoid the leakage of adsorbed myoglobin, lysozyme was covalently tethered to the internal and external surface of the mesoporous silica with glutaraldehyde as the coupling agent. The property of amino-functionalized mesoporous silica was characterized by N2 adsorption-desorption and thermogravimetric (TG) analysis. The feature of the silica-based matrix before and after myoglobin adsorption was identified by fourier transform infrared (FTIR) and UV/VIS measurement. With o-dianisidine and H2O2 as the substrate, the peroxidase activity of adsorbed myoglobin was determined. With Micrococus lysodeilicus as the substrate, the antibacterial activity of covalently tethered lysozyme was measured. Results demonstrated that the final product not only presented peroxidase activity of the myoglobin but yielded antibacterial activity of the lysozyme. PMID:23109864

  14. Solute- and temperature-responsive "smart" grafts and supported membranes formed by covalent layer-by-layer assembly.

    PubMed

    Allen, Ainsley L; Tan, Kristine J; Fu, Hui; Batteas, James D; Bergbreiter, David E

    2012-03-20

    Polymers like poly(N-isopropylacrylamide) (PNIPAM) exhibit lower critical solution temperature (LCST) behavior. A variety of reports have shown that brush grafts of PNIPAM on surfaces exhibit similar temperature responsiveness. We recently described an alternative synthetic approach to such surfaces that affords surfaces with similar LCST-like behavior. We also noted how such surfaces' wettability can change in response to the identity and concentration of solutes. Here we show that this synthetic procedure can be extended to glass surfaces and to more complex surfaces present in porous glass frits. Functionalized glass surfaces exhibit solute-dependent wetting behavior analogous to that previously reported. We further show that the resulting responsive nanocomposite grafts on such frits exhibit "smart" responsive permeability with a greater than 1000-fold difference in permeability to water versus aqueous solutions of sodium sulfate. This "smart" permeability is ascribed to the solute-dependent wettability behavior of the responsive PNIPAM component of the nanocomposite graft, which is sensitive both to the identity and concentration of the solute anion and to temperature.

  15. Enhancement of capillary electrochromatographic separation performance by conductive polymer in a layer-by-layer fabricated graphene stationary phase.

    PubMed

    Zhang, Juan; Zhang, Wenpeng; Bao, Tao; Chen, Zilin

    2014-04-25

    In this work, we fabricated a novel graphene-based capillary column for open-tubular capillary electrochromatography (OT-CEC) by a layer-by-layer strategy. To immobilize graphene onto the inner surface of silica capillary, a bio-inspired method was first used to functionalize the capillary surface with a layer of polydopamine (PDA). Graphene oxide (GO) was then introduced and can covalently react with polydopamine, realizing immobilization of graphene as a result. To enhance the modification efficiency of polydopamine, a conductive polymer, polyaniline (PANI) was introduced to be a sub-layer; polydopamine was then introduced following with GO, to generate a multilayer GO-PDA-PANI@capillary. Interestingly, separation efficiency of the graphene-based capillary was enhanced significantly by using conductive PANI as a sub-layer. The morphology of different layers modified on the capillary column was characterized by scanning electron microscopy (SEM). The electroosmotic flow (EOF) characteristics of capillaries modified with different layers were also investigated by varying the pH value of mobile phase. GO-PDA-PANI@capillary showed good separation efficiency towards alkylbenzenes by OT-CEC mode, with theoretic plate numbers up to 133,918 for benzene. The separation was found to follow a reversed-phase chromatographic retention mechanism. Repeatability of the GO-PDA-PANI@capillary was studied, with relative standard deviations for intra-day and inter-day runs less than 2.89%, and column-to-column runs less than 6.17%. The separation performance of GO-PDA-PANI@capillary was also compared with that of the reported graphene modified capillary.

  16. A molecular photovoltaic system based on Dawson type polyoxometalate and porphyrin formed by layer-by-layer self assembly.

    PubMed

    Ahmed, Iftikhar; Farha, Rana; Goldmann, Michel; Ruhlmann, Laurent

    2013-01-18

    Films based on electrostatic interactions between tetracationic porphyrin and Dawson type polyoxometalate are formed by the so called layer-by-layer method. Their photovoltaic performances are investigated by photocurrent transient measurements which showed significant photocurrent response.

  17. Development of nanostructured magnetic capsules by means of the layer by layer technique.

    PubMed

    Herrera, Oscar L; Parigi, Enrico; Habibi, Neda; Pastorino, Laura; Caneva Soumetz, Federico; Ruggiero, Carmelina

    2010-01-01

    Nanomagnetic particles have been already taken into account as drug carriers thank to the possibility to control their movement to a specific location where the treatment is required by means of high gradient magnetic fields (HGMF). In this work the layer-by-layer technique (LbL) and nanomagnetic particles were used to developed innovative nanostructured magnetic capsules (NSMC). Their potential application as magnetic drug carriers was investigated under the influence of both static and oscillating magnetic fields used respectively to control capsule displacement and shell permeability. The assembly process of the nanostructured magnetic capsules, its characterization by Quartz Crystal Microbalance (QCM), and the results obtained under the influence of the magnetic fields are presented.

  18. 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

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

    PubMed Central

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

    2016-01-01

    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

  20. 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. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

    DOEpatents

    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.

  2. Monoamine oxidase B layer-by-layer film fabrication and characterization toward dopamine detection.

    PubMed

    Miyazaki, Celina Massumi; Pereira, Tamyris Paschoal; Mascagni, Daniela Branco Tavares; de Moraes, Marli Leite; Ferreira, Marystela

    2016-01-01

    In this work nanostructured film composites of the monoamine oxidase B (MAO-B) enzyme, free or encapsulated in liposomes, were fabricated by the layer-by-layer (LbL) self-assembly technique, employing polyethylene imine (PEI) as polycation. Initially, the MAO-B enzyme was incorporated into liposomes in order to preserve its enzymatic structure ensuring their activity and catalytic stability. The LbL film growth was monitored by surface plasmon resonance (SPR) by gold resonance angle shift analysis after each bilayer deposition. Subsequently, the films were applied as amperometric biosensors for dopamine detection using Prussian Blue (PB) as the electron mediator. The biosensor fabricated by MAO-B incorporated into liposomes composed of DPPG:POPG in the ratio (1:4) (w/w) showed the best performance with a sensitivity of 0.86 (μA cm(-2))/(mmol L(-1)) and a detection limit of 0.33 mmol L(-1).

  3. Layer-by-layer synthesis of mechanically robust solvent-permeable silica nanoshells.

    PubMed

    Whitaker, Kathryn A; Furst, Eric M

    2014-01-21

    A layer-by-layer (LbL) synthesis of mechanically robust micrometer-diameter nanoshell silica was developed. Silica was templated onto polstyrene latex particles using a modified Stöber synthesis. Each subsequent silica layer was deposited after adsorbing cationic polymer poly(allylamine) hydrochloride. The silica shell grew approximately 30 nm for each reaction step. The polystyrene-silica core-shell particles were calcined at 500 °C to remove the latex core. The synthesis was adapted to nonspherical shapes using anisotropic polystyrene dicolloids as templates. The silica nanoshells were functionalized to render them organophilic or fluorescent. The rates at which water, ethanol, and aqueous sucrose solution (60% w/w) permeate the silica shells were compared using spectrophotometry and conductivity measurements. The rate of solvent uptake ranged between under 1 h to over 1 week depending on the surface chemistry of the nanoshells.

  4. Multinuclear layer-by-layer growth on Ge(1 1 1) by LPE

    NASA Astrophysics Data System (ADS)

    Maruyama, Takahiro; Matsuda, Keiji; Naritsuka, Shigeya

    2005-02-01

    Aiming at the fabrication of step-free Ge(1 1 1) surfaces of device size, liquid-phase epitaxy (LPE) growth was carried out on Ge(1 1 1) mesa structures. Reducing supersaturation by controlling the growth temperature, nearly atomically flat faces were formed on several mesas following LPE growth at less than 480 °C. Taking into account the density of edge, screw and mixed dislocations, these flat faces appear to have formed on the top surface of screw and mixed dislocation-free mesas. Observation by atomic force microscopy (AFM) showed the presence of a number of triangular hollows with monolayer step depth on the flat faces, indicating "multinuclear layer-by-layer growth". In addition, the number of triangular hollows was found to be exponentially dependent on the reciprocal of growth temperature. Taking into account the step velocity, the mechanism of two-dimensional nucleation on an atomically flat surface is discussed.

  5. Cellulose fibre networks reinforced with carboxymethyl cellulose/chitosan complex layer-by-layer.

    PubMed

    Wu, Tongfei; Farnood, Ramin

    2014-12-19

    An eco-friendly and full-polysaccharide polyelectrolyte complex system was developed to enhance the wet and dry tensile strength of cellulose fibre networks. Cellulose fibres were treated by carboxymethyl cellulose (CMC) in pulp suspension. Paper sheets made from CMC-treated fibres were further modified via the layer-by-layer (LbL) deposition of CMC/chitosan (CS) complex. The effect of number of CMC/CS layers on the strength properties of cellulose fibre networks (both under wet and dry conditions) was studied and sample structure was investigated by scanning electron microscopy (SEM). Water vapour transmission rate (WVTR) of CMC/CS-treated samples was also examined. The observed changes in the strength properties of treated samples were explained based on the competition between the rate of diffusion of CS to the fibre-fibre bond areas and the rate of disassociation of fibre-fibre interactions during the LbL deposition process.

  6. Giant circular polarization conversion in layer-by-layer nonchiral metamaterial.

    PubMed

    Zhang, Peng; Zhao, Ming; Wu, Lin; Lu, Zeqin; Xie, ZuoWei; Zheng, Yu; Duan, Jian; Yang, ZhenYu

    2013-09-01

    We studied numerically the transmission properties of a kind of layer-by-layer nonchiral metamaterial. Simulation results show that under certain off-normal incidence, giant circular polarization conversion occurs for both the right and left circularly polarized waves with a roughly 1 GHz operation band. Meanwhile, the copolarization transmissions are almost suppressed to zero, leading to the high purity circular polarization transformation. This phenomenon of giant circular polarization conversion is assumed to suffer from the strong magnetic response, which is illustrated by the surface current distributions of the structure. Compared with chiral structures, this nonchiral structure is easier to design and fabricate and is expected to be used as a promising circular polarization transformer.

  7. Bending of Layer-by-Layer Films Driven by an External Magnetic Field

    PubMed Central

    Miyazaki, Celina M.; Riul, Antonio; Dos Santos, David S.; Ferreira, Mariselma; Constantino, Carlos J. L.; Pereira-da-Silva, Marcelo A.; Paupitz, Ricardo; Galvão, Douglas S.; Oliveira, Osvaldo N.

    2013-01-01

    We report on optimized architectures containing layer-by-layer (LbL) films of natural rubber latex (NRL), carboxymethyl-chitosan (CMC) and magnetite (Fe3O4) nanoparticles (MNPs) deposited on flexible substrates, which could be easily bent by an external magnetic field. The mechanical response depended on the number of deposited layers and was explained semi-quantitatively with a fully atomistic model, where the LbL film was represented as superposing layers of hexagonal graphene-like atomic arrangements deposited on a stiffer substrate. The bending with no direct current or voltage being applied to a supramolecular structure containing biocompatible and antimicrobial materials represents a proof-of-principle experiment that is promising for tissue engineering applications in biomedicine. PMID:23797657

  8. 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.

  9. Preparation of luminescent layered zirconium phosphate nanocomposites by the layer-by-layer technique

    NASA Astrophysics Data System (ADS)

    Jiang, Qun; Liu, Meitang; Ma, Hongwen; Wang, Tianlei; Kuai, Yuqing

    2016-12-01

    In the present work, photoactive cation N, N‧-Dimenthyl-9, 9'-bisacridinium nitrate (BNMA) was assembled with exfoliated layered α-zirconium phosphate (α-ZrP) via an electrostatic layer-by-layer (LBL) assembly method. As a result, the luminescent films which were well-aligned and periodical had been successfully fabricated. Surprisingly, the lifetimes of (BNMA/ZrP)n were found to be prolonged by 16-fold for the first time, due to the isolation effect of inorganic nanosheets and hydrogen ion migration between the interlayers. Therefore, it is testified that α-ZrP can be used as the laminate and has remarkable influences on enhancing the lifetimes of chromophores. We expect that this new discovered effect can enable α-ZrP a kind of new potential material to develop novel light-emitting materials and optical devices.

  10. Automated spin-assisted layer-by-layer assembly of nanocomposites

    NASA Astrophysics Data System (ADS)

    Vozar, Steven; Poh, Yeh-Chuin; Serbowicz, Thomas; Bachner, Matthew; Podsiadlo, Paul; Qin, Ming; Verploegen, Eric; Kotov, Nicholas; Hart, A. John

    2009-02-01

    We present the design and verification of a desktop system for the automated production of nanostructured thin films via spin-assisted layer-by-layer (spin-LBL) assembly. The utility of this system is demonstrated by fabricating polyvinyl alcohol/clay nanocomposites. Ellipsometry measurements demonstrate that the automated spin-LBL method creates composites with bilayer thickness and growth rate comparable to traditional dip-LBL; however, the cycle time of the spin-LBL method is an order of magnitude faster. Small angle X-ray scattering analysis shows that the clay platelets in spin-LBL nanocomposites are more highly aligned than in dip-LBL composites. This method can significantly increase the throughput of laboratory-scale LBL discovery and processing, can enable testing of functional properties of LBL nanocomposites over wafer-scale areas, and can be scaled to larger substrates for commercial production.

  11. 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.

  12. 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.

  13. Layer-by-layer assembly and UV photoreduction of graphene-polyoxometalate composite films for electronics.

    PubMed

    Li, Haolong; Pang, Shuping; Wu, Si; Feng, Xinliang; Müllen, Klaus; Bubeck, Christoph

    2011-06-22

    Graphene oxide (GO) nanosheets and polyoxometalate clusters, H(3)PW(12)O(40) (PW), were co-assembled into multilayer films via electrostatic layer-by-layer assembly. Under UV irradiation, a photoreduction reaction took place in the films which converted GO to reduced GO (rGO) due to the photocatalytic activity of PW clusters. By this means, uniform and large-area composite films based on rGO were fabricated with precisely controlled thickness on various substrates such as quartz, silicon, and plastic supports. We further fabricated field effect transistors based on the composite films, which exhibited typical ambipolar features and good transport properties for both holes and electrons. The on/off ratios and the charge carrier mobilities of the transistors depend on the number of deposited layers and can be controlled easily. Furthermore, we used photomasks to produce conductive patterns of rGO domains on the films, which served as efficient microelectrodes for photodetector devices.

  14. 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.

  15. Layer-by-layer deposition of polyelectrolyte nanolayers on natural fibres: cotton

    NASA Astrophysics Data System (ADS)

    Hyde, Kevin; Rusa, Mariana; Hinestroza, Juan

    2005-07-01

    The layer-by-layer (LbL) deposition of poly(sodium 4-styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) over cotton fibres is reported. Cotton fibres offer unique challenges to the deposition of nanolayers because of their unique cross section as well as the chemical heterogeneity of their surface. Cationic cotton substrates were produced by using 2,3-epoxypropyltrimethylammonium chloride. Attenuated total reflectance FTIR, x-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) were used to validate the presence of the nanolayers as well as to corroborate their self-organized structure. TEM images indicated conformal and uniform coating of the cotton fibres. XPS spectral data were found to be in quantitative agreement with previous published work that studied the LbL deposition of PSS and PAH over synthetic substrates.

  16. Layer-by-layer assembly of charged nanoparticles on porous substrates: molecular dynamics simulations.

    PubMed

    Carrillo, Jan-Michael Y; Dobrynin, Andrey V

    2011-04-26

    We performed molecular dynamics simulations of a multilayer assembly of oppositely charged nanoparticles on porous substrates with cylindrical pores. The film was constructed by sequential adsorption of oppositely charged nanoparticles in layer-by-layer fashion from dilute solutions. The multilayer assembly proceeds through surface overcharging after completion of each deposition step. There is almost linear growth in the surface coverage and film thickness during the deposition process. The multilayer assembly also occurs inside cylindrical pores. The adsorption of nanoparticles inside pores is hindered by the electrostatic interactions of newly adsorbing nanoparticles with the multilayer film forming inside the pores and on the substrate. This is manifested in the saturation of the average thickness of the nanoparticle layers formed on the pore walls with an increasing number of deposition steps. The distribution of nanoparticles inside the cylindrical pore was nonuniform with a significant excess of nanoparticles at the pore entrance.

  17. Structural control of gold nanoparticles self-assemblies by layer-by-layer process.

    PubMed

    Machado, Giovanna; Feil, Adriano F; Migowski, Pedro; Rossi, Liane; Giovanela, Marcelo; Crespo, Janaina da S; Miotti, Leonardo; Sortica, Maurício A; Grande, Pedro L; Pereira, Marcelo B; Correia, Ricardo R B

    2011-04-01

    This work presents a novel way to introduce gold nanoparticles (Au NPs) in a multilayer polymer produced by the layer-by-layer (LbL) assembling technique. The technique chosen shows that, depending on the pH used, different morphological structures can be obtained from monolayer or bilayer Au NPs. The MEIS and RBS techniques allowed for the modelling of the interface polymer-NPs, as well as the understanding of the interaction of LbL system, when adjusting the pH in weak polyelectrolytes. The process reveals that the optical properties of multilayer systems could be fine-tuned by controlling the addition of metallic nanoparticles, which could also modify specific polarization responses.

  18. 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.

  19. Reversible layer-by-layer deposition on solid substrates inspired by mussel byssus cuticle.

    PubMed

    Kim, Suyeob; Kim, Dong Soo; Kang, Sung Min

    2014-01-01

    The protective coating on mussel (Mytilus galloprovincialis) byssus has attracted considerable research interest because of its excellent mechanical properties such as hardness and extensibility. These special properties are known to be highly related with specific interactions between mussel foot protein-1 and metal ions. In particular, the complexation between catechols in mfp-1 and iron(III) has been identified as a key interaction. This finding has given opportunities for pursuing promising applications. Herein, we report that emulating the properties of the mussel byssus cuticle provides an important platform for developing reversible layer-by-layer (LbL) deposition, an advanced technique for surface modification. LbL films were constructed on solid substrates by sequential immersion of substrates into solutions containing iron(III) and catecholic compounds. The thickness of the LbL films was effectively controlled by increasing the immersion steps, and the reversibility of the LbL deposition was demonstrated by addition of a chelating agent.

  20. Layer-by-layer polymer coating on discrete particles of cubic lyotropic liquid crystalline dispersions (cubosomes).

    PubMed

    Driever, Chantelle D; Mulet, Xavier; Waddington, Lynne J; Postma, Almar; Thissen, Helmut; Caruso, Frank; Drummond, Calum J

    2013-10-22

    Cubic phase lyotropic liquid crystalline colloidal dispersions (cubosomes) were surface-modified with seven polyelectrolyte layers using a layer-by-layer (LbL) approach. The first layer consisted of a copolymer synthesized from methacrylic acid and oleoyl methacrylate for enhanced incorporation within the bilayer of the cubic nanostructure. Six additional layers of poly(L-lysine) and poly(methacrylic acid) were then sequentially added, followed by a washing procedure to remove polymer aggregates from the soft matter particles. Polymer buildup was monitored via microelectrophoresis, dynamic light scattering, and small-angle X-ray scattering. Polymer-coated cubosomes were observed with cryo-transmission electron microscopy. A potential application of the modified nanostructured particles presented in this study is to reduce the burst-release effect associated with drug-loaded cubosomes. The effectiveness of this approach was demonstrated through loading and release results from a model hydrophilic small molecule (fluorescein).

  1. Brain derived neurotrophic factor release from layer-by-layer coated agarose nerve guidance scaffolds.

    PubMed

    Lynam, Daniel A; Shahriari, Dena; Wolf, Kayla J; Angart, Phillip A; Koffler, Jacob; Tuszynski, Mark H; Chan, Christina; Walton, Patrick; Sakamoto, Jeffrey

    2015-05-01

    Agarose nerve guidance scaffolds (NGS) seeded with cells expressing brain derived neurotrophic factor (BDNF) have demonstrated robust nerve regeneration in the rat central nervous system. The purpose of this work was to explore whether agarose NGS coated with hydrogen-bonded layer-by-layer (HLbL) could provide an acellular method of delivering prolonged and consistent dosages of active BDNF. Our results show that HLbL-coated agarose NGS could release BDNF over 10days in consistent dosages averaging 80.5±12.5(SD)ng/mL. Moreover, the BDNF released from HLbL was confirmed active by in vitro cell proliferation assays. To our knowledge, this is the first report demonstrating that HLbL assembled onto a hydrogel can provide consistent, prolonged release of active BDNF in clinically relevant dosages.

  2. 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.

  3. Natural oil nanoemulsions as cores for layer-by-layer encapsulation.

    PubMed

    Adamczak, M; Para, G; Simon, C; Warszyński, P

    2013-01-01

    In this study, emulsions of three different natural oils were prepared using spontaneous emulsification technique. The effect of three emulsifiers, AOT, lecithin and cholesterol on emulsion properties was studied. Their influence on interfacial tension at oil/water interface was evaluated by the pendant drop shape analysis method. Then, the mean droplet size, zeta potential and stability of emulsions were investigated in relation with the type of oil, surfactant, oil-to-ethanol ratio and surfactant concentration. We found that in the case of linseed oil, fine emulsion droplets are formed without any surfactant due to its low oil/water interfacial tension. A hydrophobic dye (Coumarin 6) was encapsulated within oil cores and its presence was confirmed by fluorescence spectroscopy and microscopy. The obtained emulsions can be used alone or as the cores for layer-by-layer encapsulation, which was demonstrated by enclosing droplets within first layer of synthetic polycation poly(allyamine hydrochloride) (PAH).

  4. 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.

  5. Fracture Mechanisms of Layer-By-Layer Polyurethane/Poly(Acrylic Acid) Nanocomposite

    NASA Astrophysics Data System (ADS)

    Kheng, Eugene R.

    A layer-by-layer(LBL) manufactured material is examined in detail in this thesis. Improvements are made to the method of its manufacture. Efforts are made to understand its fracture mechanisms and take advantage of these fracture mechanisms in the absorption of impact energy. A novel series of experiments has been performed on LBL manufactured thin films to demonstrate their unique fracture mechanisms. Polyurethane/Poly(Acrylic Acid) (PU/PAA) and PU/PAA/(PU/Clay)5 nanocomposite films readily undergo Interlaminar mode II fracture, because of the relatively weak elctrostatic bonds between monolayers. Tensile tests performed while under observation by a scanning electron microscope demonstrate the tendency of these nanocomposite films to undergo interlaminar mode II fracture even when loads are applied in the plane of nanocomposite film. It is concluded that these mechanisms of energy dissipation are responsible for the enhanced toughness of these films when used as layers between glass blocks in the prevention of impact damage to the glass. A novel automated manufacturing facility has been designed and built to deposit large sheets of Layer-by-Layer nanocomposite film. These large sheets are incorporated into a borosillicate glass composite in order to compare the ballistic characteristics of LBL PU based nanocomposite films to a single cast layer of polyurethane. It is demonstrated that shear fracture is the mode of failure in the blocks containing the nanocomposite film. The shear fracture surface in the nanocomposite after it has undergone a ballistic impact is characterized. Additional experiments are performed to characterize the interlaminar fracture stresses and toughnesses of the nanocomposite LBL layers, to assist in the implementation of a numerical crack band model that describes the nanocomposite film. The computational model predicts the failure of the ballistic nanocomposite samples, and the predicted V50 velocity is found to be in good agreement with

  6. 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.

  7. Covalent attachment of peptides to cytochrome C for automated sequence determination.

    PubMed

    Garrick, M D; Sloan, R L

    1977-01-01

    Because small peptides are lost into the organic solvents used, it is virtually impossible to obtain the complete amino acid sequence of a small peptide using only an automated peptide sequencer of the spinning cup type. To overcome this problem we have extended peptides at the carboxy terminus by attachment to equine cytochrome c by a water soluble carbodiimide, relying on the acetylated N-terminus of the cytochrome to minimize its direct contribution to recovery of PTH-amino acids. The Model Peptide H-Leu-Trp-Met-Arg-phe-Ala-OH was used for most experiments. After reaction of 3H-peptide with cytochrome c, about one-third of the tritium counts migrated with cytochrome c during gel filtration. After attachment, the amino acid sequence of the hexapeptide was readily determined with a single cleavage Quadrol program in a Beckman 890B sequencer, whereas only the N-terminal residue was recovered without attachment. The repetitive yield after attachment was 95-96%, with 21-27+ overlap and an initial yield of 18-20%. Sequence data with other peptides illustrate applications and present limitations of our approach.

  8. 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.

  9. Computational, electrochemical, and spectroscopic, studies of acetycholinesterase covalently attached to carbon nanotubes.

    PubMed

    Cabral, Murilo F; Barrios, Joseph D; Kataoka, Erica M; Machado, Sergio A S; Carrilho, Emanuel; Garcia, Carlos D; Ayon, Arturo A

    2013-03-01

    This manuscript describes results related to the characterization of electrodes modified with a composite of acetylcholinesterase covalently bound to carbon nanotubes (CNT). The characterization was performed by computational methods and complemented by cyclic voltammetry, infrared spectroscopy, and electrochemical impedance spectroscopy. In-silico simulations enabled the identification of the binding site and the calculation of the interaction energy. Besides complementing the computational studies, experimental results obtained by cyclic voltammetry showed that the addition of CNT to the surface of electrodes yielded significant increases in effective area and greatly facilitated the electron transfer reactions. These results are also in agreement with impedance spectroscopy data, which indicated a high apparent rate constant, even after the immobilization of the enzyme. These results lend new information about the physical and chemical properties of biointerfaces at the molecular level, specifically about the mechanism and consequences of the interaction of a model enzyme with CNT. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. Monolayer of Hydrazine Facilitates the Direct Covalent Attachment of C60 Fullerene to a Silicon Surface.

    PubMed

    Gao, Fei; Teplyakov, Andrew V

    2017-02-13

    The development of oxygen-free organic-inorganic interfaces has led to new schemes for the functionalization of silicon surfaces with nitrogen-based chemical groups. However, building layers of large structures directly on this functionalized surface has remained elusive. This work confirms the path to form a stable interface between silicon and buckminsterfullerene C60 based on covalent chemical bonds. The starting point for this modification is the hydrazine-reacted Si(111) surface with the diamine functionality, which is further reacted directly with the C60 molecules. The chemistry of this process is confirmed spectroscopically and microscopically and can be used to form organic-inorganic interfaces separated by a single layer of nitrogen.

  11. Voltammetric Detection of Oxalic Acid by Using Glassy Carbon Electrodes with Covalently Attached Nitrogen-containing Functional Groups.

    PubMed

    Matsuura, Hiroaki; Akabe, Syuhei; Kitamura, Tsubasa; Takahashi, Takuto; Uchiyama, Shunichi

    2015-01-01

    We report on a novel voltammetric detection of oxalic acid by using glassy carbon electrodes with covalently attached nitrogen-containing functional groups prepared by stepwise electrolysis. A glassy carbon electrode electrooxidized in an ammonium carbamate solution was electroreduced at -1.0 V (vs. Ag/AgCl) in 1.0 M sulfuric acid for a long time. We found that the electrocatalytic oxidation wave of oxalic acid obtained by this modified glassy carbon electrode was moved to a more negative potential region than that obtained by a platinum electrode in an acidic medium. A good linearity for the peak current signals was observed in the concentration range from 0.1 to 50 mM.

  12. 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

  13. 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

  14. DBD atmospheric plasma-modified, electrospun, layer-by-layer polymeric scaffolds for L929 fibroblast cell cultivation.

    PubMed

    Surucu, Seda; Turkoglu Sasmazel, Hilal

    2016-01-01

    This paper reported a study related to atmospheric pressure dielectric barrier discharge (DBD) Ar + O2 and Ar + N2 plasma modifications to alter surface properties of 3D PCL/Chitosan/PCL layer-by-layer hybrid scaffolds and to improve mouse fibroblast (L929 ATCC CCL-1) cell attachment, proliferation, and growth. The scaffolds were fabricated using electrospinning technique and each layer was electrospun sequentially on top of the other. The surface modifications were performed with an atmospheric pressure DBD plasma under different gas flow rates (50, 60, 70, 80, 90, and 100 sccm) and for different modification times (0.5-7 min), and then the chemical and topographical characterizations of the modified samples were done by contact angle (CA) measurements, scanning electron microscopy (SEM), atomic force microscopy, and X-ray photoelectron spectroscopy. The samples modified with Ar + O2 plasma for 1 min under 70 cm(3)/min O2 flow rate (71.077° ± 3.578) showed a 18.83% decrease compare to unmodified samples' CA value (84.463° ± 3.864). Comparing with unmodified samples, the average fiber diameter values for plasma-modified samples by Ar + O2 (1 min 70 sccm) and Ar + N2 (40 s 70 sccm) increased 40.756 and 54.295%, respectively. Additionally, the average inter-fiber pore size values exhibited decrease of 37.699 and 48.463% for the same Ar + O2 and Ar + N2 plasma-modified samples, respectively, compare to unmodified samples. Biocompatibility performance was determined with MTT assay, fluorescence, Giemsa, and confocal imaging as well as SEM. The results showed that Ar + O2-based plasma modification increased the hydrophilicity and oxygen functionality of the surface, thus affecting the cell viability and proliferation on/within scaffolds.

  15. Layer-by-layer assembly of chitosan and recombinant biopolymers into biomimetic coatings with multiple stimuli-responsive properties.

    PubMed

    Costa, Rui R; Custódio, Catarina A; Arias, Francisco J; Rodríguez-Cabello, José C; Mano, João F

    2011-09-19

    In this work, biomimetic smart thin coatings using chitosan and a recombinant elastin-like recombinamer (ELR) containing the cell attachment sequence arginine-glycine-(aspartic acid) (RGD) are fabricated through a layer-by-layer approach. The synthetic polymer is characterized for its molecular mass and composition using mass spectroscopy and peptide sequencing. The adsorption of each polymeric layer is followed in situ at room temperature and pH 5.5 using a quartz-crystal microbalance with dissipation monitoring, showing that both polymers can be successfully combined to conceive nanostructured, multilayered coatings. The smart properties of the coatings are tested for their wettability by contact angle (CA) measurements as a function of external stimuli, namely temperature, pH, and ionic strength. Wettability transitions are observed from a moderate hydrophobic surface (CAs approximately from 62° to 71°) to an extremely wettable one (CA considered as 0°) as the temperature, pH, and ionic strength are raised above 50 °C, 11, and 1.25 M, respectively. Atomic force microscopy is performed at pH 7.4 and pH 11 to assess the coating topography. In the latter, the results reveal the formation of large and compact structures upon the aggregation of ELRs at the surface, which increase water affinity. Cell adhesion tests are conducted using a SaOs-2 cell line. Enhanced cell adhesion is observed in the coatings, as compared to a coating with a chitosan-ending film and a scrambled arginine-(aspartic acid)-glycine (RDG) biopolymer. The results suggest that such films could be used in the future as smart biomimetic coatings of biomaterials for different biomedical applications, including those in tissue engineering or in controlled delivery systems.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  17. 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

  18. Facile preparation, optical and electrochemical properties of layer-by-layer V2O5 quadrate structures

    NASA Astrophysics Data System (ADS)

    Zhang, Yifu; Zheng, Jiqi; Wang, Qiushi; Hu, Tao; Tian, Fuping; Meng, Changgong

    2017-03-01

    Layer-by-layer V2O5 structures self-assembly by quadrate sheets like "multilayer cake" were successfully synthesized using NH4VO3 as the vanadium sources by a facile hydrothermal route and combination of the calcination. The structure and composition were characterized by field emission scanning electron microscopy, energy-dispersive X-ray spectrometer, X-ray powder diffraction, Raman and Fourier transform infrared spectroscopy. The optical properties of the as-obtained V2O5 layer-by-layer structures were investigated by the Ultraviolet-visible spectroscopy and photoluminescence spectrum. The electrochemical properties of the as-obtained V2O5 layer-by-layer structures as electrodes in supercapacitor device were measured by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) both in the aqueous and organic electrolyte. The specific capacitance is 347 F g-1 at 1 A g-1 in organic electrolyte, which is improved by 46% compared with 238 F g-1 in aqueous electrolyte. During the cycle performance, the specific capacitances of V2O5 layer-by-layer structures after 100 cycles are 30% and 82% of the initial discharge capacity in the aqueous and organic electrolyte, respectively, indicating the cycle performance is significantly improved in organic electrolyte. Our results turn out that layer-by-layer V2O5 structures are an ideal material for supercapacitor electrode in the present work.

  19. Facial Layer-by-Layer Engineering of Upconversion Nanoparticles for Gene Delivery: Near-Infrared-Initiated Fluorescence Resonance Energy Transfer Tracking and Overcoming Drug Resistance in Ovarian Cancer.

