Layer-by-layer-assembled quantum dot multilayer sensitizers: how the number of layers affects the photovoltaic properties of one-dimensional ZnO nanowire electrodes.

PubMed

Jin, Ho; Choi, Sukyung; Lim, Sang-Hoon; Rhee, Shi-Woo; Lee, Hyo Joong; Kim, Sungjee

2014-01-13

Layer cake: Multilayered CdSe quantum dot (QD) sensitizers are layer-by-layer assembled onto ZnO nanowires by making use of electrostatic interactions to study the effect of the layer number on the photovoltaic properties. The photovoltaic performance of QD-sensitized solar cells critically depends on this number as a result of the balance between light-harvesting efficiency and carrier-recombination probability. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of pH-Responsive Hollow Capsules via Layer-by-Layer Assembly of Exfoliated Layered Double Hydroxide Nanosheets and Polyelectrolytes.

PubMed

Katagiri, Kiyofumi; Shishijima, Yoshinori; Koumoto, Kunihito; Inumaru, Kei

2018-01-01

pH-Responsive smart capsules were developed by the layer-by-layer assembly with a colloidtemplating technique. Polystyrene (PS) particles were employed as core templates. Acid-soluble inorganic nanosheets were prepared from Mg-Al layered double hydroxide (LDH) by an exfoliation technique. LDH nanosheets and anionic polyelectrolytes were alternatively deposited on PS core particles by the layer-by-layer assembly using electrostatic interaction. Hollow capsules were obtained by the removal of the PS core particles. The hollow capsules obtained thus were collapsed at acidic conditions by dissolution of LDH nanosheets in the hollow shells. The dissolution rate, i.e., the responsiveness of capsule, is tunable according to the strength of acids.

Rapid electrostatics-assisted layer-by-layer assembly of near-infrared-active colloidal photonic crystals.

PubMed

Askar, Khalid; Leo, Sin-Yen; Xu, Can; Liu, Danielle; Jiang, Peng

2016-11-15

Here we report a rapid and scalable bottom-up technique for layer-by-layer (LBL) assembling near-infrared-active colloidal photonic crystals consisting of large (⩾1μm) silica microspheres. By combining a new electrostatics-assisted colloidal transferring approach with spontaneous colloidal crystallization at an air/water interface, we have demonstrated that the crystal transfer speed of traditional Langmuir-Blodgett-based colloidal assembly technologies can be enhanced by nearly 2 orders of magnitude. Importantly, the crystalline quality of the resultant photonic crystals is not compromised by this rapid colloidal assembly approach. They exhibit thickness-dependent near-infrared stop bands and well-defined Fabry-Perot fringes in the specular transmission and reflection spectra, which match well with the theoretical calculations using a scalar-wave approximation model and Fabry-Perot analysis. This simple yet scalable bottom-up technology can significantly improve the throughput in assembling large-area, multilayer colloidal crystals, which are of great technological importance in a variety of optical and non-optical applications ranging from all-optical integrated circuits to tissue engineering. Copyright © 2016 Elsevier Inc. All rights reserved.

Molecular Structure of a Helical ribbon in a Peptide Self-Assembly

NASA Astrophysics Data System (ADS)

Hwang, Wonmuk; Marini, Davide; Kamm, Roger D.; Zhang, Shuguang

2002-03-01

We have studied the molecular structure of nanometer scale helical ribbons observed during self-assembly of the peptide KFE8 (amino acid sequence: FKFEFKFE) (NanoLetters (2002, in press)). By analyzing the hydrogen bonding patterns between neighboring peptide backbones, we constructed a number of possible β-sheets. Using all possible combinations of these, we built helical ribbons with dimensions close to those found experimentally and performed molecular dynamics simulations to identify the most stable structure. Solvation effects were implemented by the analytic continuum electrostatics (ACE) model developed by Schaefer and Karplus (J. Phys. Chem. 100, 1578 (1996)). By applying electrostatic double layer theory, we incorporated the effect of pH by scaling the amount of charge on the sidechains. Our results suggest that the helical ribbon is comprised of a double β-sheet where the inner and the outer helices have distinct hydrogen bonding patterns. Our approach has general applicability to the study of helices formed by the self-assembly of β-sheet forming peptides with various amino acid sequences.

SERS Taper-Fiber Nanoprobe Modified by Gold Nanoparticles Wrapped with Ultrathin Alumina Film by Atomic Layer Deposition

PubMed Central

Xu, Wenjie; Chen, Zhenyi; Chen, Na; Zhang, Heng; Liu, Shupeng; Hu, Xinmao; Wen, Jianxiang; Wang, Tingyun

2017-01-01

A taper-fiber SERS nanoprobe modified by gold nanoparticles (Au-NPs) with ultrathin alumina layers was fabricated and its ability to perform remote Raman detection was demonstrated. The taper-fiber nanoprobe (TFNP) with a nanoscale tip size under 80 nm was made by heated pulling combined with the chemical etching method. The Au-NPs were deposited on the TFNP surface with the electrostatic self-assembly technology, and then the TFNP was wrapped with ultrathin alumina layers by the atomic layer deposition (ALD) technique. The results told us that with the increasing thickness of the alumina film, the Raman signals decreased. With approximately 1 nm alumina film, the remote detection limit for R6G aqueous solution reached 10−6 mol/L. PMID:28245618

Layer-by-layer self-assembled two-dimensional MXene/layered double hydroxide composites as cathode for alkaline hybrid batteries

NASA Astrophysics Data System (ADS)

Dong, Xiaowan; Zhang, Yadi; Ding, Bing; Hao, Xiaodong; Dou, Hui; Zhang, Xiaogang

2018-06-01

Multifarious layered materials have received extensive concern in the field of energy storage due to their distinctive two-dimensional (2D) structure. However, the natural tendency to be re-superimposed and the inherent disadvantages of a single 2D material significantly limit their performance. In this work, the delaminated Ti3C2Tx (d-Ti3C2Tx)/cobalt-aluminum layered double hydroxide (Ti3C2Tx/CoAl-LDH) composites are prepared by layer-by-layer self-assembly driven by electrostatic interaction. The alternate Ti3C2Tx and CoAl-LDH layers prevent each other from restacking and the obtained Ti3C2Tx/CoAl-LDH heterostructure combine the advantages of high electron conductivity of Ti3C2Tx and high electrochemical activity of CoAl-LDH, thus effectively improving the electrochemical reactivity of electrode materials and accelerating the kinetics of Faraday reaction. As a consequence, as a cathode for alkaline hybrid battery, the Ti3C2Tx/CoAl-LDH electrode exhibits a high specific capacity of 106 mAh g-1 at a current density of 0.5 A g-1 and excellent rate capability (78% at 10 A g-1), with an excellent cycling stability of 90% retention after 5000 cycles at 4 A g-1. This work provides an alternative route to design advanced 2D electrode materials, thus exploiting their full potentials for alkaline hybrid batteries.

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.

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

NASA Astrophysics Data System (ADS)

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

2003-01-01

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

Flexible Strain Sensor Based on Layer-by-Layer Self-Assembled Graphene/Polymer Nanocomposite Membrane and Its Sensing Properties

NASA Astrophysics Data System (ADS)

Zhang, Dongzhi; Jiang, Chuanxing; Tong, Jun; Zong, Xiaoqi; Hu, Wei

2018-04-01

Graphene is a potential building block for next generation electronic devices including field-effect transistors, chemical sensors, and radio frequency switches. Investigations of strain application of graphene-based films have emerged in recent years, but the challenges in synthesis and processing achieving control over its fabrication constitute the main obstacles towards device applications. This work presents an alternative approach, layer-by-layer self-assembly, allowing a controllable fabrication of graphene/polymer film strain sensor on flexible substrates of polyimide with interdigital electrodes. Carboxylated graphene and poly (diallyldimethylammonium chloride) (PDDA) were exploited to form hierarchical nanostructure due to electrostatic action. The morphology and structure of the film were inspected by using scanning electron microscopy, x-ray diffraction and Fourier transform infrared spectroscopy. The strain-sensing properties of the graphene/PDDA film sensor were investigated through tuning micrometer caliper exertion and a PC-assisted piezoresistive measurement system. Experimental result shows that the sensor exhibited not only excellent response and reversibility behavior as a function of deflection, but also good repeatability and acceptable linearity. The strain-sensing mechanism of the proposed sensor was attributed to the electrical resistance change resulted from piezoresistive effect.

QCM-D Investigation of Swelling Behavior of Layer-by-Layer Thin Films upon Exposure to Monovalent Ions.

PubMed

O'Neal, Joshua T; Dai, Ethan Y; Zhang, Yanpu; Clark, Kyle B; Wilcox, Kathryn G; George, Ian M; Ramasamy, Nandha E; Enriquez, Daisy; Batys, Piotr; Sammalkorpi, Maria; Lutkenhaus, Jodie L

2018-01-23

Polyelectrolyte multilayers and layer-by-layer assemblies are susceptible to structural changes in response to ionic environment. By altering the salt type and ionic strength, structural changes can be induced by disruption of intrinsically bound ion pairs within the multilayer network via electrostatic screening. Notably, high salt concentrations have been used for the purposes of salt-annealing and self-healing of LbL assemblies with KBr, in particular, yielding a remarkably rapid response. However, to date, the structural and swelling effects of various monovalent ion species on the behavior of LbL assemblies remain unclear, including a quantitative view of ion content in the LbL assembly and thickness changes over a wide concentration window. Here, we investigate the effects of various concentrations of KBr (0 to 1.6 M) on the swelling and de-swelling of LbL assemblies formed from poly(diallyldimethylammonium) polycation (PDADMA) and poly(styrene sulfonate) polyanion (PSS) in 0.5 M NaCl using quartz-crystal microbalance with dissipation (QCM-D) monitoring as compared to KCl, NaBr, and NaCl. The ion content after salt exchange is quantified using neutron activation analysis (NAA). Our results demonstrate that Br - ions have a much greater effect on the structure of as-prepared thin films than Cl - at ionic strengths above assembly conditions, which is possibly caused by the more chaotropic nature of Br - . It is also found that the anion in general dominates the swelling response as compared to the cation because of the excess PDADMA in the multilayer. Four response regimes are identified that delineate swelling due to electrostatic repulsion, slight contraction, swelling due to doping, and film destruction as ionic strength increases. This understanding is critical if such materials are to be used in applications requiring submersion in chemically dynamic environments such as sensors, coatings on biomedical implants, and filtration membranes.

Tunable drug loading and release from polypeptide multilayer nanofilms

PubMed Central

Jiang, Bingbing; Li, Bingyun

2009-01-01

Polypeptide multilayer nanofilms were prepared using electrostatic layer-by-layer self-assembly nanotechnology. Small charged drug molecules (eg, cefazolin, gentamicin, and methylene blue) were loaded in polypeptide multilayer nanofilms. Their loading and release were found to be pH-dependent and could also be controlled by changing the number of film layers and drug incubation time, and applying heat-treatment after film formation. Antibioticloaded polypeptide multilayer nanofilms showed controllable antibacterial properties against Staphylococcus aureus. The developed biodegradable polypeptide multilayer nanofilms are capable of loading both positively- and negatively-charged drug molecules and promise to serve as drug delivery systems on biomedical devices for preventing biomedical device-associated infection, which is a significant clinical complication for both civilian and military patients. PMID:19421369

Synthesis of Self-Assembled Multifunctional Nanocomposite Catalysts with Highly Stabilized Reactivity and Magnetic Recyclability

NASA Astrophysics Data System (ADS)

Yu, Xu; Cheng, Gong; Zheng, Si-Yang

2016-05-01

In this paper, a multifunctional Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite catalyst with highly stabilized reactivity and magnetic recyclability was synthesized by a self-assembled method. The magnetic Fe3O4 nanoparticles were coated with a thin layer of the SiO2 to obtain a negatively charged surface. Then positively charged poly(ethyleneimine) polymer (PEI) was self-assembled onto the Fe3O4@SiO2 by electrostatic interaction. Next, negatively charged glutathione capped gold nanoparticles (GSH-AuNPs) were electrostatically self-assembled onto the Fe3O4@SiO2@PEI. After that, silver was grown on the surface of the nanocomposite due to the reduction of the dopamine in the alkaline solution. An about 5 nm thick layer of polydopamine (PDA) was observed to form the Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite. The Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite was carefully characterized by the SEM, TEM, FT-IR, XRD and so on. The Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite shows a high saturation magnetization (Ms) of 48.9 emu/g, which allows it to be attracted rapidly to a magnet. The Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite was used to catalyze the reduction of p-nitrophenol (4-NP) to p-aminophenol (4-AP) as a model system. The reaction kinetic constant k was measured to be about 0.56 min-1 (R2 = 0.974). Furthermore, the as-prepared catalyst can be easily recovered and reused for 8 times, which didn’t show much decrease of the catalytic capability.

Self-surface charge exfoliation and electrostatically coordinated 2D hetero-layered hybrids

PubMed Central

Yang, Min-Quan; Xu, Yi-Jun; Lu, Wanheng; Zeng, Kaiyang; Zhu, Hai; Xu, Qing-Hua; Ho, Ghim Wei

2017-01-01

At present, the technological groundwork of atomically thin two-dimensional (2D) hetero-layered structures realized by successive thin film epitaxial growth is in principle constrained by lattice matching prerequisite as well as low yield and expensive production. Here, we artificially coordinate ultrathin 2D hetero-layered metal chalcogenides via a highly scalable self-surface charge exfoliation and electrostatic coupling approach. Specifically, bulk metal chalcogenides are spontaneously exfoliated into ultrathin layers in a surfactant/intercalator-free medium, followed by unconstrained electrostatic coupling with a dissimilar transition metal dichalcogenide, MoSe2, into scalable hetero-layered hybrids. Accordingly, surface and interfacial-dominated photocatalysis reactivity is used as an ideal testbed to verify the reliability of diverse 2D ultrathin hetero-layered materials that reveal high visible-light photoreactivity, efficient charge transfer and intimate contact interface for stable cycling and storage purposes. Such a synthetic approach renders independent thickness and composition control anticipated to advance the development of ‘design-and-build' 2D layered heterojunctions for large-scale exploration and applications. PMID:28146147

Electrostatic Assembly of Nanomaterials for Hybrid Electrodes and Supercapacitors

NASA Astrophysics Data System (ADS)

Hammond, Paula

2015-03-01

Electrostatic assembly methods have been used to generate a range of new materials systems of interest for electrochemical energy and storage applications. Over the past several years, it has been demonstrated that carbon nanotubes, metals, metal oxides, polymeric nanomaterials, and biotemplated materials systems can be incorporated into ultrathin films to generate supercapacitors and battery electrodes that illustrate significant energy density and power. The unique ability to control the incorporation of such a broad range of materials at the nanometer length scale allows tailoring of the final properties of these unique composite systems, as well as the capability of creating complex micron-scale to nanoporous morphologies based on the scale of the nanomaterial that is absorbed within the structure, or the conditions of self-assembly. Recently we have expanded these capabilities to achieve new electrodes that are templated atop electrospun polmer fiber scaffolds, in which the polymer can be selectively removed to achieve highly porous materials. Spray-layer-by-layer and filtration methods of functionalized multiwall carbon nanotubes and polyaniline nanofibers enable the generation of electrode systems with unusually high surface. Incorporation of psuedocapacitive nanoparticles can enhance capacitive properties, and other catalytic or metallic nanoparticles can be implemented to enhance electrochemical or catalytic function.

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.

Multilayer biomimetics: reversible covalent stabilization of a nanostructured biofilm.

PubMed

Li, Bingyun; Haynie, Donald T

2004-01-01

Designed polypeptides and electrostatic layer-by-layer self-assembly form the basis of promising research in bionanotechnology and medicine on development of polyelectrolyte multilayer films (PEMs). We show that PEMs can be formed from oppositely charged 32mers containing several cysteine residues. The polypeptides in PEMs become cross-linked under mild oxidizing conditions. This mimicking of disulfide (S-S) bond stabilization of folded protein structure confers on the PEMs a marked increase in resistance to film disassembly at acidic pH. The reversibility of S-S bond stabilization of PEMs presents further advantages for controlling physical properties of films, coatings, and other applications involving PEMs.

Photophysical study of the interaction between ZnO nanoparticles and globular protein bovine serum albumin in solution and in a layer-by-layer self-assembled film

NASA Astrophysics Data System (ADS)

Hansda, Chaitali; Maiti, Pradip; Singha, Tanmoy; Pal, Manisha; Hussain, Syed Arshad; Paul, Sharmistha; Paul, Pabitra Kumar

2018-10-01

In this study, we investigated the spectroscopic properties of the water-soluble globular protein bovine serum albumin (BSA) while interacting with zinc oxide (ZnO) semiconductor nanoparticles (NPs) in aqueous medium and in a ZnO/BSA layer-by-layer (LbL) self-assembled film fabricated on poly (acrylic acid) (PAA)-coated quartz or a Si substrate via electrostatic interactions. BSA formed a ground state complex due to its interaction with ZnO NPs, which was confirmed by ultraviolet-visible absorption, and steady state and time-resolved fluorescence emission spectroscopic techniques. However, due to its interaction with ZnO, the photophysical properties of BSA depend significantly on the concentration of ZnO NPs in the mixed solution. The quenching of the fluorescence intensity of BSA in the presence of ZnO NPs was due to the interaction between ZnO and BSA, and the formation of their stable ground state complex, as well as energy transfer from the excited BSA to ZnO NPs in the complex nano-bioconjugated species. Multilayer growth of the ZnO/BSA LbL self-assembled film on the quartz substrate was confirmed by monitoring the characteristic absorption band of BSA (280 nm), where the nature of the film growth depends on the number of bilayers deposited on the quartz substrate. BSA formed a well-ordered molecular network-type morphology due to its adsorption onto the surface of the ZnO nanostructure in the backbone of the PAA-coated Si substrate in the LbL film according to atomic force microscopic study. The as-synthesized ZnO NPs were characterized by field emission scanning electron microscopy, X-ray powder diffraction, and dynamic light scattering techniques.

Amperometric Choline Biosensor Fabricated through Electrostatic Assembly of Bienzyme/Polyelectrolyte Hybrid Layers on Carbon Nanotubes

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

Wang, Jun; Liu, Guodong; Lin, Yuehe

2006-03-01

We report a flow injection amperometric choline biosensors based on the electrostatic assembly of an enzyme of choline oxidase (ChO) and a bi-enzyme of ChO and horseradish peroxidase (HRP) onto multi-wall carbon nanotubes (MWCNT) modified glassy carbon (GC) electrodes. These choline biosensors were fabricated by immobilization of enzymes on the negatively charged MWCNT surface through alternatively assembling a cationic polydiallydiimethylammonium chloride (PDDA) layer and an enzyme layer. Using this layer-by-layer assembling approach, bioactive nanocomposite film of a PDDA/ChO/PDDA/HRP/PDDA/CNT (ChO/HRP/CNT) and a PDDA/ChO/PDDA/ CNT (ChO/ CNT) were fabricated on GC surface, respectively. Owning to the electrocatalytic effect of carbon nanotubes, themore » measurement of faradic responses resulting from enzymatic reactions has been realized at low potential with acceptable sensitivity. It is found the ChO/HRP/CNT biosensor is more sensitive than the ChO/CNT one. Experimental parameters affecting the sensitivity of biosensors, e.g. applied potential, flow rate, etc. were optimized and potential interference was examined. The response time for this choline biosensor is fast (less than a few seconds). The linear range of detection for the choline biosensor is from 5 x 10-5 to 5 x 10-3 M and the detection limit is determined to be about 1.0 x 10-5 M.« less

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

NASA Astrophysics Data System (ADS)

Zhang, Bo; Cui, Tianhong

2011-02-01

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

Reagentless biosensor based on layer-by-layer assembly of functional multiwall carbon nanotubes and enzyme-mediator biocomposite.

PubMed

Zhou, Xing-Hua; Xi, Feng-Na; Zhang, Yi-Ming; Lin, Xian-Fu

2011-06-01

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.

Self-Assembled Films of Dendrimers and Metallophthalocyanines as FET-Based Glucose Biosensors

PubMed Central

Vieira, Nirton C.S.; Figueiredo, Alessandra; de Queiroz, Alvaro A.A.; Zucolotto, Valtencir; Guimarães, Francisco E.G.

2011-01-01

Separative extended gate field effect transistor (SEGFET) type devices have been used as an ion sensor or biosensor as an alternative to traditional ion sensitive field effect transistors (ISFETs) due to their robustness, ease of fabrication, low cost and possibility of FET isolation from the chemical environment. The layer-by-layer technique allows the combination of different materials with suitable properties for enzyme immobilization on simple platforms such as the extended gate of SEGFET devices enabling the fabrication of biosensors. Here, glucose biosensors based on dendrimers and metallophthalocyanines (MPcs) in the form of layer-by-layer (LbL) films, assembled on indium tin oxide (ITO) as separative extended gate material, has been produced. NH3+ groups in the dendrimer allow electrostatic interactions or covalent bonds with the enzyme (glucose oxidase). Relevant parameters such as optimum pH, buffer concentration and presence of serum bovine albumin (BSA) in the immobilization process were analyzed. The relationship between the output voltage and glucose concentration shows that upon detection of a specific analyte, the sub-products of the enzymatic reaction change the pH locally, affecting the output signal of the FET transducer. In addition, dendritic layers offer a nanoporous environment, which may be permeable to H+ ions, improving the sensibility as modified electrodes for glucose biosensing. PMID:22163704

Rational Design of Multilayer Collagen Nanosheets with Compositional and Structural Control.

PubMed

Jiang, Tao; Vail, Owen A; Jiang, Zhigang; Zuo, Xiaobing; Conticello, Vincent P

2015-06-24

Two collagen-mimetic peptides, CP(+) and CP(-), are reported in which the sequences comprise a multiblock architecture having positively charged N-terminal (Pro-Arg-Gly)3 and negatively charged C-terminal (Glu-Hyp-Gly)3 triad extensions, respectively. CP(+) rapidly self-associates into positively charged nanosheets based on a monolayer structure. In contrast, CP(-) self-assembles to form negatively charged monolayer nanosheets at a much slower rate, which can be accelerated in the presence of calcium(II) ion. A 2:1 mixture of unassociated CP(-) peptide with preformed CP(+) nanosheets generates structurally defined triple-layer nanosheets in which two CP(-) monolayers have formed on the identical surfaces of the CP(+) nanosheet template. Experimental data from electrostatic force microscopy (EFM) image analysis, zeta potential measurements, and charged nanoparticle binding assays support a negative surface charge state for the triple-layer nanosheets, which is the reverse of the positive surface charge state observed for the CP(+) monolayer nanosheets. The electrostatic complementarity between the CP(+) and CP(-) triple helical cohesive ends at the layer interfaces promotes a (CP(-)/CP(+)/CP(-)) compositional gradient along the z-direction of the nanosheet. This structurally informed approach represents an attractive strategy for the fabrication of two-dimensional nanostructures with compositional control.

Self-similar assemblies of globular whey proteins at the air-water interface: effect of the structure.

PubMed

Mahmoudi, Najet; Gaillard, Cédric; Boué, François; Axelos, Monique A V; Riaublanc, Alain

2010-05-01

We investigated the structure of heat-induced assemblies of whey globular proteins using small angle neutron scattering (SANS), static and dynamic light scattering (SLS and DLS), and cryogenic transmission electron microscopy (Cryo-TEM). Whey protein molecules self-assemble in fractal aggregates with a structure density depending on the electrostatic interactions. We determined the static and dynamic properties of interfacial layer formed by the protein assemblies, upon adsorption and spreading at the air-water interface using surface film balance and interfacial dilatational rheology. Upon spreading, all whey protein systems show a power-law scaling behavior of the surface pressure versus concentration in the semi-dilute surface concentration regime, with an exponent ranging from 5.5 to 9 depending on the electrostatic interactions and the aggregation state. The dilatational modulus derived from surface pressure isotherms shows a main peak at 6-8 mN/m, generally considered to be the onset of a conformational change in the monolayer, and a second peak or a shoulder at 15 mN/m. Long-time adsorption kinetics give similar results for both the native whey proteins and the corresponding self-similar assemblies, with a systematic effect of the ionic strength. Copyright 2010 Elsevier Inc. All rights reserved.

Nanostructured biosensors built by layer-by-layer electrostatic assembly of enzyme-coated single-walled carbon nanotubes and redox polymers.

PubMed

Wang, Youdan; Joshi, Pratixa P; Hobbs, Kevin L; Johnson, Matthew B; Schmidtke, David W

2006-11-07

In this study, we describe the construction of glucose biosensors based on an electrostatic layer-by-layer (LBL) technique. Gold electrodes were initially functionalized with negatively charged 11-mercaptoundecanoic acid followed by alternate immersion in solutions of a positively charged redox polymer, poly[(vinylpyridine)Os(bipyridyl)2Cl(2+/3+)], and a negatively charged enzyme, glucose oxidase (GOX), or a GOX solution containing single-walled carbon nanotubes (SWNTs). The LBL assembly of the multilayer films were characterized by UV-vis spectroscopy, ellipsometry, and cyclic voltammetry, while characterization of the single-walled nanotubes was performed with transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. When the GOX solution contained single-walled carbon nanotubes (GOX-SWNTs), the oxidation peak currents during cyclic voltammetry increased 1.4-4.0 times, as compared to films without SWNTs. Similarly the glucose electro-oxidation current also increased (6-17 times) when SWNTs were present. By varying the number of multilayers, the sensitivity of the sensors could be controlled.

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

PubMed

Wang, Dongrui; Wang, Xiaogong

2011-03-01

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

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.

Controllable self-assembly of sodium caseinate with a zwitterionic vitamin-derived bolaamphiphile.

PubMed

Sun, Li-Hui; Sun, Yu-Long; Yang, Li-Jun; Zhang, Jian; Chen, Zhong-Xiu

2013-11-06

The control of self-assembly of sodium caseinate (SC) including the formation of mixed layers, microspheres, or nanoparticles is highly relevant to the microstructure of food and the design of promising drug delivery systems. In this paper, we designed a structure-switchable zwitterionic bolaamphiphile, 1,12-diaminododecanediorotate (DDO), from orotic acid, which has special binding sites and can guide the self-assembly of SC. Complexation between SC and DDO was investigated using dynamic light scattering, transmission electron microscopy, differential scanning calorimetry, and fluorescence spectra measurements. Monomeric DDO was bound to the negatively charged sites on the SC micelle and made the structure of SC more compact with decreased electrostatic repulsion between the head groups. Vesicular DDO led to reassociation of vesicles with enlarged size via preferable hydrophobic interactions. Moreover, the aggregation between SC and DDO was found to be temperature-dependent and reversible. This research provides an effective way to control the reversible self-assembly of SC by the zwitterionic vitamin-derived bolaamphiphile.

8-Anilino-1-naphthalenesulfonate/Layered Double Hydroxide Ultrathin Films: Small Anion Assembly and Its Potential Application as a Fluorescent Biosensor.

PubMed

Zhang, Ping; Li, Ling; Zhao, Yun; Tian, Zeyun; Qin, Yumei; Lu, Jun

2016-09-06

The fluorescent dye 8-anilino-1-naphthalenesulfonate (ANS) is a widely used fluorescent probe molecule for biochemistry analysis. This paper reported the fabrication of ANS/layered double hydroxide nanosheets (ANS/LDH)n ultrathin films (UTFs) via the layer-by-layer small anion assembly technique based on electrostatic interaction and two possible weak interactions: hydrogen-bond and induced electrostatic interactions between ANS and positive-charged LDH nanosheets. The obtained UTFs show a long-range-ordered periodic layered stacking structure and weak fluorescence in dry air or water, but it split into three narrow strong peaks in a weak polarity environment induced by the two-dimensional (2D) confinement effect of the LDH laminate; the fluorescence intensity increases with decreasing the solvent polarity, concomitant with the blue shift of the emission peaks, which show good sensoring reversibility. Meanwhile, the UTFs exhibit selective fluorescence enhancement to the bovine serum albumin (BSA)-like protein biomolecules, and the rate of fluorescence enhancement with the protein concentration is significantly different with the different protein aggregate states. The (ANS/LDH)n UTF has the potential to be a novel type of biological flourescence sensor material.