    PubMed

    Lin, Min; Gao, Yan; Diefenbach, Thomas J; Shen, Jacson K; Hornicek, Francis J; Park, Yong Il; Xu, Feng; Lu, Tian Jian; Amiji, Mansoor; Duan, Zhenfeng

    2017-03-08

    Development of multidrug resistance (MDR) contributes to the majority of treatment failures in clinical chemotherapy. We report facial layer-by-layer engineered upconversion nanoparticles (UCNPs) for near-infrared (NIR)-initiated tracking and delivery of small interfering RNA (siRNA) to enhance chemotherapy efficacy by silencing the MDR1 gene and resensitizing resistant ovarian cancer cells to drug. Layer-by-layer engineered UCNPs were loaded with MDR1 gene-silencing siRNA (MDR1-siRNA) by electrostatic interaction. The delivery vehicle enhances MDR1-siRNA cellular uptake, protects MDR1-siRNA from nuclease degradation, and promotes endosomal escape for silencing the MDR gene. The intrinsic photon upconversion of UCNPs provides an unprecedented opportunity for monitoring intracellular attachment and release of MDR1-siRNA by NIR-initiated fluorescence resonance energy transfer occurs between donor UCNPs and acceptor fluorescence dye-labeled MDR1-siRNA. Enhanced chemotherapeutic efficacy in vitro was demonstrated by cell viability assay. The developed delivery vehicle holds great potential in delivery and imaging-guided tracking of therapeutic gene targets for effective treatment of drug-resistant cancers.

  20. Surface-imprinted nanostructured layer-by-layer film for molecular recognition of theophylline derivatives.

    PubMed

    Niu, Jia; Liu, Zhihua; Fu, Long; Shi, Feng; Ma, Hongwei; Ozaki, Yukihiro; Zhang, Xi

    2008-10-21

    In this article we report the introduction of the cooperativity of various specific interactions combined with photo-cross-linking of the interlayers to yield binding sites that can realize better selectivity and imprinting efficiency of a surface molecularly imprinted LbL film (SMILbL), thus providing a new approach toward fabrication of nanostructured molecularly imprinted thin films. It involves preassembly of poly(acrylic acid) (PAA) conjugated of the theophylline residue template via a disulfide bridge, denoted as PAAtheo 15, in solution, and layer-by-layer (LbL) assembly of PAAtheo 15 and a positively charged photoreactive diazo resin (DAR) to form multilayer thin film with designed architecture. After photo-cross-linking of the film and template removal, binding sites specific to 7-(beta-hydroxyethyl)theophylline (Theo-ol) molecules are introduced within the film. Binding assay demonstrates that the SMILbL has a high selectivity of SMILbL to Theo-ol over caffeine. A control experiment demonstrates that the selectivity of SMILbL derives from nanostructured recognition sites among the layers. The imprinting amount per unit mass of the film can be 1 order of magnitude larger than that of the conventional bulk molecular imprinting systems. As this concept of construction SMILbL can be easily extended to the other molecules by the following similar protocol: its applications in building many other different molecular recognition systems are greatly anticipated.

  1. Chitosan-Recombinamer Layer-by-Layer Coatings for Multifunctional Implants.

    PubMed

    Govindharajulu, Jeevan Prasaad; Chen, Xi; Li, Yuping; Rodriguez-Cabello, Jose Carlos; Battacharya, Mrinal; Aparicio, Conrado

    2017-02-09

    The main clinical problems for dental implants are (1) formation of biofilm around the implant-a condition known as peri-implantitis and (2) inadequate bone formation around the implant-lack of osseointegration. Therefore, developing an implant to overcome these problems is of significant interest to the dental community. Chitosan has been reported to have good biocompatibility and anti-bacterial activity. An osseo-inductive recombinant elastin-like biopolymer (P-HAP), that contains a peptide derived from the protein statherin, has been reported to induce biomineralization and osteoblast differentiation. In this study, chitosan/P-HAP bi-layers were built on a titanium surface using a layer-by-layer (LbL) assembly technique. The difference in the water contact angle between consecutive layers, the representative peaks in diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and the changes in the topography between surfaces with a different number of bi-layers observed using atomic force microscopy (AFM), all indicated the successful establishment of chitosan/P-HAP LbL assembly on the titanium surface. The LbL-modified surfaces showed increased biomineralization, an appropriate mouse pre-osteoblastic cell response, and significant anti-bacterial activity against Streptococcus gordonii, a primary colonizer of tissues in the oral environment.

  2. 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.

  3. 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.

  4. 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.

  5. Cellular uptake and distribution of graphene oxide coated with layer-by-layer assembled polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Li, Yiye; Lu, Zhenzhen; Li, Zhongjun; Nie, Guangjun; Fang, Ying

    2014-05-01

    We report a facile approach for the fabrication of a new class of graphene oxide (GO)-based nanoassemblies by layer-by-layer (LbL) technique. The single-layer thickness and intrinsic negatively charged carboxyl groups of GO nanosheets provide a natural platform for LbL assembly of polyelectrolyte nanofilms by electrostatic forces at mild and aqueous conditions. The general applicability of our approach is demonstrated by the preparation of GO nanoassemblies with sizes of 100-200 nm using various charged polyelectrolytes, including synthetic polymers, polypeptides, and DNA oligonucleotides. Systemic assessment of cytotoxicity and acute stress response show that no discernable signs of cytotoxicity are associated with exposure of GO and its nanoassemblies [GO/PLL (poly ( l-lysine)), GO/PLL/PSS (poly(sodium-4-styrenesulfonate)), GO/PLL-PEG (PEGlayted PLL), GO/PLL/PLGA-PEG (PEGlayted poly ( l-glutamic acid))] up to 1 μg/mL. Studies on cellular uptake and subcellular localization show that a representative nanoassembly, GO/PLL-PEG, can effectively cross cell membranes and localize mainly in lysosomal compartments, without induction of noticeable harmful effects as confirmed by detection of mitochondrial depolarization and lysosomal pH.

  6. Layer-by-layer assembly of clay-filled polymer nanocomposite thin films

    NASA Astrophysics Data System (ADS)

    Jang, Woo-Sik

    2008-10-01

    A variety of functional thin films can be produced using the layer-by-layer assembly technique. In this work, assemblies of anionic clay and cationic polymer were studied with regard to film growth and gas barrier properties. A simple, yet flexible robotic dipping system, for the preparation of these thin films, was built. The robot alternately dips a substrate into aqueous mixtures with rinsing and drying in between. Thin films of sodium montmorillonite clay and cationic polymer were grown and studied on poly(ethylene terephthalate) film or a silicon wafer. After 30 clay polymer bilayers were deposited, the resulting transparent film had an oxygen transmission rate (OTR) below 0.005 cm3/m2/day/atm. This low OTR, which is unprecedented for a clay-filled polymer composite, is believed to be due to a "brick wall" nanostructure comprised of completely exfoliated clay bricks in polymeric "mortar". The growth of polymer and clay assemblies is then shown to be controlled by altering the pH of polyethylenimine (PEI). Growth, oxygen permeability, and mechanical behavior of clay-PEI assemblies were studied as a function of pH in an effort to tailor the behavior of these thin films. Thicker deposition at high pH resulted in reduced oxygen permeability and lower modulus, which highlights the tailorability of this system.

  7. 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.

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

    DOE PAGES

    Sunny, Steffi; Vogel, Nicolas; Howell, Caitlin; ...

    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

  9. 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.

  10. Charge storage in polymer acid-doped polyaniline-based layer-by-layer electrodes.

    PubMed

    Jeon, Ju-Won; O'Neal, Josh; Shao, Lin; Lutkenhaus, Jodie L

    2013-10-23

    Polymeric electrodes that can achieve high doping levels and store charge reversibly are desired for electrochemical energy storage because they can potentially achieve high specific capacities and energies. One such candidate is the polyaniline:poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PANI:PAAMPSA) complex, a water-processable complex obtained via template polymerization that is known to reversibly achieve high doping levels at potentials of up to 4.5 V versus Li/Li+. Here, for the first time, PANI:PAAMPSA is successfully incorporated into layer-by-layer (LbL) electrodes. This processing technique is chosen for its ability to blend species on a molecular level and its ability to conformally coat a substrate. Three different polyaniline-based LbL electrodes comprised of PANI/PAAMPSA, PANI/PANI:PAAMPSA, and linear poly(ethylenimine)/PANI:PAAMPSA are compared in terms of film growth, charge storage, and reversibility. We found that the reversibility of PANI:PAAMPSA is retained within the LbL electrodes and that the PANI/PANI:PAAMPSA electrode exhibits the best performance in terms of capacity and cycle life. These results provide general guidelines for the assembly of PANI:PAAMPSA in LbL films and also demonstrate their potential as electrochemically active components in electrodes.

  11. Release of polyphenolic drugs from dynamically bonded layer-by-layer films.

    PubMed

    Zhou, Lin; Chen, Mao; Tian, Lili; Guan, Ying; Zhang, Yongjun

    2013-05-01

    Layer-by-layer (LbL) assembled films have been exploited for surface-mediated drug delivery. The drugs loaded in the films were usually released via diffusion or the degradation of one of the film components. Here we demonstrate that drug release can also be achieved by exploiting the dynamic nature of hydrogen-bonded LbL films. The films were fabricated from tannic acid (TA), a model polyphenolic drug, and poly(vinyl pyrrolidone) (PVPON). The driving force for the film buildup is the hydrogen bonding between the two components, which was confirmed by Fourier transform infrared (FTIR) spectra. The film growth is linear, and the growth rate of the film decreases with increasing assembly temperature. Because of the reversible/dynamic nature of hydrogen bonding, when soaked in aqueous solutions, the PVPON/TA films disassemble gradually and thus release TA to the media. The release rate of TA increases with increasing pH and temperature but decreases with increasing ionic strength. Scanning electron microscopy (SEM) studies on the surface morphology of the film during TA release reveal that the film surface becomes smoother and then rougher again because of the dewetting of the film. The released TA can scavenge ABTS(+•) cation radicals, indicating it retains its antioxidant activity, a major biological activity of polyphenols.

  12. 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.

  13. 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.

  14. Layer-by-Layer assembly of TiO2 nanoparticles for stable hydrophilic biocompatible coatings.

    PubMed

    Kommireddy, Dinesh S; Patel, Amish A; Shutava, Tatsiana G; Mills, David K; Lvov, Yuri M

    2005-07-01

    Stable, super-hydrophilic (water contact angle approximately equal to 0 degrees) titanium dioxide nanoparticle thin films have been obtained on substrates with different initial wettability such as glass, poly(methyl methacrylate) and poly(dimethyl siloxane) using layer-by-layer nano-assembly method. Titanium dioxide nanoparticles were alternated with poly(styrene sulfonate) to form films of thickness ranging from 11 nm to 220 nm. The hydrophilicity of these thin films increases with increasing number of deposited PSS/TiO2 bilayers. It was found that 2, 5 and 20 layers were needed to form super-hydrophilic TiO2 coating on glass, PMMA and PDMS respectively. Oxygen plasma treatment of substrate surfaces enhanced the formation of homogeneous TiO2 films and accelerated the formation of hydrophilic layers. Super-hydrophilicity has been shown to be unique to PSS/TiO2 films as compared with other polyelectrolyte/nanoparticle layers, and UV irradiation may restore hydrophilicity even after months of storing of the samples. Biocompatibility of TiO2 nanoparticle films has been demonstrated by the successful cell culture of human dermal fibroblast.

  15. 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.

  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.

  17. Multielectrocatalysis by layer-by-layer films based on pararosaniline and vanadium-substituted phosphomolybdate.

    PubMed

    Fernandes, Diana M; Teixeira, Alexandra; Freire, Cristina

    2015-02-10

    Hybrid multilayer films based on the two molecular species pararosaniline (PR) and Keggin-type polyoxometalate K5[PMo11VO40)] (PMo11V) were prepared on different substrates using the electrostatic layer-by-layer (LbL) self-assembly method. The film buildup, monitored by electronic spectroscopy, showed a regular stepwise growth, and X-ray photoelectron spectroscopy data confirmed the presence of both molecular components within the LbL films. Scanning electron microscopy images revealed a completely covered surface with a nonuniform distribution of film components, and atomic force microscopy images confirmed a rough surface. The film electrochemical responses and permeability were studied by cyclic voltammetry. Films revealed three Mo-based redox processes (Mo(VI) → Mo(V)) and one V-based redox process (V(V) → V(IV)) in the potential range between 0.8 and -0.4 V vs Ag/AgCl. Studies with the redox probes [Fe(CN)6](3-/4-) and [Ru(NH3)6](3+/2+) showed that the films maintain the permeability even after six bilayers. Furthermore, the {PR/PMo11V}n multilayer films exhibit excellent Mo-based electrocatalytic activity toward reduction of iodate and V-based electrocatalytic activity toward ascorbic acid oxidation, thus acting as a versatile multielectrocatalyst.

  18. 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. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. 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.

  20. Immobilization of aloin encapsulated into liposomes in layer-by-layer films for transdermal drug delivery.

    PubMed

    Xavier, Aline Carla Farrapo; de Moraes, Marli Leite; Ferreira, Marystela

    2013-04-01

    Layer-by-layer (LbL) films have been exploited in drug delivery systems that may be used in the form of patches, but the encapsulation of poor water soluble drugs and their release with a controlled rate are still major challenges to be faced. In this paper, we demonstrate the controlled release of aloin (barbaloin), an important component of the widely used Aloe vera, encapsulated into liposomes and immobilized in LbL films with a polyelectrolyte. With a systematic study using fluorescence spectroscopy of aloin release from solutions and from LbL films with different phospholipid liposomes, we inferred that optimized release was achieved with aloin incorporated into palmitoyl oleyl phosphatidyl glycerol (POPG) or dipalmitoyl phosphatidyl glycerol (DPPG) liposomes immobilized in LbL films. Significantly, with this optimized system aloin was almost completely released within 30 h, with a small release rate at the end, which followed a sharp release in the first 5h. Upon comparing the rates of the distinct systems, we conclude that the main factors controlling the release are the electrostatic interactions involving the negatively charged phospholipids. Because these interactions can be tuned in LbL films, the approach used here opens the way for new drug delivery systems to be developed with fine control of the drug release. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. 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.

  2. 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.

  3. Controlling cell adhesion using layer-by-layer approaches for biomedical applications.

    PubMed

    Guo, Shanshan; Zhu, Xiaoying; Loh, Xian Jun

    2017-01-01

    Controlling the adhesion of mammalian and bacterial cells at the interfaces between synthetic materials and biological environments is a real challenge in the biomedical fields such as tissue engineering, antibacterial coating, implantable biomaterials and biosensors. The surface properties of materials are known to profoundly influence the adhesion processes. To mediate the adhesion processes, polymeric coatings have been used to functionalize surfaces to introduce diverse physicochemical properties. The polyelectrolyte multilayer films built via the layer-by-layer (LbL) method, introduced by Moehwald, Decher, and Lvov 20years ago, has led to significant developments ranging from the fundamental understanding of cellular processes to controlling cell adhesion for biomedical applications. In this review, we focus our attention on the modification of surface physicochemical properties, using the LbL approach, to construct films which can either promote or inhibit mammalian/bacterial cell adhesion. We also discuss the emerging field of multifunctional surfaces capable of responding to specific cellular activity but being inert to the others. Copyright © 2016. Published by Elsevier B.V.

  4. 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.

  5. Layer-by-layer rose petal mimic surface with oleophilicity and underwater oleophobicity.

    PubMed

    Huang, Hsiu-chin; Zacharia, Nicole S

    2015-01-20

    Surfaces designed with specific wetting properties are still a key challenge in materials science. We present here a facile preparation of a surface assembled by the layer-by-layer technique, using a colloidal dispersion of ionomer particles and linear polyethylene imine. The colloidal ethylene-co-methacrylic acid (EMAA) particles are on the order of half a micron in size with surface features from 40 to 100 nm in width. The resultant surface has roughness on two length scales, one on the micron scale due to the packing of particles and one on the nanoscale due to these surface features on the EMAA particles. This hierarchical structure results in a hydrophobic surface with good water pinning properties (∼550 μN). We show that there is a balance between maximizing contact angle and water pinning force. Furthermore, this surface is oleophilic with regard to many organic solvents, also demonstrating underwater oleophobicity, and given the difference in wetting between aqueous and organic phases, this material may be a candidate material for oil/water separations.

  6. Robust and Flexible Aramid Nanofiber/Graphene Layer-by-Layer Electrodes.

    PubMed

    Kwon, Se Ra; Elinski, Meagan B; Batteas, James D; Lutkenhaus, Jodie L

    2017-05-24

    Aramid nanofibers (ANFs), or nanoscale Kevlar fibers, are of interest for their high mechanical performance and functional nanostructure. The dispersible nature of ANFs opens up processing opportunities for creating mechanically robust and flexible nanocomposites, particularly for energy and power applications. The challenge is to manipulate ANFs into an electrode structure that balances mechanical and electrochemical performance to yield a robust and flexible electrode. Here, ANFs and graphene oxide (GO) sheets are blended using layer-by-layer (LbL) assembly to achieve mechanically flexible supercapacitor electrodes. After reduction, the resulting electrodes exhibit an ANF-rich structure where ANFs act as a polymer matrix that interfacially interacts with reduced graphene oxide sheets. It is shown that ANF/GO deposition proceeds by hydrogen bonding and π-π interactions, leading to linear growth (1.2 nm/layer pairs) and a composition of 75 wt % ANFs and 25 wt % GO sheets. Chemical reduction leads to a high areal capacitance of 221 μF/cm(2), corresponding to 78 F/cm(3). Nanomechanical testing shows that the electrodes have a modulus intermediate between those of the two native materials. No cracks or defects are observed upon flexing ANF/GO films 1000 times at a radius of 5 mm, whereas a GO control shows extensive cracking. These results demonstrate that electrodes containing ANFs and reduced GO sheets are promising for flexible, mechanically robust energy and power.

  7. 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.

  8. Enzyme-Encapsulated Layer-by-Layer Assemblies: Current Status and Challenges Toward Ultimate Nanodevices

    NASA Astrophysics Data System (ADS)

    Ariga, Katsuhiko; Ji, Qingmin; Hill, Jonathan P.

    Alternate layer-by-layer (LbL) adsorption has received much attention as an emerging methodology. Biocompatibility is the most prominent advantage of the LbL assembly process because the technique employs mild conditions for film construction. Most enzymes, especially water-soluble ones, have charged sites at their surfaces so that electrostatic LbL adsorption is suitable for construction of various protein organizations. In this review chapter, we summarize recent developments on enzyme-encapsulated LbL devices and their related functions where "encapsulated" does not always entail entrapment within spherical structures but generally includes immobilization of enzymes within the LbL structures. Recent examples, with various functions such as reactor sensors and medical applications, are described within a classification of structural types, i.e., thin films and spherical capsules. In addition to conventional applications, advanced systems including integration of LbL structures into advanced devices such as microchannels, field effect transistors, and flow injection amperometric sensors are introduced as well as recent developments in hybridization of LbL assemblies with functional nanomaterials such as carbon nanotube, dendrimers, nanoparticles, lipid assemblies, and mesoporous materials, all of which can enhance bio-related functions of LbL assemblies.

  9. Layer-by-layer films made from extracellular matrix macromolecules on silicone substrates.

    PubMed

    Mhanna, Rami F; Vörös, Janos; Zenobi-Wong, Marcy

    2011-03-14

    The layer-by-layer (LbL) technique has been widely used to produce nanofilms for biomedical applications. Naturally occurring polymers such as ECM macromolecules are attractive candidates for LbL film preparation. In this study, we assessed the build-up of type I collagen (Col1)/chondroitin sulfate (CS) or Col1/Heparin (HN) on polydimethylsiloxane (PDMS) substrates. The build-up was assessed by quartz crystal microbalance with dissipation (QCM-D) and atomic force microscopy (AFM). Integrin-mediated cell adhesion was assessed by studying the cytoskeletal organization of mammalian primary cells (chondrocytes) seeded on different end layers and number of layers. Data generated from the QCM-D observations showed a consistent build-up of films with more adsorption in the case of Col1/HN. Col1/CS films were stable in media, whereas Col1/HN films were not. AFM analysis showed that the layers were fibrillar in structure for both systems and between 20 and 30 nm thick. The films promoted cell adhesion when compared with tissue culture plastic in serum-free media with cycloheximide. Crosslinking of the films resulted in constrained cell spreading and a ruffled morphology. Finally, beta1 integrin blocking antibodies prevented cell spreading, suggesting that cell adhesion and spreading were mediated mainly by interaction with the collagen fibrils. The ability to construct stable ECM-based films on PDMS has particular relevance in mechanobiology, microfluidics, and other biomedical applications.

  10. Tailoring interlayer structure of molecular layer-by-layer assembled polyamide membranes for high separation performance

    NASA Astrophysics Data System (ADS)

    Gu, Joung-Eun; Lee, Jong Suk; Park, Sang-Hee; Kim, Il Tae; Chan, Edwin P.; Kwon, Young-Nam; Lee, Jung-Hyun

    2015-11-01

    A molecular layer-by-layer (mLbL) technique was recently developed to fabricate polyamide (PA) thin film composite (TFC) membranes for water purification. In this study, the interlayer structure between the selective and support layers of the mLbL-assembled TFC membrane was tailored to achieve high performance applicable to seawater desalination. Introducing interlayers on porous supports prior to mLbL deposition allowed the effective PA growth by preventing monomer deposition within the support pores. The PA layers were grown via mLbL on supports coated by a series of interlayers: poly(piperazine-amide), cross-linked poly(ethyleneimine) (PEI) and a polyelectrolyte bilayer of PEI and poly(acrylic acid) (PAA) (PEI/PAA). The density and distribution of surface carboxyl groups of the interlayer were found to be key parameters that determine the structure and performance of the mLbL-assembled membranes. Among the interlayers examined, the PEI/PAA interlayer not only yielded membranes with superior performance but also with a highly smooth surface beneficial for antifouling.

  11. 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.

  12. 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.

  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. Formation and degradation of layer-by-layer-assembled polyelectrolyte polyrotaxane capsules.

    PubMed

    Dam, Henk H; Caruso, Frank

    2013-06-18

    We report the preparation of degradable capsules via layer-by-layer assembly using polyelectrolyte (PE) polyrotaxanes (PRXs). The PRX capsules were prepared by the sequential deposition of PRXs onto silica particles followed by the dissolution of the silica cores. The colloidal stability of the PRX capsules that are formed depends on the salt/buffer solution used in the assembly process. Various salt/buffer combinations were examined to avoid aggregation of the core-shell particles during PRX assembly and core dissolution. Using appropriate assembly conditions, we prepared colloidally stable, robust capsules. PRX capsules consisting of eight layers of PE PRXs had a wall thickness of ~15 nm. The degradation of the PRX capsules was demonstrated through the disassembly of the PE PRXs using glutathione, which cleaves the disulfide bonds linking the end-capping groups of the PE PRXs. Given the supramolecular noncovalent structure of PRXs and their adjustable properties, it is expected that PRXs will be used as building blocks for assembling advanced capsules with unique and tailored properties.

  15. 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.

  16. 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

  17. 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

  18. Multilevel and Multicomponent Layer-by-Layer Assembly for the Fabrication of Nanofibrillar Films.

    PubMed

    Zhang, Yuanyuan; Sun, Junqi

    2015-07-28

    In this study, we demonstrate multilevel and multicomponent layer-by-layer (LbL) assembly as a convenient and generally applicable method for the fabrication of nanofibrillar films by exploiting the dynamic nature of polymeric complexes. The alternate deposition of poly(allylamine hydrochloride)-methyl red (PAH-MR) complexes with poly(acrylic acid) (PAA) produces nanofibrillar PAH-MR/PAA films, which involves the disassembly of PAH-MR complexes, the subsequent assembly of PAH with PAA, and the PAA-induced assembly of MR molecules into MR nanofibrils via a π-π stacking interaction. The aqueous solution of weak polyelectrolyte PAA with a low solution pH plays an important role in fabricating nanofibrillar PAH-MR/PAA films because proton transfer from acidic PAA to MR molecules induces the formation of MR nanofibrils. The generality of the multilevel and multicomponent LbL assembly is verified by alternate assembly of complexes of 1-pyrenylbutyric acid (PYA) and PAH with PAA to fabricate PAH-PYA/PAA films with organized nanofibrillar structures. Unlike the traditional static LbL assembly, the multilevel and multicomponent LbL assembly is dynamic and more flexible and powerful in controlling the interfacial assembly process and in fabricating composite films with sophisticated structures. These characteristics of multilevel and multicomponent LbL assembly will enrich the functionalities of the LbL-assembled films.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. Layer-by-Layer Epitaxial Growth of Scalable WSe2 on Sapphire by Molecular Beam Epitaxy.

    PubMed

    Nakano, Masaki; Wang, Yue; Kashiwabara, Yuta; Matsuoka, Hideki; Iwasa, Yoshihiro

    2017-09-13

    Molecular beam epitaxy (MBE) provides a simple but powerful way to synthesize large-area high-quality thin films and heterostructures of a wide variety of materials including accomplished group III-V and II-VI semiconductors as well as newly developing oxides and chalcogenides, leading to major discoveries in condensed-matter physics. For two-dimensional (2D) materials, however, main fabrication routes have been mechanical exfoliation and chemical vapor deposition by making good use of weak van der Waals bonding nature between neighboring layers, and MBE growth of 2D materials, in particular on insulating substrates for transport measurements, has been limited despite its fundamental importance for future advanced research. Here, we report layer-by-layer epitaxial growth of scalable transition-metal dichalocogenide (TMDC) thin films on insulating substrates by MBE and demonstrate ambipolar transistor operation. The proposed growth protocol is broadly applicable to other TMDCs, providing a key milestone toward fabrication of van der Waals heterostructures with various 2D materials for novel properties and functionalities.

  4. Layer-by-layer bioassembly of cellularized polylactic acid porous membranes for bone tissue engineering.

    PubMed

    Guduric, Vera; Metz, Carole; Siadous, Robin; Bareille, Reine; Levato, Riccardo; Engel, Elisabeth; Fricain, Jean-Christophe; Devillard, Raphaël; Luzanin, Ognjan; Catros, Sylvain

    2017-05-01

    The conventional tissue engineering is based on seeding of macroporous scaffold on its surface ("top-down" approach). The main limitation is poor cell viability in the middle of the scaffold due to poor diffusion of oxygen and nutrients and insufficient vascularization. Layer-by-Layer (LBL) bioassembly is based on "bottom-up" approach, which considers assembly of small cellularized blocks. The aim of this work was to evaluate proliferation and differentiation of human bone marrow stromal cells (HBMSCs) and endothelial progenitor cells (EPCs) in two and three dimensions (2D, 3D) using a LBL assembly of polylactic acid (PLA) scaffolds fabricated by 3D printing. 2D experiments have shown maintain of cell viability on PLA, especially when a co-cuture system was used, as well as adequate morphology of seeded cells. Early osteoblastic and endothelial differentiations were observed and cell proliferation was increased after 7 days of culture. In 3D, cell migration was observed between layers of LBL constructs, as well as an osteoblastic differentiation. These results indicate that LBL assembly of PLA layers could be suitable for BTE, in order to promote homogenous cell distribution inside the scaffold and gene expression specific to the cells implanted in the case of co-culture system.

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    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 1×10-4 to 1.2×10-3 M with the detect limit of 5×10-6 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.

  6. Multilayered gold-nanoparticle/polyimide composite thin film through layer-by-layer assembly.

    PubMed

    Zhang, Fengxiang; Srinivasan, M P

    2007-09-25

    A novel type of composite thin film consisting of gold nanoparticles (AuNPs) and polymide (PI) was fabricated through layer-by-layer (LBL) assembly. To fabricate such films, bare AuNPs and a poly (amic acid) bearing pendant amine groups, namely, amino poly (amic acid) or APAA, were synthesized and assembled in an LBL fashion. Without any organic encapsulation layer on their surface, AuNPs were bound directly to APAA chains at the amine sites; X-ray photoelectron spectroscopy study suggested that the binding was based on a combined effect of metal-ligand coordination and electrostatic interaction, with the former dominating over the latter. An approximately linear growth of the film started from the second layer of AuNP as revealed by the UV-vis spectroscopy, and the degree of particle aggregation was higher in the first AuNP layer than in the subsequent layers due to the differences in the density of binding sites. The resultant assembly was heated to imidize the APAA, thereby creating a robust composite structure.

  7. Time Controlled Protein Release from Layer-by-Layer Assembled Multilayer Functionalized Agarose Hydrogels

    PubMed Central

    Mehrotra, Sumit; Lynam, Daniel; Maloney, Ryan; Pawelec, Kendell M.; Tuszynski, Mark H.; Lee, Ilsoon

    2009-01-01

    Axons of the adult central nervous system exhibit an extremely limited ability to regenerate after spinal cord injury. Experimentally generated patterns of axon growth are typically disorganized and randomly oriented. Support of linear axonal growth into spinal cord lesion sites has been demonstrated using arrays of uniaxial channels, templated with agarose hydrogel, and containing genetically engineered cells that secrete brain-derived neurotrophic factor (BDNF). However, immobilizing neurotrophic factors secreting cells within a scaffold is relatively cumbersome, and alternative strategies are needed to provide sustained release of BDNF from templated agarose scaffolds. Existing methods of loading the drug or protein into hydrogels cannot provide sustained release from templated agarose hydrogels. Alternatively, here it is shown that pH-responsive H-bonded poly(ethylene glycol)(PEG)/poly(acrylic acid)(PAA)/protein hybrid layer-by-layer (LbL) thin films, when prepared over agarose, provided sustained release of protein under physiological conditions for more than four weeks. Lysozyme, a protein similar in size and isoelectric point to BDNF, is released from the multilayers on the agarose and is biologically active during the earlier time points, with decreasing activity at later time points. This is the first demonstration of month-long sustained protein release from an agarose hydrogel, whereby the drug/protein is loaded separately from the agarose hydrogel fabrication process. PMID:20200599

  8. Template-free synthesis and encapsulation technique for layer-by-layer polymer nanocarrier fabrication.

    PubMed

    Qi, Aisha; Chan, Peggy; Ho, Jenny; Rajapaksa, Anushi; Friend, James; Yeo, Leslie

    2011-12-27

    The encapsulation of therapeutic molecules within multiple layers of biocompatible and biodegradable polymeric excipients allows exquisite design of their release profile, to the extent the drug can be selectively delivered to a specific target location in vivo. Here, we develop a novel technique for the assembly of multilayer polyelectrolyte nanocarriers based on surface acoustic wave atomization as a rapid and efficient alternative to conventional layer-by-layer assembly, which requires the use of a sacrificial colloidal template over which consecutive polyelectrolyte layers are deposited. Polymer nanocarriers are synthesized by atomizing a polymer solution and suspending them within a complementary polymer solution of opposite charge subsequent to their solidification in-flight as the solvent evaporates; reatomizing this suspension produces nanocarriers with a layer of the second polymer deposited over the initial polymer core. Successive atomization-suspension layering steps can then be repeated to produce as many additional layers as desired. Specifically, we synthesize nanocarriers comprising two and three, and up to eight, alternating layers of chitosan (or polyethyleneimine) and carboxymethyl cellulose within which plasmid DNA is encapsulated and show in vitro DNA release profiles over several days. Evidence that the plasmid's viability is preserved and hence the potential of the technique for gene delivery is illustrated through efficient in vitro transfection of the encapsulated plasmid in human mesenchymal progenitor and COS-7 cells.

  9. Designing carboxymethyl cellulose based layer-by-layer capsules as a carrier for protein delivery.

    PubMed

    Tripathy, Jasaswini; Raichur, Ashok M

    2013-01-01

    Stable hollow microcapsules composed of sodium carboxymethyl cellulose (CMC) and poly (allylamine hydrochloride) (PAH) were produced by layer-by-layer adsorption of polyelectrolytes onto CaCO(3) microparticles. Subsequently the core was removed by addition of chelating agents for calcium ions. Zeta potential studies showed charge reversal with deposition of successive polyelectrolyte layers, indicating that the alternate electrostatic adsorption of polyelectrolytes of opposite charge was successfully achieved. The size and surface morphology of the capsules was characterized by various microscopy techniques. The pH responsive loading behavior was elucidated by confocal laser scanning microscopy (CLSM) studies using fluorescence labeled dextran (FITC-dextran) and labeled BSA (FITC-BSA). CLSM images confirmed the open (pH≤6) and closed state (pH≥7) of the capsules. A model drug bovine serum albumin (BSA) was spontaneously loaded below its isoelectric point into hollow microcapsules, where BSA is positively charged. The loading of the BSA into the microcapsules was found to be dependent on the feeding concentration and pH of the medium. 65% of the loaded BSA was released over 7h of which about 34% was released in the first hour. These findings demonstrate that (CMC/PAH)(2) hollow capsules can be further exploited as a potential drug delivery system. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. 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.

  11. Electrochemical performance of Sn-Sb-Cu film anodes prepared by layer-by-layer electrodeposition

    NASA Astrophysics Data System (ADS)

    Jiang, Qianlei; Xue, Ruisheng; Jia, Mengqiu

    2012-02-01

    A novel layer-by-layer electrodeposition and heat-treatment approach was attempted to obtain Sn-Sb-Cu film anode for lithium ion batteries. The preparation of Sn-Sb-Cu anodes started with galvanostatic electrochemically depositing antimony and tin sequentially on the substrate of copper foil collector. Sn-Sb and Cu-Sb alloys were formed when heated. The SEM analysis showed that the crystalline grains become bigger and the surface of the Sn-Sb-Cu anode becomes more denser after annealing. The energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) analysis showed the antimony, tin and copper were alloyed to form SnSb and Cu2Sb after heat treatment. The X-ray photoelectron spectroscopy (XPS) analysis showed the surface of the Sn-Sb-Cu electrode was covered by a thin oxide layer. Electrochemical measurements showed that the annealed Sn-Sb-Cu anode has high reversible capacity and good capacity retention. It exhibited a reversible capacity of about 962 mAh/g in the initial cycle, which still remained 715 mAh/g after 30 cycles.

  12. 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.

  13. Layer-by-layer co-immobilization of soluble complement receptor 1 and heparin on islets.

    PubMed

    Luan, Nguyen Minh; Teramura, Yuji; Iwata, Hiroo

    2011-09-01

    Early graft loss due to instant blood-mediated inflammatory reactions (IBMIRs) is a major obstacle of clinical islet transplantation; inhibition of blood coagulation and complement activation is necessary to inhibit IBMIRs. Here, human soluble form complement receptor 1 (sCR1) and heparin were co-immobilized onto the surfaces of islet cells. sCR1 molecules carrying thiol groups were immobilized through maleimide-poly(ethylene glycol)-phospholipids anchored in the lipid bilayers of islet cells. Heparin was immobilized on the sCR1 layer via the affinity between sCR1 and heparin, and additional layers of sCR1 and heparin were formed layer-by-layer. The sCR1 and heparin molecules in these layers maintained anti-complement activation and anti-coagulation activities, respectively. This promising method could be employed to reduce the number of islet cells required to reverse hyperglycemia and prolong graft survival in both allo- and xeno-islet transplantation.

  14. Layer-by-layer assembly of conjugated polyelectrolytes on magnetic nanoparticle surfaces.

    PubMed

    Sun, Bin; Zhang, Yang; Gu, Ke-Jun; Shen, Qun-Dong; Yang, Yan; Song, Heng

    2009-05-19

    Composite nanoparticles with magnetic core and fluorescent shell were facilely prepared by the layer-by-layer deposition of conjugated polyelectrolytes over the negatively charged nanoparticles (NPs) of superparamagnetic iron oxide. The alternate assembly of cationic and anionic fluorescent polyelectrolytes leads to reversal in the sign of zeta-potentials. The even numbers of adsorption layer corresponding to the anionic polyelectrolyte (PFS) have negative values (-13 to -24 mV), whereas odd numbers of coating relative to the cationic polyelectrolyte (PFN) have positive values (26 to 28 mV). The composite nanoparticles can respond to both external magnetic field and ultraviolet light excitation. Forster resonance energy transfer (FRET) between oppositely charged polyelectrolytes (PFN and ThPFS) layers was also found, indicating dense packing of the polymer coatings. The fluorescence of the positively charged nanoparticles (NPs/PFN) can be quenched with very high efficiency by a small molecule anionic quencher [Fe(CN)6(4-)], while the same quencher has far less effect on the fluorescence of the negatively charged nanoparticles (NPs/PFN/PFS).

  15. Fabrication of organic thin-film transistors using layer-by-layer assembly.

    PubMed

    Stricker, Jeffery T; Gudmundsdóttir, Anna D; Smith, Adam P; Taylor, Barney E; Durstock, Michael F

    2007-06-14

    Layer-by-layer assembly is presented as a deposition technique for the incorporation of ultrathin gate dielectric layers into thin-film transistors utilizing a highly doped organic active layer. This deposition technique enables the fabrication of device structures with a controllable gate dielectric thickness. In particular, devices with a dielectric layer comprised of poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) bilayer films were fabricated to examine the properties of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as the transistor active layer. The transistor Ion/off ratio and switching speed are shown to be controlled by the gate bias, which is dependent upon the voltage applied and the number of bilayers deposited for the gate dielectric. The devices operate in the depletion mode as a result of dedoping of the active layer with the application of a positive gate bias. The depletion and recovery rate are highly dependent on the level of hydration in the film and the environment under which the device is operated. These observations are consistent with an electrochemical dedoping of the conducting polymer during operation.

  16. 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.

  17. Thermal Properties of Linearly and Exponentially Growing Layer-by-Layer Assemblies

    NASA Astrophysics Data System (ADS)

    Vidyasagar, Ajay; Lutkenhaus, Jodie

    2011-03-01

    Polyelectrolyte multilayer thin films have received significant attention for assembling various nanostructured coatings, but their thermochemical properties are challenging to measure. Here, we present results regarding the thermochemical properties of two different ``model'' layer-by-layer (LbL) assemblies. The LbL process involves alternate deposition of positively and negatively charged polymers resulting in interpenetrating networks of layers with fine structural control. Films may grow linearly or exponentially, and each type of growth is expected to give varied internal structure. Poly(allylamine hydrochloride)/poly(styrene sulfonate) (PAH/PSS) multilayers assembled without (or with) added salt are selected as the linear (or exponential) ``models.'' Other systems explored include hydrogen bonding and PAH/poly(acrylic acid) multilayers. In general, linear growth takes place due to charge overcompensation leading to thinner films than exponential growth, where interdiffusion of polyelectrolytes is a major driving force forming much thicker films. Calorimetry and ellipsometry were used to determine glass transition and crosslinking temperatures. A standing hypothesis is that linear (or exponential) growth is observed for glassy (or rubbery) multilayers. The aim of this work is to understand the origin of linear versus exponential growth in polyelectrolytes with respect to their thermal properties.

  18. Spin-Assisted Layer-by-Layer Assembly: Variation of Stratification as Studied with Neutron Reflectivity

    SciTech Connect

    Kharlampieva, Eugenia; Kozlovskaya, Veronika; Chan, Jennifer; Ankner, John Francis; Tsukruk, Vladimir V.

    2009-01-01

    We apply neutron reflectivity to probe the internal structure of spin-assisted layer-by-layer (LbL) films composed of electrostatically assembled polyelectrolytes. We find that the level of stratification and the degree of layer intermixing can be controlled by varying the type and concentration of salt during LbL assembly. We observe well-defined layer structure in spin-assisted LbL films when deposited from salt-free solutions. These films feature 2-nm-thick bilayers, which are ~3-fold thicker than those in dipped LbL films assembled under similar conditions. Addition of a 10mM phosphate buffer promotes progressive layer inter-diffusion with increasing distance from the substrate. However, adding 0.1M NaCl to the phosphate buffer solution restores the layer stratification. We also find that spin-assisted LbL films obtained from buffer solutions are more highly stratified as compared to the highly intermixed layers seen in dipped LbL films assembled from buffer. Our results yield new insight into the mechanism of spin-assisted LbL assembly that should prove useful for biotechnological applications.

  19. 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

  20. Nanostructured layer-by-layer films containing phaeophytin-b: electrochemical characterization for sensing purposes.

    PubMed

    Pauli, Gisele Elias Nunes; Araruna, Felipe B; Eiras, Carla; Leite, José Roberto S A; Chaves, Otemberg Souza; Brito Filho, Severino Gonçalves; de Souza, Maria de Fátima Vanderlei; Chavero, Lucas Natálio; Sartorelli, Maria Luisa; Bechtold, Ivan H

    2015-02-01

    This paper reports the study and characterization of a new platform for practical applications, where the use of phaeophytin-b (phaeo-b), a compound derived from chlorophyll, was characterized and investigated for sensing purposes. Modified electrodes with nanostructured phaeo-b films were fabricated via the layer-by-layer (LbL) technique, where phaeo-b was assembled with cashew gum, a polysaccharide, or with poly(allylamine) hydrochloride (PAH). The multilayer formation was investigated with UV-Vis spectroscopy by monitoring the absorption band associated to phaeo-b at approximately 410 nm, where distinct molecular interactions between the materials were verified. The morphology of the films was analyzed by atomic force microscopy (AFM). The electrochemical properties through redox behavior of phaeo-b were studied with cyclic voltammetry. The produced films were applied as sensors for hydrogen peroxide (H2O2) detection. In terms of sensing, the cashew/phaeo-b film exhibited the most promising result, with a fast response and broad linear range upon the addition of H2O2. This approach provides a simple and inexpensive method for development of a nonenzymatic electrochemical sensor for H2O2. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Flow-Based Assembly of Layer-by-Layer Capsules through Tangential Flow Filtration.

    PubMed

    Björnmalm, Mattias; Roozmand, Ali; Noi, Ka Fung; Guo, Junling; Cui, Jiwei; Richardson, Joseph J; Caruso, Frank

    2015-08-25

    Layer-by-layer (LbL) assembly on nano- and microparticles is of interest for a range of applications, including catalysis, optics, sensors, and drug delivery. One current limitation is the standard use of manual, centrifugation-based (pellet/resuspension) methods to perform the layering steps, which can make scalable, highly controllable, and automatable production difficult to achieve. Here, we develop a fully flow-based technique using tangential flow filtration (TFF) for LbL assembly on particles. We demonstrate that multilayered particles and capsules with different sizes (from micrometers to submicrometers in diameter) can be assembled on different templates (e.g., silica and calcium carbonate) using several polymers (e.g., poly(allylamine hydrochloride), poly(styrenesulfonate), and poly(diallyldimethylammonium chloride)). The full system only contains fluidic components routinely used (and automated) in industry, such as pumps, tanks, valves, and tubing in addition to the TFF filter modules. Using the TFF LbL system, we also demonstrate the centrifugation-free assembly, including core dissolution, of drug-loaded capsules. The well-controlled, integrated, and automatable nature of the TFF LbL system provides scientific, engineering, and practical processing benefits, making it valuable for research environments and potentially useful for translating LbL assembled particles into diverse applications.

  2. Layer-by-Layer Sorting of Rhenium Disulfide via High-Density Isopycnic Density Gradient Ultracentrifugation.

    PubMed

    Kang, Joohoon; Sangwan, Vinod K; Wood, Joshua D; Liu, Xiaolong; Balla, Itamar; Lam, David; Hersam, Mark C

    2016-11-09

    Isopycnic density gradient ultracentrifugation (iDGU) has been widely applied to sort nanomaterials by their physical and electronic structure. However, the commonly used density-gradient medium iodixanol has a finite maximum buoyant density that prevents the use of iDGU for high-density nanomaterials. Here, we overcome this limit by adding cesium chloride (CsCl) to iodixanol, thus increasing its maximum buoyant density to the point where the high-density two-dimensional nanomaterial rhenium disulfide (ReS2) can be sorted in a layer-by-layer manner with iDGU. The resulting aqueous ReS2 dispersions show photoluminescence at ∼1.5 eV, which is consistent with its direct bandgap semiconductor electronic structure. Furthermore, photocurrent measurements on thin films formed from solution-processed ReS2 show a spectral response that is consistent with optical absorbance and photoluminescence data. In addition to providing a pathway for effective solution processing of ReS2, this work establishes a general methodology for sorting high-density nanomaterials via iDGU.

  3. 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

  4. Layer-by-layer graphene/TCNQ stacked films as conducting anodes for organic solar cells.

    PubMed

    Hsu, Chang-Lung; Lin, Cheng-Te; Huang, Jen-Hsien; Chu, Chih-Wei; Wei, Kung-Hwa; Li, Lain-Jong

    2012-06-26

    Large-area graphene grown by chemical vapor deposition (CVD) is a promising candidate for transparent conducting electrode applications in flexible optoelectronic devices such as light-emitting diodes or organic solar cells. However, the power conversion efficiency (PCE) of the polymer photovoltaic devices using a pristine CVD graphene anode is still not appealing due to its much lower conductivity than that of conventional indium tin oxide. We report a layer-by-layer molecular doping process on graphene for forming sandwiched graphene/tetracyanoquinodimethane (TCNQ)/graphene stacked films for polymer solar cell anodes, where the TCNQ molecules (as p-dopants) were securely embedded between two graphene layers. Poly(3-hexylthiophene)/phenyl-C61-butyric acid methyl ester (P3HT/PCBM) bulk heterojunction polymer solar cells based on these multilayered graphene/TCNQ anodes are fabricated and characterized. The P3HT/PCBM device with an anode structure composed of two TCNQ layers sandwiched by three CVD graphene layers shows optimum PCE (∼2.58%), which makes the proposed anode film quite attractive for next-generation flexible devices demanding high conductivity and transparency.

  5. Layer-by-layer nanocoating of lignocellulose fibers for enhanced paper properties.

    PubMed

    Zheng, Zhiguo; McDonald, John; Khillan, Rajneek; Su, Yi; Shutava, Tatsiana; Grozdits, George; Lvov, Yuri M

    2006-03-01

    The systematic modification of the surface charge of lignocellulose fibers was performed with a polyelectrolyte layer-by-layer (LbL) nanocoating process to produce negatively and positively charged fibers. The fibers were coated with 20-50 nm thick polymer surface layers which subsequently increased interaction between the fibers during paper formation. The modified fibers were added to standard fibers at varying proportions to produce paper with corresponding variation in properties such as strength and electrical conductivity. Paper strength was doubled by manipulating the surface charge and coating thickness of the LbL-treated pulp fibers. It is demonstrated that the LbL coating process increased the fiber interactions and that these interactions enhanced the paper properties. This process, when applied to a simulated sample of recycle grade of fibers, produce paper with an increase in tear strength as compared with untreated fiber paper. Nanocoating fibers with polythiophene/polyallylamine multilayers produced marginally conductive pulp and paper. Paper electrical conductivity was proportional to the number of the bilayers deposited.

  6. All-nanoparticle layer-by-layer surface modification of micro- and ultrafiltration membranes.

    PubMed

    Escobar-Ferrand, Luis; Li, Diya; Lee, Daeyeon; Durning, Christopher J

    2014-05-20

    Layer-by-layer (LbL) deposition using primarily inorganic silica nanoparticles is employed for surface modification of polymeric micro- and ultrafiltration (MF/UF) membranes to produce novel thin film composite (TFC) membranes intended for nanofiltration (NF) and reverse osmosis (RO) applications. A wide variety of porous substrate membranes with different surface characteristics are successfully employed. This report gives detailed results for polycarbonate track etched (PCTE), polyethersulfone (PES), and sulfonated PES (SPEES) MF/UF substrates. Both spherical (cationic/anionic) and eccentric elongated (anionic) silica nanoparticles are deposited using conditions similar to those in prior works for solid substrates (e.g., Lee et al.). Appropriate selection of the pH for anionic and cationic particle deposition enables construction of nanoparticle-only layers 100-1200 nm in thickness atop the original porous membrane substrates. The surface layer thickness appears to vary linearly with the number of bilayers deposited, i.e., with the number of anionic/cationic deposition cycles. The deposition process is optimized to eliminate drying-induced cracking and improve mechanical durability via thickness control and postdeposition hydrothermal treatment. "Dead-end" permeation tests using dextran standards reveal the hydraulic characteristics and separations capability for the PCTE-based TFC membranes. The results show that nanoparticle-based LbL surface modification of MF and UF rated media can produce TFC membranes with NF capabilities.

  7. Layer-by-layer assembly surface modified microbial biomass for enhancing biorecovery of secondary gold.

    PubMed

    Zhou, Ying; Zhu, Nengwu; Kang, Naixin; Cao, Yanlan; Shi, Chaohong; Wu, Pingxiao; Dang, Zhi; Zhang, Xiaoping; Qin, Benqian

    2017-02-01

    Enhancement of the biosorption capacity for gold is highly desirable for the biorecovery of secondary gold resources. In this study, polyethylenimine (PEI) was grafted on Shewanella haliotis surface through layer-by-layer assembly approach so as to improve the biosorption capacity of Au(III). Results showed that the relative contribution of amino group to the biosorption of Au(III) was the largest one (about 44%). After successful grafting 1, 2 and 3-layer PEI on the surface of biomass, the biosorption capacity significantly enhanced from 143.8mg/g to 597.1, 559.1, and 536.8mg/g, respectively. Interestingly, the biomass modified with 1-layer PEI exhibited 4.2 times higher biosorption capacity than the untreated control. When 1-layer modified biomass was subjected to optimizing the various conditions by response surface methodology, the theoretical maximum adsorption capacity could reach up to 727.3mg/g. All findings demonstrated that PEI modified S. haliotis was effective for enhancing gold biorecovery. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Surface modification of vitreoretinal surgical instruments with layer-by-layer films.

    PubMed

    Valentin-Rodriguez, Celimar; Tezel, Tongalp H; Ivanisevic, Albena

    2011-01-01

    Commercially available vitreoretinal surgical forceps were modified with layer-by-layer (LbL) films designed to render them the ability to specifically adhere human the inner limiting membrane. Surgical forceps with two different geometries were etched, polished, and silanized before deposition of the films composed of poly (allylamine hydrochloride), poly (styrene sulfonate), and cationic gold nanoparticles. Stability and integrity of the LbL films was scrutinized by exposing the modified forceps to commercial disinfectant Cidex-OPA and then placing the instruments in a physiological-like HEPES buffer (pH 7.4, 5 mM, 154 mM NaCl). Surface topography analysis with scanning electron microscopy revealed that the geometry of the surgical instrument may affect the integrity of the film. Analysis of the HEPES buffer with inductively coupled plasma mass spectrometry demonstrated that gold nanoparticles did not leach from the LbL film after 60 min. Copyright © 2011 Wiley Periodicals, Inc.

  9. Solution-processed sintered nanocrystal solar cells via layer-by-layer assembly.

    PubMed

    Jasieniak, Jacek; MacDonald, Brandon I; Watkins, Scott E; Mulvaney, Paul

    2011-07-13

    Solar cells made by high temperature and vacuum processes from inorganic semiconductors are at a perceived cost disadvantage when compared with solution-processed systems such as organic and dye-sensitized solar cells. We demonstrate that totally solution processable solar cells can be fabricated from inorganic nanocrystal inks in air at temperature as low as 300 °C. Focusing on a CdTe/ZnO thin-film system, we report solar cells that achieve power conversion efficiencies of 6.9% with greater than 90% internal quantum efficiency. In our approach, nanocrystals are deposited from solution in a layer-by-layer process. Chemical and thermal treatments between layers induce large scale grain formation, turning the 4 nm CdTe particles into pinhole-free films with an optimized average crystallite size of ∼70 nm. Through capacitance-voltage measurements we demonstrate that the CdTe layer is fully depleted which enables the charge carrier collection to be maximized.

  10. Chitosan-Recombinamer Layer-by-Layer Coatings for Multifunctional Implants

    PubMed Central

    Govindharajulu, Jeevan Prasaad; Chen, Xi; Li, Yuping; Rodriguez-Cabello, Jose Carlos; Battacharya, Mrinal; Aparicio, Conrado

    2017-01-01

    The main clinical problems for dental implants are (1) formation of biofilm around the implant—a condition known as peri-implantitis and (2) inadequate bone formation around the implant—lack of osseointegration. Therefore, developing an implant to overcome these problems is of significant interest to the dental community. Chitosan has been reported to have good biocompatibility and anti-bacterial activity. An osseo-inductive recombinant elastin-like biopolymer (P-HAP), that contains a peptide derived from the protein statherin, has been reported to induce biomineralization and osteoblast differentiation. In this study, chitosan/P-HAP bi-layers were built on a titanium surface using a layer-by-layer (LbL) assembly technique. The difference in the water contact angle between consecutive layers, the representative peaks in diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and the changes in the topography between surfaces with a different number of bi-layers observed using atomic force microscopy (AFM), all indicated the successful establishment of chitosan/P-HAP LbL assembly on the titanium surface. The LbL-modified surfaces showed increased biomineralization, an appropriate mouse pre-osteoblastic cell response, and significant anti-bacterial activity against Streptococcus gordonii, a primary colonizer of tissues in the oral environment. PMID:28208793

  11. 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.

  12. Polymer magnetic microactuators fabricated with hot embossing and layer-by-layer nano self-assembly.

    PubMed

    Xue, Wei; Cui, Tianhong

    2007-08-01

    Polymer-based magnetic microactuators have been fabricated with hot embossing technique and layer-by-layer (LbL) nano self-assembly. Silicon molds are fabricated with conventional UV lithography and wet etching techniques. Hot embossing is used to transfer the patterns from silicon molds to polymethylmethacrylate (PMMA) sheets. The overall processing time for the pattern transfer is less than 20 min. Low-cost devices with massive and rapid replication can be fabricated. Six layers of magnetic iron oxide (Fe2O3) nanoparticles are LbL self-assembled on the PMMA surface as the magnetically sensitive material. Positive photoresist PR1813 is used as the sacrificial layer to protect the gold electrode on the back side of the membrane. LbL nano self-assembly technique provides a simple method to obtain the magnetic film with low cost, short processing time, simple fabrication steps at room temperature. The volume of the magnetic material can be precisely controlled by the number of nano-assembled iron oxide layers. The mechanical, electrical, and magnetic properties of the microactuator are characterized by a laser interferometer. The natural frequency of the actuator is approximately 151 Hz; and the maximum deflection amplitude is about 34 nm. At all frequencies, the increase of the magnetic field increases the deflection amplitude which is in agreement with the theoretical equation.

  13. 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

  14. Superior Flame-Resistant Cellulose Nanofibril Aerogels Modified with Hybrid Layer-by-Layer Coatings.

    PubMed

    Köklükaya, Oruç; Carosio, Federico; Wågberg, Lars

    2017-08-30

    Nanometer thin films consisting of cationic chitosan (Ch), anionic poly(vinylphosphonic acid) (PVPA), and anionic montmorillonite clay (MMT) are deposited on highly porous, wet-stabilized cellulose nanofibril (CNF) aerogels via the layer-by-layer (LbL) technique. Model experiments with silicon oxide surfaces are used to study the details of LbL formation and the multilayer structure. Formation of layers on the aerogels is also investigated as a function of solution concentration by use of polyelectrolyte titration. Thermogravimetric analysis indicates that the LbL coating significantly improves thermal stability of the CNF aerogel. Horizontal flame test shows that aerogels coated with five quadlayers of Ch/PVPA/Ch/MMT, using solutions/dispersion of high concentration, are able to self-extinguish immediately after removal of flame, and LbL-coated aerogels do not ignite under heat flux (35 kW/m(2)) in cone calorimetry. The LbL-coated aerogel can prevent flame penetration from a torch focused on the surface, achieving temperature drops up to 650 °C across the 10 mm thick specimen for several minutes. LbL treatment is hence a rapid and highly effective way to specifically tailor the surface properties of CNF aerogels in order to confer unprecedented flame-retardant characteristics.

  15. 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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Polymer mediated layer-by-layer assembly of different shaped gold nanoparticles.

    PubMed

    Budy, Stephen M; Hamilton, Desmond J; Cai, Yuheng; Knowles, Michelle K; Reed, Scott M

    2017-02-01

    Gold nanoparticles (GNPs) have a wide range of properties with potential applications in electronics, optics, catalysis, and sensing. In order to demonstrate that dense, stable, and portable samples could be created for these applications, multiple layers of GNPs were assembled via drop casting on glass substrates by layer-by-layer (LBL) techniques. Two cationic polyelectrolytes, poly(diallyldimethylammonium chloride) and polyethyleneimine, one anionic polyelectrolyte, poly(sodium 4-styrene sulfonate), and one neutral polymer, polyvinylpyrrolidone, were combined with four different shapes of GNPs (spherical, rod, triangular prismatic, and octahedral) to prepare thin films. A subset of these polymer nanoparticle combinations were assembled into thin films. Synthesized GNPs were characterized via dynamic light scattering, UV-vis spectroscopy, and transmission electron microscopy and the LBL thin films were characterized using UV-vis spectroscopy and atomic force microscopy. Sensing applications of the nanoparticles in solution and thin films were tested by monitoring the localized surface plasmon resonance of the GNPs. LBL thin films were prepared ranging from 25 to 100 layers with optical densities at plasmon from 0.5 to 3.0. Sensitivity in solutions ranged from 14 to 1002nm/refractive index units (RIU) and films ranged from 18.8 to 135.1nm/RIU suggesting reduced access to the GNPs within the films.

  17. 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

    2016-03-01

    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.

  18. 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

    2008-08-05

    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).

  19. Finely tailored performance of inverted organic photovoltaics through layer-by-layer interfacial engineering.

    PubMed

    Chen, Qun; Worfolk, Brian J; Hauger, Tate C; Al-Atar, Usama; Harris, Kenneth D; Buriak, Jillian M

    2011-10-01

    Control over interfacial properties in organic photovoltaics (OPVs) is critical for many aspects of their performance. Functionalization of the transparent conducting electrode, in this case, indium tin oxide (ITO), through an electrostatic layer by layer (eLbL) approach with cationic N,N'-bis[2-(trimethylammonium)ethylene] perylene-3,4,9,10-tetracarboxyldiimide (PTCDI(+)) and anionic poly(3,4-ethylenedioxythiophene):poly(p-styrenesulfonate) (PEDOT:PSS(-)), led to high control over the surface properties. The films were studied through a variety of surface and spectroscopic techniques, including X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy, atomic force microscopy (AFM), and ellipsometry. The work function of modified ITO was measured by UV photoelectron spectroscopy (UPS) and showed oscillating values with respect to odd-even layer numbers; the strong odd-even effect is due to the differing electronic characteristics of the top layer, either PTCDI(+) or PEDOT:PSS(-). The modified ITO electrodes were then used as the cathode in a series of inverted organic photovoltaic architectures. The performance of inverted OPVs was, in parallel to the UPS results, found to be highly dependent on the layer number of coated films and showed an obvious oscillation based on layer number. Inverted OPVs were retested after 128 days of storage in air, and almost all devices maintained over 70% of original power conversion efficiency (PCE). © 2011 American Chemical Society

  20. Temperature-triggered transformations in shape of layer-by-layer microtubes in aqueous media

    NASA Astrophysics Data System (ADS)

    Sung, Choonghyun; Vidyasagar, Ajay; Hearn, Katelin; Lutkenhaus, Jodie

    2014-03-01

    Nano- and microstructured layer-by-layer (LbL) assemblies have been of considerable interest for various applications. In particular, one-dimensional LbL microtubes have garnered interest for their ability to shrink or swell in response to changes in pH. Temperature has also been known to trigger transformations in shape. In this presentation, we report on the thermal behavior of LbL microtubes of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA). PAH/PAA LbL microtubes were prepared using polycarbonate membranes as porous templates. The thermal behavior of both freely released microtubes and template-bound microtubes was investigated in aqueous media as a function of temperature and time using confocal laser scanning microscopy and scanning electron microscopy. When free microtube suspensions were incubated at high temperatures, the microtubes became shorter and ellipsoid in shape. In contrast, the template-bound microtubes showed periodic voids on the surface. In both cases, pronounced transformations occurred above the hydrated glass transition temperature of the PAH/PAA LbL microtube.

  1. 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.

  2. Preparation of gold patterns on polyimide coating via layer-by-layer deposition of gold nanoparticles.

    PubMed

    Basarir, Fevzihan; Yoon, Tae-Ho

    2010-12-01

    Gold patterns were prepared via the microcontact printing (MCP) of 3-aminopropyltriethoxysilane (γ-APS) on plasma etched polyimide films, followed by the layer-by-layer (LBL) deposition of gold nanoparticles (GNPs), O(2) plasma etching, and sintering. First, the polyimide film on silicon wafer was modified via water plasma etching, followed by the MCP of γ-APS using a flat polydimethylsiloxane (PDMS) stamp. Next, the multilayer of GNPs was formed on the γ-APS layer by the LBL deposition of citrate-capped GNPs and poly(ethyleneimine) (PEI). Then, the samples were subjected to O(2) plasma etching to remove PEI and citrates, and then sintering to produce metallic gold. Finally, gold patterns were prepared with a patterned PDMS stamp (line width of 10μm). The GNP multilayer was characterized by UV-vis/near-IR spectrometer, atomic force microscopy (AFM), optical microscopy (OM), alpha-step and electrical conductivity measurement by two-point probe method. Very clean gold patterns with electrical conductivity of 4.1×10(4)Ω(-1)cm(-1) (20-layer GNP) were obtained. Copyright © 2010 Elsevier Inc. All rights reserved.

  3. One-dimensional hybrid nanostructures: synthesis via layer-by-layer assembly and applications.

    PubMed

    Du, Ning; Zhang, Hui; Yang, Deren

    2012-09-21

    Assembly techniques are being intensely sought for preparing nanocomposites with tunable compositions and structures. Compared to other assembly techniques, the layer-by-layer (LBL) technique, which is based on the electrostatic attraction between oppositely charged species, provides a simple, versatile and powerful method to synthesize various types of one-dimensional (1D) hybrid nanostructures. In this review, we begin with the developments in the LBL synthesis of nanocomposites, with a focus on our recent results for synthesizing 1D hybrid nanostructures via LBL assembly. Compared to previous LBL processes, we conducted the in situ reaction on the surface of 1D nanostructures via electrostatic attraction between oppositely charged 1D nanostructures and ions in the solution in an attempt to produce 1D hybrid nanostructures. Moreover, these core-shell nanostructures can be transformed into nanotubes by the removal of the templates. The as-synthesized 1D hybrid nanostructures and nanotubes with tunable composition exhibited enhanced performance for various applications such as gas sensors, lithium-ion batteries and cellular imaging.

  4. 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.

  5. Porosity and tortuosity of layer-by-layer assemblies of spherical particles

    NASA Astrophysics Data System (ADS)

    Batys, Piotr; Weroński, Paweł

    2014-09-01

    We have used the extended random sequential adsorption model of hard spheres to mimic the layer by layer self-assembling process of monodisperse colloidal particles at a solid-liquid interface. We have studied five multilayers of similar thickness, each created at a different single-layer surface coverage. Our results suggest that the single-layer coverage has a significant effect on the film transport properties. The local values of multilayer porosity and tortuosity exhibit decaying oscillatory variations in the distance range dependent on the surface coverage. The mean multilayer porosity and tortuosity describe equations linear with respect to the surface coverage. The mean tortuosity and porosity of multilayers created with our model are also connected by a linear equation valid for any single-layer coverage and any number of layers. We have also determined the normalized equivalent thickness of stagnant solution layer as a function of the multilayer coverage and number of layers. This parameter grows asymptotically with the number of layers and can be approximated with good accuracy by the ratio of the squared mean tortuosity to the mean porosity of a multilayer.

  6. Bioinspired Layer-by-Layer Microcapsules Based on Cellulose Nanofibers with Switchable Permeability.

    PubMed

    Paulraj, Thomas; Riazanova, Anastasia V; Yao, Kun; Andersson, Richard L; Müllertz, Anette; Svagan, Anna J

    2017-04-10

    Green, all-polysaccharide based microcapsules with mechanically robust capsule walls and fast, stimuli-triggered, and switchable permeability behavior show great promise in applications based on selective and timed permeability. Taking a cue from nature, the build-up and composition of plant primary cell walls inspired the capsule wall assembly, because the primary cell walls in plants exhibit high mechanical properties despite being in a highly hydrated state, primarily owing to cellulose microfibrils. The microcapsules (16 ± 4 μm in diameter) were fabricated using the layer-by-layer technique on sacrificial CaCO3 templates, using plant polysaccharides (pectin, cellulose nanofibers, and xyloglucan) only. In water, the capsule wall was permeable to labeled dextrans with a hydrodynamic diameter of ∼6.6 nm. Upon exposure to NaCl, the porosity of the capsule wall quickly changed allowing larger molecules (∼12 nm) to permeate. However, the porosity could be restored to its original state by removal of NaCl, by which permeants became trapped inside the capsule's core. The high integrity of cell wall was due to the CNF and the ON/OFF alteration of the permeability properties, and subsequent loading/unloading of molecules, could be repeated several times with the same capsule demonstrating a robust microcontainer with controllable permeability properties.

  7. Layer-by-layer assembled multilayer shells for encapsulation and release of fragrance.

    PubMed

    Sadovoy, Anton V; Lomova, Maria V; Antipina, Maria N; Braun, Norbert A; Sukhorukov, Gleb B; Kiryukhin, Maxim V

    2013-09-25

    Layer-by-layer assembled shells are prospective candidates for encapsulation, stabilization, storage, and release of fragrances. A shell comprising four alternative layers of a protein and a polyphenol is employed to encapsulate the dispersed phase of a fragrance-containing oil-in-water emulsion. The model fragrance used in this work consists of 10 ingredients, covering a range of typically employed aroma molecules, all premixed in equal mass and with sunflower oil acting as the base. The encapsulated emulsion is stable after 2 months of storage at 4 °C as revealed by static light scattering and confocal laser scanning microscopy. Gas chromatography/mass spectrometry data show that the encapsulation efficiency of 8 out of 10 fragrance ingredients depends on the water solubility: the less water-soluble an ingredient, the more of it is encapsulated. The amount of these fragrance ingredients remaining encapsulated decreases linearly upon emulsion incubation at 40 °C and the multilayer shell does not hinder their release. The other two fragrance ingredients having the lowest saturation vapor pressure demonstrate sustained release over 5 days of incubation at 40 °C. The composition of released fragrance remains almost constant over 3 days of incubation, upon further incubation it becomes enriched with these two ingredients when others start to be depleted.

  8. Layer-by-layer assembly of nacre-like nanostructured composites with antimicrobial properties.

    PubMed

    Podsiadlo, Paul; Paternel, Stephen; Rouillard, Jean-Marie; Zhang, Zhengfei; Lee, Jaebeom; Lee, Jung-Woo; Gulari, Erdogan; Kotov, Nicholas A

    2005-12-06

    In a recent report, we have presented the layer-by-layer (LBL) assembly of a biomimetic nanostructured composite from Na(+)-montmorillonite clay nanosheets and poly(diallylmethylammonium chloride) (Tang, Z.; Kotov, N.; Magonov, S.; Ozturk, B. Nat. Mater. 2003, 2, 413). The structure, deformation mechanism, and mechanical properties of the material are very similar to those of natural nacre and lamellar bones. This fact prompts further investigation of these composites as potential bone implants. LBL assembly affords preparation of multifunctional composites, and here we demonstrate that not only mechanical strength, but also antibacterial activity, can be introduced in these implantable materials by alternating clay layers with starch-stabilized silver nanoparticles. The resulting composite showed excellent structural stability with no detectable levels of silver lost over a 1 month period. Evaluation of the antibacterial properties showed almost complete growth inhibition of E. coli over an 18 h period. The amount of silver eluted from the LBL composite over a 1 month period was determined to be only 0.5-3.0 microg/L. This concentration of silver did not prevent the growth of the mammalian tissue cultures. The LBL composite has shown biocompatibility with the human osteoblast cell line.