Correction: One-step coelectrodeposition-assisted layer-by-layer assembly of gold nanoparticles and reduced graphene oxide and its self-healing three-dimensional nanohybrid for an ultrasensitive DNA sensor.

PubMed

Jayakumar, Kumarasamy; Camarada, María Belén; Dharuman, Venkataraman; Ju, Huangxian; Dey, Ramendra Sundar; Wen, Yangping

2018-02-01

Correction for 'One-step coelectrodeposition-assisted layer-by-layer assembly of gold nanoparticles and reduced graphene oxide and its self-healing three-dimensional nanohybrid for an ultrasensitive DNA sensor' by Jayakumar Kumarasamy, et al., Nanoscale, 2018, DOI: 10.1039/c7nr06952a.

S-Layer Protein Self-Assembly

PubMed Central

Pum, Dietmar; Toca-Herrera, Jose Luis; Sleytr, Uwe B.

2013-01-01

Crystalline S(urface)-layers are the most commonly observed cell surface structures in prokaryotic organisms (bacteria and archaea). S-layers are highly porous protein meshworks with unit cell sizes in the range of 3 to 30 nm, and thicknesses of ~10 nm. One of the key features of S-layer proteins is their intrinsic capability to form self-assembled mono- or double layers in solution, and at interfaces. Basic research on S-layer proteins laid foundation to make use of the unique self-assembly properties of native and, in particular, genetically functionalized S-layer protein lattices, in a broad range of applications in the life and non-life sciences. This contribution briefly summarizes the knowledge about structure, genetics, chemistry, morphogenesis, and function of S-layer proteins and pays particular attention to the self-assembly in solution, and at differently functionalized solid supports. PMID:23354479

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.

Two-Dimensional Layered Oxide Structures Tailored by Self-Assembled Layer Stacking via Interfacial Strain.

PubMed

Zhang, Wenrui; Li, Mingtao; Chen, Aiping; Li, Leigang; Zhu, Yuanyuan; Xia, Zhenhai; Lu, Ping; Boullay, Philippe; Wu, Lijun; Zhu, Yimei; MacManus-Driscoll, Judith L; Jia, Quanxi; Zhou, Honghui; Narayan, Jagdish; Zhang, Xinghang; Wang, Haiyan

2016-07-06

Study of layered complex oxides emerge as one of leading topics in fundamental materials science because of the strong interplay among intrinsic charge, spin, orbital, and lattice. As a fundamental basis of heteroepitaxial thin film growth, interfacial strain can be used to design materials that exhibit new phenomena beyond their conventional forms. Here, we report a strain-driven self-assembly of bismuth-based supercell (SC) with a two-dimensional (2D) layered structure. With combined experimental analysis and first-principles calculations, we investigated the full SC structure and elucidated the fundamental growth mechanism achieved by the strain-enabled self-assembled atomic layer stacking. The unique SC structure exhibits room-temperature ferroelectricity, enhanced magnetic responses, and a distinct optical bandgap from the conventional double perovskite structure. This study reveals the important role of interfacial strain modulation and atomic rearrangement in self-assembling a layered singe-phase multiferroic thin film, which opens up a promising avenue in the search for and design of novel 2D layered complex oxides with enormous promise.

Analysis of self-assembly of S-layer protein slp-B53 from Lysinibacillus sphaericus.

PubMed

Liu, Jun; Falke, Sven; Drobot, Bjoern; Oberthuer, Dominik; Kikhney, Alexey; Guenther, Tobias; Fahmy, Karim; Svergun, Dmitri; Betzel, Christian; Raff, Johannes

2017-01-01

The formation of stable and functional surface layers (S-layers) via self-assembly of surface-layer proteins on the cell surface is a dynamic and complex process. S-layers facilitate a number of important biological functions, e.g., providing protection and mediating selective exchange of molecules and thereby functioning as molecular sieves. Furthermore, S-layers selectively bind several metal ions including uranium, palladium, gold, and europium, some of them with high affinity. Most current research on surface layers focuses on investigating crystalline arrays of protein subunits in Archaea and bacteria. In this work, several complementary analytical techniques and methods have been applied to examine structure-function relationships and dynamics for assembly of S-layer protein slp-B53 from Lysinibacillus sphaericus: (1) The secondary structure of the S-layer protein was analyzed by circular dichroism spectroscopy; (2) Small-angle X-ray scattering was applied to gain insights into the three-dimensional structure in solution; (3) The interaction with bivalent cations was followed by differential scanning calorimetry; (4) The dynamics and time-dependent assembly of S-layers were followed by applying dynamic light scattering; (5) The two-dimensional structure of the paracrystalline S-layer lattice was examined by atomic force microscopy. The data obtained provide essential structural insights into the mechanism of S-layer self-assembly, particularly with respect to binding of bivalent cations, i.e., Mg 2+ and Ca 2+ . Furthermore, the results obtained highlight potential applications of S-layers in the fields of micromaterials and nanobiotechnology by providing engineered or individual symmetric thin protein layers, e.g., for protective, antimicrobial, or otherwise functionalized surfaces.

Experimental results of antigliadin antibodies detection using long period fiber grating

NASA Astrophysics Data System (ADS)

Corres, J. M.; Matias, I. R.; Goicoechea, J.; Arregui, F. J.; Viegas, D.; Araújo, F. M.; Santos, J. L.

2008-04-01

In this work a new nano-biofilm is proposed for the detection of celiac disease (CD). A long-period fiber grating (LPFG) is used as a transducer and the surface of the fiber is coated with a precursor layer of SiO2-nanospheres using the electrostatic self-assembly technique (ESA). This layer has been designed in order to create a substrate of high porosity where the gliadins could be deposited. Under the presence of specific antibodies antigliadin antibodies (AGA) the refractive index of the overlay changes giving a detectable shift in the resonance wavelength of the LPFG. Concentrations as low as 5 ppm were detected.

Patterning layer-by-layer self-assembled multilayer by lithography and its applications to thin film devices

NASA Astrophysics Data System (ADS)

Hua, Feng

Nanoparticles are exciting materials because they exhibit unique electronic, catalytic, and optical properties. As a novel and promising nanobuilding block, it attracts considerable research efforts in its integration into a wide variety of thin film devices. Nanoparticles were adsorbed onto the substrate with layer-by-layer self-assembly which becomes of great interest due to its suitability in colloid particle assembly. Without extremely high temperatures and sophisticated equipment, molecularly organized films in an exactly pre-designed order can grow on almost all the substrates in nature. Two approaches generating spatially separated patterns comprised of nanoparticles are demonstrated, as well as two approaches patterning more than one type of nonoparticle on a silicon wafer. The structure of the thin film patterned by these approaches are analyzed and considered suitable to the thin film device. Finally, the combination of lithography and layer-by-layer (lbl) self-assembly is utilized to realize the microelectronic device with functional nonoparticles. The lbl self-assembly is the way to coat the nonoparticles and the lighography to pattern them. Based on the coating and patterning technique, a MOS-capacitor, a MOS field-effect-transistor and magnetic thin film cantilever are fabricated.

Efficiency enhancement of polymer solar cells by applying poly(vinylpyrrolidone) as a cathode buffer layer via spin coating or self-assembly.

PubMed

Wang, Haitao; Zhang, Wenfeng; Xu, Chenhui; Bi, Xianghong; Chen, Boxue; Yang, Shangfeng

2013-01-01

A non-conjugated polymer poly(vinylpyrrolidone) (PVP) was applied as a new cathode buffer layer in P3HT:PCBM bulk heterojunction polymer solar cells (BHJ-PSCs), by means of either spin coating or self-assembly, resulting in significant efficiency enhancement. For the case of incorporation of PVP by spin coating, power conversion efficiency (PCE) of the ITO/PEDOT:PSS/P3HT:PCBM/PVP/Al BHJ-PSC device (3.90%) is enhanced by 29% under the optimum PVP spin-coating speed of 3000 rpm, which leads to the optimum thickness of PVP layer of ~3 nm. Such an efficiency enhancement is found to be primarily due to the increase of the short-circuit current (J(sc)) (31% enhancement), suggesting that the charge collection increases upon the incorporation of a PVP cathode buffer layer, which originates from the conjunct effects of the formation of a dipole layer between P3HT:PCBM active layer and Al electrodes, the chemical reactions of PVP molecules with Al atoms, and the increase of the roughness of the top Al film. Incorporation of PVP layer by doping PVP directly into the P3HT:PCBM active layer leads to an enhancement of PCE by 13% under the optimum PVP doping ratio of 3%, and this is interpreted by the migration of PVP molecules to the surface of the active layer via self-assembly, resulting in the formation of the PVP cathode buffer layer. While the formation of the PVP cathode buffer layer is fulfilled by both fabrication methods (spin coating and self-assembly), the dependence of the enhancement of the device performance on the thickness of the PVP cathode buffer layer formed by self-assembly or spin coating is different, because of the different aggregation microstructures of the PVP interlayer.

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.

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

DOE PAGES

Patra, Niladri; Tkachenko, Alexei V.

2017-08-02

Here, 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 particlemore » 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. These 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.« less

Biomimetic Layer-by-Layer Self-Assembly of Nanofilms, Nanocoatings, and 3D Scaffolds for Tissue Engineering.

PubMed

Zhang, Shichao; Xing, Malcolm; Li, Bingyun

2018-06-01

Achieving surface design and control of biomaterial scaffolds with nanometer- or micrometer-scaled functional films is critical to mimic the unique features of native extracellular matrices, which has significant technological implications for tissue engineering including cell-seeded scaffolds, microbioreactors, cell assembly, tissue regeneration, etc. Compared with other techniques available for surface design, layer-by-layer (LbL) self-assembly technology has attracted extensive attention because of its integrated features of simplicity, versatility, and nanoscale control. Here we present a brief overview of current state-of-the-art research related to the LbL self-assembly technique and its assembled biomaterials as scaffolds for tissue engineering. An overview of the LbL self-assembly technique, with a focus on issues associated with distinct routes and driving forces of self-assembly, is described briefly. Then, we highlight the controllable fabrication, properties, and applications of LbL self-assembly biomaterials in the forms of multilayer nanofilms, scaffold nanocoatings, and three-dimensional scaffolds to systematically demonstrate advances in LbL self-assembly in the field of tissue engineering. LbL self-assembly not only provides advances for molecular deposition but also opens avenues for the design and development of innovative biomaterials for tissue engineering.

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…

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. Copyright © 2011 Wiley Periodicals, Inc.

Layer-by-Layer Self-Assembling Gold Nanorods and Glucose Oxidase onto Carbon Nanotubes Functionalized Sol-Gel Matrix for an Amperometric Glucose Biosensor.

PubMed

Wu, Baoyan; Hou, Shihua; Miao, Zhiying; Zhang, Cong; Ji, Yanhong

2015-09-18

A novel amperometric glucose biosensor was fabricated by layer-by-layer self-assembly of gold nanorods (AuNRs) and glucose oxidase (GOD) onto single-walled carbon nanotubes (SWCNTs)-functionalized three-dimensional sol-gel matrix. A thiolated aqueous silica sol containing SWCNTs was first assembled on the surface of a cleaned Au electrode, and then the alternate self-assembly of AuNRs and GOD were repeated to assemble multilayer films of AuNRs-GOD onto SWCNTs-functionalized silica gel for optimizing the biosensor. Among the resulting glucose biosensors, the four layers of AuNRs-GOD-modified electrode showed the best performance. The sol-SWCNTs-(AuNRs- GOD)₄/Au biosensor exhibited a good linear range of 0.01-8 mM glucose, high sensitivity of 1.08 μA/mM, and fast amperometric response within 4 s. The good performance of the proposed glucose biosensor could be mainly attributed to the advantages of the three-dimensional sol-gel matrix and stereo self-assembly films, and the natural features of one-dimensional nanostructure SWCNTs and AuNRs. This study may provide a new facile way to fabricate the enzyme-based biosensor with high performance.

Bio-mimetic Nanostructure Self-assembled from Au@Ag Heterogeneous Nanorods and Phage Fusion Proteins for Targeted Tumor Optical Detection and Photothermal Therapy

NASA Astrophysics Data System (ADS)

Wang, Fei; Liu, Pei; Sun, Lin; Li, Cuncheng; Petrenko, Valery A.; Liu, Aihua

2014-10-01

Nanomaterials with near-infrared (NIR) absorption have been widely studied in cancer detection and photothermal therapy (PTT), while it remains a great challenge in targeting tumor efficiently with minimal side effects. Herein we report a novel multifunctional phage-mimetic nanostructure, which was prepared by layer-by-layer self-assembly of Au@Ag heterogenous nanorods (NRs) with rhodamine 6G, and specific pVIII fusion proteins. Au@Ag NRs, first being applied for PTT, exhibited excellent stability, cost-effectivity, biocompatibility and tunable NIR absorption. The fusion proteins were isolated from phage DDAGNRQP specifically selected from f8/8 landscape phage library against colorectal cancer cells in a high-throughput way. Considering the definite charge distribution and low molecular weight, phage fusion proteins were assembled on the negatively charged NR core by electrostatic interactions, exposing the N-terminus fused with DDAGNRQP peptide on the surface. The fluorescent images showed that assembled phage fusion proteins can direct the nanostructure into cancer cells. The nanostructure was more efficient than gold nanorods and silver nanotriangle-based photothermal agents and was capable of specifically ablating SW620 cells after 10 min illumination with an 808 nm laser in the light intensity of 4 W/cm2. The prepared nanostructure would become an ideal reagent for simutaneously targeted optical imaging and PTT of tumor.

Lyotropic chromonic liquid crystals as materials for optical and biosensing applications

NASA Astrophysics Data System (ADS)

Tortora, L.; Park, H.-S.; Antion, K.; Finotello, D.; Lavrentovich, O. D.

2007-02-01

Lyotropic chromonic liquid crystals (LCLCs) are formed by molecules with rigid polyaromatic cores and ionic groups at the periphery that form aggregates while in water. Most of the LCLCs are not toxic to the biological cells and can be used as an amplifying medium in real-time biosensors. The detector is based on the principle that the immune aggregates growing in the LCLC bulk trigger the director distortions. Self-assembly of LCLC molecules into oriented structures allows one to use them in various structured films. For example, layer-by-layer electrostatic deposition produces monomolecular layers and stacks of layers of LCLC with long-range in-plane orientational order which sets them apart from the standard Langmuir-Blodgett films. We demonstrate that divalent and multivalent salts as well as acidic and basic materials that alter pH of the LCLC water solutions, are drastically modifying the phase diagrams of LCLC, from shifting the phase transition temperatures by tens of degrees, to causing condensation of the LCLC aggregates into more compact structures, such as birefringent bundles or formation of a columnar hexagonal phase from the nematic phase.

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

PubMed

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

2012-11-07

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

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

PubMed

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

2016-09-14

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

Side-polished fiber immunosensor based on surface plasmon resonance for detection of Legionella pneumophila

NASA Astrophysics Data System (ADS)

Tsao, Yu-Chia; Yang, Yi-Wen; Tsai, Woo-Hu; Yan, Tsong-Rong

2008-02-01

Side-polished fiber immunosensor based on surface plasmon resonance (SPR) onto self-assembled protein A layer was proposed for the detection of Legionella pneumophila. A self-assembled protein A layer on gold (Au) surface was fabricated by adsorbing a mixture of 11-mercaptoundecanoic acid (MUA) and activated by N-Ethyl-N'-(3-dimethylaminopropyl) carbodiimide/ N-Hydroxysuccinimide (EDC/NHS). The formation of self-assembled protein A and gold layer on side-polished surface and the binding of antibody and antigen in series were confirmed by SPR response on spectrum. The binding protein A layer can improve the sensitivity, which indirectly supports the configurations that antibody layer is immobilized on the binding protein A layer with a well-ordered orientation. The surface morphology analyses of self-assembled protein A layer on Au substrate and monoclonal antibody against L. pneumophila immobilized on protein A were demonstrated by SPR dip shifts on optical spectrum analyzer. The SPR fiber immunosensor for detection of L. pneumophila was developed and the detection limit was 10 CFU/ml with the SPR dip shift in wavelength from 1070 to 1105nm. The current fabrication technique of a SPR immunosensor using optical fiber for the detection of Legionella pneumophila could be applied to construct other biosensor.

Multilayer block copolymer meshes by orthogonal self-assembly

PubMed Central

Tavakkoli K. G., Amir; Nicaise, Samuel M.; Gadelrab, Karim R.; Alexander-Katz, Alfredo; Ross, Caroline A.; Berggren, Karl K.

2016-01-01

Continued scaling-down of lithographic-pattern feature sizes has brought templated self-assembly of block copolymers (BCPs) into the forefront of nanofabrication research. Technologies now exist that facilitate significant control over otherwise unorganized assembly of BCP microdomains to form both long-range and locally complex monolayer patterns. In contrast, the extension of this control into multilayers or 3D structures of BCP microdomains remains limited, despite the possible technological applications in next-generation devices. Here, we develop and analyse an orthogonal self-assembly method in which multiple layers of distinct-molecular-weight BCPs naturally produce nanomesh structures of cylindrical microdomains without requiring layer-by-layer alignment or high-resolution lithographic templating. The mechanisms for orthogonal self-assembly are investigated with both experiment and simulation, and we determine that the control over height and chemical preference of templates are critical process parameters. The method is employed to produce nanomeshes with the shapes of circles and Y-intersections, and is extended to produce three layers of orthogonally oriented cylinders. PMID:26796218

Advances in polyelectrolyte multilayer nanofilms as tunable drug delivery systems

PubMed Central

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

2009-01-01

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

Charge patterns as templates for the assembly of layered biomolecular structures.

PubMed

Naujoks, Nicola; Stemmer, Andreas

2006-08-01

Electric fields are used to guide the assembly of biomolecules in predefined geometric patterns on solid substrates. Local surface charges serve as templates to selectively position proteins on thin-film polymeric electret layers, thereby creating a basis for site-directed layered assembly of biomolecular structures. Charge patterns are created using the lithographic capabilities of an atomic force microscope, namely by applying voltage pulses between a conductive tip and the sample. Samples consist of a poly(methyl methacrylate) layer on a p-doped silicon support. Subsequently, the sample is developed in a water-in-oil emulsion, consisting of a dispersed aqueous phase containing biotin-modified immunoglobulinG molecules, and a continuous nonpolar, insulating oil phase. The electrostatic fields cause a net force of (di)electrophoretic nature on the droplet, thereby guiding the proteins to the predefined locations. Due to the functionalization of the immunoglobulinG molecules with biotin-groups, these patterns can now be used to initiate the localized layer-by-layer assembly of biomolecules based on the avidin-biotin mechanism. By binding 40 nm sized biotin-labelled beads to the predefined locations via a streptavidin linker, we verify the functionality of the previously deposited immunoglobulinG-biotin. All assembly steps following the initial deposition of the immunoglobulinG from emulsion can conveniently be conducted in aqueous solutions. Results show that pattern definition is maintained after immersion into aqueous solution.

Layer-by-Layer Self-Assembling Gold Nanorods and Glucose Oxidase onto Carbon Nanotubes Functionalized Sol-Gel Matrix for an Amperometric Glucose Biosensor

PubMed Central

Wu, Baoyan; Hou, Shihua; Miao, Zhiying; Zhang, Cong; Ji, Yanhong

2015-01-01

A novel amperometric glucose biosensor was fabricated by layer-by-layer self-assembly of gold nanorods (AuNRs) and glucose oxidase (GOD) onto single-walled carbon nanotubes (SWCNTs)-functionalized three-dimensional sol-gel matrix. A thiolated aqueous silica sol containing SWCNTs was first assembled on the surface of a cleaned Au electrode, and then the alternate self-assembly of AuNRs and GOD were repeated to assemble multilayer films of AuNRs-GOD onto SWCNTs-functionalized silica gel for optimizing the biosensor. Among the resulting glucose biosensors, the four layers of AuNRs-GOD-modified electrode showed the best performance. The sol-SWCNTs-(AuNRs-GOD)4/Au biosensor exhibited a good linear range of 0.01–8 mM glucose, high sensitivity of 1.08 μA/mM, and fast amperometric response within 4 s. The good performance of the proposed glucose biosensor could be mainly attributed to the advantages of the three-dimensional sol-gel matrix and stereo self-assembly films, and the natural features of one-dimensional nanostructure SWCNTs and AuNRs. This study may provide a new facile way to fabricate the enzyme-based biosensor with high performance. PMID:28347080

Surface layer protein characterization by small angle x-ray scattering and a fractal mean force concept: from protein structure to nanodisk assemblies.

PubMed

Horejs, Christine; Pum, Dietmar; Sleytr, Uwe B; Peterlik, Herwig; Jungbauer, Alois; Tscheliessnig, Rupert

2010-11-07

Surface layers (S-layers) are the most commonly observed cell surface structure of prokaryotic organisms. They are made up of proteins that spontaneously self-assemble into functional crystalline lattices in solution, on various solid surfaces, and interfaces. While classical experimental techniques failed to recover a complete structural model of an unmodified S-layer protein, small angle x-ray scattering (SAXS) provides an opportunity to study the structure of S-layer monomers in solution and of self-assembled two-dimensional sheets. For the protein under investigation we recently suggested an atomistic structural model by the use of molecular dynamics simulations. This structural model is now refined on the basis of SAXS data together with a fractal assembly approach. Here we show that a nondiluted critical system of proteins, which crystallize into monomolecular structures, might be analyzed by SAXS if protein-protein interactions are taken into account by relating a fractal local density distribution to a fractal local mean potential, which has to fulfill the Poisson equation. The present work demonstrates an important step into the elucidation of the structure of S-layers and offers a tool to analyze the structure of self-assembling systems in solution by means of SAXS and computer simulations.

Surface layer protein characterization by small angle x-ray scattering and a fractal mean force concept: From protein structure to nanodisk assemblies

NASA Astrophysics Data System (ADS)

Horejs, Christine; Pum, Dietmar; Sleytr, Uwe B.; Peterlik, Herwig; Jungbauer, Alois; Tscheliessnig, Rupert

2010-11-01

Surface layers (S-layers) are the most commonly observed cell surface structure of prokaryotic organisms. They are made up of proteins that spontaneously self-assemble into functional crystalline lattices in solution, on various solid surfaces, and interfaces. While classical experimental techniques failed to recover a complete structural model of an unmodified S-layer protein, small angle x-ray scattering (SAXS) provides an opportunity to study the structure of S-layer monomers in solution and of self-assembled two-dimensional sheets. For the protein under investigation we recently suggested an atomistic structural model by the use of molecular dynamics simulations. This structural model is now refined on the basis of SAXS data together with a fractal assembly approach. Here we show that a nondiluted critical system of proteins, which crystallize into monomolecular structures, might be analyzed by SAXS if protein-protein interactions are taken into account by relating a fractal local density distribution to a fractal local mean potential, which has to fulfill the Poisson equation. The present work demonstrates an important step into the elucidation of the structure of S-layers and offers a tool to analyze the structure of self-assembling systems in solution by means of SAXS and computer simulations.

Surface layer protein characterization by small angle x-ray scattering and a fractal mean force concept: From protein structure to nanodisk assemblies

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

Horejs, Christine; Pum, Dietmar; Sleytr, Uwe B.

2010-11-07

Surface layers (S-layers) are the most commonly observed cell surface structure of prokaryotic organisms. They are made up of proteins that spontaneously self-assemble into functional crystalline lattices in solution, on various solid surfaces, and interfaces. While classical experimental techniques failed to recover a complete structural model of an unmodified S-layer protein, small angle x-ray scattering (SAXS) provides an opportunity to study the structure of S-layer monomers in solution and of self-assembled two-dimensional sheets. For the protein under investigation we recently suggested an atomistic structural model by the use of molecular dynamics simulations. This structural model is now refined on themore » basis of SAXS data together with a fractal assembly approach. Here we show that a nondiluted critical system of proteins, which crystallize into monomolecular structures, might be analyzed by SAXS if protein-protein interactions are taken into account by relating a fractal local density distribution to a fractal local mean potential, which has to fulfill the Poisson equation. The present work demonstrates an important step into the elucidation of the structure of S-layers and offers a tool to analyze the structure of self-assembling systems in solution by means of SAXS and computer simulations.« less

Improvement of light extraction of LYSO scintillator by using a combination of self-assembly of nanospheres and atomic layer deposition.

PubMed

Zhu, Zhichao; Liu, Bo; Zhang, Haifeng; Ren, Weina; Cheng, Chuanwei; Wu, Shuang; Gu, Mu; Chen, Hong

2015-03-23

The self-assembled monolayer periodic array of polystyrene spheres conformally coated with TiO₂ layer using atomic layer deposition is designed to obtain a further enhancement of light extraction for LYSO scintillator. The maximum enhancement is 149% for the sample with polystyrene spheres conformally coated with TiO₂ layer, while the enhancement is only 76% for the sample with only polystyrene spheres. Such further enhancement could be contributed from the additional modes forming by TiO₂ layer due to its high refractive index, which can be approved by the simulation of electric field distribution. The experimental results are agreement with the simulated results. Furthermore, the prepared structured layer exhibits an excellent combination with the surface of scintillator, which is in favor of the practical application. Therefore, it is safely concluded that the combination of self-assembly method and atomic layer deposition is a promising approach to obtain a significant enhancement of light extraction for a large area. This method can be extended to many other luminescent materials and devices.

Observation of layered antiferromagnetism in self-assembled parallel NiSi nanowire arrays on Si(110) by spin-polarized scanning tunneling spectromicroscopy

NASA Astrophysics Data System (ADS)

Hong, Ie-Hong; Hsu, Hsin-Zan

2018-03-01

The layered antiferromagnetism of parallel nanowire (NW) arrays self-assembled on Si(110) have been observed at room temperature by direct imaging of both the topographies and magnetic domains using spin-polarized scanning tunneling microscopy/spectroscopy (SP-STM/STS). The topographic STM images reveal that the self-assembled unidirectional and parallel NiSi NWs grow into the Si(110) substrate along the [\\bar{1}10] direction (i.e. the endotaxial growth) and exhibit multiple-layer growth. The spatially-resolved SP-STS maps show that these parallel NiSi NWs of different heights produce two opposite magnetic domains, depending on the heights of either even or odd layers in the layer stack of the NiSi NWs. This layer-wise antiferromagnetic structure can be attributed to an antiferromagnetic interlayer exchange coupling between the adjacent layers in the multiple-layer NiSi NW with a B2 (CsCl-type) crystal structure. Such an endotaxial heterostructure of parallel magnetic NiSi NW arrays with a layered antiferromagnetic ordering in Si(110) provides a new and important perspective for the development of novel Si-based spintronic nanodevices.

Constructing bio-layer of heparin and type IV collagen on titanium surface for improving its endothelialization and blood compatibility.

PubMed

Zhang, Kun; Chen, Jun-ying; Qin, Wei; Li, Jing-an; Guan, Fang-xia; Huang, Nan

2016-04-01

The modification of cardiovascular stent surface for a better micro-environment has gradually changed to multi-molecule, multi-functional designation. In this study, heparin (Hep) and type IV collagen (IVCol) were used as the functional molecule to construct a bifunctional micro-environment of anticoagulation and promoting endothelialization on titanium (Ti). The surface characterization results (AFM, Alcian Blue 8GX Staining and fluorescence staining of IVCol) indicated that the bio-layer of Hep and IVCol were successfully fabricated on the Ti surface through electrostatic self-assembly. The APTT and platelet adhesion test demonstrated that the bionic layer possessed better blood compatibility compared with Ti surface. The adhesion, proliferation, migration and apoptosis tests of endothelial cells proved that the Hep/IVCol layer was able to enhance the endothelialization of the Ti surface. The in vivo animal implantation results manifested that the bionic surface could encourage new endothelialization. This work provides an important reference for the construction of multifunction micro-environment on the cardiovascular scaffold surface.