  9. 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

  10. Enhancing surface coverage and growth in layer-by-layer assembly of protein nanoparticles.

    PubMed

    Mohanta, Vaishakhi; Patil, Satish

    2013-10-29

    Thin films of bovine serum albumin (BSA) nanoparticles are fabricated via layer-by-layer assembly. The surface of BSA nanoparticles have two oppositely acting functional groups on the surface: amine (NH2) and carboxylate (COO(-)). The protonation and deprotonation of these functional groups at different pH vary the charge density on the particle surface, and entirely different growth can be observed by varying the nature of the complementary polymer and the pH of the particles. The complementary polymers used in this study are poly(dimethyldiallylammonium chloride) (PDDAC) and poly(acrylic acid) (PAA). The assembly of BSA nanoparticles based on electrostatic interaction with PDDAC suffers from the poor loading of the nanoparticles. The assembly with PAA aided by a hydrogen bonding interaction shows tremendous improvement in the growth of the assembly over PDDAC. Moreover, the pH of the BSA nanoparticles was observed to affect the loading of nanoparticles in the LbL assembly with PAA significantly.

  11. 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.

  12. Layer-by-layer-assembled high-performance broadband antireflection coatings.

    PubMed

    Shimomura, Hiroomi; Gemici, Zekeriyya; Cohen, Robert E; Rubner, Michael F

    2010-03-01

    Nanoparticles are indispensable ingredients of solution-processed optical, dielectric, and catalytic thin films. Although solution-based methods are promising low-cost alternatives to vacuum methods, they can have significant limitations. Coating uniformity, thickness control, roughness control, mechanical durability, and incorporation of a diverse set of functional organic molecules into nanoparticle thin films are major challenges. We have used the electrostatic layer-by-layer assembly technique to make uniform, conformal multistack nanoparticle thin films for optical applications with precise thickness control over each stack. Two particularly sought-after optical applications are broadband antireflection and structural color. The effects of interstack and surface roughness on optical properties of these constructs (e.g., haze and spectral response) have been studied quantitatively using a combination of Fourier-transform methods and atomic force microscopy measurements. Deconvoluting root-mean-square roughness into its large-, intermediate-, and small-scale components enables enhanced optical simulations. A 4-stack broadband antireflection coating (<0.5% average reflectance in the visible range, and 0.2% haze) composed of alternating high-index (n approximately 1.96) and low-index (n approximately 1.28) stacks has been made on glass substrate. Films calcinated at 550 degrees C endure a one-hour-long cloth cleaning test under 100 kPa normal stress.

  13. Preparation and characterization of composite membrane via layer by layer assembly for desalination

    NASA Astrophysics Data System (ADS)

    Wasim, Maria; Sabir, Aneela; Shafiq, Muhammad; Islam, Atif; Jamil, Tahir

    2017-02-01

    Cellulose acetate (CA) incorporated with sepiolite and Polyvinylpyrrolidone (PVP) multilayer composite on Polysulfone (PSf) substrate have been prepared by layer by layer (LbL) assembly method. Fourier TransformInfrared Spectroscopy (FTIR) results verified the hydrogen bonding among the components of composite membrane. Atomic force microscopy (AFM), scanning electron microscope (SEM) was carried out for the determination and elucidation of roughness and morphology of the fabricated membranes on PSf substrate. The AFM and SEM results showed the increased surface roughness with the porous and spongy structure. The performance results verified that the successful incorporation of sepiolite in membranes showed maximum MgSO4 rejection (98.9%) and flux of 38.7 L/m2 h. Whereas, in case of NaCl the rejection is 98.3% and flux is 34.9L/m2 h. The modification was evidenced to be effective in increasing the surface hydrophilicity that led to increase in surface roughness. The chlorine resistivity is improved by dropping the active sites for chlorine attack and protecting the underlying PSf substrate.

  14. Super-hydrophobic surfaces of layer-by-layer structured film-coated electrospun nanofibrous membranes

    NASA Astrophysics Data System (ADS)

    Ogawa, Tasuku; Ding, Bin; Sone, Yuji; Shiratori, Seimei

    2007-04-01

    We have recently fabricated super-hydrophobic membrane surfaces based on the inspiration of self-cleaning silver ragwort leaves. This biomimetic super-hydrophobic surface was composed of fluoroalkylsilane (FAS)-modified layer-by-layer (LBL) structured film-coated electrospun nanofibrous membranes. The rough fibre surface caused by the electrostatic LBL coating of TiO2 nanoparticles and poly(acrylic acid) (PAA) was used to imitate the rough surface of nanosized grooves along the silver ragwort leaf fibre axis. The results showed that the FAS modification was the key process for increasing the surface hydrophobicity of the fibrous membranes. Additionally, the dependence of the hydrophobicity of the membrane surfaces upon the number of LBL coating bilayers was affected by the membrane surface roughness. Moreover, x-ray photoelectron spectroscopy (XPS) results further indicated that the surface of LBL film-coated fibres absorbed more fluoro groups than the fibre surface without the LBL coating. A (TiO2/PAA)10 film-coated cellulose acetate nanofibrous membrane with FAS surface modification showed the highest water contact angle of 162° and lowest water-roll angle of 2°.

  15. Polyoxometalate nanotubes from layer-by-layer coating and thermal removal of electrospun nanofibres

    NASA Astrophysics Data System (ADS)

    Ding, Bin; Gong, Jian; Kim, Jinho; Shiratori, Seimei

    2005-06-01

    We have recently fabricated Keggin-type polyoxometalate (H4SiW12O40) nanotubes by calcining layer-by-layer (LBL) structured ultrathin hybrid film coated electrospun fibrous mats. The hybrid film coated electrospun fibrous mats were obtained from the alternate deposition of positively charged poly(allylamine hydrochloride) (PAH) and negatively charged H4SiW12O40 on the surface of negatively charged cellulose acetate (CA) nanofibres using the electrostatic LBL self-assembly technique. The fibrous mats were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared (FT-IR) spectroscopy, and wide-angle x-ray diffraction (WAXD). It was found that the morphology of hybrid PAH/H4SiW12O40 film coated fibrous mats was strongly influenced by the number of deposition bilayers and the pH of dipping solutions. The fibrous mats were contracted and H4SiW12O40 nanotubes with a wall thickness of about 50 nm can be fabricated after calcination at high temperature. Additionally, the FT-IR and WAXD results indicated that the pure H4SiW12O40 nanotubes were obtained with a Keggin structure.

  16. Non-Layer-by-Layer Assembly and Encapsulation Uses of Nanoparticle-Shelled Hollow Spheres

    NASA Astrophysics Data System (ADS)

    Kini, Gautam C.; Biswal, Sibani L.; Wong, Michael S.

    Nanoparticles (NPs, diameter range of 1-100nm) can have size-dependent physical and electronic properties that are useful in a variety of applications. Arranging them into hollow shells introduces the additional functionalities of encapsulation, storage, and controlled release that the constituent NPs do not have.This chapter examines recent developments in the synthesis routes and properties of hollow spheres formed out of NPs. Synthesis approaches reviewed here are recent developments in the electrostatics-based tandem assembly and interfacial stabilization routes to the formation of NP-shelled structures. Distinct from the well-established layer-by-layer (LBL) synthesis approach, the former route leads to NP/polymer composite hollow spheres that are potentially useful in medical therapy, catalysis, and encapsulation applications. The latter route is based on interfacial activity and stabilization by NPs with amphiphilic properties, to generate materials like colloidosomes, Pickering emulsions, and foams. The varied types of NP shells can have unique materials properties that are not found in the NP building blocks, or in polymer-based, surfactant-based, or LBL-assembled capsules.

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

    PubMed

    Keeney, M; Jiang, X Y; Yamane, M; Lee, M; Goodman, S; Yang, F

    2015-11-07

    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.

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

    PubMed

    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-ZrO(2) (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-ZrO(2). To determine the optimum addition levels for nano-ZrO(2), ceramics containing 0, 20, 25, 30, and 35 wt% nano-ZrO(2) 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-ZrO(2) 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.

  20. Thermal transitions in dry and hydrated layer-by-layer assemblies exhibiting linear and exponential growth.

    PubMed

    Vidyasagar, Ajay; Sung, Choonghyun; Gamble, Randall; Lutkenhaus, Jodie L

    2012-07-24

    Layer-by-layer (LbL) assemblies are remarkable materials, known for their tunable mechanical, optical, and surface properties in nanoscale films. However, questions related to their thermal properties still remain unclear. Here, the thermal properties of a model LbL assembly of strong polyelectrolytes, poly(diallyldimethylammonium chloride)/poly(styrene sulfonate) (PDAC/PSS), assembled from solutions of varying ionic strength (0-1.25 M NaCl) are investigated using quartz crystal microbalance with dissipation (QCM-D) and modulated differential scanning calorimetry. Hydrated exponentially growing films (assembled from 0.25 to 1.25 M NaCl) exhibited distinct thermal transitions akin to a glass transition at 49-56 °C; linearly growing films (assembled without added salt) did not exhibit a transition in the temperature range investigated and were glassy. Results support the idea that exponentially growing films have greater segmental mobility than that of linearly growing films. On the other hand, all dry LbL assemblies investigated were glassy at room temperature and did not exhibit a T(g) up to 250 °C, independent of ionic strength. For the first time, thermal transitions such as T(g) values can be measured for LbL assemblies using QCM-D by monitoring fluctuations in changes in dissipation, allowing us to probe the film's internal structure as a function of film depth.

  1. 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.

  2. Factors controlling the deposition of silk fibroin nanofibrils during layer-by-layer assembly.

    PubMed

    de Moraes, Mariana Agostini; Crouzier, Thomas; Rubner, Michael; Beppu, Marisa Masumi

    2015-01-12

    The layer-by-layer technique has been used as a powerful method to produce multilayer thin films with tunable properties. When natural polymers are employed, complicated phenomena such as self-aggregation and fibrilogenesis can occur, making it more difficult to obtain and characterize high-quality films. The weak acid and base character of such materials provides multilayer systems that may differ from those found with synthetic polymers due to strong self-organization effects. Specifically, LbL films prepared with chitosan and silk fibroin (SF) often involve the deposition of fibroin fibrils, which can influence the assembly process, surface properties, and overall film functionality. In this case, one has the intriguing possibility of realizing multilayer thin films with aligned nanofibers. In this article, we propose a strategy to control fibroin fibril formation by adjusting the assembly partner. Aligned fibroin fibrils were formed when chitosan was used as the counterpart, whereas no fibrils were observed when poly(allylamine hydrochloride) (PAH) was used. Charge density, which is higher in PAH, apparently stabilizes SF aggregates on the nanometer scale, thereby preventing their organization into fibrils. The drying step between the deposition of each layer was also crucial for film formation, as it stabilizes the SF molecules. Preliminary cell studies with optimized multilayers indicated that cell viability of NIH-3T3 fibroblasts remained between 90 and 100% after surface seeding, showing the potential application of the films in the biomedical field, as coatings and functional surfaces.

  3. Evidence for covalent attachment of phospholipid to the capsular polysaccharide of Haemophilus influenzae type b.

    PubMed Central

    Kuo, J S; Doelling, V W; Graveline, J F; McCoy, D W

    1985-01-01

    Cells of Haemophilus influenzae type b were grown in a liquid medium containing [3H]palmitate or [14C]ribose or both for two generations of exponential growth. Radiolabeled type-specific capsular polysaccharide, polyribosyl ribitol phosphate (PRP), was purified from the culture supernatant by Cetavlon precipitation, ethanol fractionation, and hydroxylapatite and Sepharose 4B chromatography. The doubly labeled ( [3H]palmitate and [14C]ribose) PRP preparation was found to coelute in a single peak from a Sepharose 4B column, suggesting that both precursors were incorporated into the purified PRP. A singly labeled ( [3H]palmitate) purified PRP preparation was found to be quantitatively immune precipitated by human serum containing antibody against PRP. The radioactivity of this preparation could not be dissociated from PRP by treatment with chloroform-methanol, 6 M urea, sodium dodecyl sulfate, or Zwittergent. Only after acid, alkaline, or phospholipase A2 treatment of PRP labeled with [3H]palmitate or [3H]palmitate and [14C]ribose followed by chloroform-methanol extraction could most of the 3H-radioactivity be recovered in the organic phase. The chloroform-soluble acid-hydrolyzed or phospholipase A2-treated product was identified as palmitic acid after thin-layer chromatography. These results strongly suggest that a phospholipid moiety is covalently associated with the H. influenzae type b polysaccharide PRP. Images PMID:3926752

  4. Evidence for covalent attachment of phospholipid to the capsular polysaccharide of Haemophilus influenzae type b

    SciTech Connect

    Kuo, J.S.; Doelling, V.W.; Graveline, J.F.; McCoy, D.W.

    1985-08-01

    Cells of Haemophilus influenzae type b were grown in a liquid medium containing (TH)palmitate or ( UC)ribose or both for two generations of exponential growth. Radiolabeled type-specific capsular polysaccharide, polyribosyl ribitol phosphate (PRP), was purified from the culture supernatant by Cetavlon precipitation, ethanol fractionation, and hydroxylapatite and Sepharose 4B chromatography. The doubly labeled ( (TH)palmitate and ( UC)ribose) PRP preparation was found to coelute in a single peak from a Sepharose 4B column, suggesting that both precursors were incorporated into the purified PRP. A singly labeled ( (TH)palmitate) purified PRP preparation was found to be quantitatively immune precipitated by human serum containing antibody against PRP. Only after acid, alkaline, or phospholipase A2 treatment of PRP labeled with (TH)palmitate or (TH)palmitate and ( UC)ribose followed by chloroform-methanol extraction could most of the TH-radioactivity be recovered in the organic phase. The chloroform-soluble acid-hydrolyzed or phospholipase A2-treated product was identified as palmitic acid after thin-layer chromatography. These results strongly suggest that a phospholipid moiety is covalently associated with the H. influenzae type b polysaccharide PRP.

  5. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Immobilization of Candida antarctica Lipase B by Covalent Attachment to Green Coconut Fiber

    NASA Astrophysics Data System (ADS)

    Brígida, Ana I. S.; Pinheiro, Álvaro D. T.; Ferreira, Andrea L. O.; Pinto, Gustavo A. S.; Gonçalves, Luciana R. B.

    The objective of this study was to covalently immobilize Candida antarctica type B lipase (CALB) onto silanized green coconut fibers. Variables known to control the number of bonds between enzyme and support were evaluated including contact time, pH, and final reduction with sodium borohydride. Optimal conditions for lipase immobilization were found to be 2h incubation at both pH 7.0 and 10.0. Thermal stability studies at 60°C showed that the immobilized lipase prepared at pH 10.0 (CALB-10) was 363-fold more stable than the soluble enzyme and 5.4-fold more stable than the biocatalyst prepared at pH 7.0 (CALB-7). CALB-7 was found to have higher specific activity and better stability when stored at 5°C. When sodium borohydride was used as reducing agent on CALB-10 there were no improvement in storage stability and at 60°C stability was reduced for both CALB-7 and CALB-10.

  7. Immobilization of Candida antarctica lipase B by covalent attachment to green coconut fiber.

    PubMed

    Brígida, Ana I S; Pinheiro, Alvaro D T; Ferreira, Andrea L O; Pinto, Gustavo A S; Gonçalves, Luciana R B

    2007-04-01

    The objective of this study was to covalently immobilize Candida antarctica type B lipase (CALB) onto silanized green coconut fibers. Variables known to control the number of bonds between enzyme and support were evaluated including contact time, pH, and final reduction with sodium borohydride. Optimal conditions for lipase immobilization were found to be 2 h incubation at both pH 7.0 and 10.0. Thermal stability studies at 60 degrees C showed that the immobilized lipase prepared at pH 10.0 (CALB-10) was 363-fold more stable than the soluble enzyme and 5.4-fold more stable than the biocatalyst prepared at pH 7.0 (CALB-7). CALB-7 was found to have higher specific activity and better stability when stored at 5 degrees C. When sodium borohydride was used as reducing agent on CALB-10 there were no improvement in storage stability and at 60 degrees C stability was reduced for both CALB-7 and CALB-10.

  8. Excited state interactions between the chiral Au38L24 cluster and covalently attached porphyrin.

    PubMed

    Varnholt, Birte; Letrun, Romain; Bergkamp, Jesse J; Fu, Yongchun; Yushchenko, Oleksandr; Decurtins, Silvio; Vauthey, Eric; Liu, Shi-Xia; Bürgi, Thomas

    2015-06-14

    A protected S-acetylthio porphyrin was synthesized and attached to the Au38(2-phenylethanethiolate)24 cluster in a ligand exchange reaction. Chiral high performance liquid chromatography of the functionalized cluster yielded enantiomeric pairs of clusters probably differing in the binding site of the porphyrin. As proven by circular dichroism, the chirality was maintained. Exciton coupling between the cluster and the chromophore is observed. Zinc can be incorporated into the porphyrin attached to the cluster, as evidenced by absorption and fluorescence spectroscopy, however, the reaction is slow. Quenching of the chromophore fluorescence is observed, which can be explained by energy transfer from the porphyrin to the cluster. Transient absorption spectra of Au38(2-phenylethanethiolate)24 and the functionalized cluster probe the bleach of the gold cluster due to ground state absorption and the characteristic excited state absorption signals. Zinc incorporation does not have a pronounced effect on the photophysical behaviour. Decay times are typical for the molecular behaviour of small monolayer protected gold clusters.

  9. 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

  10. Covalent heme attachment in Synechocystis hemoglobin is required to prevent ferrous heme dissociation

    PubMed Central

    Hoy, Julie A.; Smagghe, Benoit J.; Halder, Puspita; Hargrove, Mark S.

    2007-01-01

    Synechocystis hemoglobin contains an unprecedented covalent bond between a nonaxial histidine side chain (H117) and the heme 2-vinyl. This bond has been previously shown to stabilize the ferric protein against denaturation, and also to affect the kinetics of cyanide association. However, it is unclear why Synechocystis hemoglobin would require the additional degree of stabilization accompanying the His117–heme 2-vinyl bond because it also displays endogenous bis-histidyl axial heme coordination, which should greatly assist heme retention. Furthermore, the mechanism by which the His117–heme 2-vinyl bond affects ligand binding has not been reported, nor has any investigation of the role of this bond on the structure and function of the protein in the ferrous oxidation state. Here we report an investigation of the role of the Synechocystis hemoglobin His117–heme 2-vinyl bond on structure, heme coordination, exogenous ligand binding, and stability in both the ferrous and ferric oxidation states. Our results reveal that hexacoordinate Synechocystis hemoglobin lacking this bond is less stable in the ferrous oxidation state than the ferric, which is surprising in light of our understanding of pentacoordinate Hb stability, in which the ferric protein is always less stable. It is also demonstrated that removal of the His117–heme 2-vinyl bond increases the affinity constant for intramolecular histidine coordination in the ferric oxidation state, thus presenting greater competition for the ligand binding site and lowering the observed rate and affinity constants for exogenous ligands. PMID:17242429

  11. 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

  12. 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.

  13. 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.

  14. Optical anisotropy and sign reversal in layer-by-layer assembled films from chiral nanoparticles.

    PubMed

    Liang, Zhumei; Bernardino, Kalil; Han, Jishu; Zhou, Yunlong; Sun, Kai; de Moura, André F; Kotov, Nicholas A

    2016-10-06

    Chiral anisotropy and related optical effects at the nanoscale represent some of the most dynamic areas of nanomaterials today. Translation of optical activity of chiral semiconductor and metallic nanoparticles (NPs) into optoelectronic devices requires preparation of thin films from chiral NPs on both flat and curved surfaces. In this paper we demonstrate that chiral NP films can be made via layer-by-layer assembly (LBL) using negatively charged chiral CdS NPs, stabilized by d- and l-cysteine and positively charged polyelectrolytes, as building blocks. LBL coatings from NPs combine simplicity of preparation and strong optical activity. Circular extinction measurements using circular dichroism instruments indicate that the film possess four chiroptical bands at 280, 320, 350, and 390 nm. The latter two bands at 390 and 350 nm are associated with the band gap transitions (chiral excitons), while the former two are attributed to transitions involving surface ligands. When NPs are assembled in LBL films, the rotatory activity and the sign for circular extinction associated with the electronic transition in the inorganic core of the NPs is conserved. However, this is not true for circular extinction bands at short wavelengths: the sign of the rotatory optical activity is reversed. This effect is attributed to the change of the conformation of surface ligands in the polyelectrolyte matrix, which was confirmed both by semi-empirical and density functional (DFT) quantum mechanical calculations. Circular dichroism spectra calculated using a DFT algorithm closely match the experimental spectra of CdS NPs. These findings indicate that the spectroscopic methods sensitive to chirality of the surface ligands can be used to investigate fine structural changes in the surface layer of nanocolloids. Strong rotatory optical activity of nanostructured semiconductor films opens the possibilities for new polarization-based optical devices.

  15. Layer-by-layer deposition of rhenium-containing hyperbranched polymers and fabrication of photovoltaic cells.

    PubMed

    Tse, Chui Wan; Man, Ka Yan Kitty; Cheng, Kai Wing; Mak, Chris S K; Chan, Wai Kin; Yip, Cho Tung; Liu, Zheng Tong; Djurisić, Aleksandra B

    2007-01-01

    Multilayer thin films were prepared by the layer-by-layer (LBL) deposition method using a rhenium-containing hyperbranched polymer and poly[2-(3-thienyl)ethoxy-4-butylsulfonate] (PTEBS). The radii of gyration of the hyperbranched polymer in solutions with different salt concentrations were measured by laser light scattering. A significant decrease in molecular size was observed when sodium trifluoromethanesulfonate was used as the electrolyte. The conditions of preparing the multilayer thin films by LBL deposition were studied. The growth of the multilayer films was monitored by absorption spectroscopy and spectroscopic ellipsometry, and the surface morphologies of the resulting films were studied by atomic force microscopy. When the pH of a PTEBS solution was kept at 6 and in the presence of salt, polymer films with maximum thickness were obtained. The multilayer films were also fabricated into photovoltaic cells and their photocurrent responses were measured upon irradiation with simulated air mass (AM) 1.5 solar light. The open-circuit voltage, short-circuit current, fill factor, and power conversion efficiency of the devices were 1.2 V, 27.1 mu A cm(-2), 0.19, and 6.1x10(-3) %, respectively. The high open-circuit voltage was attributed to the difference in the HOMO level of the PTEBS donor and the LUMO level of the hyperbranched polymer acceptor. A plot of incident photon-to-electron conversion efficiency versus wavelength also suggests that the PTEBS/hyperbranched polymer junction is involved in the photosensitization process, in which a maximum was observed at approximately 420 nm. The relatively high capacitance, determined from the measured photocurrent rise and decay profiles, can be attributed to the presence of large counter anions in the polymer film.

  16. 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

  17. 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.

  18. Spontaneous surface flattening via layer-by-layer assembly of interdiffusing polyelectrolyte multilayers.

    PubMed

    Kim, Young Hun; Lee, Yong Man; Park, Juhyun; Ko, Min Jae; Park, Jong Hyeok; Jung, Woncheol; Yoo, Pil J

    2010-11-16

    We report a facile means to achieve planarization of nonflat or patterned surfaces by utilizing the layer-by-layer (LbL) assembly of highly diffusive polyelectrolytes. The polyelectrolyte pair of linear polyethylenimine (LPEI) and poly(acrylic acid) (PAA) is known to maintain intrinsic diffusive mobility atop or even inside ionically complexed films prepared by LbL deposition. Under highly hydrated and swollen conditions during the sequential film buildup process, the LbL-assembled film of LPEI/PAA undergoes a topological self-deformation for minimizing surface area to satisfy the minimum-energy state of the surface, which eventually induces surface planarization along with spontaneous filling of surface textures or nonflat structures. This result is clearly different from other cases of applying nondiffusive polyelectrolytes onto patterned surfaces or confined structures, wherein surface roughening or incomplete filling is developed with the LbL assembly. Therefore, the approach proposed in this study can readily allow for surface planarization with the deposition of a relatively thin layer of polyelectrolyte multilayers. In addition, this strategy of planarization was extended to the surface modification of an indium tin oxide (ITO) substrate, where surface smoothing and enhanced optical transmittance were obtained without sacrificing the electronic conductivity. Furthermore, we investigated the potential applicability of surface-treated ITO substrates as photoelectrodes of dye-sensitized solar cells prepared at room temperature. As a result, an enhanced photoconversion efficiency and improved device characteristics were obtained because of the synergistic role of polyelectrolyte deposition in improving the optical properties and acting as a blocking layer to prevent electron recombination with the electrolytes.

  19. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Electrochemical and electrochromic properties of layer-by-layer films from WO(3) and chitosan.

    PubMed

    Huguenin, Fritz; Gonzalez, Ernesto R; Oliveira, Osvaldo N

    2005-07-07

    The design of improved materials for electrochromic applications now involves extensive use of novel composites, thus requiring an investigation of the mechanisms responsible for electrochromism in these structures. Using films of WO(3) and chitosan produced with the layer-by-layer (LBL) technique, we demonstrate that characteristics such as the number of electrochemical active sites (K), the molar absorption coefficient (epsilon), and the electrochromic efficiency (eta) can be obtained using the quadratic logistic equation (QLE). The complexation ability between chitosan and WO(3) allowed the growth of visually uniform multilayers of the composite, with the same amount of material adsorbed in each deposition cycle. By fitting the absorbance changes (DeltaA) resulting from the electronic intervalence transfer from W(V) to W(VI) sites in four-bilayer LBL films of WO(3)/chitosan and WO(3)/chitosan with ethanol in the precursor dispersion, K was estimated to be ca. 5.5 x 10(-8) mol cm(-2) and 3.6 x 10(-8) mol cm(-2), respectively. The molar absorption coefficient and electrochromic efficiency vary with the charge injected because of the saturation of W(V) sites and the dissipation and feedback effects implicit in the QLE associated with ion-network interactions, such as the proton trapping effect. The LBL film of WO(3)/chitosan showed a smaller molar absorption coefficient and electrochromic efficiency than that containing ethanol because of a greater proton trapping effect for the LBL film with no ethanol. This enhanced trapping effect was seen as a decrease in the electronic flux involved in intervalence transfer in electrochemical impedance spectroscopy experiments.

  1. Pyrene biodegradation with layer-by-layer assembly bio-microcapsules.

    PubMed

    Deng, Fucai; Zhang, Zhengfang; Yang, Chen; Guo, Chuling; Lu, Guining; Dang, Zhi

    2017-04-01

    Biotechnology is considered as a promising technology for the removal of polycyclic aromatic hydrocarbons from the environment. Free bacteria are often sensitive to some biotic and abiotic factors in the environment to the extent that their ability to effect biodegradation of organic pollutants, such as polycyclic aromatic hydrocarbons, is hampered. Consequently, it is imperative to carry out investigations into biological systems that will obviate or aid tolerance of bacteria to harsh environmental conditions. Chitosan/alginate bio-microcapsules produced using layer-by-layer (LBL) assembly method were tested for pyrene (PYR) biodegradation under harsh environmental conditions. Morphology observation indicated that the flake bio-microcapsules could be successfully prepared through LBL assembly method. Surface analysis showed that the bio-microcapsules had large fractions of mesopores. The results of the biodegradation experiments revealed that the 95% of 10mgL(-1) PYR could be removed by the bacteria encapsulated chitosan/alginate bio-microcapsules in 3 days, which was higher than that of the free bacteria (59%). Compared to the free cells, the bacteria encapsulated chitosan/alginate bio-microcapsules produced 1-6 times higher PYR biodegradation rates at a high initial PYR concentration (50mgL(-1)) and extremely low pH values (pH =3) or temperatures (10°C or 40°C), as well as high salt stress. The results indicated that bacteria in microcapsules treatment gained a much higher tolerance to environmental stress and LBL bio-microcapsule could be promising candidate for remediating the organic pollutants. Copyright © 2016 Elsevier Inc. All rights reserved.

  2. Tunable staged release of therapeutics from layer-by-layer coatings with clay interlayer barrier.

    PubMed

    Min, Jouha; Braatz, Richard D; Hammond, Paula T

    2014-03-01

    In developing new generations of coatings for medical devices and tissue engineering scaffolds, there is a need for thin coatings that provide controlled sequential release of multiple therapeutics while providing a tunable approach to time dependence and the potential for sequential or staged release. Herein, we demonstrate the ability to develop a self-assembled, polymer-based conformal coating, built by using a water-based layer-by-layer (LbL) approach, as a dual-purpose biomimetic implant surface that provides staggered and/or sustained release of an antibiotic followed by active growth factor for orthopedic implant applications. This multilayered coating consists of two parts: a base osteoinductive component containing bone morphogenetic protein-2 (rhBMP-2) beneath an antibacterial component containing gentamicin (GS). For the fabrication of truly stratified composite films with the customized release behavior, we present a new strategy-implementation of laponite clay barriers-that allows for a physical separation of the two components by controlling interlayer diffusion. The clay barriers in a single-component GS system effectively block diffusion-based release, leading to approximately 50% reduction in bolus doses and 10-fold increase in the release timescale. In a dual-therapeutic composite coating, the top GS component itself was found to be an effective physical barrier for the underlying rhBMP-2, leading to an order of magnitude increase in the release timescale compared to the single-component rhBMP-2 system. The introduction of a laponite interlayer barrier further enhanced the temporal separation between release of the two drugs, resulting in a more physiologically appropriate dosing of rhBMP-2. Both therapeutics released from the composite coating retained their efficacy over their established release timeframes. This new platform for multi-drug localized delivery can be easily fabricated, tuned, and translated to a variety of implant applications

  3. Synthesis and characterization of novel forward osmosis membranes based on layer-by-layer assembly.

    PubMed

    Saren, Qi; Qiu, Chang Quan; Tang, Chuyang Y

    2011-06-15

    Forward osmosis (FO) has received considerable interest for water- and energy-related applications in recent years. FO does not require an applied pressure and is believed to have a low fouling tendency. However, a major challenge in FO is the lack of high performance FO membranes. In the current work, novel nanofiltration (NF)-like FO membranes with good magnesium chloride retention were synthesized using layer-by-layer (LbL) assembly. The membrane substrate was tailored (high porosity, finger-like pores, thin cross-section, and high hydrophilicity) to achieve a small structural parameter of 0.5 mm. Increasing the number of polyelectrolyte layers improved the selectivity of the LbL membranes while reducing their water permeability. The more selective membrane 6#LbL (with 6 polyelectrolyte layers) had much lower reverse solute transport compared to 3#LbL and 1#LbL. Meanwhile, the FO water flux was found to be strongly affected by both membrane water permeability and solute reverse transport. Severe solute reverse transport was observed for the active-layer-facing-draw-solution membrane orientation, likely due to the suppression of Donnan exclusion as a result of the high ionic strength of the draw solution. In contrast, the active-layer-facing-feed-solution orientation showed remarkable FO performance (15, 20, and 28 L/m².h at 0.1, 0.5, and 1.0 M MgCl₂, respectively, for membrane 3#LbL using distilled water as feed solution), superior to other NF-like FO membranes reported in the literature. To the best of the knowledge of the authors, this is the first work on the synthesis and characterization of LbL based FO membranes.

  4. 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

    2014-11-03

    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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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.

  6. 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.

  7. 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.

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

    PubMed Central

    Chen, Jun; Kuncewicz, Thomas; Kharlampieva, Eugenia; Godin, Biana

    2015-01-01

    Blood-borne objects display a non-spherical 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 (LbL) 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 5-bilayer (TA/PVPON) core-shells, hollow shells are unrecognized by J774A.1 macrophages yet interact with endothelial and breast cancer cells. Internalization of cubical shells by HMVEC (endothelial) is 5-fold more efficient and 6- and 2.5-fold more efficient for 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

  9. Electrochemistry of ATP-capped silver nanoparticles in layer-by-layer multilayer films

    NASA Astrophysics Data System (ADS)

    Singh, Poonam; Solomon, Virgil C.; Buttry, Daniel A.

    2014-07-01

    Colloidal silver nanoparticles (Ag NPs) capped with adenosine triphosphate (ATP) were prepared using borohydride reduction of Ag+ in the presence of ATP. Subsequent characterization was done using transmission electron microscopy/high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, and non-contact atomic force microscopy (NcAFM) confirming the size and composition of the Ag NPs. This report focuses on two topics: (1) the change in NP size and properties as a function of molar ratios of Ag+ to ATP capping ligand to BH4 - reductant, and (2) the electrochemical behavior of the NPs in layer-by-layer (LbL) multilayer films. On the basis of electrostatic interaction between negatively charged phosphate groups on Ag NPs and positively charged poly(diallyldimethylammonium) hydrochloride, NPs were immobilized on 3-mercaptopropionic acid (MCP)-functionalized gold electrodes using LbL assembly method followed by characterization of the film using NcAFM. Furthermore, the redox chemistry for phase transformations of immobilized Ag NPs to AgCl or Ag2O in multilayer films was examined using cyclic voltammetry (CV) in NaOH and NaCl solutions. A non-linear increase of charge with an increase in the number of bilayers in the film was observed up to five layers. Underpotential deposition of Pb on multilayer film of Ag NPs confirmed the presence of Ag in multilayer films. The stability of the LbL film toward electrochemical cycling to higher potentials (i.e., +0.8 V) in NaOH solutions was evaluated.