Flexible single-layer ionic organic-inorganic frameworks towards precise nano-size separation

NASA Astrophysics Data System (ADS)

Yue, Liang; Wang, Shan; Zhou, Ding; Zhang, Hao; Li, Bao; Wu, Lixin

2016-02-01

Consecutive two-dimensional frameworks comprised of molecular or cluster building blocks in large area represent ideal candidates for membranes sieving molecules and nano-objects, but challenges still remain in methodology and practical preparation. Here we exploit a new strategy to build soft single-layer ionic organic-inorganic frameworks via electrostatic interaction without preferential binding direction in water. Upon consideration of steric effect and additional interaction, polyanionic clusters as connection nodes and cationic pseudorotaxanes acting as bridging monomers connect with each other to form a single-layer ionic self-assembled framework with 1.4 nm layer thickness. Such soft supramolecular polymer frameworks possess uniform and adjustable ortho-tetragonal nanoporous structure in pore size of 3.4-4.1 nm and exhibit greatly convenient solution processability. The stable membranes maintaining uniform porous structure demonstrate precisely size-selective separation of semiconductor quantum dots within 0.1 nm of accuracy and may hold promise for practical applications in selective transport, molecular separation and dialysis systems.

Self-assembled Ag nanoparticle network passivated by a nano-sized ZnO layer for transparent and flexible film heaters

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

Seo, Ki-Won; Kim, Han-Ki, E-mail: imdlhkkim@khu.ac.kr; Kim, Min-Yi

2015-12-15

We investigated a self-assembled Ag nanoparticle network electrode passivated by a nano-sized ZnO layer for use in high-performance transparent and flexible film heaters (TFFHs). The low temperature atomic layer deposition of a nano-sized ZnO layer effectively filled the uncovered area of Ag network and improved the current spreading in the self-assembled Ag network without a change in the sheet resistance and optical transmittance as well as mechanical flexibility. The time-temperature profiles and heat distribution analysis demonstrate that the performance of the TFTH with the ZnO/Ag network is superior to that of a TFFH with Ag nanowire electrodes. In addition, themore » TFTHs with ZnO/Ag network exhibited better stability than the TFFH with a bare Ag network due to the effective current spreading through the nano-sized ZnO layer.« less

Photoinduced charge-transfer materials for nonlinear optical applications

DOEpatents

McBranch, Duncan W.

2006-10-24

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

Multilayered Polyelectrolyte Microcapsules: Interaction with the Enzyme Cytochrome C Oxidase

PubMed Central

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

2014-01-01

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

Method for fabricating five-level microelectromechanical structures and microelectromechanical transmission formed

DOEpatents

Rodgers, M. Steven; Sniegowski, Jeffry J.; Miller, Samuel L.; McWhorter, Paul J.

2000-01-01

A process for forming complex microelectromechanical (MEM) devices having five layers or levels of polysilicon, including four structural polysilicon layers wherein mechanical elements can be formed, and an underlying polysilicon layer forming a voltage reference plane. A particular type of MEM device that can be formed with the five-level polysilicon process is a MEM transmission for controlling or interlocking mechanical power transfer between an electrostatic motor and a self-assembling structure (e.g. a hinged pop-up mirror for use with an incident laser beam). The MEM transmission is based on an incomplete gear train and a bridging set of gears that can be moved into place to complete the gear train to enable power transfer. The MEM transmission has particular applications as a safety component for surety, and for this purpose can incorporate a pin-in-maze discriminator responsive to a coded input signal.

Self-assembled Nano-layering at the Adhesive interface.

PubMed

Yoshida, Y; Yoshihara, K; Nagaoka, N; Hayakawa, S; Torii, Y; Ogawa, T; Osaka, A; Meerbeek, B Van

2012-04-01

According to the 'Adhesion-Decalcification' concept, specific functional monomers within dental adhesives can ionically interact with hydroxyapatite (HAp). Such ionic bonding has been demonstrated for 10-methacryloyloxydecyl dihydrogen phosphate (MDP) to manifest in the form of self-assembled 'nano-layering'. However, it remained to be explored if such nano-layering also occurs on tooth tissue when commercial MDP-containing adhesives (Clearfil SE Bond, Kuraray; Scotchbond Universal, 3M ESPE) were applied following common clinical application protocols. We therefore characterized adhesive-dentin interfaces chemically, using x-ray diffraction (XRD) and energy-dispersive x-ray spectroscopy (EDS), and ultrastructurally, using (scanning) transmission electron microscopy (TEM/STEM). Both adhesives revealed nano-layering at the adhesive interface, not only within the hybrid layer but also, particularly for Clearfil SE Bond (Kuraray), extending into the adhesive layer. Since such self-assembled nano-layering of two 10-MDP molecules, joined by stable MDP-Ca salt formation, must make the adhesive interface more resistant to biodegradation, it may well explain the documented favorable clinical longevity of bonds produced by 10-MDP-based adhesives.

Kinetics of Surface-Driven Self-Assembly and Fatigue-Induced Disassembly of a Virus-Based Nanocoating.

PubMed

Valbuena, Alejandro; Mateu, Mauricio G

2017-02-28

Self-assembling protein layers provide a "bottom-up" approach for precisely organizing functional elements at the nanoscale over a large solid surface area. The design of protein sheets with architecture and physical properties suitable for nanotechnological applications may be greatly facilitated by a thorough understanding of the principles that underlie their self-assembly and disassembly. In a previous study, the hexagonal lattice formed by the capsid protein (CA) of human immunodeficiency virus (HIV) was self-assembled as a monomolecular layer directly onto a solid substrate, and its mechanical properties and dynamics at equilibrium were analyzed by atomic force microscopy. Here, we use atomic force microscopy to analyze the kinetics of self-assembly of the planar CA lattice on a substrate and of its disassembly, either spontaneous or induced by materials fatigue. Both self-assembly and disassembly of the CA layer are cooperative reactions that proceed until a phase equilibrium is reached. Self-assembly requires a critical protein concentration and is initiated by formation of nucleation points on the substrate, followed by lattice growth and eventual merging of CA patches into a continuous monolayer. Disassembly of the CA layer showed hysteresis and appears to proceed only after large enough defects (nucleation points) are formed in the lattice, whose number is largely increased by inducing materials fatigue that depends on mechanical load and its frequency. Implications of the kinetic results obtained for a better understanding of self-assembly and disassembly of the HIV capsid and protein-based two-dimensional nanomaterials and the design of anti-HIV drugs targeting (dis)assembly and biocompatible nanocoatings are discussed. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2015-08-01

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

Structure of Protein Layers in Polyelectrolyte Matrices Studied by Neutron Reflectivity

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

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

2011-01-01

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

Two-Dimensional Layered Oxide Structures Tailored by Self-Assembled Layer Stacking via Interfacial Strain

DOE PAGES

Zhang, Wenrui; Li, Mingtao; Chen, Aiping; ...

2016-06-13

Two-dimensional (2D) nanostructures emerge as one of leading topics in fundamental materials science and could enable next generation nanoelectronic devices. Beyond graphene and molybdenum disulphide, layered complex oxides are another large group of promising 2D candidates because of their strong interplay of intrinsic charge, spin, orbital and lattice. As a fundamental basis of heteroepitaxial thin film growth, interfacial strain can be used to design materials exhibiting new phenomena beyond their conventional form. Here we report the strain-driven self-assembly of Bismuth-based supercells (SC) with a 2D layered structure, and elucidate the fundamental growth mechanism with combined experimental tools and first-principles calculations.more » The study revealed that the new layered structures were formed by the strain-enabled self-assembled atomic layer stacking, i.e., alternative growth of Bi 2O 2 layer and [Fe 0.5Mn 0.5]O 6 layer. The strain-driven approach is further demonstrated in other SC candidate systems with promising room-temperature multiferroic properties. This well-integrated theoretical and experimental study inspired by the Materials Genome Initiatives opens up a new avenue in searching and designing novel 2D layered complex oxides with enormous promises.« less

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

PubMed Central

Gattás-Asfura, Kerim M.; Stabler, Cherie L.

2013-01-01

The encapsulation of viable tissues via layer-by-layer polymer assembly provides a versatile platform for cell surface engineering, with nanoscale control over 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 phosphine functionalized poly(amido amine) (PAMAM) dendrimer, nanoscale layer-by-layer coatings, covalently stabilized via Staudinger ligation, were assembled onto solid surfaces and pancreatic islets. The effects of electrostatic and/or bioorthogonal covalent interlayer interactions on the resulting coating efficiency and stability, as well as pancreatic islet viability and function, were studied. These hyperbranched polymers provide a flexible platform for the formation of covalently stabilized ultrathin coatings on viable cells and tissues. In addition, the hyperbranched nature of the polymers presents a highly functionalized surface capable of bioorthogonal conjugation of additional bioactive or labeling motifs. PMID:24063764

Nanostructured fluorescent particles for glucose sensing

NASA Astrophysics Data System (ADS)

Grant, Patrick S.; Fang, Ming; Lvov, Yuri; McShane, Michael J.

2002-05-01

Self-assembled thin films containing embedded enzymes and fluorescent indicators are being developed for use as highly specific glucose biosensors. The sensors are fabricated using electrostatic Layer-by-Layer (LBL) adsorption to create oxygen-sensitive (Ruthenium-based) layers, the fluorescent intensity of which responds to changes in local oxygen levels. Oxygen is consumed locally by the reaction between glucose oxidase (GOx) molecules and glucose. Latex particles serve as the templates for our sensors and fabrication is carried out through the alternate adsorption of multiple levels of {GOx/polycation} and {Ruthenium-polycation/polyanion} bilayers. Additional fluorescence layers as well as fluorescent latex are being considered as internal intensity references to allow ratiometric monitoring. Films adsorbed to the nanoparticle templates are being studied to understand the fundamental chemical and optical properties, including enzymatic activity, spectral shape and emission intensity. Enzymatic activity is retained and stability is improved after adsorption, and increased surface area afforded by the particles allows use of increased numbers of molecules. Fluorescence is also maintained, though blue shifts are observed in emission spectra, and indicator activity remains. In vitro characterization studies demonstrate the feasibility of the particles as glucose biosensors, and future work will aim to optimize the response for neural monitoring.

Fabricating Electrochromic Thin Films Based on Metallo-Polymers Using Layer-by-Layer Self-Assembly: An Attractive Laboratory Experiment

ERIC Educational Resources Information Center

Schott, Marco; Beck, Matthias; Winkler, Franziska; Lorrmann, Henning; Kurth, Dirk G.

2015-01-01

Metallo-supramolecular polyelectrolytes (MEPE) based on iron(II)-acetate and 1,4-bis(2,2':6',2?-terpyridin-4'-yl)benzene are assembled by layer-by-layer deposition on transparent electrode surfaces. When a potential is applied, the color of the film can be switched from blue to transparent. Due to the strong absorption and the fast switching…

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.

Epitaxially Self-Assembled Alkane Layers for Graphene Electronics.

PubMed

Yu, Young-Jun; Lee, Gwan-Hyoung; Choi, Ji Il; Shim, Yoon Su; Lee, Chul-Ho; Kang, Seok Ju; Lee, Sunwoo; Rim, Kwang Taeg; Flynn, George W; Hone, James; Kim, Yong-Hoon; Kim, Philip; Nuckolls, Colin; Ahn, Seokhoon

2017-02-01

The epitaxially grown alkane layers on graphene are prepared by a simple drop-casting method and greatly reduce the environmentally driven doping and charge impurities in graphene. Multiscale simulation studies show that this enhancement of charge homogeneity in graphene originates from the lifting of graphene from the SiO 2 surface toward the well-ordered and rigid alkane self-assembled layers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Total Scattering Analysis of Disordered Nanosheet Materials

NASA Astrophysics Data System (ADS)

Metz, Peter C.

Two dimensional materials are of increasing interest as building blocks for functional coatings, catalysts, and electrochemical devices. While increasingly sophisticated processing routes have been designed to obtain high-quality exfoliated nanosheets and controlled, self-assembled mesostructures, structural characterization of these materials remains challenging. This work presents a novel method of analyzing pair distribution function (PDF) data for disordered nanosheet ensembles, where supercell stacking models are used to infer atom correlations over as much as 50 A. Hierarchical models are used to reduce the parameter space of the refined model and help eliminate strongly correlated parameters. Three data sets for restacked nanosheet assemblies with stacking disorder are analyzed using these methods: simulated data for graphene-like layers, experimental data for 1 nm thick perovskite layers, and experimental data for highly defective delta-MnO2 layers. In each case, the sensitivity of the PDF to the real-space distribution of layer positions is demonstrated by exploring the fit residual as a function of stacking vectors. The refined models demonstrate that nanosheets tend towards local interlayer ordering, which is hypothesized to be driven by the electrostatic potential of the layer surfaces. Correctly accounting for interlayer atom correlations permits more accurate refinement of local structural details including local structure perturbations and defect site occupancies. In the delta-MnO2 nanosheet material, the new modeling approach identified 14% Mn vacancies while application of 3D periodic crystalline models to the < 7 A PDF region suggests a 25% vacancy concentration. In contrast, the perovskite nanosheet material is demonstrated to exhibit almost negligible structural relaxation in contrast with the bulk crystalline material from which it is derived.

Influence of the foundation layer on the layer-by-layer assembly of poly-L-lysine and poly(styrenesulfonate) and its usage in the fabrication of 3D microscale features.

PubMed

Zhou, Dejian; Bruckbauer, Andreas; Batchelor, Matthew; Kang, Dae-Joon; Abell, Chris; Klenerman, David

2004-10-12

The layer-by-layer (LBL) assembly of a polypeptide, poly-L-lysine (PLL), with poly(styrenesulfonate) sodium salt (PSS) on flat template-stripped gold (TSG) surfaces precoated with a self-assembled monolayer of alkanethiols terminated with positive (pyridinium), negative (carboxylic acid), and neutral [hexa(ethylene glycol)] groups is investigated. Both the topography and the rate of film thickness growth are found to be strongly dependent on the initial surface foundation layer. LBL assembly of PLL and PSS on patterned TSG surfaces produced by micro contact printing leads to structurally distinct microscale features, including pillars, ridges, and wells, whose height can be controlled with nanometer precision. Copyright 2004 American Chemical Society

Understanding self-assembly of charged-neutral block copolymer (BCP) and surfactant complexes using molecular dynamics (MD) simulation

NASA Astrophysics Data System (ADS)

Goswami, Monojoy; Sumpter, Bobby; Kilbey, Michael

Here we report the formation of phase separated BCP-surfactant complexes resulting from the electrostatic self-assembly of charge-neutral block copolymers with oppositely charged surfactants. Complexation behaviors of oppositely charged polyelectrolytes has gained considerable attention in the field of soft condensed matter physics due to their potential application as functional nanomaterials for batteries, wastewater treatment and drug delivery systems. Numerous experiments have examined the self-assembled structures resulting from complexation of charge-neutral BCP and surfactants, however, there is a lack of comprehensive understanding at the fundamental level. To help bridge this gap, we use, MD simulations to study self-assembly and dynamics of the BCP-surfactant complex at the molecular level. Our results show an overcharging effect in BCPs with hydrophobic neutral blocks and a formation of core-shell colloidal structure. Hydrophilic neutral blocks, on the other hand, show stable, hairy colloidal structures with neutral blocks forming a loosely-bound, fuzzy outer layer. Our results qualitatively agree with previous SANS and SAXS experiments. This work was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Materials Science and Engineering Division.

Self-assembled three-dimensional and compressible interdigitated thin-film supercapacitors and batteries

PubMed Central

Nyström, Gustav; Marais, Andrew; Karabulut, Erdem; Wågberg, Lars; Cui, Yi; Hamedi, Mahiar M.

2015-01-01

Traditional thin-film energy-storage devices consist of stacked layers of active films on two-dimensional substrates and do not exploit the third dimension. Fully three-dimensional thin-film devices would allow energy storage in bulk materials with arbitrary form factors and with mechanical properties unique to bulk materials such as compressibility. Here we show three-dimensional energy-storage devices based on layer-by-layer self-assembly of interdigitated thin films on the surface of an open-cell aerogel substrate. We demonstrate a reversibly compressible three-dimensional supercapacitor with carbon nanotube electrodes and a three-dimensional hybrid battery with a copper hexacyanoferrate ion intercalating cathode and a carbon nanotube anode. The three-dimensional supercapacitor shows stable operation over 400 cycles with a capacitance of 25 F g−1 and is fully functional even at compressions up to 75%. Our results demonstrate that layer-by-layer self-assembly inside aerogels is a rapid, precise and scalable route for building high-surface-area 3D thin-film devices. PMID:26021485

Charge transport in vertically aligned, self-assembled peptide nanotube junctions.

PubMed

Mizrahi, Mordechay; Zakrassov, Alexander; Lerner-Yardeni, Jenny; Ashkenasy, Nurit

2012-01-21

The self-assembly propensity of peptides has been extensively utilized in recent years for the formation of supramolecular nanostructures. In particular, the self-assembly of peptides into fibrils and nanotubes makes them promising building blocks for electronic and electro-optic applications. However, the mechanisms of charge transfer in these wire-like structures, especially in ambient conditions, are not yet fully understood. We describe here a layer-by-layer deposition methodology of short self-assembled cyclic peptide nanotubes, which results in vertically oriented nanotubes on gold substrates. Using this novel deposition methodology, we have fabricated molecular junctions with a conductive atomic force microscopy tip as a second electrode. Studies of the junctions' current-voltage characteristics as a function of the nanotube length revealed an efficient charge transfer in these supramolecular structures, with a low current attenuation constant of 0.1 Å(-1), which indicate that electron transfer is dominated by hopping. Moreover, the threshold voltage to field-emission dominated transport was found to increase with peptide length in a manner that depends on the nature of the contact with the electrodes. The flexibility in the design of the peptide monomers and the ability to control their sequential order over the nanotube by means of the layer-by-layer assembly process, which is demonstrated in this work, can be used to engineer the electronic properties of self-assembled peptide nanotubes toward device applications.

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.

Self-organization of grafted polyelectrolyte layers via the coupling of chemical equilibrium and physical interactions.

PubMed

Tagliazucchi, Mario; de la Cruz, Mónica Olvera; Szleifer, Igal

2010-03-23

The competition between chemical equilibrium, for example protonation, and physical interactions determines the molecular organization and functionality of biological and synthetic systems. Charge regulation by displacement of acid-base equilibrium induced by changes in the local environment provides a feedback mechanism that controls the balance between electrostatic, van der Waals, steric interactions and molecular organization. Which strategies do responsive systems follow to globally optimize chemical equilibrium and physical interactions? We address this question by theoretically studying model layers of end-grafted polyacids. These layers spontaneously form self-assembled aggregates, presenting domains of controlled local pH and whose morphologies can be manipulated by the composition of the solution in contact with the film. Charge regulation stabilizes micellar domains over a wide range of pH by reducing the local charge in the aggregate at the cost of chemical free energy and gaining in hydrophobic interactions. This balance determines the boundaries between different aggregate morphologies. We show that a qualitatively new form of organization arises from the coupling between physical interactions and protonation equilibrium. This optimization strategy presents itself with polyelectrolytes coexisting in two different and well-defined protonation states. Our results underline the need of considering the coupling between chemical equilibrium and physical interactions due to their highly nonadditive behavior. The predictions provide guidelines for the creation of responsive polymer layers presenting self-organized patterns with functional properties and they give insights for the understanding of competing interactions in highly inhomogeneous and constrained environments such as those relevant in nanotechnology and those responsible for biological cells function.

Formation of charge-nanopatterned templates with flexible geometry via layer by layer deposition of polyelectrolytes for directed self-assembly of gold nanoparticles

NASA Astrophysics Data System (ADS)

Sayin, Mustafa; Dahint, Reiner

2017-03-01

Nanostructure formation via self-assembly processes offers a fast and cost-effective approach to generate surface patterns on large lateral scale. In particular, if the high precision of lithographic techniques is not required, a situation typical of many biotechnological and biomedical applications, it may be considered as the method of choice as it does not require any sophisticated instrumentation. However, in many cases the variety and complexity of the surface structures accessible with a single self-assembly based technique is limited. Here, we report on a new approach which combines two different self-assembly strategies, colloidal lithography and layer-by-layer deposition of polyelectrolytes, in order to significantly expand the spectrum of accessible patterns. In particular, flat and donut-like charge-patterned templates have been generated, which facilitate subsequent deposition of gold nanoparticles in dot, grid, ring, out-of-ring and circular patch structures. Potential applications are e.g. in the fields of biofunctional interfaces with well-defined lateral dimensions, optical devices with tuned properties, and controlled three-dimensional material growth.

Self-Assembled Layering of Magnetic Nanoparticles in a Ferrofluid on Silicon Surfaces.

PubMed

Theis-Bröhl, Katharina; Vreeland, Erika C; Gomez, Andrew; Huber, Dale L; Saini, Apurve; Wolff, Max; Maranville, Brian B; Brok, Erik; Krycka, Kathryn L; Dura, Joseph A; Borchers, Julie A

2018-02-07

This article describes the three-dimensional self-assembly of monodisperse colloidal magnetite nanoparticles (NPs) from a dilute water-based ferrofluid onto a silicon surface and the dependence of the resultant magnetic structure on the applied field. The NPs assemble into close-packed layers on the surface followed by more loosely packed ones. The magnetic field-dependent magnetization of the individual NP layers depends on both the rotational freedom of the layer and the magnetization of the adjacent layers. For layers in which the NPs are more free to rotate, the easy axis of the NP can readily orient along the field direction. In more dense packing, free rotation of the NPs is hampered, and the NP ensembles likely build up quasi-domain states to minimize energy, which leads to lower magnetization in those layers. Detailed analysis of polarized neutron reflectometry data together with model calculations of the arrangement of the NPs within the layers and input from small-angle scattering measurements provide full characterization of the core/shell NP dimensions, degree of chaining, arrangement of the NPs within the different layers, and magnetization depth profile.

Titanium Surface Priming with Phase-Transited Lysozyme to Establish a Silver Nanoparticle-Loaded Chitosan/Hyaluronic Acid Antibacterial Multilayer via Layer-by-Layer Self-Assembly.

PubMed

Zhong, Xue; Song, Yunjia; Yang, Peng; Wang, Yao; Jiang, Shaoyun; Zhang, Xu; Li, Changyi

2016-01-01

The formation of biofilm around implants, which is induced by immediate bacterial colonization after installation, is the primary cause of post-operation infection. Initial surface modification is usually required to incorporate antibacterial agents on titanium (Ti) surfaces to inhibit biofilm formation. However, simple and effective priming methods are still lacking for the development of an initial functional layer as a base for subsequent coatings on titanium surfaces. The purpose of our work was to establish a novel initial layer on Ti surfaces using phase-transited lysozyme (PTL), on which multilayer coatings can incorporate silver nanoparticles (AgNP) using chitosan (CS) and hyaluronic acid (HA) via a layer-by-layer (LbL) self-assembly technique. In this study, the surfaces of Ti substrates were primed by dipping into a mixture of lysozyme and tris(2-carboxyethyl)phosphine (TCEP) to obtain PTL-functionalized Ti substrates. The subsequent alternating coatings of HA and chitosan loaded with AgNP onto the precursor layer of PTL were carried out via LbL self-assembly to construct multilayer coatings on Ti substrates. The results of SEM and XPS indicated that the necklace-like PTL and self-assembled multilayer were successfully immobilized on the Ti substrates. The multilayer coatings loaded with AgNP can kill planktonic and adherent bacteria to 100% during the first 4 days. The antibacterial efficacy of the samples against planktonic and adherent bacteria achieved 65%-90% after 14 days. The sustained release of Ag over 14 days can prevent bacterial invasion until mucosa healing. Although the AgNP-containing structure showed some cytotoxicity, the toxicity can be reduced by controlling the Ag release rate and concentration. The PTL priming method provides a promising strategy for fabricating long-term antibacterial multilayer coatings on titanium surfaces via the LbL self-assembly technique, which is effective in preventing implant-associated infections in the early stage.

Long-range energy transfer in self-assembled quantum dot-DNA cascades

NASA Astrophysics Data System (ADS)

Goodman, Samuel M.; Siu, Albert; Singh, Vivek; Nagpal, Prashant

2015-11-01

The size-dependent energy bandgaps of semiconductor nanocrystals or quantum dots (QDs) can be utilized in converting broadband incident radiation efficiently into electric current by cascade energy transfer (ET) between layers of different sized quantum dots, followed by charge dissociation and transport in the bottom layer. Self-assembling such cascade structures with angstrom-scale spatial precision is important for building realistic devices, and DNA-based QD self-assembly can provide an important alternative. Here we show long-range Dexter energy transfer in QD-DNA self-assembled single constructs and ensemble devices. Using photoluminescence, scanning tunneling spectroscopy, current-sensing AFM measurements in single QD-DNA cascade constructs, and temperature-dependent ensemble devices using TiO2 nanotubes, we show that Dexter energy transfer, likely mediated by the exciton-shelves formed in these QD-DNA self-assembled structures, can be used for efficient transport of energy across QD-DNA thin films.The size-dependent energy bandgaps of semiconductor nanocrystals or quantum dots (QDs) can be utilized in converting broadband incident radiation efficiently into electric current by cascade energy transfer (ET) between layers of different sized quantum dots, followed by charge dissociation and transport in the bottom layer. Self-assembling such cascade structures with angstrom-scale spatial precision is important for building realistic devices, and DNA-based QD self-assembly can provide an important alternative. Here we show long-range Dexter energy transfer in QD-DNA self-assembled single constructs and ensemble devices. Using photoluminescence, scanning tunneling spectroscopy, current-sensing AFM measurements in single QD-DNA cascade constructs, and temperature-dependent ensemble devices using TiO2 nanotubes, we show that Dexter energy transfer, likely mediated by the exciton-shelves formed in these QD-DNA self-assembled structures, can be used for efficient transport of energy across QD-DNA thin films. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04778a

Hydrolysis-controlled protein adsorption and antifouling behaviors of mixed charged self-assembled monolayer: A molecular simulation study.

PubMed

Liu, Jie; Zhou, Jian

2016-08-01

Understanding the mechanism of the antimicrobial and antifouling properties of mixed charged materials is of great significance. The interactions between human gamma fibrinogen (γFg) and mixed carboxylic methyl ether-terminated (COOCH3-) and trimethylamino-terminated (N(CH3)3(+)-) SAMs and the influence of hydrolysis were studied by molecular simulations. After hydrolysis, the mixed SAMs exhibit behaviors from antimicrobial to antifouling, since the COOCH3-thiols were translated into carboxylic acid (COO(-)-) terminated thiols, which carried a net charge of -1 e. Simulation results showed that the main differences between COOCH3-/N(CH3)3(+)-SAM and COO(-)-/N(CH3)3(+)-SAM are the charged property and the hydration layer above the surface. γFg could stably adsorb on the positively-charged COOCH3-/N(CH3)3(+)-SAM. The adsorption behavior is mainly induced by the strong electrostatic attraction. There is a single hydration layer bound to the surface, which is related to the N(CH3)3(+) groups. The van der Waals repulsion between γFg and the single hydration layer are not strong enough to compensate the strong electrostatic attraction. After hydrolysis, the positively-charged SAM was transferred to a neutral mixed charged surface, the electrostatic attraction between γFg and the surface disappears. Meanwhile, the SAM surface is covered by double hydration layers, which is induced by the N(CH3)3(+) and COO(-) groups; water molecules around COO(-) groups are obviously denser than that around N(CH3)3(+) groups. With the combined contribution from double hydration layers and the vanishment of electrostatic attraction, γFg is forced to desorb from the surface. After hydrolysis, the internal structure of mixed SAM appears more ordered due to the electrostatic interactions between charged groups on the top of SAMs. The antimicrobial and antifouling materials are of great importance in many biological applications. The strong hydration property of surfaces and the interactions between proteins and surfaces play a key role in resisting protein adsorption. The mixed SAMs, constructed from a 1:1 combination of COOCH3- and N(CH3)3(+)-terminated thiols, can induce protein adsorption mainly through the electrostatic interaction. When the COOCH3-terminated thiols were hydrolyzed to negatively charged COO(-)-terminated thiols, the mixed-charged SAMs switched from antimicrobial to antifouling. Due to the strong hydration property of the mixed charged SAMs, the adsorbed γFg moved away from the surface. Understanding the interactions between protein and mixed-charged SAMs in the atomistic level is important for the practical design and development of new antimicrobial and antifouling materials. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Coordination-based gold nanoparticle layers.

PubMed

Wanunu, Meni; Popovitz-Biro, Ronit; Cohen, Hagai; Vaskevich, Alexander; Rubinstein, Israel

2005-06-29

Gold nanoparticle (NP) mono- and multilayers were constructed on gold surfaces using coordination chemistry. Hydrophilic Au NPs (6.4 nm average core diameter), capped with a monolayer of 6-mercaptohexanol, were modified by partial substitution of bishydroxamic acid disulfide ligand molecules into their capping layer. A monolayer of the ligand-modified Au NPs was assembled via coordination with Zr4+ ions onto a semitransparent Au substrate (15 nm Au, evaporated on silanized glass and annealed) precoated with a self-assembled monolayer of the bishydroxamate disulfide ligand. Layer-by-layer construction of NP multilayers was achieved by alternate binding of Zr4+ ions and ligand-modified NPs onto the first NP layer. Characterization by atomic force microscopy (AFM), ellipsometry, wettability, transmission UV-vis spectroscopy, and cross-sectional transmission electron microscopy showed regular growth of NP layers, with a similar NP density in successive layers and gradually increased roughness. The use of coordination chemistry enables convenient step-by-step assembly of different ligand-possessing components to obtain elaborate structures. This is demonstrated by introducing nanometer-scale vertical spacing between a NP layer and the gold surface, using a coordination-based organic multilayer. Electrical characterization of the NP films was carried out using conductive AFM, emphasizing the barrier properties of the organic spacer multilayer. The results exhibit the potential of coordination self-assembly in achieving highly controlled composite nanostructures comprising molecules, NPs, and other ligand-derivatized components.

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

NASA Astrophysics Data System (ADS)

Prouty, Malcolm D.

2007-12-01

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

Total internal reflection ellipsometry and SPR detection of low molecular weight environmental toxins

NASA Astrophysics Data System (ADS)

Nabok, A. V.; Tsargorodskaya, A.; Hassan, A. K.; Starodub, N. F.

2005-06-01

The environmental toxins, such as herbicides simazine and atrazine, and T2 mycotoxin were registered with the optical methods of surface plasmon resonance (SPR) and recently developed total internal reflection ellipsometry (TIRE). The immune assay approach was exploited for in situ registration of the above low molecular weight toxins with specific antibodies immobilised onto the gold surface via (poly)allylamine hydrochloride layer using electrostatic self-assembly (ESA) technique. The comparison of two methods of SPR and TIRE shows a higher sensitivity of the latter.

Engineering New Layered Solids from Exfoliated Inorganics: a Periodically Alternating Hydrotalcite – Montmorillonite Layered Hybrid

PubMed Central

Chalasani, Rajesh; Gupta, Amit; Vasudevan, Sukumaran

2013-01-01

Two-dimensional (2D) nanosheets obtained by exfoliating inorganic layered crystals have emerged as a new class of materials with unique attributes. One of the critical challenges is to develop robust and versatile methods for creating new nanostructures from these 2D-nanosheets. Here we report the delamination of layered materials that belonging to two different classes - the cationic clay, montmorillonite, and the anionic clay, hydrotalcite - by intercalation of appropriate ionic surfactants followed by dispersion in a non-polar solvent. The solids are delaminated to single layers of atomic thickness with the ionic surfactants remaining tethered to the inorganic and consequently the nanosheets are electrically neutral. We then show that when dispersions of the two solids are mixed the exfoliated sheets self-assemble as a new layered solid with periodically alternating hydrotalcite and montmorillonite layers. The procedure outlined here is easily extended to other layered solids for creating new superstructures from 2D-nanosheets by self-assembly. PMID:24336682

Reduced graphene oxide-ZnO self-assembled films: tailoring the visible light photoconductivity by the intrinsic defect states in ZnO.

PubMed

Kavitha, M K; Gopinath, Pramod; John, Honey

2015-06-14

ZnO is a wide direct bandgap semiconductor; its absorption can be tuned to the visible spectral region by controlling the intrinsic defect levels. Combining graphene with ZnO can improve its performance by photo-induced charge separation by ZnO and electronic transport through graphene. When reduced graphene oxide-ZnO is prepared by a hydrothermal method, the photophysical studies indicate that oxygen vacancy defect states are healed out by diffusion of oxygen from GO to ZnO during its reduction. Because of the passivation of oxygen vacancies, the visible light photoconductivity of the hybrid is depleted, compared to pure ZnO. In order to overcome this reduction in photocurrent, a photoelectrode is fabricated by layer-by-layer (LBL) self-assembly of ZnO and reduced graphene oxide. The multilayer films are fabricated by the electrostatic LBL self-assembly technique using negatively charged poly(sodium 4-styrene sulfonate)-reduced graphene oxide (PSS-rGO) and positively charged polyacrylamide-ZnO (PAM-ZnO) as building blocks. The multilayer films fabricated by this technique will be highly interpenetrating; it will enhance the interaction between the ZnO and rGO perpendicular to the electrode surface. Upon illumination under bias voltage defect assisted excitation occurs in ZnO and the photogenerated charge carriers can transfer to graphene. The electron transferred to graphene sheets can recombine in two ways; either it can recombine with the holes in the valence band of ZnO in its bilayer or the ZnO in the next bilayer. This type of tunnelling of electrons from graphene to the successive bilayers will result in efficient charge transfer. This transfer and propagation of electron will enhance as the number of bilayers increases, which in turn improve the photocurrent of the multilayer films. Therefore this self-assembly technique is an effective approach to fabricate semiconductor-graphene films with excellent conductivity.

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.

Layer-by-layer films and colloidal dispersions of graphene oxide nanosheets for efficient control of the fluorescence and aggregation properties of the cationic dye acridine orange.

PubMed

Hansda, Chaitali; Chakraborty, Utsav; Hussain, Syed Arshad; Bhattacharjee, Debajyoti; Paul, Pabitra Kumar

2016-03-15

Chemically derived graphene oxide (GO) nanosheets have received great deal of interest for technological application such as optoelectronic and biosensors. Aqueous dispersions of GO become an efficient template to induce the association of cationic dye namely Acridine Orange (AO). Interactions of AO with colloidal GO was governed by both electrostatic and π-π stacking cooperative interactions. The type of dye aggregations was found to depend on the concentration of GO in the mixed ensemble. Spectroscopic calculations revealed the formation of both H and J-type dimers, but H-type aggregations were predominant. Preparation of layer-by-layer (LbL) electrostatic self-assembled films of AO and GO onto poly (allylamine hydrochloride) (PAH) coated quartz substrate is also reported in this article. UV-Vis absorption, steady state and time resolve fluorescence and Raman spectroscopic techniques have been employed to explore the detail photophysical properties of pure AO, AO/GO mixed solution and AO/GO LbL films. Scanning electron microscopy was also used for visual evidence of the synthesized nanodimensional GO sheets. The fluorescence quenching of AO in the presence of GO in aqueous solution was due to the interfacial photoinduced electron transfer (PET) from photoexcited AO to GO i.e. GO acts as an efficient quenching agent for the fluorescence emission of AO. The quenching is found to be static in nature. Raman spectroscopic results also confirmed the interaction of AO with GO and the electron transfer. The formation of AO/GO complex via very fast excited state electron transfer mechanism may be proposed as to prepare GO-based fluorescence sensor for biomolecular detection without direct labeling the biomolecules by fluorescent probe. Copyright © 2015 Elsevier B.V. All rights reserved.

Layer-by-layer films and colloidal dispersions of graphene oxide nanosheets for efficient control of the fluorescence and aggregation properties of the cationic dye acridine orange

NASA Astrophysics Data System (ADS)

Hansda, Chaitali; Chakraborty, Utsav; Hussain, Syed Arshad; Bhattacharjee, Debajyoti; Paul, Pabitra Kumar

2016-03-01

Chemically derived graphene oxide (GO) nanosheets have received great deal of interest for technological application such as optoelectronic and biosensors. Aqueous dispersions of GO become an efficient template to induce the association of cationic dye namely Acridine Orange (AO). Interactions of AO with colloidal GO was governed by both electrostatic and π-π stacking cooperative interactions. The type of dye aggregations was found to depend on the concentration of GO in the mixed ensemble. Spectroscopic calculations revealed the formation of both H and J-type dimers, but H-type aggregations were predominant. Preparation of layer-by-layer (LbL) electrostatic self-assembled films of AO and GO onto poly (allylamine hydrochloride) (PAH) coated quartz substrate is also reported in this article. UV-Vis absorption, steady state and time resolve fluorescence and Raman spectroscopic techniques have been employed to explore the detail photophysical properties of pure AO, AO/GO mixed solution and AO/GO LbL films. Scanning electron microscopy was also used for visual evidence of the synthesized nanodimensional GO sheets. The fluorescence quenching of AO in the presence of GO in aqueous solution was due to the interfacial photoinduced electron transfer (PET) from photoexcited AO to GO i.e. GO acts as an efficient quenching agent for the fluorescence emission of AO. The quenching is found to be static in nature. Raman spectroscopic results also confirmed the interaction of AO with GO and the electron transfer. The formation of AO/GO complex via very fast excited state electron transfer mechanism may be proposed as to prepare GO-based fluorescence sensor for biomolecular detection without direct labeling the biomolecules by fluorescent probe.

Activity and lifetime of urease immobilized using layer-by-layer nano self-assembly on silicon microchannels.

PubMed

Forrest, Scott R; Elmore, Bill B; Palmer, James D

2005-01-01

Urease has been immobilized and layered onto the walls of manufactured silicon microchannels. Enzyme immobilization was performed using layer-by-layer nano self-assembly. Alternating layers of oppositely charged polyelectrolytes, with enzyme layers "encased" between them, were deposited onto the walls of the silicon microchannels. The polycations used were polyethylenimine (PEI), polydiallyldimethylammonium (PDDA), and polyallylamine (PAH). The polyanions used were polystyrenesulfonate (PSS) and polyvinylsulfate (PVS). The activity of the immobilized enzyme was tested by pumping a 1 g/L urea solution through the microchannels at various flow rates. Effluent concentration was measured using an ultraviolet/visible spectrometer by monitoring the absorbance of a pH sensitive dye. The architecture of PEI/PSS/PEI/urease/PEI with single and multiple layers of enzyme demonstrated superior performance over the PDDA and PAH architectures. The precursor layer of PEI/PSS demonstrably improved the performance of the reactor. Conversion rates of 70% were achieved at a residence time of 26 s, on d 1 of operation, and >50% at 51 s, on d 15 with a six-layer PEI/urease architecture.

Water-Soluble Conjugated Polymers: Self-Assembly and Biosensor Applications

NASA Astrophysics Data System (ADS)

Bazan, Guillermo

2005-03-01

Homogeneous assays can be designed which take advantage of the optical amplification of conjugated polymers and the self-assembly characteristic of aqueous polyelectrolytes. For example, a ssDNA sequence sensor comprises an aqueous solution containing a cationic water soluble conjugated polymer such as poly(9,9-bis(trimethylammonium)-hexyl)-fluorene phenylene) with a peptide nucleic acid (PNA) labeled with a dye (PNA-C*). Signal transduction is controlled by hybridization of the neutral PNA-C* probe and the negative ssDNA target, resulting in favorable electrostatic interactions between the hybrid complex and the cationic polymer. Distance requirements for Förster energy transfer are thus met only when ssDNA of complementary sequence to the PNA-C* probe is present. Signal amplification by the conjugated polymer provides fluorescein emission >25 times higher than that of the directly excited dye. Transduction by electrostatic interactions followed by energy transfer is a general strategy. Examples involving other biomolecular recognition events, such as DNA/DNA, RNA/protein and RNA/RNA, will also be provided. The mechanism of biosensing will be discussed, with special attention to the varying contributions of hydrophobic and electrostatic forces, polymer conformation, charge density, local concentration of C*s and tailored defect sites for aggregation-induced optical changes. Finally, the water solubility of these conjugated polymers opens possibilities for spin casting onto organic materials, without dissolving the underlying layers. This property is useful for fabricating multilayer organic optoelectronic devices by simple solution techniques.

Nanosheets of oxides and hydroxides: Ultimate 2D charge-bearing functional crystallites.

PubMed

Ma, Renzhi; Sasaki, Takayoshi

2010-12-01

A wide variety of cation-exchangeable layered transition metal oxides and their relatively rare counterparts, anion-exchangeable layered hydroxides, have been exfoliated into individual host layers, i.e., nanosheets. Exfoliation is generally achieved via a high degree of swelling, typically driven either by intercalation of bulky organic ions (quaternary ammonium cations, propylammonium cations, etc.) for the layered oxides or by solvation with organic solvents (formamide, butanol, etc.) for the hydroxides. Ultimate two-dimensional (2D) anisotropy for the nanosheets, with thickness of around one nanometer versus lateral size ranging from submicrometer to several tens of micrometers, allows them to serve either as an ideal quantum system for fundamental study or as a basic building block for functional assembly. The charge-bearing inorganic macromolecule-like nanosheets can be assembled or organized through various solution-based processing techniques (e.g., flocculation, electrostatic sequential deposition, or the Langmuir-Blodgett method) to produce a range of nanocomposites, multilayer nanofilms, and core-shell nanoarchitectures, which have great potential for electronic, magnetic, optical, photochemical, and catalytic applications.

New biosensing platforms based on the layer-by-layer self-assembling of polyelectrolytes on Nafion/carbon nanotubes-coated glassy carbon electrodes.

PubMed

Rivas, Gustavo A; Miscoria, Silvia A; Desbrieres, Jacques; Barrera, Gustavo D

2007-01-15

We are proposing for the first time the use of a Nafion/multi-walled carbon nanotubes dispersion deposited on glassy carbon electrodes (GCE) as a new platform for developing enzymatic biosensors based on the self-assembling of a chitosan derivative and different oxidases. The electrodes are obtained by deposition of a layer of Nafion/multi-wall carbon nanotubes dispersion on glassy carbon electrodes, followed by the adsorption of a chitosan derivative as polycation and glucose oxidase, l-aminoacid oxidase or polyphenol oxidase, as polyanions and biorecognition elements. The optimum configuration for glucose biosensors has allowed a highly sensitive (sensitivity=(0.28+/-0.02)muAmM(-1), r=0.997), fast (4s in reaching the maximum response), and highly selective (0% interference of ascorbic acid and uric acid at maximum physiological levels) glucose quantification at 0.700V with detection and quantification limits of 0.035 and 0.107mM, respectively. The repetitivity for 10 measurements was 5.5%, while the reproducibility was 8.4% for eight electrodes. The potentiality of the new platform was clearly demonstrated by using the carbon nanotubes/Nafion layer as a platform for the self-assembling of l-aminoacid oxidase and polyphenol oxidase. Therefore, the platform we are proposing here, that combines the advantages of nanostructured materials with those of the layer-by-layer self-assembling of polyelectrolytes, opens the doors to new and exciting possibilities for the development of enzymatic and affinity biosensors using different transdution modes.

Characterization of a Biomimetic Polymeric-Lipid Bilayer by Phase Sensitive Neutron Reflectivity

NASA Astrophysics Data System (ADS)

Perez-Salas, Ursula A.; Krueger, Susan; Majkrzak, Charles F.; Berk, Norman F.; Faucher, Keith M.; Chaikof, Elliot L.

2003-03-01

Lipid membranes, the boundaries for cellular and intracellular structures, regulate many crucial biological processes. Planar supported mimics of cell membranes are of great interest as model systems for the study of membrane structure/function phenomena in fundamental biophysics research. We studied a supported biomedically relevant membrane-mimetic system composed of a polyelectrolyte cushion, a terpolymer and a self-assembled phospholipid monolayer and obtained a detailed profile characterization of the system by neutron reflectometry. The water-swellable hydrophilic polyelectrolyte acts as a support for the biomembrane, not unlike the cytoskeletal support found in actual mammalian cell membranes. The "cushion" polymers are fixed to the flat, hard surface by having the polymer interact with it electrostatically. The terpolymer has the following desirable features: it tethers to the polyelectrolyte layer and it creates a hydrophilic and a hydrophobic region. Unilamellar phospholipid vesicle fusion on to the hydrophobic region of the terpolymer creates the hybrid tethered membrane. For added stability to external force fields (such as shear flow), the phospholipid monolayer is then polymerized in situ, effectively anchoring the lipid layer to the hydrophobic region of the terpolymer. Neutron reflectivity measurements were done on the polyelectrolyte layer, the polyelectrolyte layer plus terpolymer and the polylectrolyte layer plus terpolymer plus phospholipid. The layers were studied dry and hydrated and under 95α D_2O and 50% \\ 50% α H_2O \\ α D_2O) on the polyelectrolyte layer plus terpolymer and the polylectrolyte layer plus terpolymer plus phospholipid the distribution of water in the layers was obtained. The results will be correlated to impedance measurements flourescence measurements and infrared spectroscopy measurements made on equivalent samples.

A S-Layer Protein of Bacillus anthracis as a Building Block for Functional Protein Arrays by In Vitro Self-Assembly.

PubMed

Wang, Xu-Ying; Wang, Dian-Bing; Zhang, Zhi-Ping; Bi, Li-Jun; Zhang, Ji-Bin; Ding, Wei; Zhang, Xian-En

2015-11-18

S-layer proteins create a cell-surface layer architecture in both bacteria and archaea. Because S-layer proteins self-assemble into a native-like S-layer crystalline structure in vitro, they are attractive building blocks in nanotechnology. Here, the potential use of the S-layer protein EA1 from Bacillus anthracis in constructing a functional nanostructure is investigated, and apply this nanostructure in a proof-of-principle study for serological diagnosis of anthrax. EA1 is genetically fused with methyl parathion hydrolase (MPH), to degrade methyl parathion and provide a label for signal amplification. EA1 not only serves as a nanocarrier, but also as a specific antigen to capture anthrax-specific antibodies. As results, purified EA1-MPH forms a single layer of crystalline nanostructure through self-assembly. Our chimeric nanocatalyst greatly improves enzymatic stability of MPH. When applied to the detection of anthrax-specific antibodies in serum samples, the detection of our EA1-MPH nanostructure is nearly 300 times more sensitive than that of the unassembled complex. Together, it is shown that it is possible to build a functional and highly sensitive nanosensor based on S-layer protein. In conclusion, our present study should serve as a model for the development of other multifunctional nanomaterials using S-layer proteins. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigating the Modification of Spontaneous Emission using Layer-by-Layer Self-Assembly

NASA Astrophysics Data System (ADS)

Ashry, Islam Ahmed Ibrahim Youssef

The process of spontaneous emission can be dramatically modified by optical micro- and nanostructures. We studied the modification of fluorescence dynamics using a polymer spacer layer fabricated through layer-by-layer (LbL) self-assembly. The advantages of this method are numerous: The self-assembled spacers can possess exceptional smooth surface morphology; The thickness of the spacer can be controlled with nanometer accuracy; And depending on fabrication conditions, the spacer layer is stimuli responsive and its thickness can be dynamically tuned. This thesis contains three interlinked components. First, we vary LbL spacer layer thickness and explore the change in fluorescence lifetime induced by the modified photonic density of states (PDOS), i.e., Purcell effects. Our experimental results agree well with theoretical predictions based on a classical dipole model, which also yields consistent values for the fluorophores' intrinsic fluorescence lifetime and quantum yield near a dielectric as well as a plasmonic interface. Based on this observation, we further demonstrate that self-assembled fluorophores can be used to probe the modified PDOS near optical micro- and nano-structures. These results naturally lead to the second component of our research. In particularly, based on the PDOS-induced changes in fluorescent lifetime, we develop a non-contact method that can measure morphological changes with nanoscale resolution. Our method relies on quantitatively linking fluorophore position with PDOS, and is validated through direct comparison with ellipsometry and atomic force microscopy (AFM) measurements. To demonstrate the potential application of this method, we investigated the swelling/deswelling of LbL films induced by pH changes. Our results indicate significant difference between a LbL film composed of a single polymer monolayer and a LbL film with 3 monolayers. Such stimuli-responsive polymers can be used to construct active and tunable plasmonic nano-devices. As a proof-of-principle demonstration, we experimentally confirm that it is possible to utilize the swelling/deswelling behavior of stimuli-responsive films to dynamically control the separation between Au nanoparticles and Texas Red (TR) dyes. This result is based on the strong correlation of TR fluorescence lifetime and nanoparticles-TR separation. Finally, we investigate the impact of different lithography processes on the fluorescence properties of self-assembled fluorophores. We consider three methods: direct fluorophore patterning through ultraviolet (UV) ablation, focused ion beam (FIB) milling of self-assembled fluorophores, and self-assembly of fluorescent materials over plasmonic nano-patterns.

Fabrication of Hierarchical Layer-by-Layer Assembled Diamond-based Core-Shell Nanocomposites as Highly Efficient Dye Absorbents for Wastewater Treatment

NASA Astrophysics Data System (ADS)

Zhao, Xinna; Ma, Kai; Jiao, Tifeng; Xing, Ruirui; Ma, Xilong; Hu, Jie; Huang, Hao; Zhang, Lexin; Yan, Xuehai

2017-03-01

The effective chemical modification and self-assembly of diamond-based hierarchical composite materials are of key importance for a broad range of diamond applications. Herein, we report the preparation of novel core-shell diamond-based nanocomposites for dye adsorption toward wastewater treatment through a layer-by-layer (LbL) assembled strategy. The synthesis of the reported composites began with the carboxyl functionalization of microdiamond by the chemical modification of diamond@graphene oxide composite through the oxidation of diamond@graphite. The carboxyl-terminated microdiamond was then alternatively immersed in the aqueous solution of amine-containing polyethylenimine and carboxyl-containing poly acrylic acid, which led to the formation of adsorption layer on diamond surface. Alternating (self-limiting) immersions in the solutions of the amine-containing and carboxyl-containing polymers were continued until the desired number of shell layers were formed around the microdiamond. The obtained core-shell nanocomposites were successfully synthesized and characterized by morphological and spectral techniques, demonstrating higher surface areas and mesoporous structures for good dye adsorption capacities than nonporous solid diamond particles. The LbL-assembled core-shell nanocomposites thus obtained demonstrated great adsorption capacity by using two model dyes as pollutants for wastewater treatment. Therefore, the present work on LbL-assembled diamond-based composites provides new alternatives for developing diamond hybrids as well as nanomaterials towards wastewater treatment applications.

Paradigm shift from self-assembly to commanded assembly of functional materials: recent examples in porphyrin/fullerene supramolecular systems

NASA Astrophysics Data System (ADS)

Li, Mao; Ishihara, Shinsuke; Ji, Qingmin; Akada, Misaho; Hill, Jonathan P.; Ariga, Katsuhiko

2012-10-01

Current nanotechnology based on top-down nanofabrication may encounter a variety of drawbacks in the near future so that development of alternative methods, including the so-called bottom-up approach, has attracted considerable attention. However, the bottom-up strategy, which often relies on spontaneous self-assembly, might be inefficient in the development of the requisite functional materials and systems. Therefore, assembly processes controlled by external stimuli might be a plausible strategy for the development of bottom-up nanotechnology. In this review, we demonstrate a paradigm shift from self-assembly to commanded assembly by describing several examples of assemblies of typical functional molecules, i.e. porphyrins and fullerenes. In the first section, we describe recent progress in the design and study of self-assembled and co-assembled supramolecular architectures of porphyrins and fullerenes. Then, we show examples of assembly induced by external stimuli. We emphasize the paradigm shift from self-assembly to commanded assembly by describing the recently developed electrochemical-coupling layer-by-layer (ECC-LbL) methodology.

Directed Self-Assembly on Photo-Crosslinked Polystyrene Sub-Layers: Nanopattern Uniformity and Orientation

PubMed Central

Koh, Haeng-Deog; Kim, Mi-Jeong

2016-01-01

A photo-crosslinked polystyrene (PS) thin film is investigated as a potential guiding sub-layer for polystyrene-block-poly (methyl methacrylate) block copolymer (BCP) cylindrical nanopattern formation via topographic directed self-assembly (DSA). When compared to a non-crosslinked PS brush sub-layer, the photo-crosslinked PS sub-layer provided longer correlation lengths of the BCP nanostructure, resulting in a highly uniform DSA nanopattern with a low number of BCP dislocation defects. Depending on the thickness of the sub-layer used, parallel or orthogonal orientations of DSA nanopattern arrays were obtained that covered the entire surface of patterned Si substrates, including both trench and mesa regions. The design of DSA sub-layers and guide patterns, such as hardening the sub-layer by photo-crosslinking, nano-structuring on mesas, the relation between trench/mesa width, and BCP equilibrium period, were explored with a view to developing defect-reduced DSA lithography technology. PMID:28773768

DC voltage fields generated by RF plasmas and their influence on film growth morphology through static attraction to metal wetting layers: Beyond ion bombardment effects

NASA Astrophysics Data System (ADS)

Butcher, K. S. A.; Terziyska, P. T.; Gergova, R.; Georgiev, V.; Georgieva, D.; Binsted, P. W.; Skerget, S.

2017-01-01

It is shown that attractive electrostatic interactions between regions of positive charge in RF plasmas and the negative charge of metal wetting layers, present during compound semiconductor film growth, can have a greater influence than substrate temperature on film morphology. Using GaN and InN film growth as examples, the DC field component of a remote RF plasma is demonstrated to electrostatically affect metal wetting layers to the point of actually determining the mode of film growth. Examples of enhanced self-seeded nanopillar growth are provided in the case where the substrate is directly exposed to the DC field generated by the plasma. In another case, we show that electrostatic shielding of the DC field from the substrate can result in the growth of Ga-face GaN layers from gallium metal wetting layers at 490 °C with root-mean-square roughness values as low as 0.6 nm. This study has been carried out using a migration enhanced deposition technique with pulsed delivery of the metal precursor allowing the identification of metal wetting layers versus metal droplets as a function of the quantity of metal source delivered per cycle. It is also shown that electrostatic interactions with the plasma can affect metal rich growth limits, causing metal droplet formation for lower metal flux than would otherwise occur. Accordingly, film growth rates can be increased when shielding the substrate from the positive charge region of the plasma. For the example shown here, growth rates were more than doubled using a shielding grid.

Layer-by-Layer Alginate and Fungal Chitosan Based Edible Coatings Applied to Fruit Bars.

PubMed

Bilbao-Sainz, Cristina; Chiou, Bor-Sen; Punotai, Kaylin; Olson, Donald; Williams, Tina; Wood, Delilah; Rodov, Victor; Poverenov, Elena; McHugh, Tara

2018-05-30

Food waste is currently being generated at an increasing rate. One proposed solution would be to convert it to biopolymers for industrial applications. We recovered chitin from mushroom waste and converted it to chitosan to produce edible coatings. We then used layer-by-layer (LbL) electrostatic deposition of the polycation chitosan and the polyanion alginate to coat fruit bars enriched with ascorbic acid. The performance of the LbL coatings was compared with those containing single layers of fungal chitosan, animal origin chitosan and alginate. Bars containing alginate-chitosan LbL coatings showed increased ascorbic acid content, antioxidant capacity, firmness and fungal growth prevention during storage. Also, the origin of the chitosan did not affect the properties of the coatings. Mushroom stalk bases could be an alternative source for isolating chitosan with similar properties to animal-based chitosan. Also, layer-by-layer assembly is a cheap, simple method that can improve the quality and safety of fruit bars. © 2018 Institute of Food Technologists®.