  10. Fabrication of hierarchical hybrid structures using bio-enabled layer-by-layer self-assembly.

    PubMed

    Hnilova, Marketa; Karaca, Banu Taktak; Park, James; Jia, Carol; Wilson, Brandon R; Sarikaya, Mehmet; Tamerler, Candan

    2012-05-01

    Development of versatile and flexible assembly systems for fabrication of functional hybrid nanomaterials with well-defined hierarchical and spatial organization is of a significant importance in practical nanobiotechnology applications. Here we demonstrate a bio-enabled self-assembly technique for fabrication of multi-layered protein and nanometallic assemblies utilizing a modular gold-binding (AuBP1) fusion tag. To accomplish the bottom-up assembly we first genetically fused the AuBP1 peptide sequence to the C'-terminus of maltose-binding protein (MBP) using two different linkers to produce MBP-AuBP1 hetero-functional constructs. Using various spectroscopic techniques, surface plasmon resonance (SPR) and localized surface plasmon resonance (LSPR), we verified the exceptional binding and self-assembly characteristics of AuBP1 peptide. The AuBP1 peptide tag can direct the organization of recombinant MBP protein on various gold surfaces through an efficient control of the organic-inorganic interface at the molecular level. Furthermore using a combination of soft-lithography, self-assembly techniques and advanced AuBP1 peptide tag technology, we produced spatially and hierarchically controlled protein multi-layered assemblies on gold nanoparticle arrays with high molecular packing density and pattering efficiency in simple, reproducible steps. This model system offers layer-by-layer assembly capability based on specific AuBP1 peptide tag and constitutes novel biological routes for biofabrication of various protein arrays, plasmon-active nanometallic assemblies and devices with controlled organization, packing density and architecture.

  11. 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.

  12. 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.

  13. Layer-by-layer self-assembly of ceramic particles for complex shape coating synthesis

    NASA Astrophysics Data System (ADS)

    Qiu, Hongwei

    Layer-by-layer (LbL) self-assembly was explored as a non-line-of-sight method for uniform infiltration and deposition of a multilayer of ceramic particles into complex structures. Key parameters for controlling the LbL self-assembly process were studied using a model system which consisted of a silicon substrate, 100 nm and 500 nm silica particles, and a polycation/polyanion combination. We correlated the surface coverage of the silica particles to the NaCl concentration used in deposition of the polyelectrolyte layers and to the number of the polyelectrolyte layers deposited. The effect of particle size on the surface coverage was rationally explained based on the screening length. We found that the effects of particle size, polydispersity, and electrolyte concentration in the particle suspension on the surface coverage and morphology of the first silica particle layer deposited on the polyelectrolyte layer surface were highly coupled, and resolving these effects was important for infiltrating a uniform coating of multilayer silica particle assemblies into a cellular structure as an ultimate complex substrate. Based on this understanding, the Lbl, self-assembly method was applied as a method of assembling, infiltrating, and immobilizing a 4-layer coating of negatively charged ˜3 mum Pd/NaAI(Si)O catalyst particles in the confined space of the cellular structure with ˜400 mum interconnected cells. The 4-layer coating deposited on the inner wall of a stainless steel capillary tube was mechanically stable under water flow rate up to 10 ml/min over the pH range of 3 to 11. Scotch tape peeling evaluation suggested that failure locations were mostly within the catalyst particle assembly, but near the assembly-PEM interface region.

  14. Formation of multilayered structures in the layer by layer deposition of colloid particles.

    PubMed

    Adamczyk, Zbigniew; Weroński, Paweł; Barbasz, Jakub

    2008-01-01

    Theoretical calculations of particle film formation in the layer by layer (LbL) self-assembling processes have been performed according to the generalized random sequential adsorption (RSA) scheme. The first (precursor) layer was generated using the standard RSA scheme pertinent to homogeneous surface. Formation of the consecutive layers (up to twenty) was simulated for two kinds of particles of equal size. The interaction of two particles of different kind resulted in irreversible and localized adsorption upon contact, whereas particles of the same kind were assumed to interact via the hard potential (no adsorption possible). Using this algorithm particle coverage (2D density) and volume fraction (3D density) were calculated as well as the film thickness as a function of the number of layers. Additionally, the structure of the film was quantitatively characterized in terms of the 2D and 3D pair correlation functions. The simulations revealed that particle concentration distribution in the film was more uniform for low precursor layer density than for higher density, where well-defined layers of closely packed particles appeared. It was also predicted theoretically that the averaged value of particle volume fraction in the uniform film region was rho(LbL)=0.42, which is very close to the maximum packing density equal to 0.382 predicted from the 3D RSA model. On the other hand, the roughness of the film was the lowest at the highest precursor layer density. It was shown that for low precursor layer density the film thickness increased with the number of layers in a nonlinear way. However, for high precursor layer density, the film thickness increased linearly with the number of layers and the average layer thickness was close to the hexagonal layer thickness equal to 1.73a p. It was concluded that our theoretical results can be effectively exploited for interpretation of the LbL processes involving colloid particles and polyelectrolytes.

  15. A layer-by-layer approach to natural polymer-derived bioactive coatings on magnesium alloys.

    PubMed

    Kunjukunju, Sangeetha; Roy, Abhijit; Ramanathan, Madhumati; Lee, Boeun; Candiello, Joe E; Kumta, Prashant N

    2013-11-01

    The development of polyelectrolyte multilayered coatings on magnesium alloy substrates that can be used for controlled delivery of growth factors and required biomolecules from the surface of these degradable implants could have a significant impact in the field of bone tissue regeneration. The current work reports on the fabrication of multilayered coatings of alginate and poly-L-lysine on alkaline- and fluoride-pretreated AZ31 substrates using a layer-by-layer (LbL) technique under physiological conditions. Furthermore, these coatings were surface functionalized by chemical cross-linking and fibronectin immobilization, and the resultant changes in surface properties have been shown to influence the cellular activity of these multilayered films. The physicochemical characteristics of these coated substrates have been investigated using attenuated total reflectance Fourier transform infrared spectroscopy, atomic force microscopy, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Cytocompatibility studies using MC3T3-E1 osteoblasts show that the fluoride-pretreated, cross-linked and fibronectin-immobilized LbL-coated substrates are more bioactive and less cytotoxic than the hydroxide-pretreated, cross-linked and fibronectin-immobilized LbL-coated samples. The in vitro degradation results show that the multilayered coatings of these natural polysaccharide- and synthetic polyamino acid-based polyelectrolytes do not alter the degradation kinetics of the substrates; however, the pretreatment conditions have a significant impact on the overall coating degradation behavior. These preliminary results collectively show the potential use of LbL coatings on magnesium-based degradable scaffolds to improve their surface bioactivity.

  16. 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.

  17. Tunable Staged Release of Therapeutics from Layer-by-Layer Coatings with Clay Interlayer Barrier

    PubMed Central

    Min, Jouha; Braatz, Richard D.; Hammond, Paula T.

    2014-01-01

    In developing new generations of coatings for medical devices and tissue engineering scaffolds, there is a need for thin coatings that provide controlled sequential release of multiple therapeutics while providing a tunable approach to time dependence and the potential for sequential or staged release. Herein, we demonstrate the ability to develop a self-assembled, polymer-based conformal coating, built by using a water-based layer-by-layer (LbL) approach, as a dual-purpose biomimetic implant surface that provides staggered and/or sustained release of an antibiotic followed by active growth factor for orthopedic implant applications. This multilayered coating consists of two parts: a base osteoinductive component containing bone morphogenetic protein-2 (rhBMP-2) beneath an antibacterial component containing gentamicin (GS). For the fabrication of truly stratified composite films with the customized release behavior, we present a new strategy—implementation of laponite clay barriers—that allows for a physical separation of the two components by controlling interlayer diffusion. The clay barriers in a single-component GS system effectively block diffusion-based release, leading to approximately 50% reduction in bolus doses and 10-fold increase in the release timescale. In a dual-therapeutic composite coating, the top GS component itself was found to be an effective physical barrier for the underlying rhBMP-2, leading to an order of magnitude increase in the release timescale compared to the single-component rhBMP-2 system. The introduction of a laponite interlayer barrier further enhanced the temporal separation between release of the two drugs, resulting in a more physiologically appropriate dosing of rhBMP-2. Both therapeutics released from the composite coating retained their efficacy over their established release timeframes. This new platform for multi-drug localized delivery can be easily fabricated, tuned, and translated to a variety of implant

  18. 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

  19. Thermal transitions in hydrated layer-by-layer assemblies observed using electrochemical impedance spectroscopy.

    PubMed

    Sung, Choonghyun; Hearn, Katelin; Lutkenhaus, Jodie

    2014-09-14

    Layer-by-layer (LbL) assemblies have been of great interest due to their versatile functionality and ease of fabrication, but their response to temperature is not completely understood. It has been recently shown that hydrated LbL assemblies of poly(diallyldimethylammonium chloride) (PDAC) and poly(styrene sulfonate) (PSS) under go a thermal transition much like a "glass-melt" transition. This thermal transition is of great interest because many LbL applications are found in water. Here, we report upon the nature of this thermal transition as probed using electrochemical impedance spectroscopy (EIS) as a function of assembly salt concentration, film thickness, and outermost layer. EIS reveals that the transition is signified by a structural rearrangement of virtual pores, resulting in increased conductivity and decreased surface coverage of the electrode. Two separate thermal transitions are obtained from changes in the film resistance (Ttr,Rf) and the charge transfer resistance (Ttr,Rct). Only Ttr,Rct is strongly dependent on film thickness, salt concentration, and outermost layer, for which values ranging from 50 to 64 °C were observed. As the assembly salt concentration increases from 0.5 M to 1.0 M NaCl, Ttr,Rct increases by about 10 °C. Below 20 layers, deviations of Ttr,Rct with respect to outermost layer appear, in which PSS-capped LbL films tend to show elevated Ttr,Rct values. These results suggest that extrinsic charge compensation plays a large role in the value of Ttr,Rct in which a large degree of extrinsic charge compensation drives Ttr,Rct towards higher values. On the other hand, Ttr,Rf is largely unaffected by assembly parameters, and closer in value to prior reports via calorimetry and quartz crystal microbalance with dissipation.

  20. 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

  1. 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.

  2. 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 Central

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

    2015-01-01

    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

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

  6. Layer-by-layer self-assembly of PDDA/PWA-Nafion composite membranes for direct methanol fuel cells.

    PubMed

    Yang, Meng; Lu, Shanfu; Lu, Jinlin; Jiang, San Ping; Xiang, Yan

    2010-03-07

    A novel PDDA/PWA-Nafion composite electrolyte membrane with enhanced proton conductivity (sigma) to methanol permeability (P) ratio, sigma/P, was fabricated by layer-by-layer self-assembly of negatively charged water soluble PWA and positively charged polyelectrolyte PDDA.

  7. Supramolecular polymerization at the interface: layer-by-layer assembly driven by host-enhanced π-π interaction.

    PubMed

    Yang, Hui; Ma, Zhan; Yuan, Bin; Wang, Zhiqiang; Zhang, Xi

    2014-10-04

    Host-enhanced π-π interaction as a new driving force was used for fabricating layer-by-layer (LbL) films. This kind of LbL assembly can be regarded as a sort of supramolecular polymerization at the interface and its degree of supramolecular polymerization can be controlled efficiently by adjusting layer pairs similar to living polymerization in solution.

  8. 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

  9. Layer-by-layer nanoparticles as an efficient siRNA delivery vehicle for SPARC silencing.

    PubMed

    Tan, Yang Fei; Mundargi, Raghavendra C; Chen, Min Hui Averil; Lessig, Jacqueline; Neu, Björn; Venkatraman, Subbu S; Wong, Tina T

    2014-05-14

    Efficient and safe delivery systems for siRNA therapeutics remain a challenge. Elevated secreted protein, acidic, and rich in cysteine (SPARC) protein expression is associated with tissue scarring and fibrosis. Here we investigate the feasibility of encapsulating SPARC-siRNA in the bilayers of layer-by-layer (LbL) nanoparticles (NPs) with poly(L-arginine) (ARG) and dextran (DXS) as polyelectrolytes. Cellular binding and uptake of LbL NPs as well as siRNA delivery were studied in FibroGRO cells. siGLO-siRNA and SPARC-siRNA were efficiently coated onto hydroxyapatite nanoparticles. The multilayered NPs were characterized with regard to particle size, zeta potential and surface morphology using dynamic light scattering and transmission electron microscopy. The SPARC-gene silencing and mRNA levels were analyzed using ChemiDOC western blot technique and RT-PCR. The multilayer SPARC-siRNA incorporated nanoparticles are about 200 nm in diameter and are efficiently internalized into FibroGRO cells. Their intracellular fate was also followed by tagging with suitable reporter siRNA as well as with lysotracker dye; confocal microscopy clearly indicates endosomal escape of the particles. Significant (60%) SPARC-gene knock down was achieved by using 0.4 pmole siRNA/μg of LbL NPs in FibroGRO cells and the relative expression of SPARC mRNA reduced significantly (60%) against untreated cells. The cytotoxicity as evaluated by xCelligence real-time cell proliferation and MTT cell assay, indicated that the SPARC-siRNA-loaded LbL NPs are non-toxic. In conclusion, the LbL NP system described provides a promising, safe and efficient delivery platform as a non-viral vector for siRNA delivery that uses biopolymers to enhance the gene knock down efficiency for the development of siRNA therapeutics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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

    2015-02-03

    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

  11. 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

  12. 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

  13. 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

  14. Facile Method for the Site-Specific, Covalent Attachment of full-length IgG onto Nanoparticles

    PubMed Central

    Hui, James Zhe; Al Zaki, Ajlan; Cheng, Zhiliang; Popik, Vladimir; Zhang, Hongtao; Luning Prak, Eline T.

    2014-01-01

    Antibodies, most commonly IgGs, have been widely used as targeting ligands in research and therapeutic applications due to their wide array of targets, high specificity and proven efficacy. Many of these applications require antibodies to be conjugated onto surfaces (e.g. nanoparticles and microplates); however, most conventional bioconjugation techniques exhibit low crosslinking efficiencies, reduced functionality due to non-site-specific labeling and random surface orientation, and/or require protein engineering (e.g. cysteine handles), which can be technically challenging. To overcome these limitations, we have recombinantly expressed Protein Z, which binds the Fc region of IgG, with an UV active non-natural amino acid benzoylphenyalanine (BPA) within its binding domain. Upon exposure to long wavelength UV light, the BPA is activated and forms a covalent link between the Protein Z and the bound Fc region of IgG. This technology was combined with expressed protein ligation (EPL), which allowed for the introduction of a fluorophore and click chemistry-compatible azide group onto the C-terminus of Protein Z during the recombinant protein purification step. This enabled crosslinked-Protein Z-IgG complexes to be efficiently and site-specifically attached to aza-dibenzycyclooctyne-modified nanoparticles, via copper-free click chemistry. PMID:24729432

  15. 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.

  16. 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

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

    PubMed

    Clafshenkel, William P; Murata, Hironobu; Andersen, Jill; Creeger, Yehuda; Koepsel, Richard R; 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.

  18. Site-specific, covalent attachment of poly(dT)-modified peptides to solid surfaces for microarrays.

    PubMed

    Kimura, Naoki; Okegawa, Takashi; Yamazaki, Kiyokazu; Matsuoka, Koji

    2007-01-01

    The present study reported proof-of-principle for a kinase assay approach that can detect specific peptide phosphorylation events. The method involves attachment of peptides onto commercial aminosilane and polycarbodiimide-coated glass slides, using a newly developed DNattach linker system that consists of a poly(dT) tail (Nisshinbo Industries Inc.), followed by a detection step using fluorescently labeled antiphosphoamino acid antibodies. The linker-modified peptides are efficiently synthesized by Michael addition between maleimido-modified peptides and thiol-containing DNattach. Specific covalent immobilization of the modified peptides onto aminosilane and poly carbodiimide-coated slides is then achieved by short exposure to UV-light. Highly selective and quantitative recognition by standard antiphosphoamino acid antibodies (antiphosphotyrosine and anti-phosphoGFAP) and kinases (c-Src and PKA) to the corresponding modified peptides on the microarray spots is demonstrated. Furthermore, we found that this immobilization method provides greater signal-to-noise ratio and better discrimination ability of phosphorylated amino acids than does the conventional immobilization technique. The phosphorylation pattern of target sequences, detected using fluorescently labeled antiphosphoamino acid antibodies, revealed that the linker system preference of the kinase is determined by its activity profile.

  19. Covalent attachment of lipid vesicles to a fluid supported bilayer allows observation of DNA-mediated vesicle interactions

    PubMed Central

    van Lengerich, Bettina; Rawle, Robert J.; Boxer, Steven G.

    2010-01-01

    Specific membrane interactions such as lipid vesicle docking and fusion can be mediated by synthetic DNA-lipid conjugates as a model for the protein-driven processes that are ubiquitous in biological systems. Here we present a method of tethering vesicles to a supported lipid bilayer that allows simultaneous deposition of cognate vesicle partners displaying complementary DNA, resulting in well-mixed populations of tethered vesicles that are laterally mobile. Vesicles are covalently attached to a supporting lipid bilayer using a DNA-templated click reaction; then DNA-mediated interactions between tethered vesicles are triggered by spiking the salt concentration. These interactions, such as docking and fusion, can then be observed for individual vesicles as they collide on the surface. The architecture of this new system also permits control over the number of lipid anchors that tether the vesicle to the supporting bilayer. The diffusion coefficient of tethered vesicles anchored by two lipids is approximately 1.6-fold slower than that of vesicles anchored only with a single lipid, consistent with a simple physical model. PMID:20180548

  20. Covalent attachment of lipid vesicles to a fluid-supported bilayer allows observation of DNA-mediated vesicle interactions.

    PubMed

    van Lengerich, Bettina; Rawle, Robert J; Boxer, Steven G

    2010-06-01

    Specific membrane interactions such as lipid vesicle docking and fusion can be mediated by synthetic DNA-lipid conjugates as a model for the protein-driven processes that are ubiquitous in biological systems. Here we present a method of tethering vesicles to a supported lipid bilayer that allows the simultaneous deposition of cognate vesicle partners displaying complementary DNA, resulting in well-mixed populations of tethered vesicles that are laterally mobile. Vesicles are covalently attached to a supporting lipid bilayer using a DNA-templated click reaction; then DNA-mediated interactions between tethered vesicles are triggered by spiking the salt concentration. These interactions, such as docking and fusion, can then be observed for individual vesicles as they collide on the surface. The architecture of this new system also permits control over the number of lipid anchors that tether the vesicle to the supporting bilayer. The diffusion coefficient of tethered vesicles anchored by two lipids is approximately 1.6-fold slower than that of vesicles anchored only with a single lipid, consistent with a simple physical model.

  1. 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.

  2. Covalent attachment of flavin adenine dinucleotide (FAD) and flavin mononucleotide (FMN) to enzymes: the current state of affairs.

    PubMed Central

    Mewies, M.; McIntire, W. S.; Scrutton, N. S.

    1998-01-01

    The first identified covalent flavoprotein, a component of mammalian succinate dehydrogenase, was reported 42 years ago. Since that time, more than 20 covalent flavoenzymes have been described, each possessing one of five modes of FAD or FMN linkage to protein. Despite the early identification of covalent flavoproteins, the mechanisms of covalent bond formation and the roles of the covalent links are only recently being appreciated. The main focus of this review is, therefore, one of mechanism and function, in addition to surveying the types of linkage observed and the methods employed for their identification. Case studies are presented for a variety of covalent flavoenzymes, from which general findings are beginning to emerge. PMID:9514256

  3. 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

  4. 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

  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

    2016-06-05

    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. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

    Uğur, Şule S.; Sarıışık, Merih; Aktaş, A. Hakan; Uçar, M. Çiğdem; Erden, Emre

    2010-07-01

    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.

  7. 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

  8. Novel electrochemical sensors with electrodes based on multilayers fabricated by layer-by-layer synthesis and their analytical potential

    NASA Astrophysics Data System (ADS)

    Ermakov, S. S.; Nikolaev, K. G.; Tolstoy, V. P.

    2016-08-01

    The results of studies on layer-by-layer synthesis of multilayers on the electrode surface in order to design electrochemical sensors for the determination of concentrations of inorganic, organic and bioorganic compounds are summarized and analyzed. The principle of the method is discoursed and the key advantages of the approach are highlighted, such as the possibility of single layer synthesis with specified thickness and composition under mild conditions with further fabrication of multilayers. Charge transfer conditions in the layers on the electrode surface between the analyte molecules and electrode redox centres and the operating conditions for the optimal electrode are considered. The role of electrocatalysts and intermediates of these processes is noted. Particular attention is devoted to the methods for synthesis of gold nanoparticles with different diameters. Analytical characteristics for electrochemical sensors are presented and application prospects of the layer-by-layer synthesis to electrode fabrication are discussed. The bibliography includes 241 references.

  9. Layer-by-layer construction of the heparin/fibronectin coatings on titanium surface:stability and functionality

    NASA Astrophysics Data System (ADS)

    Li, Guicai; Yang, Ping; Huang, Nan

    Layer-by-layer assembly as a versatile bottom-up nanofabrication technique has been widely used in the development of biomimetic materials with superior mechanical and biological properties. In this study, layer-by-layer assembled heparin/fibronectin biofunctional films were fabricated on titanium (Ti) surface to enhance the blood anticoagulation and accelerate the endothelialization simultaneously. The wettability and chemical changes of the assembled films were investigated by static water contact angle measurement and fourier transform infrared spectroscopy (FTIR). The morphology of modified Ti surfaces were observed using scanning electron microscopy (SEM). The real time assembly process was in-situ monitored by quartz crystal microbalance with dissipation (QCM-D). The stability of the films was evaluated by measuring the changes in wettability and the quantity of heparin and fibronectin on the surfaces. The anticoagulation properties of the films were quantitatively rated using Activated partial thromboplastin time (APTT) analysis. New peaks of hydroxyl and amino group were observed on the assembled Ti srufaces by FTIR. The contact angles varied among the films with different bilayer numbers, indicating the successful graft of the heparin and fibronectin layer-by-layer. QCM-D results showed that the frequency shift increased with the bilayer numbers, and the heparin and fibronectin could form multilayers. The assembly films were stable after incubation in PBS for 24 h based on the results of the contact angle measurement and the quantity of heparin and fibronectin analysis. APTT results suggested that the assembled films kept excellent antithrombotic properties. All these results revealed that the assembled heparin/fibronectin films with stabiltiy and anticoagulation property could be firmly formed on titanium surfaces. Our study further demonstrates that layer-by-layer assembly of heparin and fibronectin will provide a potential and effective tool for

  10. Scalable manufacture of built-to-order nanomedicine: spray-assisted layer-by-layer functionalization of PRINT nanoparticles.

    PubMed

    Morton, Stephen W; Herlihy, Kevin P; Shopsowitz, Kevin E; Deng, Zhou J; Chu, Kevin S; Bowerman, Charles J; Desimone, Joseph M; Hammond, Paula T

    2013-09-14

    Scalable methods, PRINT particle fabrication, and spray-assisted Layer-by-Layer deposition are combined to generate uniform and functional nanotechnologies with precise control over composition, size, shape, and surface functionality. A modular and tunable approach towards design of built-to-order nanoparticle systems, spray coating on PRINT particles is demonstrated to achieve technologies capable of targeted interactions with cancer cells for applications in drug delivery. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Cu and Cu(Mn) films deposited layer-by-layer via surface-limited redox replacement and underpotential deposition

    NASA Astrophysics Data System (ADS)

    Fang, J. S.; Sun, S. L.; Cheng, Y. L.; Chen, G. S.; Chin, T. S.

    2016-02-01

    The present paper reports Cu and Cu(Mn) films prepared layer-by-layer using an electrochemical atomic layer deposition (ECALD) method. The structure and properties of the films were investigated to elucidate their suitability as Cu interconnects for microelectronics. Previous studies have used primarily a vacuum-based atomic layer deposition to form a Cu metallized film. Herein, an entirely wet chemical process was used to fabricate a Cu film using the ECALD process by combining underpotential deposition (UPD) and surface-limited redox replacement (SLRR). The experimental results indicated that an inadequate UPD of Pb affected the subsequent SLRR of Cu and lead to the formation of PbSO4. A mechanism is proposed to explain the results. Layer-by-layer deposition of Cu(Mn) films was successfully performed by alternating the deposition cycle-ratios of SLRR-Cu and UPD-Mn. The proposed self-limiting growth method offers a layer-by-layer wet chemistry-based deposition capability for fabricating Cu interconnects.

  12. 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.

  13. Influence of layer-by-layer assembled electrospun poly (L-lactic acid) nanofiber mats on the bioactivity of endothelial cells

    NASA Astrophysics Data System (ADS)

    Wu, Keke; Zhang, Xiazhi; Yang, Wufeng; Liu, Xiaoyan; Jiao, Yanpeng; Zhou, Changren

    2016-12-01

    Electrospun poly(L-lactic acid) (PLLA) nanofiber mats were successfully modified by deposition of multilayers with chitosan (CS), heparin (Hep) and graphene oxide (GO) through electrostatic layer-by-layer (LBL) self-assembly method. In this study, the surface properties of PLLA nanofiber mats before and after modification were investigated via scanning electron microscope (SEM), atomic force microscopy (AFM), attenuated total reflectance fourier transformation infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. In addition, the cytocompatibility of the modified PLLA nanofiber mats were investigated by testing endothelial cells compatibility, including cell attachment, cell proliferation and cell cycle. The results revealed that the surfaces of modified PLLA nanofiber mats become much rougher, stifiness and the hydrophilicity of the LBL modified PLLA nanofiber mats were improved compared to original PLLA one. Moreover, the modified PLLA nanofiber mats had promoted the endothelial cells viability attachment significantly. Besides, we studied the PLLA nanofiber mats on the expression of necrosis factor (TNF-α), interleukine-1β (IL-1β), monocyte chemoattractant protein-1 (MCP-1) and vascular cell adhesion molecule-1 (VCAM-1) in endothelial cells. The results showed that modified PLLA nanofiber mats had inhibited the inflammatory response to some extent.

  14. 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.

  15. 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

    2015-12-07

    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.

  16. 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.

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

    PubMed

    Carosio, F; Alongi, J

    2016-03-01

    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.

  18. Influence of annealing on composition and optical properties of CdTe nanoparticle layer-by-layer films.

    PubMed

    Briscoe, Joe; Gallardo, Diego E; Lesnyak, Vladimir; Dunn, Steve

    2011-06-01

    CdTe nanoparticle-polymer composite films were deposited conformally using a layer-by-layer (LbL) process onto planar or ZnO nanorod-coated substrates. Films were annealed between 150-450 degrees C. Under air this led to oxidation of the nanoparticles while under vacuum their composition was retained. Annealing at 450 degrees C led to complete removal of the polymer with a loss of quantum confinement as shown by UV-vis spectroscopy. Annealing at 350 degrees C gave partial removal of the polymer and retained quantum confinement. Such annealed nanoparticle composite systems may have application in photovoltaics.

  19. 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

    2012-11-07

    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.

  20. Electromotive force measurements in the combustion wave front during layer-by-layer surface laser sintering of exothermic powder compositions.

    PubMed

    Shishkovskiy, Igor V; Morozov, Yury G; Kuznetsov, Maxim V; Parkin, Ivan P

    2009-05-14

    Electric potentials arise between the combustion wave front and final products during layer-by-layer surface laser sintering of exothermic powder compositions (Ni-Ti, Ni-Al, Ti-Al). By using an analog-digital-analog converter to control the laser movement and hence the exothermic reaction itself, we show that near optimal conditions can be obtained for the formation of layered 3D articles. Comparative results of the structural-phase transformations that occur during laser-controlled SHS in related reaction-capable compositions are also presented.

  1. Evaluation of the maximum speed of layer-by-layer heterodyne analysis of light scattering characteristics in volume optical media

    NASA Astrophysics Data System (ADS)

    Tverdokhleb, P. E.; Shchepetkin, Yu. A.

    2017-03-01

    A method of layer-by-layer heterodyne analysis of volume optical media is described. The results of a theoretical evaluation, computer modeling, and experimental investigation of the dependence of the maximum speed of the analysis on the parameters of the optical circuit and medium are given. The effect of the analysis speed on the resolution of the method along the thickness of the optical medium and on the pattern of the dependence of the output signal on the depth of the studied layer is evaluated. A method for increasing the maximum scanning speed is proposed. The obtained results are confirmed experimentally..

  2. Catalytic membranes prepared using layer-by-layer adsorption of polyelectrolyte/metal nanoparticle films in porous supports.

    PubMed

    Dotzauer, David M; Dai, Jinhua; Sun, Lei; Bruening, Merlin L

    2006-10-01

    Layer-by-layer adsorption of polyelectrolytes and gold nanoparticles within porous supports provides a convenient method for forming catalytic membranes. The polyelectrolyte film effectively immobilizes the gold nanoparticles without inhibiting access to catalytic sites, as shown by the similar rate constants for nanoparticle-catalyzed 4-nitrophenol reduction in solution and in membranes. Modified alumina membranes reduce >99% of 0.4 mM 4-nitrophenol at linear flow rates of 0.98 cm/s, and the modification process is also applicable to track-etched polycarbonate supports.

  3. Catechol-based layer-by-layer assembly of composite coatings: a versatile platform to hierarchical nano-materials.

    PubMed

    Wang, C X; Braendle, A; Menyo, M S; Pester, C W; Perl, E E; Arias, I; Hawker, C J; Klinger, D

    2015-08-21

    Inspired by the marine mussel's ability to adhere to surfaces underwater, an aqueous catechol-based dip coating platform was developed. Using a catechol-functionalized polyacrylamide binder in combination with inorganic nanoparticles enables the facile fabrication of robust composite coatings via a layer-by-layer process. This modular assembly of well-defined building blocks provides a versatile alternative to electrostatic driven approaches with layer thickness and refractive indices being readily tunable. The platform nature of this approach enables the fabrication of hierarchically ordered nano-materials such as Bragg stacks.

  4. Control of optical properties in cyanine dye thin film fabricated by a layer-by-layer method

    NASA Astrophysics Data System (ADS)

    Kojima, Osamu; Fujii, Ryoji; Kita, Takashi; Shim, YongGu

    2014-02-01

    We report the fabrication of cyanine dye molecule thin films by a layer-by-layer (LBL) method. In the LBL thin film, the photoluminescence properties can be controlled by the separation between the donor and acceptor dye molecule layers. While the distance dependence of the energy-transfer rate changes around 2 nm, which is comparable with the lengths of the molecules, the energy-transfer rate as evaluated from the photoluminescence decay time shows a maximum value of approximately 15 ns-1. The thin films fabricated by the LBL method will be therefore applicable for ultrafast optical switches with higher repetition rate.

  5. Using optical diagnostics to determine the melt temperature field in layer-by-layer laser alloying of metal powder

    NASA Astrophysics Data System (ADS)

    Zavalov, Yu. N.; Dubrov, A. V.; Mirzade, F. Kh.; Dubrovin, N. G.; Makarova, E. S.; Dubrov, V. D.

    2017-07-01

    The results of application of optical diagnostics in the estimation of the temperature field at the melt surface in layer-by-layer laser alloying of metal powder are presented. It is demonstrated that surface concavity induced by the thermocapillary effect upon nonuniform heating may distort pyrometry data considerably. The use of external illumination provides an opportunity to determine the shape of the melt surface. The obtained minimum estimate of the temperature gradient in the metal region affected by laser radiation is 2.8 × 104 K/cm.

  6. The linker-free covalent attachment of collagen to plasma immersion ion implantation treated polytetrafluoroethylene and subsequent cell-binding activity.

    PubMed

    Bax, Daniel V; McKenzie, David R; Weiss, Anthony S; Bilek, Marcela M M

    2010-03-01

    It is desirable that polymers used for the fabrication of prosthetic implants promote biological functions such as cellular adhesion, differentiation and viability. In this study, we have used plasma immersion ion implantation (PIII) to modify the surface of polytetrafluoroethylene (PTFE), thereby modulating the binding mechanism of collagen. The amount of collagen bound to the polymer surface following PIII-treatment was similar to that bound by non-covalent physisorption. In a manner consistent with previous enzyme and tropoelastin binding data, the collagen bound to the PIII-treated PTFE surface was resistant to sodium dodecyl sulfate (SDS) elution whilst collagen bound to the untreated surface was fully removed. This demonstrates the capability of PIII-treated surfaces to covalently attach collagen without employing chemical linking molecules. Only the collagen bound to the PIII-treated PTFE surface supported human dermal fibroblast attachment and spreading. This indicates that collagen on the PIII-treated surface possesses increased adhesive activity as compared to that on the untreated surface. Cell adhesion was inhibited by EDTA when the collagen was bound to PIII-treated PTFE, as expected for integrin involvement. Additionally this adhesion was sensitive to the conformation of the bound collagen. Increased actin cytoskeletal assembly was observed on cells spreading onto collagen-coated PIII-treated PTFE compared to the collagen-coated untreated PTFE. These data demonstrate the retention of collagen's biological properties following its attachment to PIII-treated PTFE, suggesting advantages for tissue engineering and prosthetic design.