Fabrication of Au nanoparticles supported on CoFe2O4 nanotubes by polyaniline assisted self-assembly strategy and their magnetically recoverable catalytic properties

NASA Astrophysics Data System (ADS)

Zhang, Zhen; Jiang, Yanzhou; Chi, Maoqiang; Yang, Zezhou; Nie, Guangdi; Lu, Xiaofeng; Wang, Ce

2016-02-01

This article reports the fabrication of magnetically responsive Au nanoparticles supported on CoFe2O4 nanotubes through polyaniline (PANI) assisted self-assembly strategy which can be used as an efficient magnetically recoverable nanocatalyst. The central magnetic CoFe2O4 nanotubes possess a strong magnetic response under an externally magnetic field, enabling an easy and efficient separation from the reaction system for reuse. The thorn-like PANI layer on the surface of CoFe2O4 nanotubes provides large surface area for supporting Au nanocatalysts due to the electrostatic interactions. The as-prepared CoFe2O4/PANI/Au nanotube assemblies exhibit a high catalytic activity for the hydrogenation of 4-nitrophenol by sodium borohydride (NaBH4) at room temperature, with an apparent kinetic rate constant (Kapp) of about 7.8 × 10-3 s-1. Furthermore, the composite nanocatalyst shows a good recoverable property during the catalytic process. This work affords a reliable way in developing multifunctional nanocomposite for catalysis and other potential applications in many fields.

Triply responsive films in bioelectrocatalysis with a binary architecture: combined layer-by-layer assembly and hydrogel polymerization.

PubMed

Yao, Huiqin; Hu, Naifei

2011-05-26

In this work, triply responsive films with a specific binary architecture combining layer-by-layer assembly (LbL) and hydrogel polymerization were successfully prepared. First, concanavalin A (Con A) and dextran (Dex) were assembled into {Con A/Dex}(5) LbL layers on electrode surface by the lectin-sugar biospecific interaction between them. The poly(N,N-diethylacrylamide) (PDEA) hydrogels with entrapped horseradish peroxidase (HRP) were then synthesized by polymerization on the surface of LbL inner layers, forming {Con A/Dex}(5)-(PDEA-HRP) films. The films demonstrated reversible pH-, thermo-, and salt-responsive on-off behavior toward electroactive probe Fe(CN)(6)(3-) in its cyclic voltammetric responses. This multiple stimuli-responsive films could be further used to realize triply switchable electrochemical reduction of H(2)O(2) catalyzed by HRP immobilized in the films and mediated by Fe(CN)(6)(3-) in solution. The responsive mechanism of the films was explored and discussed. The pH-sensitive property of the system was attributed to the electrostatic interaction between the {Con A/Dex}(5) inner layers and the probe at different pH, and the thermo- and salt-responsive behaviors should be ascribed to the structure change of PDEA hydrogels for the PDEA-HRP outermost layers under different conditions. The concept of binary architecture was also used to fabricate {Con A/Dex}(5)-(PDEA-GOD) films on electrodes, where GOD = glucose oxidase, which was applied to realize the triply switchable bioelectrocatalysis of glucose by GOD in the films with ferrocenedicarboxylic acid as the mediator in solution. This film system with the unique binary architecture may establish a foundation for fabricating a novel type of multicontrollable biosensors based on bioelectrocatalysis with immobilized enzymes.

Solid-state probe based electrochemical aptasensor for cocaine: a potentially convenient, sensitive, repeatable, and integrated sensing platform for drugs.

PubMed

Du, Yan; Chen, Chaogui; Yin, Jianyuan; Li, Bingling; Zhou, Ming; Dong, Shaojun; Wang, Erkang

2010-02-15

Aptamers, which are artificial oligonucleotides selected in vitro, have been employed to design novel biosensors (i.e., aptasensors). In this work, we first constructed a label-free electrochemical aptasensor introducing a probe immobilization technique by the use of a layer-by-layer (LBL) self-assembled multilayer with ferrocene-appended poly(ethyleneimine) (Fc-PEI) on an indium tin oxide (ITO) array electrode for detection of cocaine. The Fc-PEI and gold nanoparticles (AuNPs) were LBL assembled on the electrode surface via electrostatic interaction. Then, cocaine aptamer fragments, SH-C2, were covalently labeled onto the outermost AuNP layer. When the target cocaine and cocaine aptamer C1 were present simultaneously, the SH-C2 layer hybridized partly with C1 to bind the cocaine, which led to a decreased differential pulse voltammetry (DPV) signal of Fc-PEI. This DPV signal change could be used to sensitively detect cocaine with the lowest detectable concentration down to 0.1 microM and the detection range up to 38.8 microM, which falls in the the expected range for medical use of detecting drug abuse involving cocaine. Meanwhile, the sensor was specific to cocaine in complex biologic fluids such as human plasma, human saliva, etc. The sensing strategy had general applicability, and the detection of thrombin could also be realized, displayed a low detection limit, and exhibited worthiness to other analytes. The aptasensor based on the array electrode held promising potential for integration of the sensing ability in multianalysis for simultaneous detection.

Molecular lego for the assembly of biosensing layers.

PubMed

Mano, N; Kuhn, A

2005-03-31

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

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

PubMed Central

Buck, Maren E.

2010-01-01

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

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...

Improved light output of plastic scintillator by a modified self-assembled photonic crystal

NASA Astrophysics Data System (ADS)

Chen, Liang; Zhu, Zhichao; Liu, Bo; Cheng, Chuanwei; Liu, Jinliang; Ruan, Jinlu; Zhang, Zhongbin; Ouyang, Xiaoping; Gu, Mu; Chen, Hong

2017-11-01

In this investigation, we have demonstrated that a modified self-assembled photonic crystal with conformal high refractive index material TiO2 can achieve a great enhancement of light extraction efficiency. A 2.26 fold wavelength- and angle-integrated enhancement ratio can be achieved. The conformal layer increases the number of leaky modes and thus improve the extraction efficiency. The enhancement is attributed to the leaky modes based on the individual microspheres with conformal layer. Their low quality factors with a broadband characteristic are advantageous to the broadband enhancement for the emission spectra of plastic scintillator. Furthermore, the dense conformal layers have excellent combination with the self-assembled microspheres and the whole preparation process cannot destroy the plastic scintillator, which is beneficial to the practical application.

Laboratory observation of multiple double layer resembling space plasma double layer

NASA Astrophysics Data System (ADS)

Alex, Prince; Arumugam, Saravanan; Sinha, Suraj

2017-10-01

Perceptible double layer consisting of more than one layers were produced in laboratory using a double discharge plasma setup. The confinement of oppositely charged particles in each layer with sharply defined luminous boarder is attributed to the self-organization scenario. This structure is generated in front of a positively biased electrode when the electron drift velocity (νd) exceeds 1.3 times the electron thermal velocity (νte) . Stable multiple double layer structures were observed only between 1.3 νte <=νd <= 3 νte. At νd = 1.3 νte, oscillations were excited in the form of large amplitude burst followed by a high frequency stable oscillation. Beyond νd = 3 νte, multiple double layer begins to collapse which is characterized by an emergence in turbulence. Long range dependence in the corresponding electrostatic potential fluctuations indicates the role of self-organized criticality in the emergence of turbulence. The algebraic decaying tale of the autocorrelation function and power law behavior in the power spectrum are consistent with the observation.

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

Temperature and anion responsive self-assembly of ionic liquid block copolymers coating gold nanoparticles

NASA Astrophysics Data System (ADS)

Li, Junbo; Zhao, Jianlong; Wu, Wenlan; Liang, Ju; Guo, Jinwu; Zhou, Huiyun; Liang, Lijuan

2016-06-01

In this paper, double hydrophilic ionic liquid block copolymers (ILBCs), poly poly[1-methyl-3-(2-methacryloyloxy propylimidazolium bromine)]- block-(N-isopropylacrylamide) (PMMPImB- b-PNIPAAm) was first synthesized by reversible additionfragmentation chain transfer (RAFT) and then attached on the surface of gold nanoparticles (Au NPs) via a strong gold-sulfur bonding for preparing hybrid nanoparticles (PMMPImB- b-PNIPAAm-@-Au NPs). The hybrid NPs had a three layers micelle-like structure, including a gold core, thermo-responsive inner shell and anion responsive outer corona. The self-assembling behavior of thermal- and anion-response from shell and corona were respectively investigated by change of temperature and addition of (CF3SO2)2N-. The results showed the hybrid NPs retained a stable dispersion beyond the lower critical solution temperature (LCST) because of the space or electrostatic protecting by outer PMMPImB. However, with increasing concentration of (CF3SO2)2N-, the micellization of self-assembling PMMPImB- b-PNIPAAm-@-Au NPs was induced to form micellar structure containing the core with hydrophobic PMMPImB-(CF3SO2)2N- surrounded by composite shell of Au NPs-PNIPAAm via the anionresponsive properties of ILBCs. These results indicated that the block copolymers protected plasmonic nanoparticles remain self-assembling properties of block copolymers when phase transition from outer corona polymer.

Corrosion resistance and antibacterial properties of polysiloxane modified layer-by-layer assembled self-healing coating on magnesium alloy.

PubMed

Zhao, Yanbin; Shi, Liqian; Ji, Xiaojing; Li, Jichen; Han, Zhuangzhuang; Li, Shuoqi; Zeng, Rongchang; Zhang, Fen; Wang, Zhenlin

2018-04-18

Magnesium (Mg) alloys have shown great potential in biomedical materials due to their biocompatibility and biodegradability. However, rapid corrosion rate, which is an inevitable obstacle, hinders their clinical applications. Besides, it is necessary to endow Mg alloys with antibacterial properties, which are crucial for temporary implants. In this study, silver nanoparticles (AgNPs) and polymethyltrimethoxysilane (PMTMS) were introduced into AZ31 Mg alloys via layer-by-layer (LbL) assembly and siloxane self-condensation reaction. The characteristics of the composite films were investigated by SEM, UV-vis, FT-IR, and XRD measurements. Corrosion resistance of the samples was measured by electrochemical and hydrogen evolution tests. Antibacterial activities of the films against Staphylococcus aureus were evaluated by plate-counting method. The results demonstrated that the composite film with smooth and uniform morphologies could enhance the corrosion resistance of Mg alloys owing to the physical barrier and the self-healing functionality of polysiloxane. Moreover, the composite coating possessed antibacterial properties and could prolong the release of assembled silver ions. Copyright © 2018 Elsevier Inc. All rights reserved.

One-step coelectrodeposition-assisted layer-by-layer assembly of gold nanoparticles and reduced graphene oxide and its self-healing three-dimensional nanohybrid for an ultrasensitive DNA sensor.

PubMed

Kumarasamy, Jayakumar; Camarada, María Belén; Venkatraman, Dharuman; Ju, Huangxian; Dey, Ramendra Sundar; Wen, Yangping

2018-01-18

A layer-by-layer (LBL) assembly was employed for preparing multilayer thin films with a controlled architecture and composition. In this study, we report the one-step coelectrodeposition-assisted LBL assembly of both gold nanoparticles (AuNPs) and reduced graphene oxide (rGO) on the surface of a glassy carbon electrode (GCE) for the ultrasensitive electrochemical impedance sensing of DNA hybridization. A self-healable nanohybrid thin film with a three-dimensional (3D) alternate-layered nanoarchitecture was obtained by the one-step simultaneous electro-reduction of both graphene oxide and gold chloride in a high acidic medium of H 2 SO 4 using cyclic voltammetry and was confirmed by different characterization techniques. The DNA bioelectrode was prepared by immobilizing the capture DNA onto the surface of the as-obtained self-healable AuNP/rGO/AuNP/GCE with a 3D LBL nanoarchitecture via gold-thiol interactions, which then served as an impedance sensing platform for the label-free ultrasensitive electrochemical detection of DNA hybridization over a wide range from 1.0 × 10 -9 to 1.0 × 10 -13 g ml -1 , a low limit of detection of 3.9 × 10 -14 g ml -1 (S/N = 3), ultrahigh sensitivity, and excellent selectivity. This study presents a promising electrochemical sensing platform for the label-free ultrasensitive detection of DNA hybridization with potential application in cancer diagnostics and the preparation of a self-healable nanohybrid thin film with a 3D alternate-layered nanoarchitecture via a one-step coelectrodeposition-assisted LBL assembly.

Insertion of Ag atoms into layered MoO{sub 3} via a template route

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

Shao, Ke, E-mail: shaoke@szu.edu.cn; Wang, Hao

2012-11-15

Graphical abstract: PVP–Ag{sup +} complex self-assembled with inorganic (Mo{sub x}O{sub y}){sub ∞}{sup n−} chains into a layered hybrid, in which the PVP–Ag complex was intercalated between the (Mo{sub x}O{sub y}){sub ∞}{sup n−} layers. Calcinations of this hybrid at 500 °C lead to formation of Ag/MoO{sub 3} nanohybrid. By this method we have successfully inserted Ag atoms into the semiconductor MoO{sub 3} lattice. Display Omitted Highlights: ► We fabricated a PVP–Ag/polyoxomolybdate layered hybrid via in situ self-assembly. ► The PVP–Ag complex has been inserted between the molybdenum oxide layers. ► This layered hybrid transformed into Ag/MoO{sub 3} nanocomposite after calcinations. ►more » HR-TEM images show that Ag atoms of about 1 nm have been inserted in the MoO{sub 3} layers. -- Abstract: We report insertion of Ag atoms into layered MoO{sub 3} via an in situ template route. PVP–Ag{sup +} complex self-assembled with inorganic (Mo{sub x}O{sub y}){sub ∞}{sup n−} chains into a layered hybrid, in which the PVP–Ag complex was intercalated between the (Mo{sub x}O{sub y}){sub ∞}{sup n−} layers. Calcinations of this hybrid at 500 °C lead to formation of Ag/MoO{sub 3} hybrid, in which Ag nanoparticles of about 1 nm have been inserted between the MoO{sub 3} layers. By this method pillared MoO{sub 3} has been obtained very easily. We believe that this research opens new routes to fabricate novel intercalation compounds and metal/semiconductor nanohybrids via an efficient and green route.« less

Synthetic ion channels via self-assembly: a route for embedding porous polyoxometalate nanocapsules in lipid bilayer membranes.

PubMed

Carr, Rogan; Weinstock, Ira A; Sivaprasadarao, Asipu; Müller, Achim; Aksimentiev, Aleksei

2008-11-01

Porous polyoxometalate nanocapsules of Keplerate type are known to exhibit the functionality of biological ion channels; however, their use as an artificial ion channel is tempered by the high negative charge of the capsules, which renders their spontaneous incorporation into a lipid bilayer membrane unlikely. In this Letter we report coarse-grained molecular dynamics simulations that demonstrate a route for embedding negatively charged nanocapsules into lipid bilayer membranes via self-assembly. A homogeneous mixture of water, cationic detergent, and phospholipid was observed to spontaneously self-assemble around the nanocapsule into a layered, liposome-like structure, where the nanocapsule was enveloped by a layer of cationic detergent followed by a layer of phospholipid. Fusion of such a layered liposome with a lipid bilayer membrane was observed to embed the nanocapsule into the lipid bilayer. The resulting assembly was found to remain stable even after the surface of the capsule was exposed to electrolyte. In the latter conformation, water was observed to flow into and out of the capsule as Na(+) cations entered, suggesting that a polyoxometalate nanocapsule can form a functional synthetic ion channel in a lipid bilayer membrane.

Synthetic Ion Channels via Self-Assembly: a Route for Embedding Porous Polyoxometalate Nanocapsules in Lipid Bilayer Membranes

PubMed Central

Carr, Rogan; Weinstock, Ira A.; Sivaprasadarao, Asipu; Müller, Achim; Aksimentiev, Aleksei

2010-01-01

Porous polyoxometalate nanocapsules of Keplerate type are known to exhibit the functionality of biological ion channels, however, their use as artificial ion channel is tempered by the high negative charge of the capsules, which renders their spontaneous incorporation into a lipid bilayer membrane unlikely. In this letter we report coarse-grained molecular dynamics simulations that demonstrate a route for embedding negatively charged nanocapsules into lipid bilayer membranes via self-assembly. A homogeneous mixture of water, cationic detergent, and phospholipid was observed to spontaneously self-assemble around the nanocapsule into a layered, liposome-like structure, where the nanocapsule was enveloped by a layer of cationic detergent followed by a layer of phospholipid. Fusion of such a layered liposome with a lipid bilayer membrane was observed to embed the nanocapsule into the lipid bilayer. The resulting assembly was found to remain stable even after the surface of the capsule was exposed to electrolyte. In the latter conformation, water was observed to flow into and out of the capsule as Na+ cations entered, suggesting that a polyoxometalate nanocapsule can form a functional synthetic ion channel in a lipid bilayer membrane. PMID:18844424

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

PubMed

Han, Uiyoung; Seo, Younghye; Hong, Jinkee

2016-04-07

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

Self-assembly of dodecaphenyl POSS thin films

NASA Astrophysics Data System (ADS)

Handke, Bartosz; Klita, Łukasz; Niemiec, Wiktor

2017-12-01

The self-assembly abilities of Dodecaphenyl Polyhedral Oligomeric Silsesquioxane thin films on Si(1 0 0) surfaces were studied. Due to their thermal properties - relatively low sublimation temperature and preservation of molecular structure - cage type silsesquioxanes are ideal material for the preparation of a thin films by Physical Vapor Deposition. The Ultra-High Vacuum environment and the deposition precision of the PVD method enable the study of early stages of thin film growth and its molecular organization. X-ray Reflectivity and Atomic Force Microscopy measurements allow to pursuit size-effects in the structure of thin films with thickness ranges from less than a single molecular layer up to several tens of layers. Thermal treatment of the thin films triggered phase change: from a poorly ordered polycrystalline film into a well-ordered multilayer structure. Self-assembly of the layers is the effect of the π-stacking of phenyl rings, which force molecules to arrange in a superlattice, forming stacks of alternating organic-inorganic layers.

Flame retardant polymer-clay nanocoatings on cotton textile substrates using a newly developed, continuous layer-by-layer deposition 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 most synthetic fabrics. In this study, a continuous layer-by-layer self-assembly technique was used to deposit polymer-clay nan...

Flexible MXene/Graphene Films for Ultrafast Supercapacitors with Outstanding Volumetric Capacitance

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

Yan, Jun; Ren, Chang E.; Maleski, Kathleen

A strategy to prepare flexible and conductive MXene/graphene (reduced graphene oxide, rGO) supercapacitor electrodes by using electrostatic self-assembly between positively charged rGO modified with poly(diallyldimethylammonium chloride) and negatively charged titanium carbide MXene nanosheets is presented. After electrostatic assembly, rGO nanosheets are inserted in-between MXene layers. As a result, the self-restacking of MXene nanosheets is effectively prevented, leading to a considerably increased interlayer spacing. Accelerated diffusion of electrolyte ions enables more electroactive sites to become accessible. The freestanding MXene/rGO-5 wt% electrode displays a volumetric capacitance of 1040 F cm –3 at a scan rate of 2 mV s –1, an impressivemore » rate capability with 61% capacitance retention at 1 V s –1 and long cycle life. Moreover, the fabricated binder-free symmetric supercapacitor shows an ultrahigh volumetric energy density of 32.6 Wh L –1, which is among the highest values reported for carbon and MXene based materials in aqueous electrolytes. Furthermore, this work provides fundamental insight into the effect of interlayer spacing on the electrochemical performance of 2D hybrid materials and sheds light on the design of next-generation flexible, portable and highly integrated supercapacitors with high volumetric and rate performances.« less

High stroke pixel for a deformable mirror

DOEpatents

Miles, Robin R.; Papavasiliou, Alexandros P.

2005-09-20

A mirror pixel that can be fabricated using standard MEMS methods for a deformable mirror. The pixel is electrostatically actuated and is capable of the high deflections needed for spaced-based mirror applications. In one embodiment, the mirror comprises three layers, a top or mirror layer, a middle layer which consists of flexures, and a comb drive layer, with the flexures of the middle layer attached to the mirror layer and to the comb drive layer. The comb drives are attached to a frame via spring flexures. A number of these mirror pixels can be used to construct a large mirror assembly. The actuator for the mirror pixel may be configured as a crenellated beam with one end fixedly secured, or configured as a scissor jack. The mirror pixels may be used in various applications requiring high stroke adaptive optics.

Multiple and configurable optical logic systems based on layered double hydroxides and chromophore assemblies.

PubMed

Shi, Wenying; Fu, Yi; Li, Zhixiong; Wei, Min

2015-01-14

Multiple and configurable fluorescence logic gates were fabricated via self-assembly of layered double hydroxides and various chromophores. These logic gates were operated by observation of different emissions with the same excitation wavelength, which achieve YES, NOT, AND, INH and INHIBIT logic operations, respectively.

Quantitative fabrication of functional polymer surfaces

NASA Astrophysics Data System (ADS)

Rengifo, Hernan R.

Polymeric surfaces and films have very broad applications in industry. They have been employed as anticorrosive, abrasive and decorative coatings for many years. More recently, the applications of functional polymer films in microelectronics, optics, nanocomposites, DNA microarrays, and enzyme immobilizations has drawn a lot of attention. There are a number of challenges associated with the implementation of functional polymeric surfaces, and these challenges are especially important in the field of surface modification. In this thesis, three different challenges in the field of polymeric functional surfaces are addressed: first of all, a set of rules for the molecular design are presented in chapters 3 and 4 according to the surface needs. Second, some latent energy source must be incorporated into the material design to quantitative modify a surface. Third, the morphology of the surface, the method use to fabricate the design surface and their new applications are presented in chapters 4 and 5. The new polymeric surface functionalization method described in Chapter 3 is based upon an end-functionalized diblock copolymer design to self-assemble at the surface of both hard and soft surfaces. It is demonstrated that alkyne end-functional diblock copolymers can be used to provide precise control over areal densities of reactive functionality. The areal density of alkyne functional groups is precisely controlled by adjusting the thickness of the block copolymer monolayer, which is accomplished by changing either the spin coating conditions (i.e., rotational speed and solution concentration) or the copolymer molecular weight. The modified surfaces are characterized by atomic force microscopy (AFM), contact angle, ellipsometry, fluorescent imaging and angle-dependent X-ray photoelectron spectroscopy (ADXPS) measurements. In Chapter 4, a simple means is demonstrated to covalently bond DNA to polymer-modified substrates; the method provides quantitative control of the DNA areal density. The approach is based upon synthesis of an alkyne-end-functional diblock copolymer alpha-alkyne-o-Br-poly(tBA- b-MMA). The block copolymer self-assembles to form a bilayer on the substrate and directs alkyne groups to the surface. Azido-functionalized DNA is immobilized on alkyne functionalized substrates by a "click" reaction. The density of immobilized DNA can be quantitatively controlled by varying the parameters used for spin-coating the polymer film or by adjusting the hydrophilicity of the polymer surface underlying the reactive alkyne functional groups. In Chapter 5, Layer by layer (LbL) assembly techniques construct multilayer thin films by sequential deposition of monomolecular layers of organic molecules. One of the drawbacks associated with their use is that monomolecular layers are usually held together by relatively weak forces such as Van der Waals, electrostatic and hydrogen bonding interactions, and can therefore be lacking in mechanical integrity. In this chapter, it is demonstrated that heterobifunctional polymers, functionalized with one azide chain terminus and a protected alkyne group as the other chain terminus, constitute a powerful and versatile means for the covalent layer-by-layer (CLbL) assembly of thin polymer films. Each monomolecular polymer layer is covalently bound to both the preceding and following layers to produce a robust multilayer structure. Because the coupling chemistry used, "click" chemistry, is highly chemoselective, the layering process is virtually independent of the chemical nature of the polymer so that the constitution of each layer can be selected at will. Unlike other layer-by-layer deposition techniques, the layer thickness in CLbL is not equivalent to the diameter of the polymer chain, but is related to the polymer chain length and can be controlled by adjustment of either the polymer molecular weight or the areal density of surface alkyne groups.

Anti-flammable properties of cotton fabrics using eco friendly inorganic materials by layering self-assisted processing

USDA-ARS?s Scientific Manuscript database

A flame retardant surface has been prepared by the layer-by layer assemblies of branched polyethylenimine (BPEI), kaolin, urea, diammonium phosphate (dibasic) on cotton fabrics. Four different kinds of cotton fabrics (print cloth, mercerized print cloth, mercerized twill, and fleece) were prepared ...

Directed Self-Assembly of Diblock Copolymer Thin Films on Prepatterned Metal Nanoarrays.

PubMed

Chang, Tongxin; Huang, Haiying; He, Tianbai

2016-01-01

The sequential layer by layer self-assembly of block copolymer (BCP) nanopatterns is an effective approach to construct 3D nanostructures. Here large-scale highly ordered metal nano-arrays prepared from solvent annealed thin films of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer are used to direct the assembly of the same BCP. The influence of initial loading concentration of metal precursor, the type of metal nanoparticle (gold, platinum, and silver), and the nanoparticle-substrate interaction on the directed assembly behavior of the upper BCP layer have been focused. It is found that the upper BCP film can be completely directed by the gold nanoarray with P2VP domain exclusively located between two adjacent gold nanowires or nanodots, which behaves the same way as on the platinum nanoarray. While the silver nanoarray can be destroyed during the upper BCP self-assembly with the silver nanoparticles assembled into the P2VP domain. Based on the discussions of the surface energy of nanoparticles and the interplay between nanoparticle-substrate interaction and nanoparticle-polymer interaction, it is concluded that the effect of immobilization of nanoparticles on the substrate, together with entropy effect to minimize the energetically unfavorable chain stretching contributes to the most effective alignment between each layer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

pH-controlled drug loading and release from biodegradable microcapsules.

PubMed

Zhao, Qinghe; Li, Bingyun

2008-12-01

Microcapsules made of biopolymers are of both scientific and technological interest and have many potential applications in medicine, including their use as controlled drug delivery devices. The present study makes use of the electrostatic interaction between polycations and polyanions to form a multilayered microcapsule shell and also to control the loading and release of charged drug molecules inside the microcapsule. Micron-sized calcium carbonate (CaCO3) particles were synthesized and integrated with chondroitin sulfate (CS) through a reaction between sodium carbonate and calcium nitrate tetrahydrate solutions suspended with CS macromolecules. Oppositely charged biopolymers were alternately deposited onto the synthesized particles using electrostatic layer-by-layer self-assembly, and glutaraldehyde was introduced to cross-link the multilayered shell structure. Microcapsules integrated with CS inside the multilayered shells were obtained after decomposition of the CaCO3 templates. The integration of a matrix (i.e., CS) permitted the subsequent selective control of drug loading and release. The CS-integrated microcapsules were loaded with a model drug, bovine serum albumin labeled with fluorescein isothiocyanate (FITC-BSA), and it was shown that pH was an effective means of controlling the loading and release of FITC-BSA. Such CS-integrated microcapsules may be used for controlled localized drug delivery as biodegradable devices, which have advantages in reducing systemic side effects and increasing drug efficacy.