  7. 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.

  8. EMF measurements across the front of combustion wave during layer by layer surface laser sintering of exothermal powder compositions

    NASA Astrophysics Data System (ADS)

    Shishkovskiy, I.; Sherbakov, V.; Morozov, Yu.

    2007-06-01

    Rapid prototyping (RP) and manufacturing (M) is a novel layer-by-layer fabrication technique which has become increasingly popular due to its inherent flexibility for the manufacture of simple and complex 3D parts. Early we had been shown opportunity of selective laser sintering (SLS) of different type powder systems (intermetallics, ceramics, ferrites, high-temperature superconductors), traditional use for self-propagated high-temperature synthesis (SHS). The non-thermal heating affect of an external electromagnetic field during SHS is related to the specific system under study due to differences in movement of defects and ions at the 'plasma-like' molten combustion wave front. We have developed and refined the testing scheme for electro-thermal phenomena studies which can directly influence on the SHS combustion wave front. This work studies electromotive force (EMF) measurements across the front of combustion wave during layer by layer surface laser sintering of exothermal powder compositions (Ni-Ti, Ni-Al). Analysis using an analog-digital-analog computer converter allowed some control of the laser movement and hence some control of the exothermal reaction - in so doing it provided near optimum conditions for forming layered 3D articles. Comparative results of structural-phase transformation during laser control SHS in reaction-capable compositions are presented.

  9. 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

  10. Micromechanical Properties of Nanostructured Clay-Oxide Multilayers Synthesized by Layer-by-Layer Self-Assembly.

    PubMed

    Hou, Dongwei; Zhang, Guoping; Pant, Rohit Raj; Wei, Zhongxin; Shen, Shuilong

    2016-11-08

    Clay-based nanostructured multilayers, such as clay-polymer multilayers and clay-oxide multilayers, have attracted growing attention owing to their remarkable mechanical properties and promising application in various fields. In this paper, synthesis of a new kind of nanostructured clay-oxide multilayers by layer-by-layer self-assembly was explored. Nano-mechanical characterization of 18 clay-based multilayer samples, prepared under as-deposited (i.e., air-dried) and annealing conditions at 400 °C/600 °C with different precursor cations and multilayer structure, were carried out using nanoindentation testing, atomic force microscopy (AFM), and X-ray diffraction (XRD). The influencing factors, including as-deposited and annealing conditions and clay concentrations on the mechanical properties were analyzed. Results show that all of the multilayers exhibit high bonding strength between interlayers. Higher modulus and hardness of clay-based multilayers were obtained with lower clay concentrations than that with higher clay concentrations. Different relationships between the modulus and hardness and the annealing temperature exist for a specific type of clay-oxide multilayer. This work offers the basic and essential knowledge on design of clay-based nanostructured multilayers by layer-by-layer self-assembly.

  11. High-Performance Small Molecule/Polymer Ternary Organic Solar Cells Based on a Layer-By-Layer Process.

    PubMed

    Chen, Weichao; Du, Zhengkun; Xiao, Manjun; Zhang, Jidong; Yang, Chunpeng; Han, Liangliang; Bao, Xichang; Yang, Renqiang

    2015-10-21

    The layer-by-layer process method, which had been used to fabricate a bilayer or bulk heterojunction organic solar cell, was developed to fabricate highly efficient ternary blend solar cells in which small molecules and polymers act as two donors. The active layer could be formed by incorporating the small molecules into the polymer based active layer via a layer-by-layer method: the small molecules were first coated on the surface of poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) ( PSS), and then the mixed solution of polymer and fullerene derivative was spin-coated on top of a small molecule layer. In this method, the small molecules in crystalline state were effectively mixed in the active layer. Without further optimization of the morphology of the ternary blend, a high power conversion efficiency (PCE) of 8.76% was obtained with large short-circuit current density (Jsc) (17.24 mA cm(-2)) and fill factor (FF) (0.696). The high PCE resulted from not only enhanced light harvesting but also more balanced charge transport by incorporating small molecules.

  12. 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.

  13. Electroactive layer-by-layer films of heme protein-coated polystyrene latex beads with poly(styrene sulfonate).

    PubMed

    Sun, Hong; Hu, Naifei

    2005-01-01

    In this work, a novel two-step construction strategy for protein layer-by-layer assembly films was proposed. In the first step, positively charged hemoglobin (Hb) or myoglobin (Mb) at pH 5.0 was adsorbed on the negatively charged surface of 500 nm diameter-sized polystyrene (PS) latex beads, forming core-shell structured PS-protein particles. In the next step, the PS-protein particles were further assembled layer by layer with oppositely charged poly(styrene sulfonate)(PSS) on various solid surfaces under suitable conditions. Cyclic voltammetry (CV), quartz crystal microbalance (QCM), and UV-vis spectroscopy were used to monitor the growth of {(PS-protein)/PSS}(n) films. The stable {(PS-protein)/PSS}(n) films modified on pyrolytic graphite (PG) electrodes demonstrated good electroactivity in protein-free buffer, which was originated from protein heme Fe(III)/Fe(II) redox couples, and the electroactivity extended to six (PS-protein)/PSS bilayers. UV-vis spectroscopy showed that Hb and Mb in the films retained their near-native structure in the medium pH range. {(PS-protein)/PSS}(n) films catalyzed electrochemical reduction of oxygen, hydrogen peroxide, trichloroacetic acid (TCA) and nitrite with a significant lowering of overpotential, and displayed better catalytic activity than corresponding cast PS-protein films.

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

    PubMed

    Brown, Philip S; Bhushan, Bharat

    2015-03-03

    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.

  15. 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.

  16. Micromechanical Properties of Nanostructured Clay-Oxide Multilayers Synthesized by Layer-by-Layer Self-Assembly

    PubMed Central

    Hou, Dongwei; Zhang, Guoping; Pant, Rohit Raj; Wei, Zhongxin; Shen, Shuilong

    2016-01-01

    Clay-based nanostructured multilayers, such as clay-polymer multilayers and clay-oxide multilayers, have attracted growing attention owing to their remarkable mechanical properties and promising application in various fields. In this paper, synthesis of a new kind of nanostructured clay-oxide multilayers by layer-by-layer self-assembly was explored. Nano-mechanical characterization of 18 clay-based multilayer samples, prepared under as-deposited (i.e., air-dried) and annealing conditions at 400 °C/600 °C with different precursor cations and multilayer structure, were carried out using nanoindentation testing, atomic force microscopy (AFM), and X-ray diffraction (XRD). The influencing factors, including as-deposited and annealing conditions and clay concentrations on the mechanical properties were analyzed. Results show that all of the multilayers exhibit high bonding strength between interlayers. Higher modulus and hardness of clay-based multilayers were obtained with lower clay concentrations than that with higher clay concentrations. Different relationships between the modulus and hardness and the annealing temperature exist for a specific type of clay-oxide multilayer. This work offers the basic and essential knowledge on design of clay-based nanostructured multilayers by layer-by-layer self-assembly. PMID:28335332

  17. Tetanus toxoid-loaded layer-by-layer nanoassemblies for efficient systemic, mucosal, and cellular immunostimulatory response following oral administration.

    PubMed

    Harde, Harshad; Agrawal, Ashish Kumar; Jain, Sanyog

    2015-10-01

    The present study reports the tetanus toxoid (TT)-loaded layer-by-layer nanoassemblies (layersomes) with enhanced protection, permeation, and presentation for comprehensive oral immunization. The stable and lyophilized TT-loaded layersomes were prepared by a thin-film hydration method followed by alternate layer-by-layer coating of an electrolyte. The developed system was assessed for in vitro stability of antigen and formulation, cellular uptake, ex vivo intestinal uptake, and immunostimulatory response using a suitable experimental protocol. Layersomes improved the stability in simulated biological media as well as protected the integrity/conformation and native 3D structure of TT as confirmed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), circular dichroism (CD), and fluorescence spectroscopy, respectively. The cell culture studies demonstrated a 3.8-fold higher permeation of layersomes in Caco-2 cells and an 8.5-fold higher uptake by antigen-presenting cells (RAW 264.7). The TT-loaded layersomes elicited a complete immunostimulatory profile consisting of higher systemic (serum IgG titer), mucosal (sIgA titer), and cellular (interleukin-2 (IL-2) and interferon-γ (IFN-γ) levels) immune response after peroral administration in mice. The modified TT inhibition assay further confirmed the elicitation of complete protective levels of anti-TT antibody (>0.1 IU/mL) by layersomes. In conclusion, the proposed strategy is expected to contribute significantly in the field of stable liposome technology for mass immunization through the oral route.

  18. Direct electrochemistry of Shewanella loihica PV-4 on gold nanoparticles-modified boron-doped diamond electrodes fabricated by layer-by-layer technique.

    PubMed

    Wu, Wenguo; Xie, Ronggang; Bai, Linling; Tang, Zuming; Gu, Zhongze

    2012-05-01

    Microbial Fuel Cells (MFCs) are robust devices capable of taping biological energy, converting pollutants into electricity through renewable biomass. The fabrication of nanostructured electrodes with good bio- and electrochemical activity, play a profound role in promoting power generation of MFCs. Au nanoparticles (AuNPs)-modified Boron-Doped Diamond (BDD) electrodes are fabricated by layer-by-layer (LBL) self-assembly technique and used for the direct electrochemistry of Shewanella loihica PV-4 in an electrochemical cell. Experimental results show that the peak current densities generated on the Au/PAH multilayer-modified BDD electrodes increased from 1.25 to 2.93 microA/cm(-2) as the layer increased from 0 to 6. Different cell morphologies of S. loihica PV-4 were also observed on the electrodes and the highest density of cells was attached on the (Au/PAH)6/BDD electrode with well-formed three-dimensional nanostructure. The electrochemistry of S. loihica PV-4 was enhanced on the (Au/PAH)4/BDD electrode due to the appropriate amount of AuNPsand thickness of PAH layer.

  19. Synergistic interaction between gold nanoparticles and nickel phthalocyanine in layer-by-layer (LbL) films: evidence of constitutional dynamic chemistry (CDC).

    PubMed

    Alencar, Wagner S; Crespilho, Frank N; Martins, Marccus V A; Zucolotto, Valtencir; Oliveira, Osvaldo N; Silva, Welter C

    2009-07-07

    The concept of constitutional dynamic chemistry (CDC) based on the control of non-covalent interactions in supramolecular structures is promising for having a large impact on nanoscience and nanotechnology if adequate nanoscale manipulation methods are used. In this study, we demonstrate that the layer-by-layer (LbL) technique may be used to produce electroactive electrodes with ITO coated by tetrasulfonated nickel phthalocyanine (NiTsPc) alternated with poly(allylamine hydrochloride) (PAH) incorporating gold nanoparticles (AuNP), in which synergy has been achieved in the interaction between the nanoparticles and NiTsPc. The catalytic activity toward hydrogen peroxide (H(2)O(2)) in multilayer films was investigated using cyclic voltammetry, where oxidation of H(2)O(2) led to increased currents in the PAH-AuNP/NiTsPc films for the electrochemical processes associated with the phthalocyanine ring and nickel at 0.52 and 0.81 V vs. SCE, respectively, while for PAH/NiTsPc films (without AuNP) only the first redox process was affected. In control experiments we found out that the catalytic activity was not solely due to the presence of AuNP, but rather to the nanoparticles inducing NiTsPc supramolecular structures that favored access to their redox sites, thus yielding strong charge transfer. The combined effects of NiTsPc and AuNP, which could only be observed in nanostructured LbL films, point to another avenue to pursue within the CDC paradigm.

  20. 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

    Buck, Maren E; Lynn, David M

    2010-05-01

    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 cross-linked 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 postfabrication 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 postfabrication 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 nonwoven mats) of potential utility in a broad range of consumer, industrial, and biomedical contexts.

  1. 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.

  2. 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

  3. Aqueous oxidation reaction enabled layer-by-layer corrosion of semiconductor nanoplates into single-crystalline 2D nanocrystals with single layer accuracy and ionic surface capping.

    PubMed

    Ji, Muwei; Xu, Meng; Zhang, Jun; Liu, Jiajia; Zhang, Jiatao

    2016-02-25

    A controllable aqueous oxidation reaction enabled layer-by-layer corrosion has been proposed to prepare high-quality two-dimensional (2D) semiconductor nanocrystals with single layer accuracy and well-retained hexagonal shapes. The appropriate oxidizing agent, such as H2O2, Fe(NO3)3, and HNO3, could not only corrode the layered-crystalline-structured Bi2Te3 nanoplates layer-by-layer to be a single quintuple layer, but also replace the organic barriers to be ionic ligands on the surface synergistically. AFM analysis was used to confirm the layer-by-layer exfoliation from the side to the center. Together with precise XRD, LRTEM and HRTEM characterizations, the controllable oxidation reaction enabled aqueous layer-by-layer corrosion mechanism has been studied.

  4. Quantum size effects in the low temperature layer-by-layer growth of Pb on Ge(0 0 1)

    NASA Astrophysics Data System (ADS)

    Floreano, L.; Cvetko, D.; Bruno, F.; Bavdek, G.; Cossaro, A.; Gotter, R.; Verdini, A.; Morgante, A.

    2003-08-01

    The electronic properties of thin metallic films deviate from the corresponding bulk ones when the film thickness is comparable with the wavelength of the electrons at the Fermi level. This phenomenon, referred to as quantum size effect (QSE), is also expected to affect the film morphology and structure leading to the “electronic growth” of metals on semiconductors. Such effect may be observed when metals are grown on substrates held at low temperature and are manifested through the occurrence of “magical” thickness islands or critical thickness for layer-by-layer growth. In particular, layer-by-layer growth of Pb(1 1 1) films has been reported for deposition on Ge(0 0 1) below ∼130 K. An extremely flat morphology is preserved throughout deposition from four up to a dozen of monolayers. These flat films are shown to be metastable and to reorganize into large clusters uncovering the first Pb layer pseudomorphic to the underlying Ge(0 0 1) substrate already at room temperature. Indications of QSE induced structural variations of the growing films have been reported for Pb growth on both Si(1 1 1) and Ge(0 0 1). In the latter case, the apparent height of the Pb(1 1 1) monatomic step was shown to change in an oscillatory fashion by He atom scattering (HAS) during layer-by-layer growth at low temperature. The extent of the structural QSE has been obtained by a comparison of the HAS data with X-ray diffraction (XRD) and reflectivity experiments. Whereas step height variations as large as 20% have been measured by HAS reflectivity, the displacement of the atomic planes from their bulk position, as measured by XRD, has been found to mainly affect the topmost Pb layer, but with a lower extent, i.e. the QSE observed by HAS are mainly due to a perpendicular displacement of the topmost layer charge density. The effect of the variable surface relaxation on the surface vibration has been studied from the acoustic dispersion of the low energy phonons, as measured by

  5. Facile Fabrication of 3D Layer-by-layer Graphene-gold Nanorod Hybrid Architecture for Hydrogen Peroxide Based Electrochemical Biosensor

    DTIC Science & Technology

    2015-01-01

    Facile fabrication of 3D layer-by-layer graphene-gold nanorod hybrid architecture for hydrogen peroxide based electrochemical biosensor Chenming Xue...detection Biosensor a b s t r a c t Three-dimensional (3D) layer-by-layer graphene-gold nanorod (GNR) architecture has been constructed. The resulting...disposable biosensor platform. Cyclic voltam- metry and amperometry were used to characterize and assess the performance of the biosensor . The 3D layer

  6. 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.

  7. An imaging pH optode for cell studies based on covalent attachment of 8-hydroxypyrene-1,3,6-trisulfonate to amino cellulose acetate films.

    PubMed

    Strömberg, Niklas; Mattsson, Erik; Hakonen, Aron

    2009-03-16

    The objective of this study was to create a thin film optode for fast pH measurements that meets the requirements for imaging pH-responses from cells as well as for a future hybrid design for detection of multiple analytes simultaneously. The sensor is based on the covalent attachment of 8-hydroxypyrene-1,3,6-trisulfonate (HPTS) to a film forming cellulose acetate material through a sulfonamide linkage. The synthesis routes of the cellulose material and regio-specific covalent attachment of the dye are described in detail. The sensor was sterilized in two different ways and showed excellent biocompatibility with Chinese hamster ovary cells. Imprints from cells and mum thin cell extensions were visualized when altering pH of the surrounding solution. The sensor was tested together with time-dependent sigmoidal calibrations giving pH determinations with an exceptional precision and accuracy during measurement within pH 6-8. The precision of the optode, calculated as pooled S.D. (n=8) according to IUPAC recommendations between pH 6.641 and 7.742 was 0.0029. The accuracy was significantly better than the electrode used as reference during the measurements. The response time (0-95%) was 100s between pH 6.641 and 7.742 and the reverse response (95-0%) was 80s. The sensor shows great potential for extra-cellular pH determination over time during cell growth and pharmacological exposure.

  8. 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.

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

    PubMed

    Feeney, Matthew J; Hu, Xiaoran; Srinivasan, Rati; Van, Nhi; Hunter, Martin; Georgakoudi, Irene; Thomas, Samuel W

    2017-10-02

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

  10. 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.

  11. Highly efficient layer-by-layer-assisted infiltration for high-performance and cost-effective fabrication of nanoelectrodes.

    PubMed

    Choi, Yuri; Choi, Sihyuk; Jeong, Hu Young; Liu, Meilin; Kim, Byeong-Su; Kim, Guntae

    2014-10-22

    We present a novel cathode fabrication technique for improved performance and production efficiency of SOFCs based on an infiltration method assisted by layer-by-layer (LbL) assembly of polyelectrolytes. Preparation of the electrode with LbL-assisted infiltration leads to a 6.5-fold reduction in the electrode fabrication time while providing uniform and small formation of Pr0.7Sr0.3CoO3-δ (PSC) particles on the electrode. The increased surface area by 24.5% and number of active sites of the prepared electrode exhibits superior electrochemical performance up to 36.1% while preserving the electrical properties of the electrode. Because of its versatility and tenability, the LbL-assisted infiltration process may become a new route for fabrication of composite electrodes for other energy storage and conversion devices.

  12. 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.

  13. Layer-by-layer assembled hydrophobic coatings for cellulose nanofibril films and textiles, made of polylysine and natural wax particles.

    PubMed

    Forsman, Nina; Lozhechnikova, Alina; Khakalo, Alexey; Johansson, Leena-Sisko; Vartiainen, Jari; Österberg, Monika

    2017-10-01

    Herein we present a simple method to render cellulosic materials highly hydrophobic while retaining their breathability and moisture buffering properties, thus allowing for their use as functional textiles. The surfaces are coated via layer-by-layer deposition of two natural components, cationic poly-l-lysine and anionic carnauba wax particles. The combination of multiscale roughness, open film structure, and low surface energy of wax colloids, resulted in long-lasting superhydrophobicity on cotton surface already after two bilayers. Atomic force microscopy, interference microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy were used to decouple structural effects from changes in surface energy. Furthermore, the effect of thermal annealing on the coating was evaluated. The potential of this simple and green approach to enhance the use of natural cellulosic materials is discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Preparation of porous hollow silica spheres via a layer-by-layer process and the chromatographic performance

    NASA Astrophysics Data System (ADS)

    Wei, Xiaobing; Gong, Cairong; Chen, Xujuan; Fan, Guoliang; Xu, Xinhua

    2017-01-01

    Hollow silica spheres possessing excellent mechanical properties were successfully prepared through a layer-by-layer process using uniform polystyrene (PS) latex fabricated by dispersion polymerization as template. The formation of hollow SiO2 micro-spheres, structures and properties were observed in detail by zeta potential, SEM, TEM, FTIR, TGA and nitrogen sorption porosimetry. The results indicated that the hollow spheres were uniform with particle diameter of 1.6 μm and shell thickness of 150 nm. The surface area was 511 m2/g and the pore diameter was 8.36 nm. A new stationary phase for HPLC was obtained by using C18-derivatized hollow SiO2 micro-spheres as packing materials and the chromatographic properties were evaluated for the separation of some regular small molecules. The packed column showed low column pressure, high values of efficiency (up to about 43 000 plates/m) and appropriate asymmetry factors.

  15. Quantum dot layer-by-layer assemblies as signal amplification labels for ultrasensitive electronic detection of uropathogens.

    PubMed

    Xiang, Yun; Zhang, Haixia; Jiang, Bingying; Chai, Yaqin; Yuan, Ruo

    2011-06-01

    The preparation and use of a new class of signal amplification label, quantum dot (QD) layer-by-layer (LBL) assembled polystyrene microsphere composite, for amplified ultrasensitive electronic detection of uropathogen-specific DNA sequences is described. The target DNA is sandwiched between the capture probes immobilized on the magnetic beads and the signaling probes conjugated to the QD LBL assembled polystyrene beads. Because of the dramatic signal amplification by the numerous QDs involved in each single DNA binding event, subfemtomolar level detection of uropathogen-specific DNA sequences is achieved, which makes our strategy among the most sensitive electronic approach for nucleic acid-based monitoring of pathogens. Our signal amplified detection scheme could be readily expanded to monitor other important biomolecules (e.g., proteins, peptides, amino acids, cells, etc.) in ultralow levels and thus holds great potential for early diagnosis of disease biomarkers.

  16. Characterization of Ultrathin Ta-oxide Films Formed on Ge(100) by ALD and Layer-by-Layer Methods

    NASA Astrophysics Data System (ADS)

    Mishima, K.; Murakami, H.; Ohta, A.; Sahari, S. K.; Fujioka, T.; Higashi, S.; Miyazaki, S.

    2013-03-01

    Atomic layer deposition (ALD) and Layer-by-Layer deposition of Ta-oxide films on Ge(100) with using tris (tert-butoxy) (tert-butylimido) tantalum have been studied systematically. From the analysis of the chemical bonding features of the interface between TaOx and Ge(100) using x-ray photoelectron spectroscopy (XPS), Ge atom diffusion into the Ta oxide layer and resultant TaGexOy formation during deposition at temperatures higher than 200°C were confirmed. Also, we have demonstrated that nanometer-thick deposition of Tantalum oxide as an interfacial layer effectively suppresses the formation of GeOx in the HfO2 ALD on Ge. By the combination of TaOx pre-deposition on Ge(100) and subsequent ALD of HfO2, a capacitance equivalent thickness (CET) of 1.35 nm and relative dielectric constant of 23 were achieved.

  17. Nitrogen-doped carbon capsules via poly(ionic liquid)-based layer-by-layer assembly.

    PubMed

    Zhao, Qiang; Fellinger, Tim-Patrick; Antonietti, Markus; Yuan, Jiayin

    2012-07-13

    Layer-by-layer (LbL) assembly technique is applied for the first time for the preparation of nitrogen-doped carbon capsules. This approach uses colloid silica as template and two polymeric deposition components, that is, poly(ammonium acrylate) and a poly (ionic liquid) poly(3-cyanomethyl-1-vinylimidazolium bromide), which acts as both the carbon precursor and nitrogen source. Nitrogen-doped carbon capsules are prepared successfully by polymer wrapping, subsequent carbonization and template removal. The as-synthesized carbon capsules contain ≈7 wt% of nitrogen and have a structured specific surface area of 423 m(2) g(-1). Their application as supercapacitor has been briefly introduced. This work proves that LbL assembly methodology is available for preparing carbon structures of complex morphology. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Simultaneous determination of dopamine and uric acid using layer-by-layer graphene and chitosan assembled multilayer films.

    PubMed

    Weng, Xuexiang; Cao, Qingxue; Liang, Lixin; Chen, Jianrong; You, Chunping; Ruan, Yongmin; Lin, Hongjun; Wu, Lanju

    2013-12-15

    Multilayer films containing graphene (Gr) and chitosan (CS) were prepared on glassy carbon electrodes with layer-by-layer (LBL) assembly technique. After being characterized with cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM), the electrochemical sensor based on the resulted films was developed to simultaneously determine dopamine (DA) and uric acid (UA). The LBL assembled electrode showed excellent electrocatalytic activity towards the oxidation of DA and UA. In addition, the self-assembly electrode possessed an excellent sensing performance for detection of DA and UA with a linear range from 0.1 μM to 140 µM and from 1.0 µM to 125 µM with the detection limit as low as 0.05 µM and 0.1 µM based on S/N=3, respectively.

  19. A self-limiting layer-by-layer etching technique for 2H-MoS2

    NASA Astrophysics Data System (ADS)

    Lee, Choong Hee; Lee, Edwin W., II; McCulloch, William; Jamal-Eddine, Zane; Krishnamoorthy, Sriram; Newburger, Michael J.; Kawakami, Roland K.; Wu, Yiying; Rajan, Siddharth

    2017-03-01

    We report controlled layer-by-layer removal of large-area, sulfurized, single-crystal molybdenum disulfide (MoS2) films using a digital etching technique, which utilizes oxidation and removal of the oxidized layer. We demonstrate a self-limiting oxidation process where Mo oxide covered the surface of MoS2. A constant etching rate of one monolayer/cycle and the uniformity of the etching process were also verified. We show that the etching of an integer number of MoS2 layers can be precisely controlled. No noticeable film quality degradation was observed after multiple cycles of digital etching, as confirmed by Raman mapping of the ratio of the \\text{E}\\text{2g}1 and A1g peak intensities.

  20. Highly stable surface functionalization of microgas chromatography columns using layer-by-layer self-assembly of silica nanoparticles.

    PubMed

    Wang, Dong; Shakeel, Hamza; Lovette, John; Rice, Gary W; Heflin, James R; Agah, Masoud

    2013-09-03

    A controllable and high-yield surface functionalization of silicon microchannels using layer-by-layer (LbL) self-assembly of SiO2 nanoparticles (SNPs) is presented. The application of SNPs (45 nm average diameter) coating as a stationary phase for chromatographic separation is also demonstrated with surface functionalization using chloroalkylsilanes. This method facilitates a simple, low-cost, and parallel processing scheme that also provides homogeneous and stable nanoparticle-based stationary phases with ease of control over the coating thickness. The SNP-functionalized microfabricated columns with either single capillary channels (1 m long, 150 μm wide, 240 μm deep) or very narrow multicapillary channels (25 cm long, 30 μm wide, 240 μm deep, 16 parallel channels) successfully separated a multicomponent gas mixture with a wide range of boiling points with high reproducibility.

  1. Fabrication of macroporous films with closed honeycomb-like pores from exponentially growing layer-by-layer assembled polyelectrolyte multilayers.

    PubMed

    Chen, Xiaoling; Sun, Junqi

    2014-08-01

    We report an innovative method for the fabrication of macroporous films with closed honeycomb-like pores of several micrometers by post-treatment of micrometer-thick poly(acrylic acid) (PAA)/poly(allylamine hydrochloride) (PAH) films. The precursor PAA/PAH films are fabricated by exponential layer-by-layer assembly of PAA and PAH, which produces PAA/PAH films with highly interpenetrated structures. We disclose that the high mobility of PAA and PAH, which originates from the highly interpenetrated film structures, allows a large-scale phase separation to take place upon post-treatment to produce micrometer-sized honeycomb pores. These macroporous PAA/PAH films can be conveniently released from substrates to produce free-standing films with satisfactory mechanical stability.

  2. 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.

  3. 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.

  4. Fabrication and photoelectric response of poly(allylamine hydrochloride)/PM thin films by layer-by-layer deposition technique.

    PubMed

    Chu, Jinfang; Li, Xingchang; Zhang, Jianping; Tang, Ji'an

    2003-05-23

    Thin films of poly(allylamine hydrochloride) (PAH) and bacteriorhodopsin (bR) embedded in purple membrane (PM) have been prepared by layer-by-layer (LBL) self-assembly technique. The results obtained by UV-Vis spectroscopy and atomic force microscopy (AFM) analysis showed that the biological activity of bR was preserved and PM fragments could be well oriented onto the ITO substrate. A photo-electrochemical cell with the structure of ITO/(PAH/PM)(n)/electrolyte (0.5M KCl)/Pt was fabricated and studied. The photocurrent peaks of (PAH/PM)(6) corresponding to light-on and light-off were about 200 and 100 nA/cm(2), respectively, with the former enhanced 30% higher than that of the reference films made of (PDAC/PM)(6).

  5. Photochromic paper from wood pulp modification via layer-by-layer assembly of pulp fiber/chitosan/spiropyran.

    PubMed

    Tian, Xiaojun; Wang, Bin; Li, Jinpeng; Zeng, Jinsong; Chen, Kefu

    2017-02-10

    Cellulosic fiber introducing with photochromic properties can be used in many fields such as security packaging, printing paper, and rewritable paper. To introduce photochromic property to individual fiber, a polyelectrolyte composite layer composed of cationic chitosan (CS) and anionic carboxyl-containing spiropyran (SPCOOH) on pulp fibers was designed using layer-by-layer assembly technique. Scanning electron microscope observation showed that the SPCOOH was successfully absorbed onto the surface of fiber. The photochromic characteristic of LbL-treated fiber could be triggered by UV-vis absorption spectrum and the LbL-treated fibers had a good compatibility with pulp fibers. This study gives a highly effective method to impart the photochromic characteristic to paper.

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  8. Layer-by-layer self-assembled conductor network composites in ionic polymer metal composite actuators with high strain response

    NASA Astrophysics Data System (ADS)

    Liu, Sheng; Montazami, Reza; Liu, Yang; Jain, Vaibhav; Lin, Minren; Heflin, James R.; Zhang, Q. M.

    2009-07-01

    We investigate the electromechanical response of conductor network composite (CNC) fabricated by the layer-by-layer (LbL) self-assembly method. The process makes it possible for CNCs to be fabricated at submicron thickness with high precision and quality. This CNCs exhibits high strain ˜6.8% under 4 V, whereas the RuO2/Nafion CNCs exhibit strain ˜3.3%. The high strain and submicron thickness of the LbL layers in an ionic polymer metal composite (IPMC) yield large and fast actuation. The response time of a 26 μm thick IPMC with 0.4 μm thick LbL CNCs to step voltage of 4 V is 0.18 s.

  9. 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

  10. 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

  11. Preparation of a novel composite nanofiber gel-encapsulated human placental extract through layer-by-layer self-assembly.

    PubMed

    Liu, Guohui; Chen, X I; Zhou, W U; Yang, Shuhua; Ye, Shunan; Cao, Faqi; Liu, Y I; Xiong, Yuan

    2016-04-01

    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.

  12. Electrorheological properties of carbon nanotube/ polyelectrolyte composite silica nanoparticles by layer-by-layer self-assembly.

    PubMed

    Kim, Byung-Soo; Kim, Bumsu; Suh, Kyung-Do

    2008-08-01

    Multiwall carbon nanotubes (MCNTs)/silica (SiO2) composite particles were prepared by layer-by-layer (LbL) self-assembly method using polyelectrolytes and functionalized MCNTs (fMCNTs). The fMCNTs prepared by chemical oxidation method were incorporated on the outermost layer of polyelectrolyte-coated SiO2 particles. The amount of fMCNTs was varied by LbL self assembly. In the process the number of fMCNT layers on SiO2 particles could be controlled. The fMCNT-coated SiO2 particles were characterized by zeta-potential analysis, transmission electron microscopy (TEM), and optical microscopy (OM). In addition, the electrorheological (ER) properties of multilayers containing fMCNTs on silica particles were investigated under controlled electric fields. The ER properties of the composite particles were influenced by the amount of fMCNTs in multilayers.

  13. 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).

  14. Preparation of porous hollow silica spheres via a layer-by-layer process and the chromatographic performance

    NASA Astrophysics Data System (ADS)

    Wei, Xiaobing; Gong, Cairong; Chen, Xujuan; Fan, Guoliang; Xu, Xinhua

    2017-03-01

    Hollow silica spheres possessing excellent mechanical properties were successfully prepared through a layer-by-layer process using uniform polystyrene (PS) latex fabricated by dispersion polymerization as template. The formation of hollow SiO2 micro-spheres, structures and properties were observed in detail by zeta potential, SEM, TEM, FTIR, TGA and nitrogen sorption porosimetry. The results indicated that the hollow spheres were uniform with particle diameter of 1.6 μm and shell thickness of 150 nm. The surface area was 511 m2/g and the pore diameter was 8.36 nm. A new stationary phase for HPLC was obtained by using C18-derivatized hollow SiO2 micro-spheres as packing materials and the chromatographic properties were evaluated for the separation of some regular small molecules. The packed column showed low column pressure, high values of efficiency (up to about 43 000 plates/m) and appropriate asymmetry factors.

  15. 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.

  16. 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

    2015-10-07

    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.

  17. Layer-by-layer assemblies of highly connected polyelectrolyte capped-Pt nanoparticles for electrocatalysis of hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Fenoy, Gonzalo E.; Maza, Eliana; Zelaya, Eugenia; Marmisollé, Waldemar A.; Azzaroni, Omar

    2017-09-01

    Herein we present a simple one-step method to produce polyelectrolyte-capped Pt nanoparticles able to be assembled into layer-by-layer arrays with a linear dependence of the amount of deposited material on the number of dipping cycles. The resulting supramolecular films where fully characterized by AFM, XPS and ATR-FTIR. The electrochemical evaluation by cyclic voltammetry showed good electrochemical connection between the nanoparticles in both acidic and neutral solutions. The films assembled on graphite electrodes showed catalysis of the H2 production and the interconnection between nanoparticles proved to be effective up to 20 bilayers. Results presented here reveal an easy procedure to obtain stable arrays of well-dispersed electroactive 2 nm-diameter Pt nanoparticles on a variety of substrates with direct potential applications in energy conversion devices.