Temperature Oscillation Modulated Self-Assembly of Periodic Concentric Layered Magnesium Carbonate Microparticles

PubMed Central

Li, Shihong; Wang, Zheng Jim; Chang, Ting-Tung

2014-01-01

Intriguing patterns of periodic, concentric, layered, mineral microstructure are present in nature and organisms, yet they have elusive geneses. We hypothesize temperature oscillation can be an independent factor that causes the self-assembly of such patterns in mineral phases synthesized in solution. Static experiments verify that rhythmic concentric multi-layered magnesium carbonate microhemispheres can be synthesized from bicarbonate solution by temperature oscillation, without use of a chemical template, additive or gel-diffusion system. Appropriate reactant concentration and initial pH value can restrain the competitive growth of other mineral generations. Polarized light microscopy images indicate the microhemispheres are crystalline and the crystallinity increases with incubation time. The thickness of a single mineral layer of microhemisphere in microscale is precisely controlled by the waveform parameters of the temperature oscillation, while the layer number, which can reach tens to about one hundred, is constrained by the temperature oscillation period number. FT-IR spectra show that these microhemispheres synthesized under different conditions can be identified as the basic form of magnesium carbonate, hydromagnesite (Mg5(CO3)4(OH)2⋅4H2O). SEM images exhibit the characteristic microscopic texture of the alternating dark and light rings of these microhemispheres. TEM images and ED patterns suggest the nanoflakes of microhemispheres are present in polycrystalline form with some degree of oriented assembly. The temperature oscillation modulated self-assembly may offer a new mechanism to understand the formation of layered microstructure of minerals in solution, and provide a non-invasive and programmable means to synthesize hierarchically ordered materials. PMID:24520410

Fluorescence Correlation Spectroscopy to Study Diffusion of Polymer Chains within Layered Hydrogen-Bonded Polymer Films

NASA Astrophysics Data System (ADS)

Pristinski, Denis; Kharlampieva, Evguenia; Sukhishvili, Svetlana

2002-03-01

Fluorescence Correlation Spectroscopy (FCS) has been used to probe molecular motions within polymer multilayers formed by hydrogen-bonding sequential self-assembly. Polyethylene glycol (PEG) molecules were end-labeled with the fluorescent tags, and self-assembled with polymethacrylic acid (PMAA) using layer-by-layer deposition. We have found that molecules included in the top adsorbed layer have significant mobility at the millisecond time scale, probably due to translational diffusion. However, their dynamics deviate from classical Brownian motion with a single diffusion time. Possible reasons for the deviation are discussed. We found that motions were significantly slowed with increasing depth within the PEG/PMAA multilayer. This phenomena occured in a narrow pH range around 4.0 in which intermolecular interactions were relatively weak.

Anti-fouling and high water permeable forward osmosis membrane fabricated via layer by layer assembly of chitosan/graphene oxide

NASA Astrophysics Data System (ADS)

Salehi, Hasan; Rastgar, Masoud; Shakeri, Alireza

2017-08-01

To date, forward osmosis (FO) has received considerable attention due to its potential application in seawater desalination. FO does not require external hydraulic pressure and consequently is believed to have a low fouling propensity. Despite the numerous privileges of FO process, a major challenge ahead for its development is the lack of high performance membranes. In this study, we fabricated a novel highly-efficient FO membrane using layer-by-layer (LbL) assembly of positive chitosan (CS) and negative graphene oxide (GO) nanosheets via electrostatic interaction on a porous support layer. The support layer was prepared by blending hydrophilic sulfonated polyethersulfone (SPES) into polyethersulfone (PES) matrix using wet phase inversion process. Various characterization techniques were used to confirm successful fabrication of LbL membrane. The number of layers formed on the SPES-PES support layer was easily adjusted by repeating the CS and GO deposition cycles. Thin film composite (TFC) membrane was also prepared by the same SPES-PES support layer and polyamide (PA) active layer to compare membranes performances. The water permeability and salt rejection of the fabricated membranes were obtained by two kinds of draw solutions (including Na2SO4 and sucrose) under two different membrane orientations. The results showed that membrane coated by a CS/GO bilayers had water flux of 2-4 orders of magnitude higher than the TFC one. By increasing the number of CS/GO bilayers, the selectivity of the LbL membrane was improved. The novel fabricated LbL membrane showed better fouling resistance than the TFC one in the feed solution containing 200 ppm of sodium alginate as a foulant model.

S-layer fusion proteins — construction principles and applications

PubMed Central

Ilk, Nicola; Egelseer, Eva M; Sleytr, Uwe B

2011-01-01

Crystalline bacterial cell surface layers (S-layers) are the outermost cell envelope component of many bacteria and archaea. S-layers are monomolecular arrays composed of a single protein or glycoprotein species and represent the simplest biological membrane developed during evolution. The wealth of information available on the structure, chemistry, genetics and assembly of S-layers revealed a broad spectrum of applications in nanobiotechnology and biomimetics. By genetic engineering techniques, specific functional domains can be incorporated in S-layer proteins while maintaining the self-assembly capability. These techniques have led to new types of affinity structures, microcarriers, enzyme membranes, diagnostic devices, biosensors, vaccines, as well as targeting, delivery and encapsulation systems. PMID:21696943

Hierarchical self-assembly of hexagonal single-crystal nanosheets into 3D layered superlattices with high conductivity.

PubMed

Tao, Yulun; Shen, Yuhua; Yang, Liangbao; Han, Bin; Huang, Fangzhi; Li, Shikuo; Chu, Zhuwang; Xie, Anjian

2012-06-21

While the number of man-made nano superstructures realized by self-assembly is growing in recent years, assemblies of conductive polymer nanocrystals, especially for superlattices, are still a significant challenge, not only because of the simplicity of the shape of the nanocrystal building blocks and their interactions, but also because of the poor control over these parameters in the fabrication of more elaborate nanocrystals. Here, we firstly report a facile and general route to a new generation of 3D layered superlattices of polyaniline doped with CSA (PANI-CSA) and show how PANI crystallize and self-assemble, in a suitable single solution environment. In cyclohexane, 1D amorphous nanofibers transformed to 1D nanorods as building blocks, and then to 2D single-crystal nanosheets with a hexagonal phase, and lastly to 3D ordered layered superlattices with the narrowest polydispersity value (M(w)/M(n) = 1.47). Remarkably, all the instructions for the hierarchical self-assembly are encoded in the layered shape in other non-polar solvents (hexane, octane) and their conductivity in the π-π stacking direction is improved to about 50 S cm(-1), which is even higher than that of the highest previously reported value (16 S cm(-1)). The method used in this study is greatly expected to be readily scalable to produce superlattices of conductive polymers with high quality and low cost.

Precise, Self-Limited Epitaxy of Ultrathin Organic Semiconductors and Heterojunctions Tailored by van der Waals Interactions.

PubMed

Wu, Bing; Zhao, Yinghe; Nan, Haiyan; Yang, Ziyi; Zhang, Yuhan; Zhao, Huijuan; He, Daowei; Jiang, Zonglin; Liu, Xiaolong; Li, Yun; Shi, Yi; Ni, Zhenhua; Wang, Jinlan; Xu, Jian-Bin; Wang, Xinran

2016-06-08

Precise assembly of semiconductor heterojunctions is the key to realize many optoelectronic devices. By exploiting the strong and tunable van der Waals (vdW) forces between graphene and organic small molecules, we demonstrate layer-by-layer epitaxy of ultrathin organic semiconductors and heterostructures with unprecedented precision with well-defined number of layers and self-limited characteristics. We further demonstrate organic p-n heterojunctions with molecularly flat interface, which exhibit excellent rectifying behavior and photovoltaic responses. The self-limited organic molecular beam epitaxy (SLOMBE) is generically applicable for many layered small-molecule semiconductors and may lead to advanced organic optoelectronic devices beyond bulk heterojunctions.

A Stimuli-Responsive Biosensor of Glucose on Layer-by-Layer Films Assembled through Specific Lectin-Glycoenzyme Recognition.

PubMed

Yao, Huiqin; Gan, Qianqian; Peng, Juan; Huang, Shan; Zhu, Meilin; Shi, Keren

2016-04-20

The research on intelligent bioelectrocatalysis based on stimuli-responsive materials or interfaces is of great significance for biosensors and other bioelectronic devices. In the present work, lectin protein concanavalin A (Con A) and glycoenzyme glucose oxidase (GOD) were assembled into {Con A/GOD}n layer-by-layer (LbL) films by taking advantage of the biospecific lectin-glycoenzyme affinity between them. These film electrodes possess stimuli-responsive properties toward electroactive probes such as ferrocenedicarboxylic acid (Fc(COOH)₂) by modulating the surrounding pH. The CV peak currents of Fc(COOH)₂ were quite large at pH 4.0 but significantly suppressed at pH 8.0, demonstrating reversible stimuli-responsive on-off behavior. The mechanism of stimuli-responsive property of the films was explored by comparative experiments and attributed to the different electrostatic interaction between the films and the probes at different pH. This stimuli-responsive films could be used to realize active/inactive electrocatalytic oxidation of glucose by GOD in the films and mediated by Fc(COOH)₂ in solution, which may establish a foundation for fabricating novel stimuli-responsive electrochemical biosensors based on bioelectrocatalysis with immobilized enzymes.

A Stimuli-Responsive Biosensor of Glucose on Layer-by-Layer Films Assembled through Specific Lectin-Glycoenzyme Recognition

PubMed Central

Yao, Huiqin; Gan, Qianqian; Peng, Juan; Huang, Shan; Zhu, Meilin; Shi, Keren

2016-01-01

The research on intelligent bioelectrocatalysis based on stimuli-responsive materials or interfaces is of great significance for biosensors and other bioelectronic devices. In the present work, lectin protein concanavalin A (Con A) and glycoenzyme glucose oxidase (GOD) were assembled into {Con A/GOD}n layer-by-layer (LbL) films by taking advantage of the biospecific lectin-glycoenzyme affinity between them. These film electrodes possess stimuli-responsive properties toward electroactive probes such as ferrocenedicarboxylic acid (Fc(COOH)2) by modulating the surrounding pH. The CV peak currents of Fc(COOH)2 were quite large at pH 4.0 but significantly suppressed at pH 8.0, demonstrating reversible stimuli-responsive on-off behavior. The mechanism of stimuli-responsive property of the films was explored by comparative experiments and attributed to the different electrostatic interaction between the films and the probes at different pH. This stimuli-responsive films could be used to realize active/inactive electrocatalytic oxidation of glucose by GOD in the films and mediated by Fc(COOH)2 in solution, which may establish a foundation for fabricating novel stimuli-responsive electrochemical biosensors based on bioelectrocatalysis with immobilized enzymes. PMID:27104542

Optimized plasma etch window of block copolymers and neutral brush layers for enhanced direct self-assembly pattern transfer into a hardmask layer

NASA Astrophysics Data System (ADS)

Brakensiek, Nickolas; Xu, Kui; Sweat, Daniel; Hockey, Mary Ann

2018-03-01

Directed self-assembly (DSA) of block copolymers (BCPs) is one of the most promising patterning technologies for future lithography nodes. However, one of the biggest challenges to DSA is the pattern transfer by plasma etching from BCP to hardmask (HM) because the etch selectivity between BCP and neutral brush layer underneath is usually not high enough to enable robust pattern transfer. This paper will explore the plasma etch conditions of both BCPs and neutral brush layers that may improve selectivity and allow a more robust pattern transfer of DSA patterns into the hardmask layer. The plasma etching parameters that are under investigation include the selection of oxidative or reductive etch chemistries, as well as plasma gas pressure, power, and gas mixture fractions. Investigation into the relationship between BCP/neutral brush layer materials with varying chemical compositions and the plasma etching conditions will be highlighted. The culmination of this work will demonstrate important etch parameters that allow BCPs and neutral brush layers to be etched into the underlying hardmask layer with a large process window.

Tuning plasmons layer-by-layer for quantitative colloidal sensing with surface-enhanced Raman spectroscopy.

PubMed

Anderson, William J; Nowinska, Kamila; Hutter, Tanya; Mahajan, Sumeet; Fischlechner, Martin

2018-04-19

Surface-enhanced Raman spectroscopy (SERS) is well known for its high sensitivity that emerges due to the plasmonic enhancement of electric fields typically on gold and silver nanostructures. However, difficulties associated with the preparation of nanostructured substrates with uniform and reproducible features limit reliability and quantitation using SERS measurements. In this work we use layer-by-layer (LbL) self-assembly to incorporate multiple functional building blocks of collaborative assemblies of nanoparticles on colloidal spheres to fabricate SERS sensors. Gold nanoparticles (AuNPs) are packaged in discrete layers, effectively 'freezing nano-gaps', on spherical colloidal cores to achieve multifunctionality and reproducible sensing. Coupling between layers tunes the plasmon resonance for optimum SERS signal generation to achieve a 10 nM limit of detection. Significantly, using the layer-by-layer construction, SERS-active AuNP layers are spaced out and thus optically isolated. This uniquely allows the creation of an internal standard within each colloidal sensor to enable highly reproducible self-calibrated sensing. By using 4-mercaptobenzoic acid (4-MBA) as the internal standard adenine concentrations are quantified to an accuracy of 92.6-99.5%. Our versatile approach paves the way for rationally designed yet quantitative colloidal SERS sensors and their use in a variety of sensing applications.

Hierarchical self-assembly of hexagonal single-crystal nanosheets into 3D layered superlattices with high conductivity

NASA Astrophysics Data System (ADS)

Tao, Yulun; Shen, Yuhua; Yang, Liangbao; Han, Bin; Huang, Fangzhi; Li, Shikuo; Chu, Zhuwang; Xie, Anjian

2012-05-01

While the number of man-made nano superstructures realized by self-assembly is growing in recent years, assemblies of conductive polymer nanocrystals, especially for superlattices, are still a significant challenge, not only because of the simplicity of the shape of the nanocrystal building blocks and their interactions, but also because of the poor control over these parameters in the fabrication of more elaborate nanocrystals. Here, we firstly report a facile and general route to a new generation of 3D layered superlattices of polyaniline doped with CSA (PANI-CSA) and show how PANI crystallize and self-assemble, in a suitable single solution environment. In cyclohexane, 1D amorphous nanofibers transformed to 1D nanorods as building blocks, and then to 2D single-crystal nanosheets with a hexagonal phase, and lastly to 3D ordered layered superlattices with the narrowest polydispersity value (Mw/Mn = 1.47). Remarkably, all the instructions for the hierarchical self-assembly are encoded in the layered shape in other non-polar solvents (hexane, octane) and their conductivity in the π-π stacking direction is improved to about 50 S cm-1, which is even higher than that of the highest previously reported value (16 S cm-1). The method used in this study is greatly expected to be readily scalable to produce superlattices of conductive polymers with high quality and low cost.While the number of man-made nano superstructures realized by self-assembly is growing in recent years, assemblies of conductive polymer nanocrystals, especially for superlattices, are still a significant challenge, not only because of the simplicity of the shape of the nanocrystal building blocks and their interactions, but also because of the poor control over these parameters in the fabrication of more elaborate nanocrystals. Here, we firstly report a facile and general route to a new generation of 3D layered superlattices of polyaniline doped with CSA (PANI-CSA) and show how PANI crystallize and self-assemble, in a suitable single solution environment. In cyclohexane, 1D amorphous nanofibers transformed to 1D nanorods as building blocks, and then to 2D single-crystal nanosheets with a hexagonal phase, and lastly to 3D ordered layered superlattices with the narrowest polydispersity value (Mw/Mn = 1.47). Remarkably, all the instructions for the hierarchical self-assembly are encoded in the layered shape in other non-polar solvents (hexane, octane) and their conductivity in the π-π stacking direction is improved to about 50 S cm-1, which is even higher than that of the highest previously reported value (16 S cm-1). The method used in this study is greatly expected to be readily scalable to produce superlattices of conductive polymers with high quality and low cost. Electronic supplementary information (ESI) available: SEM, and TEM images. See DOI: 10.1039/c2nr30743j

Preparation and characterization of highly water-soluble magnetic Fe3O4 nanoparticles via surface double-layered self-assembly method of sodium alpha-olefin sulfonate

NASA Astrophysics Data System (ADS)

Li, Honghong; Qin, Li; Feng, Ying; Hu, Lihua; Zhou, Chunhua

2015-06-01

A kind of double-layered self-assembly sodium alpha-olefin sulfonate (AOS) capped Fe3O4 magnetic nanoparticles (Fe3O4-AOS-MN) with highly water-solubility was prepared by a wet co-precipitation method with a pH of 4.8. The resulting Fe3O4-AOS-MN could be dispersed into water to form stable magnetic fluid without other treatments. The result of X-ray diffraction (XRD) indicated that the Fe3O4-AOS-MN maintained original crystalline structure and exhibited a diameter of about 7.5 nm. The iron oxide phase of nanoparticles determined by Raman spectroscopy is Fe3O4. Transmission electron microscopy (TEM) analysis confirmed that the Fe3O4-AOS-MN with spherical morphology were uniformly dispersed in water. FT-IR spectroscopy (FT-IR) and thermo-gravimetric analysis (TGA) verified the successful preparation of Fe3O4-AOS-MN capped with double-layered self-assembled AOS. The corresponding capacities of monolayer chemical absorption and the second-layer self-assembly absorption were respectively 4.07 and 14.71 wt% of Fe3O4-MN, which were much lower than those of other surfactants. Vibrating sample magnetometer (VSM) test result showed Fe3O4-AOS-MN possessed superparamagnetic behavior with the saturation magnetization value of about 44.45 emu/g. The blocking temperature TB of Fe3O4-AOS-MN capped with double-layered AOS is 170 K.

Non-native three-dimensional block copolymer morphologies

DOE PAGES

Rahman, Atikur; Majewski, Pawel W.; Doerk, Gregory; ...

2016-12-22

Self-assembly is a powerful paradigm, wherein molecules spontaneously form ordered phases exhibiting well-defined nanoscale periodicity and shapes. However, the inherent energy-minimization aspect of self-assembly yields a very limited set of morphologies, such as lamellae or hexagonally packed cylinders. Here, we show how soft self-assembling materials—block copolymer thin films—can be manipulated to form a diverse library of previously unreported morphologies. In this iterative assembly process, each polymer layer acts as both a structural component of the final morphology and a template for directing the order of subsequent layers. Specifically, block copolymer films are immobilized on surfaces, and template successive layers throughmore » subtle surface topography. As a result, this strategy generates an enormous variety of three-dimensional morphologies that are absent in the native block copolymer phase diagram.« less

Non-native three-dimensional block copolymer morphologies

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

Rahman, Atikur; Majewski, Pawel W.; Doerk, Gregory

Self-assembly is a powerful paradigm, wherein molecules spontaneously form ordered phases exhibiting well-defined nanoscale periodicity and shapes. However, the inherent energy-minimization aspect of self-assembly yields a very limited set of morphologies, such as lamellae or hexagonally packed cylinders. Here, we show how soft self-assembling materials—block copolymer thin films—can be manipulated to form a diverse library of previously unreported morphologies. In this iterative assembly process, each polymer layer acts as both a structural component of the final morphology and a template for directing the order of subsequent layers. Specifically, block copolymer films are immobilized on surfaces, and template successive layers throughmore » subtle surface topography. As a result, this strategy generates an enormous variety of three-dimensional morphologies that are absent in the native block copolymer phase diagram.« less

Characterization of self-assembled redox polymer and antibody molecules on thiolated gold electrodes.

PubMed

Calvo, E J; Danilowicz, C; Lagier, C M; Manrique, J; Otero, M

2004-05-15

Multilayer immobilization of antibody and redox polymer molecules on a gold electrode was achieved, as a strategy for the potential development of an amperometric immunosensor. The step-by-step assembly of antibiotin IgG on Os(bpy)(2)ClPyCH(2)NH poly(allylamine) redox polymer (PAH-Os) adsorbed on thiolated gold electrodes was proved by quartz crystal microbalance (QCM) and atomic force microscopy (AFM) experiments, confirming the electrochemical evidence. The increase of redox charge during the layer-by-layer deposition demonstrated that charge propagation within the layers is feasible. The multilayer structure proved to be effective for the molecular recognition of horseradish peroxidase-biotin conjugate (HRP-biotin), as confirmed by the QCM measurements and the electrocatalytic reduction current obtained upon H(2)O(2) addition. The catalytic current resulting from PAH-Os mediation was shown to increase with the number of assembled layers. Furthermore, the inventory of IgG molecules on the supramolecular self-assembled structure and the specific and non-specific binding of HRP-biotin conjugate were confirmed by the QCM transient studies, giving information on the kinetics of IgG deposition and HRP-biotin conjugate binding to the IgG.

Electrostatic Self-Assembly of Sandwich-Like CoAl-LDH/Polypyrrole/Graphene Nanocomposites with Enhanced Capacitive Performance.

PubMed

Zhang, Yu; Du, Dongfeng; Li, Xuejin; Sun, Hongman; Li, Li; Bai, Peng; Xing, Wei; Xue, Qingzhong; Yan, Zifeng

2017-09-20

A novel sandwich-like composite with ultrathin CoAl-layered double hydroxide (LDH) nanoplates electrostatically assembled on both sides of two-dimensional polypyrrole/graphene (PG) substrate has been successfully fabricated using facile hydrothermal techniques. The PG not only serves as an excellent conductive and structural scaffold to enhance the transmission of electrons and prevent aggregation of CoAl-LDH nanoplates but also contributes to the enhancement of the specific capacitance. Owing to the homogeneous dispersion of CoAl-LDH nanoplates and its intimate interaction with PG substrate, the resulting CoAl-LDH/PG nanocomposite material exhibits excellent capacitive performance, for example, enhanced gravimetric specific capacitance (864 F g -1 at 1 A g -1 ), high rate performance (75% retention at 20 A g -1 ), and excellent cycle life (almost no degradation in supercapacitor performance after 5000 cycles) in aqueous KOH solution. Furthermore, the assembled asymmetric capacitor is able to deliver a superhigh energy density of 46.8 Wh kg -1 at 1.2 kW kg -1 and maintain 90.1% of its initial capacitance after 10 000 cycles. These results indicate a rational assembly strategy toward a high-performance pseudocapacitive electrode material with excellent rate performance, high specific capacitance, and outstanding cycle stability.

Note: Influence of rinsing and drying routines on growth of multilayer thin films using automated deposition system.

PubMed

Gamboa, Daniel; Priolo, Morgan A; Ham, Aaron; Grunlan, Jaime C

2010-03-01

A versatile, high speed robot for layer-by-layer deposition of multifunctional thin films, which integrates concepts from previous dipping systems, has been designed with dramatic improvements in software, positioning, rinsing, drying, and waste removal. This system exploits the electrostatic interaction of oppositely charged species to deposit nanolayers (1-10 nm thick) from water onto the surface of a substrate. Dip times and number of deposited layers are adjustable through a graphical user interface. In between dips the system spray rinses and dries the substrate by positioning it in the two-tiered rinse-dry station. This feature significantly reduces processing time and provides the flexibility to choose from four different procedures for rinsing and drying. Assemblies of natural montmorillonite clay and polyethylenimine are deposited onto 175 microm poly(ethylene terephthalate) film to demonstrate the utility of this automated deposition system. By altering the type of rinse-dry procedure, these clay-based assemblies are shown to exhibit variations in film thickness and oxygen transmission rate. This type of system reproducibly deposits films containing 20 or more layers and may also be useful for other types of coatings that make use of dipping.

Surface modification of graphene oxide nanosheets by protamine sulfate/sodium alginate for anti-cancer drug delivery application

NASA Astrophysics Data System (ADS)

Xie, Meng; Zhang, Feng; Liu, Lijiao; Zhang, Yanan; Li, Yeping; Li, Huaming; Xie, Jimin

2018-05-01

In order to improve the efficiency of anticancer drug delivery, a graphene oxide (GO) based drug delivery system modificated by natural peptide protamine sulfate (PRM) and sodium alginate (SA) was established via electrostatic attraction at each step of adsorption based on layer-by-layer self-assembly. The nanocomposites were then loaded with anticancer drug doxorubicin hydrochloride (DOX) to estimate the feasibility as drug carriers. The nanocomposites loaded with DOX revealed a remarkable pH-sensitive drug release property. The modification with protamine sulfate and sodium alginate could not only impart the nanocomposites an improved dispersibility and stability under physiological pH, but also suppress the protein adhesion. Due to the high water dispersibility and the small particle size, GO-PRM/SA nanocomposites were able to be uptaken by MCF-7 cells. It was found that GO-PRM/SA nanocomposites exhibited no obvious cytotoxicity towards MCF-7 cells, while GO-PRM/SA-DOX exhibited better cytotoxicity than GO-DOX. Therefore, the GO-PRM/SA nanocomposites were feasible as drug delivery vehicles.

Frequency Dependence of Low-Voltage Electrowetting Investigated by Impedance Spectroscopy.

PubMed

Li, Ying-Jia; Cahill, Brian P

2017-11-14

An electrowetting-on-dielectric (EWOD) electrode was developed that facilitates the use of low alternating voltages (≤5 V AC ). This allows online investigation of the frequency dependence of electrowetting by means of impedance spectroscopy. The EWOD electrode is based on a dielectric bilayer consisting of an anodic tantalum pentoxide (Ta 2 O 5 ) thin film (d = 59.35 nm) with a high relative permittivity (ε d = 26.3) and a self-assembled hydrophobic silane monolayer. The frequency dependence of electrowetting was studied using an aqueous μL-sized sessile droplet on the planar EWOD electrode in oil. Experiments using electrochemical impedance spectroscopy and optical imaging indicate the frequency dependence of all three variables in the Young-Lippmann equation: the voltage drop across the dielectric layers, capacitance per unit area, and contact angle under voltage. The electrowetting behavior induced by AC voltages is shown to be well described by the Young-Lippmann equation for AC applications below a frequency threshold. Moreover, the dielectric layers act as a capacitor and the stored electrostatic potential energy is revealed to only partially contribute to the electrowetting.

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

NASA Astrophysics Data System (ADS)

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

2013-10-01

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

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

Self assembling proteins

DOEpatents

Yeates, Todd O.; Padilla, Jennifer; Colovos, Chris

2004-06-29

Novel fusion proteins capable of self-assembling into regular structures, as well as nucleic acids encoding the same, are provided. The subject fusion proteins comprise at least two oligomerization domains rigidly linked together, e.g. through an alpha helical linking group. Also provided are regular structures comprising a plurality of self-assembled fusion proteins of the subject invention, and methods for producing the same. The subject fusion proteins find use in the preparation of a variety of nanostructures, where such structures include: cages, shells, double-layer rings, two-dimensional layers, three-dimensional crystals, filaments, and tubes.

Self assembled multi-layer nanocomposite of graphene and metal oxide materials

DOEpatents

Liu, Jun; Aksay, Ilhan A; Choi, Daiwon; Kou, Rong; Nie, Zimin; Wang, Donghai; Yang, Zhenguo

2013-10-22

Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.

Self assembled multi-layer nanocomposite of graphene and metal oxide materials

DOEpatents

Liu, Jun; Aksay, Ilhan A; Choi, Daiwon; Kou, Rong; Nie, Zimin; Wang, Donghai; Yang, Zhenguo

2015-04-28

Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.

Self assembled multi-layer nanocomposite of graphene and metal oxide materials

DOEpatents

Liu, Jun; Choi, Daiwon; Kou, Rong; Nie, Zimin; Wang, Donghai; Yang, Zhenguo

2014-09-16

Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.

Metal deposition using seed layers

DOEpatents

Feng, Hsein-Ping; Chen, Gang; Bo, Yu; Ren, Zhifeng; Chen, Shuo; Poudel, Bed

2013-11-12

Methods of forming a conductive metal layers on substrates are disclosed which employ a seed layer to enhance bonding, especially to smooth, low-roughness or hydrophobic substrates. In one aspect of the invention, the seed layer can be formed by applying nanoparticles onto a surface of the substrate; and the metallization is achieved by electroplating an electrically conducting metal onto the seed layer, whereby the nanoparticles serve as nucleation sites for metal deposition. In another approach, the seed layer can be formed by a self-assembling linker material, such as a sulfur-containing silane material.

A regenerating ultrasensitive electrochemical impedance immunosensor for the detection of adenovirus.

PubMed

Lin, Donghai; Tang, Thompson; Jed Harrison, D; Lee, William E; Jemere, Abebaw B

2015-06-15

We report on the development of a regenerable sensitive immunosensor based on electrochemical impedance spectroscopy for the detection of type 5 adenovirus. The multi-layered immunosensor fabrication involved successive modification steps on gold electrodes: (i) modification with self-assembled layer of 1,6-hexanedithiol to which gold nanoparticles were attached via the distal thiol groups, (ii) formation of self-assembled monolayer of 11-mercaptoundecanoic acid onto the gold nanoparticles, (iii) covalent immobilization of monoclonal anti-adenovirus 5 antibody, with EDC/NHS coupling reaction on the nanoparticles, completing the immunosensor. The immunosensor displayed a very good detection limit of 30 virus particles/ml and a wide linear dynamic range of 10(5). An electrochemical reductive desorption technique was employed to completely desorb the components of the immunosensor surface, then re-assemble the sensing layer and reuse the sensor. On a single electrode, the multi-layered immunosensor could be assembled and disassembled at least 30 times with 87% of the original signal intact. The changes of electrode behavior after each assembly and desorption processes were investigated by cyclic voltammetry, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy techniques. Copyright © 2014 Elsevier B.V. All rights reserved.

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. © 2013 Elsevier B.V. All rights reserved.

Formation of a 1,8-octanedithiol self-assembled monolayer on Au(111) prepared in a lyotropic liquid-crystalline medium.

PubMed

García Raya, Daniel; Madueño, Rafael; Blázquez, Manuel; Pineda, Teresa

2010-07-20

A characterization of the 1,8-octanedithiol (ODT) self-assembled monolayer (SAM) formed from a Triton X-100 lyotropic medium has been conducted by electrochemical techniques. It is found that an ODT layer of standing-up molecules is obtained at short modification time without removing oxygen from the medium. The electrochemical study shows that the ODT layer formed after 15 min of modification time has similar electron-transfer blocking properties to the layers formed from organic solvents at much longer modification times. On the basis of XPS data, it is demonstrated that the inability to bind gold nanoparticles (AuNPs) is due to the presence of extra ODT molecules either interdigited or on top of the layer. Treatment consisting of an acid washing step following the formation of the ODT-Au(111) SAM produces a layer that is able to attach AuNPs as demonstrated by electrochemical techniques and atomic force microscopy (AFM) images.

Architecture and assembly of the Bacillus subtilis spore coat.

PubMed

Plomp, Marco; Carroll, Alicia Monroe; Setlow, Peter; Malkin, Alexander J

2014-01-01

Bacillus spores are encased in a multilayer, proteinaceous self-assembled coat structure that assists in protecting the bacterial genome from stresses and consists of at least 70 proteins. The elucidation of Bacillus spore coat assembly, architecture, and function is critical to determining mechanisms of spore pathogenesis, environmental resistance, immune response, and physicochemical properties. Recently, genetic, biochemical and microscopy methods have provided new insight into spore coat architecture, assembly, structure and function. However, detailed spore coat architecture and assembly, comprehensive understanding of the proteomic composition of coat layers, and specific roles of coat proteins in coat assembly and their precise localization within the coat remain in question. In this study, atomic force microscopy was used to probe the coat structure of Bacillus subtilis wild type and cotA, cotB, safA, cotH, cotO, cotE, gerE, and cotE gerE spores. This approach provided high-resolution visualization of the various spore coat structures, new insight into the function of specific coat proteins, and enabled the development of a detailed model of spore coat architecture. This model is consistent with a recently reported four-layer coat assembly and further adds several coat layers not reported previously. The coat is organized starting from the outside into an outermost amorphous (crust) layer, a rodlet layer, a honeycomb layer, a fibrous layer, a layer of "nanodot" particles, a multilayer assembly, and finally the undercoat/basement layer. We propose that the assembly of the previously unreported fibrous layer, which we link to the darkly stained outer coat seen by electron microscopy, and the nanodot layer are cotH- and cotE- dependent and cotE-specific respectively. We further propose that the inner coat multilayer structure is crystalline with its apparent two-dimensional (2D) nuclei being the first example of a non-mineral 2D nucleation crystallization pattern in a biological organism.

Architecture and Assembly of the Bacillus subtilis Spore Coat

PubMed Central

Plomp, Marco; Carroll, Alicia Monroe; Setlow, Peter; Malkin, Alexander J.

2014-01-01

Bacillus spores are encased in a multilayer, proteinaceous self-assembled coat structure that assists in protecting the bacterial genome from stresses and consists of at least 70 proteins. The elucidation of Bacillus spore coat assembly, architecture, and function is critical to determining mechanisms of spore pathogenesis, environmental resistance, immune response, and physicochemical properties. Recently, genetic, biochemical and microscopy methods have provided new insight into spore coat architecture, assembly, structure and function. However, detailed spore coat architecture and assembly, comprehensive understanding of the proteomic composition of coat layers, and specific roles of coat proteins in coat assembly and their precise localization within the coat remain in question. In this study, atomic force microscopy was used to probe the coat structure of Bacillus subtilis wild type and cotA, cotB, safA, cotH, cotO, cotE, gerE, and cotE gerE spores. This approach provided high-resolution visualization of the various spore coat structures, new insight into the function of specific coat proteins, and enabled the development of a detailed model of spore coat architecture. This model is consistent with a recently reported four-layer coat assembly and further adds several coat layers not reported previously. The coat is organized starting from the outside into an outermost amorphous (crust) layer, a rodlet layer, a honeycomb layer, a fibrous layer, a layer of “nanodot” particles, a multilayer assembly, and finally the undercoat/basement layer. We propose that the assembly of the previously unreported fibrous layer, which we link to the darkly stained outer coat seen by electron microscopy, and the nanodot layer are cotH- and cotE- dependent and cotE-specific respectively. We further propose that the inner coat multilayer structure is crystalline with its apparent two-dimensional (2D) nuclei being the first example of a non-mineral 2D nucleation crystallization pattern in a biological organism. PMID:25259857

Hierarchical Composite Membranes with Robust Omniphobic Surface Using Layer-By-Layer Assembly Technique.

PubMed

Woo, Yun Chul; Kim, Youngjin; Yao, Minwei; Tijing, Leonard D; Choi, June-Seok; Lee, Sangho; Kim, Seung-Hyun; Shon, Ho Kyong

2018-02-20

In this study, composite membranes were fabricated via layer-by-layer (LBL) assembly of negatively charged silica aerogel (SiA) and 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FTCS) on a polyvinylidene fluoride phase inversion membrane and interconnecting them with positively charged poly(diallyldimethylammonium chloride) (PDDA) via electrostatic interaction. The results showed that the PDDA-SiA-FTCS coated membrane had significantly enhanced the membrane structure and properties. New trifluoromethyl and tetrafluoroethylene bonds appeared at the surface of the coated membrane, which led to lower surface free energy of the composite membrane. Additionally, the LBL membrane showed increased surface roughness. The improved structure and property gave the LBL membrane an omniphobic property, as indicated by its good wetting resistance. The membrane performed a stable air gap membrane distillation (AGMD) flux of 11.22 L/m 2 h with very high salt rejection using reverse osmosis brine from coal seam gas produced water as feed with the addition of up to 0.5 mM SDS solution. This performance was much better compared to those of the neat membrane. The present study suggests that the enhanced membrane properties with good omniphobicity via LBL assembly make the porous membranes suitable for long-term AGMD operation with stable permeation flux when treating challenging saline wastewater containing low surface tension organic contaminants.

Biocatalytic response of multi-layer assembled collagen/hyaluronic acid nanoengineered capsules.

PubMed

Sousa, Fernanda; Kreft, Oliver; Sukhorukov, Gleb B; Möhwald, Helmuth; Kokol, Vanja

2014-01-01

Biodegradable hollow capsules filled with fluorescently labelled bovine serum albumin (BSA) as a model drug were prepared via layer-by-layer (LbL) self-assembly of type-I collagen (COL) and hyaluronic acid (HA) using calcium carbonate micro-particles and co-precipitation method. Capsules loaded with fluorescein isothiocyanate (FITC)-BSA, tetramethylrhodamin isothiocyanate (TRITC)-BSA or Alex-Fluor-488-BSA, respectively, were characterised before and after core removal using Confocal Laser Scanning Microscopy (CLSM), whilst the morphologies of individual hollow capsules were assessed using Atomic Force Microscopy (AFM). The sustained release of the encapsulated FITC-BSA protein was attained using enzymatic degradation of the capsule shells by collagenase. The released profile of the fluorescently-labelled BSA indicated that it could be successfully controlled by modulating the number of layers and/or by collagen crosslinking either before or after the capsule's assembly.

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

PubMed

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

2016-11-29

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

Aligned Layers of Silver Nano-Fibers.

PubMed

Golovin, Andrii B; Stromer, Jeremy; Kreminska, Liubov

2012-02-01

We describe a new dichroic polarizers made by ordering silver nano-fibers to aligned layers. The aligned layers consist of nano-fibers and self-assembled molecular aggregates of lyotropic liquid crystals. Unidirectional alignment of the layers is achieved by means of mechanical shearing. Aligned layers of silver nano-fibers are partially transparent to a linearly polarized electromagnetic radiation. The unidirectional alignment and density of the silver nano-fibers determine degree of polarization of transmitted light. The aligned layers of silver nano-fibers might be used in optics, microwave applications, and organic electronics.

A novel amperometric biosensor based on covalently attached multilayer assemblies of gold nanoparticles, diazo-resins and acetylcholinesterase for the detection of organophosphorus pesticides.

PubMed

Jiang, Bin; Dong, Pei; Zheng, Jianbin

2018-06-01

Using an ionic layer-by-layer self-assembly technique, colloidal gold nanoparticles (AuNPs) and diazo-resins (DAR) were immobilised on the surface of a p-aminobenzenesulfonic acid-modified glassy carbon electrode to form a matrix composite membrane for acetylcholinesterase (AChE) immobilisation. Photo-sensitive DAR was used as the assembly interlayer to convert the ionic bond into a covalent bond to improve the biosensor stability. These fabrication processes were followed by electrochemical impedance spectroscopy and cyclic voltammetry to verify the membrane formation. Because of the introduction of AuNPs/DAR/AChE biofilms, the modified electrode exhibited excellent electron transfer mediation and electrical conductivity. In addition, it exhibited high sensitivity in the range of linear concentration from 1.0 × 10 -8 to 1.0 × 10 -12 g L -1 with the detection limit of 5.12 × 10 -13 and 5.85 × 10 -13 g L -1 for malathion and methyl parathion, respectively. More importantly, the presented biosensor considerably improved stability because the electrostatic interaction was converted into covalent bonds by UV irradiation. It is a simple, cheap and stable method for quantitative detection of organophosphorus pesticides, and this method may pave a way for the sensitive, simple detection of different analytes without the need of expensive instrumentation. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrostatics at the nanoscale.

PubMed

Walker, David A; Kowalczyk, Bartlomiej; de la Cruz, Monica Olvera; Grzybowski, Bartosz A

2011-04-01

Electrostatic forces are amongst the most versatile interactions to mediate the assembly of nanostructured materials. Depending on experimental conditions, these forces can be long- or short-ranged, can be either attractive or repulsive, and their directionality can be controlled by the shapes of the charged nano-objects. This Review is intended to serve as a primer for experimentalists curious about the fundamentals of nanoscale electrostatics and for theorists wishing to learn about recent experimental advances in the field. Accordingly, the first portion introduces the theoretical models of electrostatic double layers and derives electrostatic interaction potentials applicable to particles of different sizes and/or shapes and under different experimental conditions. This discussion is followed by the review of the key experimental systems in which electrostatic interactions are operative. Examples include electroactive and "switchable" nanoparticles, mixtures of charged nanoparticles, nanoparticle chains, sheets, coatings, crystals, and crystals-within-crystals. Applications of these and other structures in chemical sensing and amplification are also illustrated.

pH-controlled drug loading and release from biodegradable microcapsules

PubMed Central

Zhao, Qinghe; Li, Bingyun

2013-01-01

Microcapsules made of biopolymers are of both scientific and technological interest and have many potential applications in medicine including their use as controlled drug delivery devices. The present study employs the electrostatic interaction between polycations and polyanions to form a multilayered microcapsule shell and also to control the loading and release of charged drug molecules inside the microcapsule. Micron-sized CaCO3 particles were synthesized and integrated with chondroitin sulfate (CS) through a reaction between Na2CO3 and Ca(NO3)2 solutions suspended with CS macromolecules. Oppositely-charged biopolymers were alternately deposited onto the synthesized particles using electrostatic layer-by-layer self-assembly, and glutaraldehyde was introduced to crosslink the multilayered shell structure. Microcapsules integrated with CS inside the multilayered shells were obtained after decomposition of the CaCO3 templates. The integration of a matrix, i.e. CS, enabled the subsequent selective control of drug loading and release. The CS integrated microcapsules were loaded with a model drug, i.e. bovine serum albumin labeled with fluorescein isothiocyanate (FITC-BSA), and it was shown that pH was an effective means of controlling the loading and release of FITC-BSA. Such CS integrated microcapsules may be used for controlled localized drug delivery as biodegradable devices, which have advantages in reducing systemic side effects and increasing drug efficacy. PMID:18657478

Layer-by-Layer Self-Assembly of Plexcitonic Nanoparticles

DTIC Science & Technology

2013-08-12

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

Bienzyme bionanomultilayer electrode for glucose biosensing based on functional carbon nanotubes and sugar-lectin biospecific interaction.

PubMed

Chen, Huan; Xi, Fengna; Gao, Xia; Chen, Zhichun; Lin, Xianfu

2010-08-01

Bienzyme bionanomultilayer electrode for glucose biosensing was constructed based on functional carbon nanotubes and sugar-lectin biospecific interaction through layer-by-layer (LBL) assembly. After being functionalized by wrapping with polyelectrolyte, multiwalled carbon nanotubes (MCNTs) were water soluble and positively charged. MCNT-bienzyme bionanomultilayer electrode was then fabricated by LBL assembly of horseradish peroxidase (HRP) and glucose oxidase (GOD) on functional MCNT modified electrode. The attachment of the MCNT-bienzyme bionanomultilayer with the underlying electrode and each layer in the bionanomultilayer was based on reliably electrostatic or sugar-lectin biospecific interaction. The developed bienzyme biosensor exhibited fast amperometric response for the determination of glucose. The linear response of the developed biosensor for the determination of glucose ranged from 2.0 x 10(-6) to 1.7 x 10(-4) M with a detection limit of 2.5 x 10(-7) M. The biosensor can be used directly to determine glucose in serum. The construction of the bienzyme biosensor showed potential for the preparation of MCNT-enzyme nanocomposite with controllability and high performance. Copyright 2010 Elsevier Inc. All rights reserved.

Self-Assembly of Nanoclusters into Mono-, Few-, and Multilayered Sheets via Dipole-Induced Asymmetric van der Waals Attraction.

PubMed

Wu, Zhennan; Liu, Jiale; Li, Yanchun; Cheng, Ziyi; Li, Tingting; Zhang, Hao; Lu, Zhongyuan; Yang, Bai

2015-06-23

Two-dimensional (2D) nanomaterials possessing regular layered structures and versatile chemical composition are highly expected in many applications. Despite the importance of van der Waals (vdW) attraction in constructing and maintaining layered structures, the origin of 2D anisotropy is not fully understood, yet. Here, we report the 2D self-assembly of ligand-capped Au15 nanoclusters into mono-, few-, and multilayered sheets in colloidal solution. Both the experimental results and computer simulation reveal that the 2D self-assembly is initiated by 1D dipolar attraction common in nanometer-sized objects. The dense 1D attachment of Au15 leads to a redistribution of the surface ligands, thus generating asymmetric vdW attraction. The deliberate control of the coordination of dipolar and vdW attraction further allows to manipulate the thickness and morphologies of 2D self-assembly architectures.

Conformal Nanocoatings with Uniform and Controllable Thickness on Microstructured Surfaces: A General Assembly Route.

PubMed

Hou, Yi; Wang, Zhen; Cai, Chao; Hao, Xi; Li, Dongdong; Zhao, Ning; Zhao, Yiping; Chen, Li; Ma, Hongwei; Xu, Jian

2018-02-01

Assembling nanoparticles (NPs) on various surfaces are intensively investigated for the construction of functional nanocoatings; however, it is still a challenge to fabricate conformal nanocoatings uniformly on surfaces having micro- or nanostructures. Herein, it is demonstrated that the negatively charged SiO 2 NPs and the positively charged silicon coupling agent can be assembled layer-by-layer on the microstructures based on the combination of electrostatic interaction and condensation reaction. Conformal nanocoatings with controllable thickness are formed on the microstructured surfaces with different compositions and morphologies. The formation mechanism is confirmed by using quartz crystal microbalance with dissipation (QCM-D) to study the assembly process in real time. The universality of this method is illustrated by using other reactive building blocks with opposite charge to build up the conformal nanocoatings. Application in the preparation of antireflective nanocoatings on nonplanar optical materials is demonstrated. This simple, versatile, and scalable strategy for the preparation of conformal nanocoatings is promising for practical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of the Secondary Cell Wall Polymer on the Reassembly, Recrystallization, and Stability Properties of the S-Layer Protein from Bacillus stearothermophilus PV72/p2

PubMed Central

Sára, Margit; Dekitsch, Christine; Mayer, Harald F.; Egelseer, Eva M.; Sleytr, Uwe B.

1998-01-01

The high-molecular-weight secondary cell wall polymer (SCWP) from Bacillus stearothermophilus PV72/p2 is mainly composed of N-acetylglucosamine (GlcNAc) and N-acetylmannosamine (ManNAc) and is involved in anchoring the S-layer protein via its N-terminal region to the rigid cell wall layer. In addition to this binding function, the SCWP was found to inhibit the formation of self-assembly products during dialysis of the guanidine hydrochloride (GHCl)-extracted S-layer protein. The degree of assembly (DA; percent assembled from total S-layer protein) that could be achieved strongly depended on the amount of SCWP added to the GHCl-extracted S-layer protein and decreased from 90 to 10% when the concentration of the SCWP was increased from 10 to 120 μg/mg of S-layer protein. The SCWP kept the S-layer protein in the water-soluble state and favored its recrystallization on solid supports such as poly-l-lysine-coated electron microscopy grids. Derived from the orientation of the base vectors of the oblique S-layer lattice, the subunits had bound with their charge-neutral outer face, leaving the N-terminal region with the polymer binding domain exposed to the ambient environment. From cell wall fragments about half of the S-layer protein could be extracted with 1 M GlcNAc, indicating that the linkage type between the S-layer protein and the SCWP could be related to that of the lectin-polysaccharide type. Interestingly, GlcNAc had an effect on the in vitro self-assembly and recrystallization properties of the S-layer protein that was similar to that of the isolated SCWP. The SCWP generally enhanced the stability of the S-layer protein against endoproteinase Glu-C attack and specifically protected a potential cleavage site in position 138 of the mature S-layer protein. PMID:9696762

Solid surface dependent layering of self-arranged structures with fibril-like assemblies of alpha-synuclein

NASA Astrophysics Data System (ADS)

Bukauskas, V.; Šetkus, A.; Šimkienė, I.; Tumėnas, S.; Kašalynas, I.; Rėza, A.; Babonas, J.; Časaitė, V.; Povilonienė, S.; Meškys, R.

2012-03-01

In present work the formation of hybrid constructions composed of alpha-synuclein-based colloidal solutions on various solid surfaces (silica coated Si, mica, CaF2 and KBr) is investigated by scanning probe microscopy, spectrocopic ellipsometry, Fourier transformed infrared spectroscopy and vibrational circular dichroism. Prior to the modification of the solids, the proteins were intentionally fibrilled under special conditions. It is proved that the multi-component coatings are self-arranged on the solid substrates. Depending on the substrate material, the interface films consisting of individual biomolecules can be detected on the solid surfaces. The coatings with fibril-like alpha-synuclein objects can be obtained on solid surfaces with negligible or comparatively thick interface films. The results are interpreted in terms of the charged surface-controlled electrostatic interaction between the substrate and the biomolecules. Solubility of solids is considered in this interpretation.

Low-dislocation-density epitatial layers grown by defect filtering by self-assembled layers of spheres

DOEpatents

Wang, George T.; Li, Qiming

2013-04-23

A method for growing low-dislocation-density material atop a layer of the material with an initially higher dislocation density using a monolayer of spheroidal particles to bend and redirect or directly block vertically propagating threading dislocations, thereby enabling growth and coalescence to form a very-low-dislocation-density surface of the material, and the structures made by this method.

Facile and controllable one-step fabrication of molecularly imprinted polymer membrane by magnetic field directed self-assembly for electrochemical sensing of glutathione.

PubMed

Zhu, Wanying; Jiang, Guoyi; Xu, Lei; Li, Bingzhi; Cai, Qizhi; Jiang, Huijun; Zhou, Xuemin

2015-07-30

Based on magnetic field directed self-assembly (MDSA) of the ternary Fe3O4@PANI/rGO nanocomposites, a facile and controllable molecularly imprinted electrochemical sensor (MIES) was fabricated through a one-step approach for detection of glutathione (GSH). The ternary Fe3O4@PANI/rGO nanocomposites were obtained by chemical oxidative polymerization and intercalation of Fe3O4@PANI into the graphene oxide layers via π-π stacking interaction, followed by reduction of graphene oxide in the presence of hydrazine hydrate. In molecular imprinting process, the pre-polymers, including GSH as template molecule, Fe3O4@PANI/rGO nanocomposites as functional monomers and pyrrole as both cross-linker and co-monomer, was assembled through N-H hydrogen bonds and the electrostatic interaction, and then was rapidly oriented onto the surface of MGCE under the magnetic field induction. Subsequently, the electrochemical GSH sensor was formed by electropolymerization. In this work, the ternary Fe3O4@PANI/rGO nanocomposites could not only provide available functionalized sites in the matrix to form hydrogen bond and electrostatic interaction with GSH, but also afford a promoting network for electron transfer. Moreover, the biomimetic sensing membrane could be controlled more conveniently and effectively by adjusting the magnetic field strength. The as-prepared controllable sensor showed good stability and reproducibility for the determination of GSH with the detection limit reaching 3 nmol L(-1) (S/N = 3). In addition, the highly sensitive and selective biomimetic sensor has been successfully used for the clinical determination of GSH in biological samples. Copyright © 2015 Elsevier B.V. All rights reserved.

On the use of (3-trimethoxysilylpropyl)diethylenetriamine self-assembled monolayers as seed layers for the growth of Mn based copper diffusion barrier layers

NASA Astrophysics Data System (ADS)

Brady-Boyd, A.; O'Connor, R.; Armini, S.; Selvaraju, V.; Hughes, G.; Bogan, J.

2018-01-01

In this work x-ray photoelectron spectroscopy is used to investigate in-vacuo, the interaction of metallic manganese with a (3-trimethoxysilylpropyl)diethylenetriamine (DETA) self-assembled monolayer (SAM) on SiO2 and non-porous low-k dielectric materials. Subsequent deposition of a ∼0.5 nm thick Mn, followed by a 200 °C anneal results in the Mn diffusing through the SAM to interact with the underlying SiO2 layer to form a Mn-silicate layer. Furthermore, there is evidence that the Mn interacts with the carbon and nitrogen within the SAM to form Mn-carbide and Mn-nitride, respectively. When deposited on low-k materials the Mn is found to diffuse through to the SAM on deposition and interact both with the SAM and the underlying substrate in a similar fashion.

Preparation, chromatographic evaluation and application of adenosine 5'-monophosphate modified ZrO2/SiO2 stationary phase in hydrophilic interaction chromatography.

PubMed

Wang, Qing; Luo, Zhi-Yuan; Ye, Mao; Wang, Yu-Zhuo; Xu, Li; Shi, Zhi-Guo; Xu, Lanying

2015-02-27

The zirconia-coated silica (ZrO2/SiO2) material was obtained by coupling layer-by-layer (LbL) self-assembly method and sol-gel technology, to take dual advantages of the suitable porous structure of SiO2 and basic resistance of ZrO2. Adenosine 5'-monophosphate (5'-AMP) was then self-assembled onto ZrO2/SiO2 via Lewis acid-base interaction, generating 5'-AMP-ZrO2/SiO2. The chromatographic properties of 5'-AMP-ZrO2/SiO2 were systemically studied by evaluating the effect of acetonitrile content, pH and buffer concentration in the mobile phase. The results demonstrated that the 5'-AMP-ZrO2/SiO2 possessed hydrophilic interaction chromatographic (HILIC) property comprising hydrophilic, hydrogen-bonding, electrostatic and ion-exchange interactions. For basic analytes, the column efficiency of ZrO2/SiO2 and 5'-AMP-ZrO2/SiO2 was superior to the bare ZrO2, and different selectivity was obtained after the introduction of 5'-AMP. For acidic analytes, good resolution was obtained on 5'-AMP-ZrO2/SiO2 while the analysis failed on the bare ZrO2 column owing to strong adsorption. Hence, the proposed 5'-AMP-ZrO2/SiO2 had great potential in analyzing acidic compounds in HILIC mode. It was an extended application of ZrO2 based SP. Copyright © 2015 Elsevier B.V. All rights reserved.

Self-assembled anchor layers/polysaccharide coatings on titanium surfaces: a study of functionalization and stability

PubMed Central

Zemek, Josef; Neykova, Neda; Demianchuk, Roman; Chánová, Eliška Mázl; Šlouf, Miroslav; Houska, Milan; Rypáček, František

2015-01-01

Summary Composite materials based on a titanium support and a thin, alginate hydrogel could be used in bone tissue engineering as a scaffold material that provides biologically active molecules. The main objective of this contribution is to characterize the activation and the functionalization of titanium surfaces by the covalent immobilization of anchoring layers of self-assembled bisphosphonate neridronate monolayers and polymer films of 3-aminopropyltriethoxysilane and biomimetic poly(dopamine). These were further used to bind a bio-functional alginate coating. The success of the titanium surface activation, anchoring layer formation and alginate immobilization, as well as the stability upon immersion under physiological-like conditions, are demonstrated by different surface sensitive techniques such as spectroscopic ellipsometry, infrared reflection–absorption spectroscopy and X-ray photoelectron spectroscopy. The changes in morphology and the established continuity of the layers are examined by scanning electron microscopy, surface profilometry and atomic force microscopy. The changes in hydrophilicity after each modification step are further examined by contact angle goniometry. PMID:25821702

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-, and 20-bilayer nanofilm beds revealed increasing cell metabolic activity for BSA with increasing bilayers. Micropatterned multilayer beds having poly-L-lysine, poly-D-lysine, laminin poly(dimethyldiallyl-ammonium chloride) and poly(ethyleneimine) as the terminating layers were fabricated using the Layer-by-layer Lift-off (LbL-LO) method that combines photolithography and LbL self-assembly. Most importantly, micropatterned co-culture platforms consisting of anti-CD 44 rat monoclonal and anti-rat osteopontin (MPIIIB101) antibodies were constructed using the LbL-LO method for the first time. These co-culture platforms have several applications especially for studies of stem and progenitor cells. Co-culture platforms exhibiting spatiotempora-based differentiation can be built with LbL-LO for the differentiation of stem cells into the desired cell lineage.