  18. Tunable disintegration of layer-by-layer assembly multilayer films based on hydrolytical-polybetaine at wide-range time.

    PubMed

    Gui, Zhangliang; Qian, Jinwen; He, Yuan; An, Quanfu; Wang, Xuesan; Tian, Chengpeng; Sun, Wendan

    2011-09-01

    A cationic hydrolytical-polycarboxybetaine (HPCB), poly(N-ethyl acetate-4-vinylpyridinium bromide) was synthesized by incorporating ester group into the side chain of polycarboxybetaine (PCB). The hydrolytic behaviors of HPCB samples in pH 7.4 phosphate buffer saline (PBS) were investigated by FT-IR and (1)H NMR. The layer-by-layer (LbL) assembly of HPCB/poly (sodium 4-styrenesulfonate) PSS and the disintegration of HPCB/PSS multilayer films were monitored by UV-vis absorption spectroscopy, quartz crystal microbalance (QCM) and atomic force microscopy (AFM). The disintegrated behavior of multilayer films was studied in detail by changing the cationic degree of HPCB and the pH of the immersion solution (PBS) in the disintegration process. The disintegration time of HPCB/PSS multilayer films could be controlled widely from 2 min to 30 days in PBS. Crown Copyright © 2011. Published by Elsevier Inc. All rights reserved.

  19. Electron molecular beam epitaxy: Layer-by-layer growth of complex oxides via pulsed electron-beam deposition

    SciTech Connect

    Comes, Ryan; Liu Hongxue; Lu Jiwei; Gu, Man; Khokhlov, Mikhail; Wolf, Stuart A.

    2013-01-14

    Complex oxide epitaxial film growth is a rich and exciting field, owing to the wide variety of physical properties present in oxides. These properties include ferroelectricity, ferromagnetism, spin-polarization, and a variety of other correlated phenomena. Traditionally, high quality epitaxial oxide films have been grown via oxide molecular beam epitaxy or pulsed laser deposition. Here, we present the growth of high quality epitaxial films using an alternative approach, the pulsed electron-beam deposition technique. We demonstrate all three epitaxial growth modes in different oxide systems: Frank-van der Merwe (layer-by-layer); Stranski-Krastanov (layer-then-island); and Volmer-Weber (island). Analysis of film quality and morphology is presented and techniques to optimize the morphology of films are discussed.

  20. Highly ductile multilayered films by layer-by-layer assembly of oppositely charged polyurethanes for biomedical applications.

    PubMed

    Podsiadlo, Paul; Qin, Ming; Cuddihy, Meghan; Zhu, Jian; Critchley, Kevin; Kheng, Eugene; Kaushik, Amit K; Qi, Ying; Kim, Hyoung-Sug; Noh, Si-Tae; Arruda, Ellen M; Waas, Anthony M; Kotov, Nicholas A

    2009-12-15

    Multilayered thin films prepared with the layer-by-layer (LBL) assembly technique are typically "brittle" composites, while many applications such as flexible electronics or biomedical devices would greatly benefit from ductile, and tough nanostructured coatings. Here we present the preparation of highly ductile multilayered films via LBL assembly of oppositely charged polyurethanes. Free-standing films were found to be robust, strong, and tough with ultimate strains as high as 680% and toughness of approximately 30 MJ/m(3). These results are at least 2 orders of magnitude greater than most LBL materials presented until today. In addition to enhanced ductility, the films showed first-order biocompatibility with animal and human cells. Multilayered structures incorporating polyurethanes open up a new research avenue into the preparation of multifunctional nanostructured films with great potential in biomedical applications.

  1. 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.

  2. Development of "all natural" layer-by-layer redispersible solid lipid nanoparticles by nano spray drying technology.

    PubMed

    Wang, Taoran; Hu, Qiaobin; Zhou, Mingyong; Xia, Yan; Nieh, Mu-Ping; Luo, Yangchao

    2016-10-01

    Solid lipid nanoparticles (SLNs) have gained tremendous attraction as carriers for controlled drug delivery. Despite numerous advances in the field, one long-standing historical challenge for their practical applications remains unmet: redispersibility after drying. In this work, a novel design of SLNs using a layer-by-layer (LbL) technique was developed and the formulations were optimized by surface response methodology (Box-Behnken design). To the best of our knowledge, this is the first study reporting the fabrication of SLNs from all natural ingredients in the absence of any synthetic surfactants or coatings. The SLNs were prepared by a combined solvent-diffusion and hot homogenization method, with soy lecithin as natural emulsifier (first layer), followed by the subsequent coating with sodium caseinate (second layer) and pectin (third layer), both of which are natural food biopolymers. The adsorption of pectin coating onto caseinate was reinforced by hydrophobic and electrostatic interactions induced by a pH-driven process along with thermal treatment. The innovative nano spray drying technology was further explored to obtain ultra-fine powders of SLNs. Compared to uncoated or single-layer coated SLNs powders, which showed severe aggregation after spray drying, the well-separated particles with spherical shape and smooth surface were obtained for layer-by-layer (LbL) SLNs, which were redispersible into water without variation of dimension, shape and morphology. The SLNs were characterized by Fourier transform infrared and high-performance differential scanning calorimetry for their physical properties. The LbL-coated SLNs based on all natural ingredients have promising features for future applications as drug delivery systems, overcoming the major obstacles in conventional spray drying and redispersing SLNs-based formulations. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. 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

    2015-09-07

    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.

  4. Site-specific and covalent attachment of his-tagged proteins by chelation assisted photoimmobilization: a strategy for microarraying of protein ligands.

    PubMed

    Ericsson, Emma M; Enander, Karin; Bui, Lan; Lundström, Ingemar; Konradsson, Peter; Liedberg, Bo

    2013-09-17

    A novel strategy for site-specific and covalent attachment of proteins has been developed, intended for robust and controllable immobilization of histidine (His)-tagged ligands in protein microarrays. The method is termed chelation assisted photoimmobilization (CAP) and was demonstrated using human IgG-Fc modified with C-terminal hexahistidines (His-IgGFc) as the ligand and protein A as the analyte. Alkanethiols terminated with either nitrilotriacetic acid (NTA), benzophenone (BP), or oligo(ethylene glycol) were synthesized and mixed self-assembled monolayers (SAMs) were prepared on gold and thoroughly characterized by infrared reflection absorption spectroscopy (IRAS), ellipsometry, and contact angle goniometry. In the process of CAP, NTA chelates Ni(2+) and the complex coordinates the His-tagged ligand in an oriented assembly. The ligand is then photoimmobilized via BP, which forms covalent bonds upon UV light activation. In the development of affinity biosensors and protein microarrays, site-specific attachment of ligands in a fashion where analyte binding sites are available is often preferred to random coupling. Analyte binding performance of ligands immobilized either by CAP or by standard amine coupling was characterized by surface plasmon resonance in combination with IRAS. The relative analyte response with randomly coupled ligand was 2.5 times higher than when site-specific attachment was used. This is a reminder that also when immobilizing ligands via residues far from the binding site, there are many other factors influencing availability and activity. Still, CAP provides a valuable expansion of protein immobilization techniques since it offers attractive microarraying possibilities amenable to applications within proteomics.

  5. Anti-inflammatory and Antibacterial Effects of Covalently Attached Biomembrane-Mimic Polymer Grafts on Gore-Tex Implants.

    PubMed

    Jin, Young Ju; Kang, Sunah; Park, Pona; Choi, Dongkil; Kim, Dae Woo; Jung, Dongwook; Koh, Jaemoon; Jeon, Joohee; Lee, Myoungjin; Ham, Jiyeon; Seo, Ji-Hun; Jin, Hong-Ryul; Lee, Yan

    2017-06-07

    Expanded polytetrafluoroethylene (ePTFE), also known as Gore-Tex, is widely used as an implantable biomaterial in biomedical applications because of its favorable mechanical properties and biochemical inertness. However, infection and inflammation are two major complications with ePTFE implantations, because pathogenic bacteria can inhabit the microsized pores, without clearance by host immune cells, and the limited biocompatibility can induce foreign body reactions. To minimize these complications, we covalently grafted a biomembrane-mimic polymer, poly(2-methacryloyloxylethyl phosphorylcholine) (PMPC), by partial defluorination followed by UV-induced polymerization with cross-linkers on the ePTFE surface. PMPC grafting greatly reduced serum protein adsorption as well as fibroblast adhesion on the ePTFE surface. Moreover, the PMPC-grafted ePTFE surface exhibited a dramatic inhibition of the adhesion and growth of Staphylococcus aureus, a typical pathogenic bacterium in ePTFE implants, in the porous network. On the basis of an analysis of immune cells and inflammation-related factors, i.e., transforming growth factor-β (TGF-β) and myeloperoxidase (MPO), we confirmed that inflammation was efficiently alleviated in tissues around PMPC-grafted ePTFE plates implanted in the backs of rats. Covalent PMPC may be an effective strategy for promoting anti-inflammatory and antibacterial functions in ePTFE implants and to reduce side effects in biomedical applications of ePTFE.

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

    PubMed Central

    Jiang, Yongying; Trnka, Michael J.; Medzihradszky, Katalin F.; Ouellet, Hugues; Wang, Yongqiang; Ortiz de Montellano, Paul R.

    2009-01-01

    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 (Jiang, Y., Ortiz de Montellano, P.R., Inorg. Chem., 47, 3480-3482 (2008)), indicate that a selenyl radical is formed in the hHO1 His25SeCys mutant that adds to a heme vinyl group. PMID:19135260

  7. Covalent attachment and dissociative loss of sinapinic acid to/from cysteine-containing proteins from bacterial cell lysates analyzed by MALDI-TOF-TOF mass spectrometry.

    PubMed

    Fagerquist, Clifton K; Garbus, Brandon R; Williams, Katherine E; Bates, Anna H; Harden, Leslie A

    2010-05-01

    We report covalent attachment via a thiol ester linkage of 3,5-dimethoxy-4-hydroxycinnamic acid (sinapinic acid or SA) to cysteine-containing protein biomarkers from bacterial cell lysates of E. coli analyzed by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry when using SA as the matrix. Evidence to support this conclusion is the appearance of additional peaks in the MS spectra when using SA, which are absent when using alpha-cyano-4-hydroxycinnamic acid (HCCA). The additional peaks appear at a mass-to-charge (m/z) approximately 208 greater to the m/z of a more abundant protein ion peak. Protein biomarkers were identified by tandem mass spectrometry (MS/MS) using a MALDI time-of-flight/time-of-flight (TOF-TOF) mass spectrometer and top-down proteomics. Three protein biomarkers, HdeA, HdeB, and homeobox or YbgS (each containing two cysteine residues) were identified as having reactivity to SA. Non-cysteine-containing protein biomarkers showed no evidence of reactivity to SA. MS ions and MS/MS fragment ions were consistent with covalent attachment of SA via a thiol ester linkage to the side-chain of cysteine residues. MS/MS of a protein biomarker ion with a covalently attached SA revealed fragment ion peaks suggesting dissociative loss SA. We propose dissociative loss of SA is facilitated by a pentacyclic transition-state followed by proton abstraction of the beta-hydrogen of the bound SA by a sulfur lone pair followed by dissociative loss of 3-(4-hydroxy-3,5-dimethoxyphenyl)prop-2-ynal. The apparent reactivity of SA to cysteine/disulfide-containing proteins may complicate identification of such proteins, however the apparent differential reactivity of SA and HCCA toward cysteine/disulfide-containing proteins may be exploited for identification of unknown cysteine-containing proteins. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

  8. 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

  9. 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

  10. Layer-by-layer paper-stacking nanofibrous membranes to deliver adipose-derived stem cells for bone regeneration.

    PubMed

    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/cm(3). 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

  11. 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

  12. 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

    2016-02-09

    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

  13. Spectroscopic investigation of photoinduced charge-transfer processes in FTO/TiO2/N719 photoanodes with and without covalent attachment through silane-based linkers.

    PubMed

    Pandit, Bill; Luitel, Tulashi; Cummins, Dustin R; Thapa, Arjun K; Druffel, Thad; Zamborini, Frank; Liu, Jinjun

    2013-12-19

    Understanding electron-transfer (ET) processes in dye-sensitized solar cells (DSSCs) is crucial to improving their device performance. Recently, covalent attachment of dye molecules to mesoporous semiconductor nanoparticle films via molecular linkers has been employed to increase the stability of DSSC photoanodes. The power conversion efficiency (PCE) of these DSSCs, however, is lower than DSSCs with conventional unmodified photoanodes in this study. Ultrafast transient absorption pump-probe spectroscopy (TAPPS) has been used to study the electron injection process from N719 dye molecules to TiO2 nanoparticles (NPs) in DSSC photoanodes with and without the presence of two silane-based linker molecules: 3-aminopropyltriethoxysilane (APTES) and p-aminophenyltrimethoxysilane (APhS). Ultrafast biphasic electron injection kinetics were observed in all three photoanodes using a 530 nm pump wavelength and 860 nm probe wavelength. Both the slow and fast decay components, attributed to electron injection from singlet and triplet excited states, respectively, of the N719 dye to the TiO2 conduction band, are hindered by the molecular linkers. The hindering effect is less significant with the APhS linker than the APTES linker and is more significant for the singlet-state channel than the triplet-state one. Electron injection from the vibrationally excited states is less affected by the linkers. The spectroscopic results are interpreted on the basis of the standard ET theory and can be used to guide selection of molecular linkers for DSSCs with better device performance. Other factors that affect the efficiency and stability of the DSSCs are also discussed. The relatively lower PCE of the covalently attached photoanodes is attributed to the multilayer and aggregation of the dye molecules as well as the linkers.

  14. 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.

  15. Enhanced survival of probiotic Lactobacillus acidophilus by encapsulation with nanostructured polyelectrolyte layers through layer-by-layer approach.

    PubMed

    Priya, Angel J; Vijayalakshmi, S P; Raichur, Ashok M

    2011-11-09

    The encapsulation of probiotic Lactobacillus acidophilus through layer-by-layer self-assembly of polyelectrolytes (PE) chitosan (CHI) and carboxymethyl cellulose (CMC) has been investigated to enhance its survival in adverse conditions encountered in the GI tract. The survival of encapsulated cells in simulated gastric (SGF) and intestinal fluids (SIF) is significant when compared to nonencapsulated cells. On sequential exposure to SGF and SIF for 120 min, almost complete death of free cells is observed. However, for cells coated with three nanolayers of PEs (CHI/CMC/CHI), about 33 log % of the cells (6 log cfu/500 mg) survived under the same conditions. The enhanced survival rate of encapsulated L. acidophilus can be attributed to the impermeability of polyelectrolyte nanolayers to large enzyme molecules like pepsin and pancreatin that cause proteolysis and to the stability of the polyelectrolyte nanolayers in gastric and intestinal pH. The PE coating also serves to reduce viability losses during freezing and freeze-drying. About 73 and 92 log % of uncoated and coated cells survived after freeze-drying, and the losses occurring between freezing and freeze-drying were found to be lower for the coated cells.

  16. Illustrating the processability of magnetic layered double hydroxides: layer-by-layer assembly of magnetic ultrathin films.

    PubMed

    Coronado, E; Martí-Gastaldo, C; Navarro-Moratalla, E; Ribera, A; Tatay, S

    2013-05-20

    We report the preparation of single-layer layered double hydroxide (LDH) two-dimensional (2D) nanosheets by exfoliation of highly crystalline NiAl-NO3 LDH. Next, these unilamellar moieties have been incorporated layer-by-layer (LbL) into a poly(sodium 4-styrenesulfonate)/LDH nanosheet multilayer ultrathin film (UTF). Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible light (UV-vis), and X-ray diffraction (XRD) profiles have been used to follow the uniform growth of the UTF. The use of a magnetic LDH as the cationic component of the multilayered architecture enables study of the resulting magnetic properties of the UTFs. Our magnetic data show the appearance of spontaneous magnetization at ∼5 K, thus confirming the effective transfer of the magnetic properties of the bulk LDH to the self-assembled film that displays glassy-like ferromagnetic behavior. The high number of bilayers accessible-more than 80-opens the door for the preparation of more-complex hybrid multifunctional materials that combine magnetism with the physical properties provided by other exfoliable layered inorganic hosts.

  17. 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. Copyright © 2016 Elsevier Inc. All rights reserved.

  18. Layer-by-Layer assembled hybrid multilayer thin film electrodes based on transparent cellulose nanofibers paper for flexible supercapacitors applications

    NASA Astrophysics Data System (ADS)

    Wang, Xi; Gao, Kezheng; Shao, Ziqiang; Peng, Xiaoqing; Wu, Xue; Wang, Feijun

    2014-03-01

    Cellulose nanofibers (CNFs) paper with low thermal expansion and electrolyte absorption properties is considered to be a good potential substrate for supercapacitors. Unlike traditional substrates, such as glass or plastic, CNFs paper saves surfaces pretreatment when Layer-by-Layer (LbL) assembly method is used. In this study, negatively charged graphene oxide (GO) nanosheets and poly(3,4-ethylenedioxythiophene: poly(styrene sulfonate)) (PEDOT:PSS) nanoparticles are deposited onto CNFs paper with positively charged polyaniline (PANI) nanowires as agents to prepare multilayer thin film electrodes, respectively. Due to the different nanostructures of reduced graphene oxide (RGO) and PEDOT:PSS, the microstructures of the electrodes are distinguishing. Our work demonstrate that CNFs paper/PANI/RGO electrode provides a more effective pathway for ion transport facilitation compared with CNFs paper/PANI/PEDOT:PSS electrode. The supercapacitor fabricated by CNFs/[PANI-RGO]8 (S-PG-8) exhibits an excellent areal capacitance of 5.86 mF cm-2 at a current density of 0.0043 mA cm-2, and at the same current density the areal capacitance of the supercapacitor fabricated by CNFs/[PANI-PEDOT:PSS]8 (S-PP-8) is 4.22 mF cm-2. S-PG-8 also exhibits good cyclic stability. This study provides a novel method using CNFs as substrate to prepare hybrid electrodes with diverse microstructures that are promising for future flexible supercapacitors.

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

    PubMed

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

    2012-08-01

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

  20. 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.

  1. 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.

  2. Combination of collagen and fibronectin to design biomimetic interfaces: Do these proteins form layer-by-layer assemblies?

    PubMed

    Mauquoy, Sara; Dupont-Gillain, Christine

    2016-11-01

    Layer-by-layer (LbL) assembly is a surface modification method which may bring complexity to biointerfaces designed to control cell-material interactions. This work aims at investigating the LbL assembly of two extracellular matrix proteins, collagen (Col) and fibronectin (Fn), on polystyrene substrates. LbL assembly, which is widely applied to polyelectrolytes, is not easily transferred to proteins. Different buffers and conditions are tested, and LbL assembly is compared to the simultaneous adsorption of Fn and Col. Build-up and properties of the films are monitored using quartz crystal microbalance, ellipsometry, water contact angle measurements, and atomic force microscopy. Results show that denatured Col leads to smoother films, and that the addition of a polyethyleneimine anchoring layer increases film thickness. A more regular construction and thicker films are obtained with Hepes (pH 7.4) compared to other buffers. However, the LbL assembly is not sustainable and stops after the deposition of a few layers. Films obtained by simultaneous adsorption have lower water contact angles, different morphologies, lower water content and are as thick or thicker compared to the ones prepared by the LbL method. The present work shows that collagen and fibronectin are not involved in a true LbL assembly process. The obtained biointerfaces however exhibit different properties compared to those obtained by the one-step adsorption of these proteins. These differences could be exploited to control cell fate.

  3. Strategies to optimize biosensors based on impedance spectroscopy to detect phytic acid using layer-by-layer films.

    PubMed

    Moraes, Marli L; Maki, Rafael M; Paulovich, Fernando V; Rodrigues Filho, Ubirajara P; de Oliveira, Maria Cristina F; Riul, Antonio; de Souza, Nara C; Ferreira, Marystela; Gomes, Henrique L; Oliveira, Osvaldo N

    2010-04-15

    Impedance spectroscopy has been proven a powerful tool for reaching high sensitivity in sensor arrays made with nanostructured films in the so-called electronic tongue systems, whose distinguishing ability may be enhanced with sensing units capable of molecular recognition. In this study we show that for optimized sensors and biosensors the dielectric relaxation processes involved in impedance measurements should also be considered, in addition to an adequate choice of sensing materials. We used sensing units made from layer-by-layer (LbL) films with alternating layers of the polyeletrolytes, poly(allylamine) hydrochloride (PAH) and poly(vinyl sulfonate) (PVS), or LbL films of PAH alternated with layers of the enzyme phytase, all adsorbed on gold interdigitate electrodes. Surprisingly, the detection of phytic acid was as effective in the PVS/PAH sensing system as with the PAH/phytase system, in spite of the specific interactions of the latter. This was attributed to the dependence of the relaxation processes on nonspecific interactions such as electrostatic cross-linking and possibly on the distinct film architecture as the phytase layers were found to grow as columns on the LbL film, in contrast to the molecularly thin PAH/PVS films. Using projection techniques, we were able to detect phytic acid at the micromolar level with either of the sensing units in a data analysis procedure that allows for further optimization.

  4. 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.

  5. Borax mediated layer-by-layer self-assembly of neutral poly(vinyl alcohol) and chitosan.

    PubMed

    Manna, Uttam; Patil, Satish

    2009-07-09

    We report a multilayer film of poly(vinyl alcohol) (PVA)-borate complex and chitosan by using a layer-by-layer approach. PVA is an uncharged polymer, but hydroxyl functional groups of PVA can be cross-linked by using borax as a cross-linking agent. As a result electrostatic charges and intra- and interchain cross-links are introduced in the PVA chain and provide physically cross-linked networks. The PVA-borate was then deposited on a flat substrate as well as on colloidal particles with chitosan as an oppositely charged polyelectrolyte. Quartz crystal microbalance, scanning electron microscopy, and atomic force microscopy were used to follow the growth of thin film on flat substrate. Analogous experiments were performed on melamine formaldehyde colloidal particles (3-3.5 microm) to quantify the process for the preparation of hollow microcapsules. Removal of the core in 0.1 N HCl results in hollow microcapsules. Characterization of microcapsules by transmission electron microscopy revealed formation of stable microcapsules. Further, self-assembly of PVA-borate/chitosan was loaded with the anticancer drug doxorubicin, and release rates were determined at different pH values to highlight the drug delivery potential of this system.

  6. Antimicrobial and antioxidant surface modification of cellulose fibers using layer-by-layer deposition of chitosan and lignosulfonates.

    PubMed

    Li, Hui; Peng, Lincai

    2015-06-25

    To confer cellulose fibers antimicrobial and antioxidant activities, chitosan (CS)/lignosulfonates (LS) multilayers were constructed on fibers surfaces through layer-by-layer deposition technique. The formation of CS/LS multilayers on cellulose fibers surfaces was verified by X-ray photoelectron spectroscopy (XPS) and zeta potential measurement. The surface morphologies of CS/LS multilayers on fibers surfaces were observed by atomic force microscopy (AFM). The results showed that characteristic element (i.e. N and S element) content increased with increasing bilayers number, the surface LS content increased linearly as a function of bilayers. Zeta potential of modified fibers was inversed after deposition of each layer. AFM phase images indicated that the cellulose microfibrils on fibers surfaces were gradually covered by granular LS aggregate. The antimicrobial testing results demonstrated that CS/LS multilayers modified fibers with CS in the outermost layer exhibited higher antimicrobial activity against Escherichia coli. The antioxidant testing results showed that antioxidant activity of CS/LS multilayers modified fibers was better than that of original fibers under the same oxidation conditions.

  7. Photoinduced phenomena in layer-by-layer films of poly(allylamine hydrochloride) and Brilliant Yellow azodye.

    PubMed

    Zucolotto, Valtencir; Barbosa Neto, Newton M; Rodrigues, José J; Constantino, Carlos J L; Zílio, Sérgio C; Mendonça, Cléber R; Aroca, Ricardo F; Oliveira, Osvaldo N

    2004-09-01

    The nanoscale interactions between adjacent layers of layer-by-layer (LBL) films from poly(allylamine hydrochloride) (PAH) and azodye Brilliant Yellow (BY) have been investigated, with the films employed for optical storage and the formation of surface-relief gratings. Using Fourier transform infrared spectroscopy, we identified interactions involving SO3- groups from BY and NH+ groups from PAH. These electrostatic interactions were responsible for the slow kinetics of writing in the optical storage experiments, due to a tendency to hinder photoisomerization and the subsequent reorientation of the azochromophores. The photoinduced birefringence did not saturate after one hour of exposure to the writing laser, whereas in azopolymer films, saturation is normally reached within a few minutes. On the other hand, the presence of such interactions prevented thermal relaxation of the chromophores after the writing laser was switched off, leading to a very stable written pattern. Moreover, the nanoscale interactions promoted mass transport for photoinscription of surface-relief gratings on PAH/BY LBL films, with the azochromophores being able to drag the inert PAH chains when undergoing the trans-cis-trans photoisomerization cycles. A low level of chromophore degradation was involved in the SRG photoinscription, which was confirmed with micro-Raman and fluorescence spectroscopies.

  8. Layer-by-layer structured polysaccharides-based multilayers on cellulose acetate membrane: Towards better hemocompatibility, antibacterial and antioxidant activities

    NASA Astrophysics Data System (ADS)

    Peng, Lincai; Li, Hui; Meng, Yahong

    2017-04-01

    The development of multifunctional cellulose acetate (CA) membranes with enhanced hemocompatibility and antibacterial and antioxidant activities is extremely important for biomedical applications. In this work, significant improvements in hemocompatibility and antibacterial and antioxidant activities of cellulose acetate (CA) membranes were achieved via layer-by-layer (LBL) deposition of chitosan (CS) and water-soluble heparin-mimicking polysaccharides (i.e., sulfated Cantharellus cibarius polysaccharides, SCP) onto their surface. The surface chemical compositions, growth manner, surface morphologies, and wetting ability of CS/SCP multilayer-modified CA membranes were characterized, respectively. The systematical evaluation of hemocompatibility revealed that CS/SCP multilayer-modified CA membranes significantly improved blood compatibility including resistance to non-specific protein adsorption, suppression of platelet adhesion and activation, prolongation of coagulation times, inhibition of complement activation, as well as reduction in blood hemolysis. Meanwhile, CS/SCP multilayer-modified CA membranes exhibited strong growth inhibition against Escherichia coli and Staphylococcus aureus, as well as high scavenging abilities against superoxide and hydroxyl radicals. In summary, the CS/SCP multilayers could confer CA membranes with integrated hemocompatibility and antibacterial and antioxidant activities, which might have great potential application in the biomedical field.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. Layer-by-layer assembled carbon nanotube films with molecule recognition function and lower capacitive background current.

    PubMed

    Kong, Bo; Zeng, Jinxiang; Luo, Guangming; Luo, Shenglian; Wei, Wanzhi; Li, Jun

    2009-02-01

    Multilayer films of multiwalled carbon nanotubes (MWCNTs) with molecule recognition function were assembled on glassy carbon (GC) electrode with lower capacitive background current by two steps: first, MWCNTs interacted with beta-cyclodextrin (beta-CD) with the aid of sonication to form beta-CD-MWCNTs nanocomposite, then the beta-CD-MWCNTs nanocomposite was assembled on GC electrode using layer-by-layer (LBL) method based on electrostatic interaction of positively charged biopolymer chitosan and negatively charged MWCNTs. The assembled beta-CD-MWCNTs multilayer films were characterized by scanning electron microscopy (SEM) and cyclic voltammetry. The SEM indicated that the MWCNTs multilayer films with beta-CD were somewhat more compact than that of the MWCNTs multilayer films without beta-CD. The cyclic voltammetric results indicated that the assembled MWCNTs with beta-CD on GC electrode exhibited lower capacitive background current than the assembled MWCNTs without beta-CD. The MWCNTs multilayer films with beta-CD were studied with respect to the electrocatalytic activity toward dopamine (DA). Compared with the MWCNTs multilayer films without beta-CD, the MWCNTs multilayer films with beta-CD possesses a much lower capacitive background current and higher electrocatalytic activity in phosphate buffer, which was ascribed to the relatively compact three-dimensional structure of the MWCNTs multilayer films with beta-CD and the excellent molecule recognition function of beta-CD.

  14. Layer-by-layer assembled carbon nanotubes for selective determination of dopamine in the presence of ascorbic acid.

    PubMed

    Zhang, Meining; Gong, Kuanping; Zhang, Hongwu; Mao, Lanqun

    2005-01-15

    Multilayer films of shortened multi-walled carbon nanotubes (MWNTs) are homogeneously and stably assembled on glassy carbon (GC) electrodes using layer-by-layer (LBL) method based on electrostatic interaction of positively charged poly(diallyldimethylammonium chloride) (PDDA) and negatively charged shortened MWNTs. The assembled MWNT multilayer films were studied with respect to the electrocatalytic activity toward ascorbic acid (AA) and dopamine (DA) and were further applied for selective determination of DA in the presence of AA. Scanning electron microscopy (SEM) used for characterization of MWNT films indicates that the assembled MWNTs are almost in a form of small bundles or single nanotubes on the electrodes. Cyclic voltammetric results with assembled MWNT electrode indicate that the strategy based on the LBL method for assembling the MWNT multilayer films on substrate well retains the electrochemical catalytic activity of the MWNTs toward AA and DA, offering some advantages particularly attractive for analytical applications, such as the form of MWNTs assembled on the substrate, i.e., small bundles or single tubes, homogeneity and stability of the as-assembled MWNT films. These features make the assembled MWNTs relatively potential for selective and sensitive determination of DA in the presence of AA.

  15. Layer-by-layer deposition on a heterogeneous surface: Effect of sorption kinetics on the growth of polyelectrolyte multilayers.

    PubMed

    Bellanger, Hervé; Casdorff, Kirstin; Muff, Livius F; Ammann, Rebecca; Burgert, Ingo; Michen, Benjamin

    2017-08-15

    Surface functionalization by means of controlled deposition of charged polymers or nanoparticles using the layer-by-layer (LbL) approach has been used to modify mostly engineered materials with well-defined surface chemistry and morphology. In this regard, natural and inhomogeneous interfaces have gained very little attention. Furthermore, natural substrates are susceptible to alterations by factors commonly used to control the growth of multilayers, such as pH, temperature and ionic strength. Here, we study the impact of sorption kinetics of a bilayer system (Poly(diallyldimethylammonium chloride) (PDDA) and Poly(sodium 4-styrenesulfonate) (PSS)) on a natural heterogeneous wood surface at neutral pH, without salt addition, on the multilayer buildup. To overcome analytical limitations we introduce a complementary approach based on UV reflectance spectroscopy, atomic force microscopy (AFM) and zeta potential measurements. Compared to immersion times used for ideal substrates, we found that a high surface coverage requires relatively long immersion, approximately 30min, into polyelectrolyte solutions, while a sufficient removal of polyelectrolyte excess during the washing step, requires even longer, about 100min. Based on these findings, we show that film growth can be controlled kinetically. Long immersion times provide well-defined and regular multilayers. The obtained data points to specific requirements to be considered when LbL treatments are applied to rough, porous and heterogeneous surfaces, and thereby sets a basis for a successful transfer of various surface functionalization approaches already shown on ideal surfaces. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. 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.

  17. Layer-By-Layer Nanoparticle Vaccines Carrying the G Protein CX3C Motif Protect against RSV Infection and Disease

    PubMed Central

    Jorquera, Patricia A.; Oakley, Katie E.; Powell, Thomas J.; Palath, Naveen; Boyd, James G.; Tripp, Ralph A.

    2015-01-01

    Respiratory syncytial virus (RSV) is the single most important cause of serious lower respiratory tract infections in young children; however no effective treatment or vaccine is currently available. Previous studies have shown that therapeutic treatment with a monoclonal antibody (clone 131-2G) specific to the RSV G glycoprotein CX3C motif, mediates virus clearance and decreases leukocyte trafficking to the lungs of RSV-infected mice. In this study, we show that vaccination with layer-by-layer nanoparticles (LbL-NP) carrying the G protein CX3C motif induces blocking antibodies that prevent the interaction of the RSV G protein with the fractalkine receptor (CX3CR1) and protect mice against RSV replication and disease pathogenesis. Peptides with mutations in the CX3C motif induced antibodies with diminished capacity to block G protein-CX3CR1 binding. Passive transfer of these anti-G protein antibodies to mice infected with RSV improved virus clearance and decreased immune cell trafficking to the lungs. These data suggest that vaccination with LbL-NP loaded with the CX3C motif of the RSV G protein can prevent manifestations of RSV disease by preventing the interaction between the G protein and CX3CR1 and recruitment of immune cells to the airways. PMID:26473935

  18. 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.

  19. Fabrication of hybrid graphene oxide/polyelectrolyte capsules by means of layer-by-layer assembly on erythrocyte cell templates.

    PubMed

    Irigoyen, Joseba; Politakos, Nikolaos; Diamanti, Eleftheria; Rojas, Elena; Marradi, Marco; Ledezma, Raquel; Arizmendi, Layza; Rodríguez, J Alberto; Ziolo, Ronald F; Moya, Sergio E

    2015-01-01

    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.

  20. 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

  1. Layer-by-Layer Quantum Dot Assemblies for the Enhanced Energy Transfers and Their Applications toward Efficient Solar Cells.

    PubMed

    Choi, Sukyung; Jin, Ho; Bang, Jiwon; Kim, Sungjee

    2012-12-06

    Two different quantum dots (QDs) with an identical optical band gap were prepared: one without the inorganic shell and short surface ligands (BQD) and the other with thick inorganic shells and long surface ligands (OQD). They were surface-derivatized to be positively or negatively charged and were used for layer-by-layer assemblies on TiO2. By sandwiching BQD between OQD and TiO2, OQD photoluminescence showed seven times faster decay, which is attributed to the combined effect of the efficient energy transfer from OQD to BQD with the FRET efficiency of 86% and fast electron transfer from BQD to TiO2 with the rate of 1.2 × 10(9) s(-1). The QD bilayer configuration was further applied to solar cells, and showed 3.6 times larger photocurrent and 3.8 times larger photoconversion efficiency than those of the device with the OQD being sandwiched by BQD and TiO2. This showcases the importance of sophisticated control of QD layer assembly for the design of efficient QD solar cells.

  2. 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.

  3. Preparation, characterization and properties of amino-functionalized montmorillonite and composite layer-by-layer assembly with inorganic nanosheets

    NASA Astrophysics Data System (ADS)

    Huang, Guo-bo; Ge, Chang-hua; He, Bing-jing

    2011-06-01

    An amino-functionalized montmorillonite (APTMS-MMT) was prepared by the grafting of 3-aminopropyltrimethoxysilane (APTMS) on the surface of MMT via the ultrasonic synthesis process and characterized by a variety of techniques: FT-IR, thermogravimetic analysis (TGA), particles size analysis and ζ-potential measurement. The results showed the size and size distribution of APTMS-MMT particles were decreased, and the ζ-potential of particles was increased obviously via the ultrasonic synthesis process. The particles of 30% APTMS-MMT US (MMT modified with 30 wt% APTMS with ultrasonic synthesis process) had a z-average diameter of about 500 nm and a polydispersity index of 0.2. The resultant 30% APTMS-MMT US was dispersed uniformly and stably in water. The poly(acrylic acid) (PAA)/APTMS-MMT multilayer films were grown through layer-by-layer (LBL) deposition of PAA and APTMS-MMT. SEM results indicated that the ultrasonic synthesis of APTMS-MMT increased dispersability of clay sheets at high loadings. The thermal stability and mechanical properties of PAA/APTMS-MMT composites were investigated by TGA and tensile test respectively. The results showed the ultrasonic synthesis of APTMS-MMT enhanced the thermal stability and mechanical properties of PAA/APTMS-MMT composites significantly. PAA/30% APTMS-MMT US composite displayed 3 times higher strength and 6 times higher Young's modulus when compared with pure PAA polymer.

  4. 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.

  5. 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

  6. Layer by layer self-assembly of poly[2-(methacryloyloxy) ethyl phosphorylcholine] multilayer via the ionic complexation with zirconium.

    PubMed

    Pang, Shaopeng; Zhu, Congshan; Xu, Fangming; Chen, Chaojian; Ji, Jian

    2012-06-01

    Zirconium-phosphonate (Zr-P) ionic complexation chemistry is explored as a new approach to fabricate poly[2-(methacryloyloxy) ethyl phosphorylcholine] (PMPC) multilayer film by layer-by-layer self-assembly method. Quartz crystal microbalance with dissipation (QCM-D) and optical ellipsometry measurements demonstrated that PMPC layer can be fully absorbed on each Zr(4+) layer. The thickness of the multilayer film with a good linear relationship was followed by the ellipsometry in situ adlayer characterization. The influence of pH of the PMPC and Zr(4+) solutions on the multilayer deposition were investigated by optical ellipsometry. QCM-D results indicated that the multilayer film is stable in a PBS flowing chamber at a high flow rate of 5.2×10(-3)m/s. The ellipsometry data demonstrated that 67.2% of the film still remained on the silicon wafer after being strong shaken in PBS at 80 rpm for 12h. The adsorption of bovine serum albumin (BSA) and fetal bovine serum (FBS) on the PMPC surface was monitored by the QCM-D and spectroscopic ellipsometry, and the results showed the multilayer film have excellent protein resistance.

  7. Layer-by-layer coating of bacteria with noble metal nanoparticles for surface-enhanced Raman scattering.

    PubMed

    Kahraman, Mehmet; Zamaleeva, Alsu I; Fakhrullin, Rawil F; Culha, Mustafa

    2009-12-01

    A simple layer-by-layer method to coat the bacterial cells with gold and silver nanoparticles (AuNPs and AgNPs) for the acquisition of surface-enhanced Raman scattering (SERS) spectra is reported. First, the bacteria cell wall is coated with poly (allylamine hydrochloride) (PAH), a positively charged polymer, and then with citrate reduced Au or AgNPs. In order to increase the stability of the coating, another layer of PAH is prepared on the surface. The SEM and AFM images indicate that the nanoparticles are in the form of both isolated and aggregated nanoparticles on the bacterial wall. The coating of bacterial cells with AgNPs or AuNPs not only serves for their preparation for SERS measurement but also helps to visualize the coated of bacterial cells under the ordinary white-light microscope objective due to efficient light-scattering properties of Au and AgNPs. A comparative study single versus aggregates of bacterial cells is also demonstrated for possible single bacterial detection with SERS. The two bacteria that differ in shape and cell wall biochemical structure, Escherichia coli and Staphylococcus cohnii, Gram-negative and -positive, respectively, are used as models. The preliminary results reveal that the approach could be used for single bacterial cell identification.

  8. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  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. 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. Fabrication of positively charged nanofiltration membrane via the layer-by-layer assembly of graphene oxide and polyethylenimine for desalination

    NASA Astrophysics Data System (ADS)

    Nan, Qian; Li, Pei; Cao, Bing

    2016-11-01

    Highly positively charged nanofiltration (NF) membranes have been prepared via a layer-by-layer (LbL) self-assembly technique using graphene oxide (GO) and polyethyleneimine (PEI). The high aspect ratio and unique 2D structure of GO nanosheets enabled them to be easily assembled on the membrane surface, and the intrinsic low resistant channels within the GO nanosheets resulted in a high water flux of the membrane. By assembled a PEI layer on the membrane outer surface, the composite membrane exhibited high positive charge and resulted in the high rejections to multivalent ions. The effects of deposition time, PEI and GO concentrations on separation performance of the NF membranes were detailed studied. The best performance among all the membranes was achieved with salt rejections of 93.9% and 38.1% for Mg2+ and Na+, and a water flux of 4.2 L/m2 h bar at 30 °C and 0.5 MPa. The attractive performance of these NF membranes showed a great potential in the industrial application of water softening.

  12. 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. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Effect of layer-by-layer confinement of polypeptides and polysaccharides onto thermoresponsive microgels: a comparative study.

    PubMed

    Díez-Pascual, Ana M; Wong, John E

    2010-07-01

    The confinement of polyelectrolyte multilayers of poly-L-lysine (PLL)/poly-L-glutamic acid (PGA) and chitosan (CHIT)/dextran sulfate (DEX) onto soft and porous thermoresponsive poly(N-isopropylacrylamide-co-methacrylic acid) (P(NiPAM-co-MAA)) microgel was studied by dynamic light scattering (DLS) and electrophoretic measurements. DLS demonstrates an "odd-even" effect in the hydrodynamic radius depending on the type of polyelectrolyte in the outermost layer and that coated microgels retain their native thermoresponsive property. Strong hysteresis is found between the swelling and deswelling processes of microgels coated with polypeptides, whilst for those coated with polysaccharides are nearly reversible. Electrophoretic mobility results indicate charge reversal after each layer deposition, which magnitude decreases with increasing number of layers. Microgels coated with polysaccharides exhibit higher mobility values. Stability studies reveal spatial and temporal reorganization of the polymer chains over several weeks. Upon increasing time, the hydrodynamic radius of polypeptide-terminated microgels decreases, whereas that of polysaccharide-terminated increases to almost the original size of the uncoated microgel. Both systems exhibit an exponential growth of the bilayer thickness with the number of deposition steps, more pronounced for microgels coated with polypeptides. Our results demonstrate the feasibility of the layer-by-layer assembly of these biopolymers onto microgels, which could have potential application for storage and release of biomolecules.

  14. Preparation and characterization of fouling-resistant composite membranes based on layer-by-layer self-assembly technique.

    PubMed

    Duan, J L; Zhang, H M; Wang, C C; Li, H Y; Yang, F L

    2011-01-01

    This paper introduces a versatile approach for surface modification of 621-terylene filtration fabric (FF) self-assembled by a dynamic layer-by-layer technique. The hexadecyl trimethyl ammonium bromide (HTAB) and cross-linked polyvinyl alcohol microspheres (PVA-MS) were alternatively deposited on support membrane under a pressure of 0.01 MPa to modify FF. Morphological changes and hydrophilicity of the modified FF were characterized in detail by scanning electron micrograph and water contact angle measurements. Results revealed that PVA-MS could be adsorbed mainly on the surface of FF and water contact angle decreased with the increase of HTAB/PVA-MS bilayer numbers indicating an enhanced hydrophilicity for the modified FF. Backwash experiments of the modified FF exhibited much higher stability of PVA-MS. Protein adsorption experiments were conducted to evaluate the antifouling property of the modified FF. Results indicated that protein adsorption of the membrane surface could be obviously improved by modification, which exhibited superior antifouling property of the modified FF.

  15. Highly Anisotropic Thermal Conductivity of Layer-by-Layer Assembled Nanofibrillated Cellulose/Graphene Nanosheets Hybrid Films for Thermal Management.

    PubMed

    Song, Na; Jiao, Dejin; Cui, Siqi; Hou, Xingshuang; Ding, Peng; Shi, Liyi

    2017-01-25

    An anisotropic thermally conductive film with tailorable microstructures and macroproperties is fabricated using a layer-by-layer (LbL) assembly of graphene oxide (GO) and nanofibrillated cellulose (NFC) on a flexible NFC substrate driven by hydrogen bonding interactions, followed by chemical reduction process. The resulting NFC/reduced graphene oxide (RGO) hybrid film reveals an orderly hierarchical structure in which the RGO nanosheets exhibit a high degree of orientation along the in-plane direction. The assembly cycles dramatically increase the in-plane thermal conductivity (λX) of the hybrid film to 12.6 W·m(-1)·K(-1), while the cross-plane thermal conductivity (λZ) shows a lower value of 0.042 W·m(-1)·K(-1) in the hybrid film with 40 assembly cycles. The thermal conductivity anisotropy reaches up to λX/λZ = 279, which is substantially larger than that of similar polymeric nanocomposites, indicating that the LbL assembly on a flexible NFC substrate is an efficient technique for the preparation of polymeric nanocomposites with improved heat conducting property. Moreover, the layered hybrid film composed of 1D NFC and 2D RGO exhibits synergetic mechnical properties with outstanding flexibility and a high tensile strength (107 MPa). The combination of anisotropic thermal conductivity and superior mechanical performance may facilitate the applications in thermal management.

  16. Preparation and characterization of lanthanide-azo-dye coordination polymers and polymer thin films via layer-by-layer depositions.

    PubMed

    Han, Li-Wei; Lü, Jian; Liu, Tian-Fu; Gao, Shui-Ying; Cao, Rong

    2010-12-07

    A series of tartrazine-lanthanide dye compounds has been synthesized and characterized. Structural studies reveal that the light rare-earth elements La, Ce, Pr and Nd form coordination compounds with tartrazine ligands in a 1:1 ratio and result in 1-D 'fish-bone' chain-like structures having uncoordinated organosulfonate groups on each side of the chain. However, reactions of tartrazine and heavy rare-earth elements Ho, Er, Tm and Yb, in the presence of auxiliary 1,10-phenanthroline, give new 1-D coordination polymers in which uncoordinated organosulfonate groups are located on the same side of the chains. The tartrazine ligands display similar but slightly different coordination modes in both types of structures and the 1,10-phenanthroline plays a vital role in the formation of heavy rare-earth dye compounds. Based on the knowledge of their structures, the light rare-earth dye compounds were utilized to assemble with positively-charged PEI into multilayer thin films by means of layer-by-layer depositions. The as-synthesized thin films showed enhanced stability and consistency on solid surfaces.

  17. Nonuniform Growth of Composite Layer-by-Layer Assembled Coatings via Three-Dimensional Expansion of Hydrophobic Magnetite Nanoparticles.

    PubMed

    Voronin, Denis V; Grigoriev, Dmitry; Möhwald, Helmuth; Shchukin, Dmitry G; Gorin, Dmitry A

    2015-12-30

    Nanocomposite coatings are promising for a range of practical applications, and layer-by-layer assembly (LbL) is a versatile tool for nanocomposite formation. However, conventional LbL is a quite laborious procedure taking a lot of time to reach a sufficient thickness of the coatings required for practical applications. Herein, we proposed a novel variant of the LbL approach based on the deposition of hydrophilic polyelectrolyte molecules from a polar solvent and hydrophobic magnetite nanoparticles (NPs) from a nonpolar dispersion medium with an intermediate washing in the same polar solvent. The composite multilayers formed in this way exhibit exponential growth of the thickness and mass. On the basis of quartz crystal microbalance (QCM), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), and surface profile measurements, we propose a model describing the driving force of multilayer formation and the factors leading to nonlinear growth of their mass and thickness. The results allow one to expand the understanding of the mechanism of the LbL assembly in order to form multifunctional nanocomposites in a more efficient way.

  18. Tuning Thermal Transitions in Dry and Hydrated Polyelectrolyte Layer by Layer Assemblies with Ionic Strength and pH

    NASA Astrophysics Data System (ADS)

    Vidyasagar, Ajay; Lutkenhaus, Jodie

    2012-02-01

    Layer-by-layer (LbL) assemblies are of significant interest for their potential applications in diverse fields such as energy and drug delivery. However, characterizing their thermal properties has remained a challenge. Here, we present the characterization of dry and of hydrated LbL films containing strong polyelectrolytes poly(diallyldimethylammonium chloride) (PDAC) and poly(styrene sulfonate) PSS) using modulated differential scanning calorimetry (MDSC) and temperature controlled quartz crystal microbalance with dissipation (QCM-D). Our results suggest that hydrated exponentially growing (assembled from 0.25-1.25 M NaCl solutions) PDAC/PSS LbL films have glass transition temperatures (Tg's) between 48-51 ^oC, while linearly growing (assembled from 0 M NaCl) films did not. Other systems explored include poly(allylamine hydrochloride)/poly(acrylic acid)(PAH/PAA) LbL assemblies, which demonstrate linear/exponential growth depending on assembly pH conditions. These results support a standing hypothesis in that linear (or exponential) growth is observed for glassy (or rubbery) LbL films. We have also demonstrated for the first time, thermal transitions in thin PDAC/PSS LbL films using QCM-D by monitoring fluctuations in film hydration and viscoelasticity by probing the film's internal structure as a function of film depth.

  19. Layer-by-layer assembly of bi-protein/layered double hydroxide ultrathin film and its electrocatalytic behavior for catechol.

    PubMed

    Kong, Xianggui; Rao, Xiuying; Han, Jingbin; Wei, Min; Duan, Xue

    2010-10-15

    This paper reports the fabrication of a bi-protein/layered double hydroxide (LDH) ultrathin film in which hemoglobin (HB) and horseradish peroxidase (HRP) molecules were assembled alternately with LDH nanosheets via the layer-by-layer (LBL) deposition technique, and its electrocatalytic performances for oxidation of catechol were demonstrated. The results of XRD indicate that the HB-HRP/LDH ultrathin film possesses a long range stacking order in the normal direction of the substrate, with the two proteins accommodated in the LDH gallery respectively as monolayer arrangement. SEM images show that the film surface exhibits a continuous and uniform morphology, and AFM reveals the Root-Mean-Square (RMS) roughness of ∼10.2 nm for the film. A stable direct electrochemical redox behavior of the proteins was successfully obtained for the HB-HRP/LDH film modified electrode. In addition, it exhibits remarkable electrocatalytic activity towards oxidation of catechol, based on the synergistic effect of the two proteins. The catechol biosensor in this work displays a wide linear response range (6-170 μM, r=0.999), low detection limit (5 μM), high sensitivity and good reproducibility.

  20. Releasable layer-by-layer assembly of stabilized lipid nanocapsules on microneedles for enhanced transcutaneous vaccine delivery.

    PubMed

    DeMuth, Peter C; Moon, James J; Suh, Heikyung; Hammond, Paula T; Irvine, Darrell J

    2012-09-25

    Here we introduce a new approach for transcutaneous drug delivery, using microneedles coated with stabilized lipid nanocapsules, for delivery of a model vaccine formulation. Poly(lactide-co-glycolide) microneedle arrays were coated with multilayer films via layer-by-layer assembly of a biodegradable cationic poly(β-amino ester) (PBAE) and negatively charged interbilayer-cross-linked multilamellar lipid vesicles (ICMVs). To test the potential of these nanocapsule-coated microneedles for vaccine delivery, we loaded ICMVs with a protein antigen and the molecular adjuvant monophosphoryl lipid A. Following application of microneedle arrays to the skin of mice for 5 min, (PBAE/ICMV) films were rapidly transferred from microneedle surfaces into the cutaneous tissue and remained in the skin following removal of the microneedle arrays. Multilayer films implanted in the skin dispersed ICMV cargos in the treated tissue over the course of 24 h in vivo, allowing for uptake of the lipid nanocapsules by antigen presenting cells in the local tissue and triggering their activation in situ. Microneedle-mediated transcutaneous vaccination with ICMV-carrying multilayers promoted robust antigen-specific humoral immune responses with a balanced generation of multiple IgG isotypes, whereas bolus delivery of soluble or vesicle-loaded antigen via intradermal injection or transcutaneous vaccination with microneedles encapsulating soluble protein elicited weak, IgG(1)-biased humoral immune responses. These results highlight the potential of lipid nanocapsules delivered by microneedles as a promising platform for noninvasive vaccine delivery applications.

  1. Graphene as a spacer to layer-by-layer assemble electrochemically functionalized nanostructures for molecular bioelectronic devices.

    PubMed

    Wang, Xiang; Wang, Jingfang; Cheng, Hanjun; Yu, Ping; Ye, Jianshan; Mao, Lanqun

    2011-09-06

    This study demonstrates the capability of graphene as a spacer to form electrochemically functionalized multilayered nanostructures onto electrodes in a controllable manner through layer-by-layer (LBL) chemistry. Methylene green (MG) and positively charged methylimidazolium-functionalized multiwalled carbon nanotubes (MWNTs) were used as examples of electroactive species and electrochemically useful components for the assembly, respectively. By using graphene as the spacer, the multilayered nanostructures of graphene/MG and graphene/MWNT could be readily formed onto electrodes with the LBL method on the basis of the electrostatic and/or π-π interaction(s) between graphene and the electrochemically useful components. Scanning electron microscopy (SEM), ultraviolet-visible spectroscopy (UV-vis), and cyclic voltammetry (CV) were used to characterize the assembly processes, and the results revealed that nanostructure assembly was uniform and effective with graphene as the spacer. Electrochemical studies demonstrate that the assembled nanostructures possess excellent electrochemical properties and electrocatalytic activity toward the oxidation of NADH and could thus be used as electronic transducers for bioelectronic devices. This potential was further demonstrated by using an alcohol dehydrogenase-based electrochemical biosensor and glucose dehydrogenase-based glucose/O(2) biofuel cell as typical examples. This study offers a simple route to the controllable formation of graphene-based electrochemically functionalized nanostructures that can be used for the development of molecular bioelectronic devices such as biosensors and biofuel cells.

  2. 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.

  3. Layer-by-layer engineered Co-Al hydroxide nanosheets/graphene multilayer films as flexible electrode for supercapacitor.

    PubMed

    Dong, Xinyi; Wang, Lei; Wang, Dong; Li, Cheng; Jin, Jian

    2012-01-10

    Multilayer films of Co-Al layered double hydroxide nanosheets (Co-Al LDH-NS) and graphene oxide (GO) were fabricated through layer-by-layer (LBL) assembly. By using a three-electrode system, the electrochemical performances of the films were investigated to evaluate their potential as electrode materials to be used in flexible supercapacitor devices. The Co-Al LDH-NS/GO multilayer films exhibited a high specific capacitance of 880 F/g and area capacitance of 70 F/m(2) under the scan rate of 5 mV/s. And the film exhibited good cycle stability over 2000 cycles. After treating the films at 200 °C in H(2) atmosphere, the specific capacitance and area capacitance were largely increased up to 1204 F/g and 90 F/m(2) due to partial reduction of GO. A flexible electrode by depositing Co-Al LDH-NS/GO multilayer film onto PET substrate was prepared to show the potential of Co-Al LDH-NS/GO films for flexible energy storage.

  4. 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.

  5. Improved and targeted delivery of bioactive molecules to cells with magnetic layer-by-layer assembled microcapsules.

    PubMed

    Pavlov, Anton M; Gabriel, Samantha A; Sukhorukov, Gleb B; Gould, David J

    2015-06-07

    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.

  6. 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.

  7. Microscopic Characterization of Individual Submicron Bubbles during the Layer-by-Layer Deposition: Towards Creating Smart Agents

    PubMed Central

    Kato, Riku; Frusawa, Hiroshi

    2015-01-01

    We investigated the individual properties of various polyion-coated bubbles with a mean diameter ranging from 300 to 500 nm. Dark field microscopy allows one to track the individual particles of the submicron bubbles (SBs) encapsulated by the layer-by-layer (LbL) deposition of cationic and anionic polyelectrolytes (PEs). Our focus is on the two-step charge reversals of PE-SB complexes: the first is a reversal from negatively charged bare SBs with no PEs added to positive SBs encapsulated by polycations (monolayer deposition), and the second is overcharging into negatively charged PE-SB complexes due to the subsequent addition of polyanions (double-layer deposition). The details of these phenomena have been clarified through the analysis of a number of trajectories of various PE-SB complexes that experience either Brownian motion or electrophoresis. The contrasted results obtained from the analysis were as follows: an amount in excess of the stoichiometric ratio of the cationic polymers was required for the first charge-reversal, whereas the stoichiometric addition of the polyanions lead to the electrical neutralization of the PE-SB complex particles. The recovery of the stoichiometry in the double-layer deposition paves the way for fabricating multi-layered SBs encapsulated solely with anionic and cationic PEs, which provides a simple protocol to create smart agents for either drug delivery or ultrasound contrast imaging. PMID:28793432

  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. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. 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.

  10. Layer-by-layer fabrication of broad-band superhydrophobic antireflection coatings in near-infrared region.

    PubMed

    Zhang, Lianbin; Li, Yang; Sun, Junqi; Shen, Jiacong

    2008-03-01

    Broad-band superhydrophobic antireflective (AR) coatings in near infrared (NIR) region were readily fabricated on silicon or quartz substrates by a layer-by-layer (LbL) assembly technique. First, a porous poly(diallyldimethylammonium chloride) (PDDA)/SiO2 nanoparticle multilayer coating with AR property was prepared by LbL deposition of PDDA and 200 nm SiO2 nanoparticles. PDDA was then alternately assembled with sodium silicate on the PDDA/SiO2 nanoparticle coating to prepare a two-level hierarchical surface. Superhydrophobic AR coating with a water contact angle of 154 degrees was finally obtained after chemical vapor deposition of a layer of fluoroalkylsilane on the hierarchical surface. Quartz substrate with the as-fabricated superhydrophobic AR coating has a maximal transmittance above 98% of incidence light in the NIR region, which is increased by five percent compared with bare quartz substrate. Simultaneously, the superhydrophobic property endows the AR coating with water-repellent ability. Such superhydrophobic AR coatings can effectively avoid the disturbance of water vapor on their AR property and are expected to be applicable under humid environments.

  11. Improving the Flame Retardant Efficiency of Layer by Layer Coatings Containing Deoxyribonucleic Acid by Post-Diffusion of Hydrotalcite Nanoparticles

    PubMed Central

    Carosio, Federico; Alongi, Jenny; Paravidino, Chiara; Frache, Alberto

    2017-01-01

    This work deals with the use of hydrotalcite nanoparticle post-diffusion in layer by layer (LbL) coatings with the aim of improving their flame retardant action on cotton. The selected LbL components, which encompass polydiallyldimethylammonium chloride and deoxyribonucleic acid, aim at the deposition of an intumescent coating. Infrared spectra pointed out a super-linear growth of the investigated assembly, indicating the ability to deposit thick coatings while maintaining a relatively low deposition number. A post-diffusion process, performed by exposing the LbL-treated fabrics to two different concentrations of hydrotalcite water suspensions (0.1 or 1 wt %), was carried out to improve the fireproofing efficiency of these coatings. Coatings treated with the lowest concentration suspension partially swelled as a consequence of their structural rearrangements while the use of the highest concentration led to nanoparticle aggregates. Horizontal flame spread tests were used for assessing the achieved flame retardant properties. The post-diffusion performed at the lowest hydrotalcite concentration lowers the minimum number of Bi-Layers required for obtaining cotton self-extinguishment while samples treated with the highest concentration showed detrimental effects on the performances of treated fabrics. This behavior is ascribed to the effects of hydrotalcite particles on the intumescence of LbL coatings, as evidenced by the morphological analyses of post-combustion residues. PMID:28773071

  12. 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.

  13. Quantitative Nanomechanical Properties of Multilayer Films Made of Polysaccharides through Spray Assisted Layer-by-Layer Assembly.

    PubMed

    Criado, Miryam; Rebollar, Esther; Nogales, Aurora; Ezquerra, Tiberio A; Boulmedais, Fouzia; Mijangos, Carmen; Hernández, Rebeca

    2017-01-09

    Nanomechanical properties of alginate/chitosan (Alg/Chi) multilayer films, obtained through spray assisted layer-by-layer assembly, were studied by means of PeakForce quantitative nanomechanical mapping atomic force microscopy (PF-QNM AFM). Prepared at two different alginate concentrations (1.0 and 2.5 mg/mL) and a fixed chitosan concentration (1.0 mg/mL), Alg/Chi films have an exponential growth in thickness with a transition to a linear growth toward a plateau by increasing the number of deposited bilayers. Height, elastic modulus, deformation, and adhesion maps were simultaneously recorded depending on the number of deposited bilayers. The elastic modulus of Alg/Chi films was found to be related to the mechanism of growth in contrast to the adhesion and deformation. A comparison of the nanomechanical properties obtained for non-cross-linked and thermally cross-linked Alg/Chi films revealed an increase of the elastic modulus after cross-linking regardless alginate concentration. The incorporation of iron oxide nanoparticles (NPs), during the spray preparation of the films, gave rise to nanocomposite Alg/Chi films with increased elastic moduli with the number of incorporated NPs layers. Deformation maps of the films strongly suggested the presence of empty spaces associated with the method of preparation. Finally, adhesion measurements point out to a significant role of NPs on the increase of the adhesion values found for nanocomposite films.

  14. Study of layer-by-layer films on thermoresponsive nanogels using temperature-controlled dual-focus fluorescence correlation spectroscopy.

    PubMed

    Wong, John E; Müller, Claus B; Díez-Pascual, Ana M; Richtering, Walter

    2009-12-10

    While a few studies have reported on the layer-by-layer (LbL) assembly of polyelectrolytes on soft and porous templates, none have really demonstrated direct proof that the layers are actually on the template. Thermoresponsive nanogels present challenges that render a quantitative proof of successful polyelectrolyte deposition extremely difficult. Additionally, the fate of the polyelectrolyte has never been investigated during the phase transition of the coated nanogel. Here, the auto- and cross-correlation functions of a labeled polyelectrolyte assembled via the LbL technique onto soft and porous thermoresponsive labeled nanogels using dual-focus fluorescence correlation spectroscopy (2f-FCS) are presented. Performing 2f-FCS as a function of temperature, hydrodynamic radii of nanogels coated with various numbers of layers are determined, which are found to be in excellent agreement with values obtained from dynamic light scattering. This study presents irrefutable quantitative evidence of successful LbL assembly on thermoresponsive nanogels and demonstrates that the layers are not stripped off during the phase transition of the nanogels. Forster Resonance Energy Transfer (FRET) detection also supports our findings.

  15. Layer-by-Layer Assembly of Biopolyelectrolytes onto Thermo/pH-Responsive Micro/Nano-Gels

    PubMed Central

    Díez-Pascual, Ana M.; Shuttleworth, Peter S.

    2014-01-01

    This review deals with the layer-by-layer (LbL) assembly of polyelectrolyte multilayers of biopolymers, polypeptides (i.e., poly-l-lysine/poly-l-glutamic acid) and polysaccharides (i.e., chitosan/dextran sulphate/sodium alginate), onto thermo- and/or pH-responsive micro- and nano-gels such as those based on synthetic poly(N-isopropylacrylamide) (PNIPAM) and poly(acrylic acid) (PAA) or biodegradable hyaluronic acid (HA) and dextran-hydroxyethyl methacrylate (DEX-HEMA). The synthesis of the ensembles and their characterization by way of various techniques is described. The morphology, hydrodynamic size, surface charge density, bilayer thickness, stability over time and mechanical properties of the systems are discussed. Further, the mechanisms of interaction between biopolymers and gels are analysed. Results demonstrate that the structure and properties of biocompatible multilayer films can be finely tuned by confinement onto stimuli-responsive gels, which thus provides new perspectives for biomedical applications, particularly in the controlled release of biomolecules, bio-sensors, gene delivery, tissue engineering and storage. PMID:28788259

  16. Layer-by-Layer Assembly of Biopolyelectrolytes onto Thermo/pH-Responsive Micro/Nano-Gels.

    PubMed

    Díez-Pascual, Ana M; Shuttleworth, Peter S

    2014-11-21

    This review deals with the layer-by-layer (LbL) assembly of polyelectrolyte multilayers of biopolymers, polypeptides (i.e., poly-l-lysine/poly-l-glutamic acid) and polysaccharides (i.e., chitosan/dextran sulphate/sodium alginate), onto thermo- and/or pH-responsive micro- and nano-gels such as those based on synthetic poly(N-isopropylacrylamide) (PNIPAM) and poly(acrylic acid) (PAA) or biodegradable hyaluronic acid (HA) and dextran-hydroxyethyl methacrylate (DEX-HEMA). The synthesis of the ensembles and their characterization by way of various techniques is described. The morphology, hydrodynamic size, surface charge density, bilayer thickness, stability over time and mechanical properties of the systems are discussed. Further, the mechanisms of interaction between biopolymers and gels are analysed. Results demonstrate that the structure and properties of biocompatible multilayer films can be finely tuned by confinement onto stimuli-responsive gels, which thus provides new perspectives for biomedical applications, particularly in the controlled release of biomolecules, bio-sensors, gene delivery, tissue engineering and storage.

  17. 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.

  18. Quantitative Collection and Enzymatic Activity of Glucose Oxidase Nanotubes Fabricated by Templated Layer-by-Layer Assembly.

    PubMed

    Zhang, Shouwei; Demoustier-Champagne, Sophie; Jonas, Alain M

    2015-08-10

    We report on the fabrication of enzyme nanotubes in nanoporous polycarbonate membranes via the layer-by-layer (LbL) alternate assembly of polyethylenimine (PEI) and glucose oxidase (GOX), followed by dissolution of the sacrificial template in CH2Cl2, collection, and final dispersion in water. An adjuvant-assisted filtration methodology is exploited to extract quantitatively the nanotubes without loss of activity and morphology. Different water-soluble CH2Cl2-insoluble adjuvants are tested for maximal enzyme activity and nanotube stability; whereas NaCl disrupts the tubes by screening electrostatic interactions, the high osmotic pressure created by fructose also contributes to loosening the nanotubular structures. These issues are solved when using neutral, high molar mass dextran. The enzymatic activity of intact free nanotubes in water is then quantitatively compared to membrane-embedded nanotubes, showing that the liberated nanotubes have a higher catalytic activity in proportion to their larger exposed surface. Our study thus discloses a robust and general methodology for the fabrication and quantitative collection of enzymatic nanotubes and shows that LbL assembly provides access to efficient enzyme carriers for use as catalytic swarming agents.

  19. Nano-Molar Deltamethrin Sensor Based on Electrical Impedance of PAH/PAZO Layer-by-Layer Sensing Films

    PubMed Central

    Abegão, Luís Miguel Gomes; Ribeiro, Jorge Humberto Fernandes; Ribeiro, Paulo António; Raposo, Maria

    2013-01-01

    This work reports a novel deltamethrin (DM) sensor able to detect nano-molar concentrations in ethanol solutions. The sensing layer consists of a thin film, obtained via a layer-by-layer technique, from alternate adsorption of poly(allylamine chloride) (PAH) and poly[1-[4-(3-carboxy-4-hydroxyphenylazo)-benzenesulfonamide)-1,2-ethanediyl]sodium salt] (PAZO) onto a solid support with interdigitaded gold electrodes. The sensor response, obtained from impedance spectroscopy measurements, was revealed to be linear with respect to the real part of impedance, taken at 100 Hz, when plotted as a function of the logarithm of deltamethrin molar concentrations in the micro- to nano-molar range. Sensor sensitivity was of 41.1 ± 0.7 kΩ per decade of concentration for an immersion time above 2 min and the reproducibility is approximately 2% in a binary solution of ethanol and deltamethrin. The main insight of this work concerns to DM detection limits as the sensor revealed to be able to detect concentrations below 0.1 nM, a value which is significantly lower than any reported in the literature and close what is appropriate for in situ environmental contaminant detection. PMID:23966185

  20. 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