Preparation of graphene foam with high performance by modified self-assembly method

NASA Astrophysics Data System (ADS)

Zhang, Wenhui; Sun, Youyi; Liu, Tantan; Li, Diansen; Hou, Chunlin; Gao, Li; Liu, Yaqing

2016-03-01

Recently, self-assembly method was applied for preparation of graphene foam. However, it is still a great challenge to obtain a three-dimensional graphene network with high performance (e.g., low density, high mechanical strength and high conductivity together) for the self-assembly method. Herein, a modified self-assembly method applied for preparation of graphene foam was investigated, in which, L-ascorbic acid and HI were firstly chosen as the reducing agent, and further reduced by hydrazine hydrate. The results demonstrated that the graphene foam showed high compressive strength (ca. 320 kPa), high electrical conductivity (20.6 S/m) and low density (14.7 mg/cm-1). Especially, the obtained compressive strength (ca. 320 kPa) is the highest value compared to the data of graphene foam reported in previous works. This phenomenon may be due to following three reasons: (1) the reaction between hydrazine hydrate and graphene brought some covalent bonds among graphene sheets; (2) graphene foam was achieved by high hydrophobicity and electrostatic repulsion which inhibit the restacking of graphene sheets; (3) the removal of the oxygen groups by hydrazine hydrate efficiently restores conjugation of sp2 regions and the π-π interaction in the cross-linking sites, which tightly bonds the sheets together. The obtained graphene foam not only had good porous structure and mechanical strength, but also showed excellent satisfactory double-layer capacitive behavior with good electrochemical cyclic stability and high specific capacitance of 171.0 F/g for application in electrode of supercapacitors and absorption capacities for the removal of various oils and dyes from water.

Reassembly of S-layer proteins

NASA Astrophysics Data System (ADS)

Pum, Dietmar; Sleytr, Uwe B.

2014-08-01

Crystalline bacterial cell surface layers (S-layers) represent the outermost cell envelope component in a broad range of bacteria and archaea. They are monomolecular arrays composed of a single protein or glycoprotein species and represent the simplest biological membranes developed during evolution. They are highly porous protein mesh works with unit cell sizes in the range of 3 to 30 nm, and pore sizes of 2 to 8 nm. S-layers are usually 5 to 20 nm thick (in archaea, up to 70 nm). S-layer proteins are one of the most abundant biopolymers on earth. One of their key features, and the focus of this review, is the intrinsic capability of isolated native and recombinant S-layer proteins to form self-assembled mono- or double layers in suspension, at solid supports, the air-water interface, planar lipid films, liposomes, nanocapsules, and nanoparticles. The reassembly is entropy-driven and a fascinating example of matrix assembly following a multistage, non-classical pathway in which the process of S-layer protein folding is directly linked with assembly into extended clusters. Moreover, basic research on the structure, synthesis, genetics, assembly, and function of S-layer proteins laid the foundation for their application in novel approaches in biotechnology, biomimetics, synthetic biology, and nanotechnology.

Preparation of novel stable antibacterial nanoparticles using hydroxyethylcellulose and application in paper.

PubMed

Wei, Dafu; Chen, Yan; Zhang, Youwei

2016-01-20

Taking advantage of the self-assembly between the components, novel stable antibacterial nanoparticles were efficiently fabricated via a facile one-step co-polymerization of acrylic acid (AA) and N,N'-methylenebisacrylamide (MBA) on a mixed aqueous solution of poly(hexamethylene guanidine hydrochloride) (PHMG) and hydroxyethylcellulose (HEC). The z-average hydrodynamic diameters of the nanoparticles ranged from 220 nm to 450 nm. The inner layer of the nanoparticles is composed of water-insoluble interpolymer complexes of PHMG and PAA networks, while the outer layer is composed of PHMG and HEC. The nanoparticles are stabilized by electrostatic interactions, hydrogen bonding interactions, and the chemical bonds. The nanoparticle solution remained stable in a wide pH range of 2.0-12.0 and at salt concentrations below 0.25 mol/L. The nanoparticles were incorporated into handsheets using a dipping treatment. The resulted handsheets exhibited excellent antimicrobial activities even after multiple water washing treatments. The nanoparticles are promising in fabricating paper, water-based coatings and textiles with permanent antibacterial activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Self-Assembled Layered Supercell Structure of Bi2AlMnO6 with Strong Room-Temperature Multiferroic Properties.

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

Li, Leigang; Boullay, Philippe; Lu, Ping

2017-02-01

Room-temperature (RT) multiferroics, possessing ferroelectricity and ferromagnetism simultaneously at RT, hold great promise in miniaturized devices including sensors, actuators, transducers, and multi-state memories. In this work, we report a novel 2D layered RT multiferroic system with self-assembled layered supercell structure consisting of two mismatch-layered sub-lattices of [Bi 3O 3+δ] and [MO 2] 1.84 (M=Al/Mn, simply named as BAMO), i.e., alternative layered stacking of two mutually incommensurate sublattices made of a three-layer-thick Bi-O slab and a one-layer-thick Al/Mn-O octahedra slab along the out-of-plane direction. Strong room-temperature multiferroic responses, e.g., ferromagnetic and ferroelectric properties, have been demonstrated and attributed to the highlymore » anisotropic 2D nature of the non-ferromagnetic and ferromagnetic sublattices which are highly mismatched. The work demonstrates an alternative design approach for new 2D layered oxide materials that hold promises as single-phase multiferroics, 2D oxides with tunable bandgaps, and beyond.« less

Layer-by-layer self-assembled graphene oxide/silica microsphere composites as stationary phase for high performance liquid chromatography.

PubMed

Liang, Xiaojing; Liu, Shujuan; Song, Xinwang; Zhu, Yangwen; Jiang, Shengxiang

2012-11-21

Graphene oxide (GO) has been layer-by-layer assembled onto silica microspheres to form a GO/SiO(2) composite stationary phase. All the characterizations of GO/SiO(2) by elemental analysis, Raman spectroscopy and Fourier transformed infrared spectrometry confirmed that with the increase of the assembled layer, GO gradually increases on the silica surface. The chromatographic properties of bare SiO(2) and GO/SiO(2) with different GO assembled layers show that the amount of GO plays an important role in the separation of analytes. Only the appropriate amount of GO on SiO(2) can perform a good chromatographic separation. The comparison between chromatographic performances of bare SiO(2) column, GO/SiO(2)-2 column and C18 commercial column clearly show that GO/SiO(2)-2 and C18 columns obtained a better separation; GO/SiO(2)-2 exhibits a large π-electron system and C18 exhibits hydrophobicity. The eluting order, peak width and resolution of analyte on GO/SiO(2)-2 column was highly dependent on the size of its π-electron system, while on the C18 column the decisive factor is its hydrophobic property.

Self-assembly and continuous growth of hexagonal graphene flakes on liquid Cu

NASA Astrophysics Data System (ADS)

Cho, Seong-Yong; Kim, Min-Sik; Kim, Minsu; Kim, Ki-Ju; Kim, Hyun-Mi; Lee, Do-Joong; Lee, Sang-Hoon; Kim, Ki-Bum

2015-07-01

Graphene growth on liquid Cu has received great interest, owing to the self-assembly behavior of hexagonal graphene flakes with aligned orientation and to the possibility of forming a single grain of graphene through a commensurate growth of these graphene flakes. Here, we propose and demonstrate a two-step growth process which allows the formation of self-assembled, completely continuous graphene on liquid Cu. After the formation of full coverage on the liquid Cu, grain boundaries were revealed via selective hydrogen etching and the original grain boundaries were clearly resolved. This result indicates that, while the flakes self-assembled with the same orientation, there still remain structural defects, gaps and voids that were not resolved by optical microscopy or scanning electron microscopy. To overcome this limitation, the two-step growth process was employed, consisting of a sequential process of a normal single-layer graphene growth and self-assembly process with a low carbon flux, followed by the final stage of graphene growth at a high degree of supersaturation with a high carbon flux. Continuity of the flakes was verified via hydrogen etching and a NaCl-assisted oxidation process, as well as by measuring the electrical properties of the graphene grown by the two-step process. Two-step growth can provide a continuous graphene layer, but commensurate stitching should be further studied.Graphene growth on liquid Cu has received great interest, owing to the self-assembly behavior of hexagonal graphene flakes with aligned orientation and to the possibility of forming a single grain of graphene through a commensurate growth of these graphene flakes. Here, we propose and demonstrate a two-step growth process which allows the formation of self-assembled, completely continuous graphene on liquid Cu. After the formation of full coverage on the liquid Cu, grain boundaries were revealed via selective hydrogen etching and the original grain boundaries were clearly resolved. This result indicates that, while the flakes self-assembled with the same orientation, there still remain structural defects, gaps and voids that were not resolved by optical microscopy or scanning electron microscopy. To overcome this limitation, the two-step growth process was employed, consisting of a sequential process of a normal single-layer graphene growth and self-assembly process with a low carbon flux, followed by the final stage of graphene growth at a high degree of supersaturation with a high carbon flux. Continuity of the flakes was verified via hydrogen etching and a NaCl-assisted oxidation process, as well as by measuring the electrical properties of the graphene grown by the two-step process. Two-step growth can provide a continuous graphene layer, but commensurate stitching should be further studied. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03352g

Self-assembled metal nano-multilayered film prepared by co-sputtering method

NASA Astrophysics Data System (ADS)

Xie, Tianle; Fu, Licai; Qin, Wen; Zhu, Jiajun; Yang, Wulin; Li, Deyi; Zhou, Lingping

2018-03-01

Nano-multilayered film is usually prepared by the arrangement deposition of different materials. In this paper, a self-assembled nano-multilayered film was deposited by simultaneous sputtering of Cu and W. The Cu/W nano-multilayered film was accumulated by W-rich layer and Cu-rich layer. Smooth interfaces with consecutive composition variation and semi-coherent even coherent relationship were identified, indicating that a spinodal-like structure with a modulation wavelength of about 20 nm formed during co-deposition process. The participation of diffusion barrier element, such as W, is believed the essential to obtain the nano-multilayered structure besides the technological parameters.

Study of electrostatically self-assembled thin films of CdS and ZnS nanoparticle semiconductors

NASA Astrophysics Data System (ADS)

Suryajaya

In this work, CdS and ZnS semiconducting colloid nanoparticles coated with organic shell, containing either SO[3-] or NH[2+] groups, were deposited as thin films using the technique of electrostatic self-assembly. The films produced were characterized with UV-vis spectroscopy and spectroscopic ellipsometry - for optical properties; atomic force microscopy (AFM) - for morphology study; mercury probe - for electrical characterisation; and photon counter - for electroluminescence study. UV-vis spectra show a substantial blue shift of the main absorption band of both CdS and ZnS, either in the form of solutions or films, with respect to the bulk materials. The calculation of nanoparticles' radii yields the value of about 1.8 nm for both CdS and ZnS.The fitting of standard ellipsometry data gave the thicknesses (d) of nanoparticle layers of around 5 nm for both CdS and ZnS which corresponds well to the size of particles evaluated from UV-vis spectral data if an additional thickness of the organic shell is taken into account. The values of refractive index (n) and extinction coefficient (k) obtained were about 2.28 and 0.7 at 633 nm wavelength, for both CdS and ZnS.Using total internal reflection (TIRE), the process of alternative deposition of poly-allylamine hydrochloride (PAH) and CdS (or ZnS) layers could be monitored in-situ. The dynamic scan shows that the adsorption kinetic of the first layer of PAH or nanoparticles was slower than that of the next layer. The fitting of TIRE spectra gavethicknesses of about 7 nm and 12 nm for CdS and ZnS, respectively. It supports the suggestion of the formation of three-dimensional aggregates of semiconductor nanoparticles intercalated with polyelectrolyte.AFM images show the formation of large aggregates of nanoparticles, about 40-50 nm, for the films deposited from original colloid solutions, while smaller aggregates, about 12-20 nm, were obtained if the colloid solutions were diluted.Current-voltage (I-V) and capacitance-frequency (C-f) measurements of polyelectrolyte/nanoparticles (CdS or ZnS) films suggest the tunnelling behaviour in the films while capacitance- voltage (C-V) and conductance-voltage (G-V) measurements suggest that these nanoparticles are conductive. The electroluminescence was detected in sandwich structures of (PAH/CdS/PAH)[N] using a photon counting detector, but not in the case of ZnS films.

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

NASA Astrophysics Data System (ADS)

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

2013-11-01

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

Shrink-induced graphene sensor for alpha-fetoprotein detection with low-cost self-assembly and label-free assay

NASA Astrophysics Data System (ADS)

Sando, Shota; Zhang, Bo; Cui, Tianhong

2017-12-01

Combination of shrink induced nano-composites technique and layer-by-layer (LbL) self-assembled graphene challenges controlling surface morphology. Adjusting shrink temperature achieves tunability on graphene surface morphology on shape memory polymers, and it promises to be an alternative in fields of high-surface-area conductors and molecular detection. In this study, self-assembled graphene on a shrink polymer substrate exhibits nanowrinkles after heating. Induced nanowrinkles on graphene with different shrink temperature shows distinct surface roughness and wettability. As a result, it becomes more hydrophilic with higher shrink temperatures. The tunable wettability promises to be utilized in, for example, microfluidic devices. The graphene on shrink polymer also exhibits capability of being used in sensing applications for pH and alpha-fetoprotein (AFP) detection with advantages of label free and low cost, due to self-assembly technique, easy functionalization, and antigen-antibody reaction on graphene surface. The detection limit of AFP detection is down to 1 pg/mL, and therefore the sensor also has a significant potential for biosensing as it relies on low-cost self-assembly and label-free assay.

Real time analysis of self-assembled InAs/GaAs quantum dot growth by probing reflection high-energy electron diffraction chevron image

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

Kudo, Takuya; Inoue, Tomoya; Kita, Takashi

2008-10-01

Self-assembling process of InAs/GaAs quantum dots has been investigated by analyzing reflection high-energy electron diffraction chevron images reflecting the crystal facet structure surrounding the island. The chevron image shows dramatic changes during the island formation. From the temporal evolution of the chevron tail structure, the self-assembling process has been found to consist of four steps. The initial islands do not show distinct facet structures. Then, the island surface is covered by high-index facets, and this is followed by the formation of stable low-index facets. Finally, the flow of In atoms from the islands occurs, which contributes to flatten the wettingmore » layer. Furthermore, we have investigated the island shape evolution during the GaAs capping layer growth by using the same real-time analysis technique.« less

Superhydrophobic and transparent coatings prepared by self-assembly of dual-sized silica particles

NASA Astrophysics Data System (ADS)

Xu, Qian-Feng; Wang, Jian-Nong

2010-06-01

Superhydrophobic and transparent coatings have been prepared by self-assembly of dual-sized silica particles from a mixed dispersion. The desirable micro/nano hierarchical structure for superhydrophobicity is constructed simply by adjusting the size and ratio of the dual-sized particles without organic/inorganic templates. The transparency of the prepared coatings is also researched, and the light scattering can be reduced by lowering the ratio of big sub-micro particles while the superhydrophobicity maintains unchanged. When nano particles with a diameter of 50 nm and sub-micro particles with a diameter of 350 nm are assembled, a superhydrophobic property with a water contact angle of 161° is achieved. Additionally, the coated glass is also very transparent. The highest transmittance of the coated glass can reach 85%. Compared to traditional colloid self-assembly approach, which often involves dozens of steps of layer-by-layer processing and organic/inorganic templates, the present approach is much simpler and has advantages for large-scale coating.

Sheet-like assemblies of spherical particles with point-symmetrical patches.

PubMed

Mani, Ethayaraja; Sanz, Eduardo; Roy, Soumyajit; Dijkstra, Marjolein; Groenewold, Jan; Kegel, Willem K

2012-04-14

We report a computational study on the spontaneous self-assembly of spherical particles into two-dimensional crystals. The experimental observation of such structures stabilized by spherical objects appeared paradoxical so far. We implement patchy interactions with the patches point-symmetrically (icosahedral and cubic) arranged on the surface of the particle. In these conditions, preference for self-assembly into sheet-like structures is observed. We explain our findings in terms of the inherent symmetry of the patches and the competition between binding energy and vibrational entropy. The simulation results explain why hollow spherical shells observed in some Keplerate-type polyoxometalates (POM) appear. Our results also provide an explanation for the experimentally observed layer-by-layer growth of apoferritin--a quasi-spherical protein.

Trapping effect of metal nanoparticle mono- and multilayer in the organic field-effect transistor

NASA Astrophysics Data System (ADS)

Lee, Keanchuan; Weis, Martin; Lin, Jack; Taguchi, Dai; Majková, Eva; Manaka, Takaaki; Iwamoto, Mitsumasa

2011-03-01

The effect of silver nanoparticles self-assembled monolayer (Ag NPs SAM) on charge transport in pentacene organic field-effect transistors (OFET) was investigated by both steady-state and transient-state methods, which are current-voltage measurements in steady-state and time-resolved microscopic (TRM) second harmonic generation (SHG) in transient-state, respectively. The analysis of electronic properties revealed that OFET with SAM exhibited significant charge trapping effect due to the space-charge field formed by immobile charges. Lower transient-state mobility was verified by the direct probing of carrier motion by TRM-SHG technique. It was shown that the trapping effect rises together with increase of SAM layers suggesting the presence of traps in the bulk of NP films. The model based on the electrostatic charge barrier is suggested to explain the phenomenon.

Robust, flexible, and bioadhesive free-standing films for the co-delivery of antibiotics and growth factors.

PubMed

Chen, Dongdong; Wu, Mingda; Chen, Jie; Zhang, Chunqiu; Pan, Tiezheng; Zhang, Bing; Tian, Huayu; Chen, Xuesi; Sun, Junqi

2014-11-25

Free-standing polymer films that adhere strongly to tissue and can codeliver multiple therapeutic agents in a controlled manner are useful as medical plasters. In this study, a bilayer polymer film comprising a drug reservoir layer and a supporting layer is fabricated by spin-coating poly(lactic-co-glycolic acid) (PLGA) on top of a layer-by-layer assembled film of poly(β-amino esters) (PAE), alginate sodium (ALG), and recombinant human basic fibroblast growth factor (bFGF). Apart from bFGF, the bilayer film can also load antibiotic drug ceftriaxone sodium (CTX) by a postdiffusion process. The PLGA supporting layer facilitates the direct peeling of the bilayer film from substrate to produce a robust and flexible free-standing film with excellent adhesion onto the human skin and porcine liver. The excellent adhesion of the bilayer film originates from the ALG component in the drug reservoir layer. CTX is quickly released by easily breaking its electrostatic interaction with the drug reservoir layer, whereas the sustained release of bFGF is due to the slow degradation of PAE component in the drug reservoir layer. Wounds can be synergetically treated by fast release of CTX to effectively eradicate invasive bacteria and by sustained release of bFGF to accelerate wound healing. Our results serve as a basis for designing multifunctional free-standing films with combination therapy for biomedical applications.

Polyelectrolyte multilayer assembly as a function of pH and ionic strength using the polysaccharides chitosan and heparin.

PubMed

Boddohi, Soheil; Killingsworth, Christopher E; Kipper, Matt J

2008-07-01

The goal of this work is to explore the effects of solution ionic strength and pH on polyelectrolyte multilayer (PEM) assembly, using biologically derived polysaccharides as the polyelectrolytes. We used the layer-by-layer (LBL) technique to assemble PEM of the polysaccharides heparin (a strong polyanion) and chitosan (a weak polycation) and characterized the sensitivity of the PEM composition and layer thickness to changes in processing parameters. Fourier-transform surface plasmon resonance (FT-SPR) and spectroscopic ellipsometry provided in situ and ex situ measurements of the PEM thickness, respectively. Vibrational spectroscopy and X-ray photoelectron spectroscopy (XPS) provided details of the chemistry (i.e., composition, electrostatic interactions) of the PEM. We found that when PEM were assembled from 0.2 M buffer, the PEM thickness could be increased from less than 2 nm per bilayer to greater than 4 nm per bilayer by changing the solution pH; higher and lower ionic strength buffer solutions resulted in narrower ranges of accessible thickness. Molar composition of the PEM was not very sensitive to solution pH or ionic strength, but pH did affect the interactions between the sulfonates in heparin and amines in chitosan when PEM were assembled from 0.2 M buffer. Changes in the PEM thickness with pH and ionic strength can be interpreted through descriptions of the charge density and conformation of the polyelectrolyte chains in solution.

From 1D Polymers to 2D Polymers: Preparation of Free-Standing Single-Monomer-Thick Two-Dimensional Conjugated Polymers in Water.

PubMed

Zhang, Na; Wang, Taisheng; Wu, Xing; Jiang, Chen; Zhang, Taiming; Jin, Bangkun; Ji, Hengxing; Bai, Wei; Bai, Ruke

2017-07-25

Recently, investigation on two-dimensional (2D) organic polymers has made great progress, and conjugated 2D polymers already play a dynamic role in both academic and practical applications. However, a convenient, noninterfacial approach to obtain single-layer 2D polymers in solution, especially in aqueous media, remains challenging. Herein, we present a facile, highly efficient, and versatile "1D to 2D" strategy for preparation of free-standing single-monomer-thick conjugated 2D polymers in water without any aid. The 2D structure was achieved by taking advantage of the side-by-side self-assembly of a rigid amphiphilic 1D polymer and following topochemical photopolymerization in water. The spontaneous formation of single-layer polymer sheets was driven by synergetic association of the hydrophobic interactions, π-π stacking interactions, and electrostatic repulsion. Both the supramolecular sheets and the covalent sheets were confirmed by spectroscopic analyses and electron microscope techniques. Moreover, in comparison of the supramolecular 2D polymer, the covalent 2D polymer sheets exhibited not only higher mechanical strength but also higher conductivity, which can be ascribed to the conjugated network within the covalent 2D polymer sheets.

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.

Periodic nanoscale patterning of polyelectrolytes over square centimeter areas using block copolymer templates

DOE PAGES

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

2016-04-07

Nano-patterned materials are beneficial for applications such as solar cells, opto-electronics, and sensing owing to their periodic structure and high interfacial area. We present a non-lithographic approach for assembling polyelectrolytes into periodic nanoscale patterns over cm 2 -scale areas. We used chemically modified block copolymer thin films featuring alternating charged and neutral domains as patterned substrates for electrostatic self-assembly. In-depth characterization of the deposition process using spectroscopy and microscopy techniques, including the state-of-the-art scanning transmission X-ray microscopy (STXM), reveals both the selective deposition of the polyelectrolyte on the charged copolymer domains as well as gradual changes in the film topographymore » that arise from further penetration of the solvent molecules and possibly also the polyelectrolyte into these domains. Our results demonstrate the feasibility of creating nano-patterned polyelectrolyte layers, which opens up new opportunities for structured functional coating fabrication.« less

Spatial and directional control of self-assembled wrinkle patterns by UV light absorption

NASA Astrophysics Data System (ADS)

Kortz, C.; Oesterschulze, E.

2017-12-01

Wrinkle formation on surfaces is a phenomenon that is observed in layered systems with a compressed elastic thin capping layer residing on a viscoelastic film. So far, the properties of the viscoelastic material could only be changed replacing it by another material. Here, we propose to use a photosensitive material whose viscoelastic properties, Young's modulus, and glass transition temperature can easily be adjusted by the absorption of UV light. Employing UV lithography masks during the exposure, we gain additionally spatial and directional control of the self-assembled wrinkle pattern formation that relies on a spinodal decomposition process. Inspired by the results on surface wrinkling and its dependence on the intrinsic stress, we also derive a method to avoid wrinkling locally by tailoring the mechanical stress distribution in the layered system choosing UV masks with convex patterns. This is of particular interest in technical applications where the buckling of surfaces is undesirable.

Immobilization of Superoxide Dismutase on Polyelectrolyte-Functionalized Titania Nanosheets.

PubMed

Rouster, Paul; Pavlovic, Marko; Szilagyi, Istvan

2018-02-16

The superoxide dismutase (SOD) enzyme was successfully immobilized on titania nanosheets (TNS) functionalized with the poly(diallyldimethylammonium chloride) (PDADMAC) polyelectrolyte. The TNS-PDADMAC solid support was prepared by hydrothermal synthesis followed by self-assembled polyelectrolyte layer formation. It was found that SOD strongly adsorbed onto oppositely charged TNS-PDADMAC through electrostatic and hydrophobic interactions. The TNS-PDADMAC-SOD material was characterized by light scattering and microscopy techniques. Colloidal stability studies revealed that the obtained nanocomposites possessed good resistance against salt-induced aggregation in aqueous suspensions. The enzyme kept its functional integrity upon immobilization; therefore, TNS-PDADMAC-SOD showed excellent superoxide radical anion scavenging activity. The developed system is a promising candidate for applications in which suspensions of antioxidant activity are required in the manufacturing processes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Air Force Journal of Logistics. Volume 35, Numbers 1 and 2. Spring/Summer 2011

DTIC Science & Technology

2011-01-01

be used for integration into two layers of the suit. The outer layer could self - heal if punctured and the inner layer could monitor vital signs and...nanoscale robotics , the possibility of another nanotechnology Holy Grail, self -assembly, comes closer to reality. Professor Carlo Montemagno, of the...exploitation. Genetics, robotics , information technology, and nanotechnology are truly transformative technologies with the potential to impact national

Characterization of stable, electroactive protein cage/synthetic polymer multilayer thin films prepared by layer-by-layer assembly

NASA Astrophysics Data System (ADS)

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

2013-04-01

We have fabricated electroactive multilayer thin films containing ferritin protein cages. The multilayer thin films were prepared on a solid substrate by the alternate electrostatic adsorption of (apo)ferritin and poly( N-isopropylacrylamide- co-2-carboxyisopropylacrylamide) (NIPAAm- co-CIPAAm) in pH 3.5 acetate buffer solution. The assembly process was monitored using a quartz crystal microbalance. The (apo)ferritin/poly(NIPAAm- co-CIPAAm) multilayer thin films were then cross-linked using a water-soluble carbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide. The cross-linked films were stable under a variety of conditions. The surface morphology and thickness of the multilayer thin films were characterized by atomic force microscopy, and the ferritin iron cores were observed by scanning electron microscopy to confirm the assembly mechanism. Cyclic voltammetry measurements showed different electrochemical properties for the cross-linked ferritin and apoferritin multilayer thin films, and the effect of stability of the multilayer film on its electrochemical properties was also examined. Our method for constructing multilayer films containing protein cages is expected to be useful in building more complex functional inorganic nanostructures.

Self-Assembled Nanoporous Biofilms from Functionalized Nanofibrous M13 Bacteriophage.

PubMed

Devaraj, Vasanthan; Han, Jiye; Kim, Chuntae; Kang, Yong-Cheol; Oh, Jin-Woo

2018-06-12

Highly periodic and uniform nanostructures, based on a genetically engineered M13 bacteriophage, displayed unique properties at the nanoscale that have the potential for a variety of applications. In this work, we report a multilayer biofilm with self-assembled nanoporous surfaces involving a nanofiber-like genetically engineered 4E-type M13 bacteriophage, which was fabricated using a simple pulling method. The nanoporous surfaces were effectively formed by using the networking-like structural layers of the M13 bacteriophage during self-assembly. Therefore, an external template was not required. The actual M13 bacteriophage-based fabricated multilayered biofilm with porous nanostructures agreed well with experimental and simulation results. Pores formed in the final layer had a diameter of about 150⁻500 nm and a depth of about 15⁻30 nm. We outline a filter application for this multilayered biofilm that enables selected ions to be extracted from a sodium chloride solution. Here, we describe a simple, environmentally friendly, and inexpensive fabrication approach with large-scale production potential. The technique and the multi-layered biofilms produced may be applied to sensor, filter, plasmonics, and bio-mimetic fields.

Quantized Self-Assembly of Discotic Rings in a Liquid Crystal Confined in Nanopores

NASA Astrophysics Data System (ADS)

Sentker, Kathrin; Zantop, Arne W.; Lippmann, Milena; Hofmann, Tommy; Seeck, Oliver H.; Kityk, Andriy V.; Yildirim, Arda; Schönhals, Andreas; Mazza, Marco G.; Huber, Patrick

2018-02-01

Disklike molecules with aromatic cores spontaneously stack up in linear columns with high, one-dimensional charge carrier mobilities along the columnar axes, making them prominent model systems for functional, self-organized matter. We show by high-resolution optical birefringence and synchrotron-based x-ray diffraction that confining a thermotropic discotic liquid crystal in cylindrical nanopores induces a quantized formation of annular layers consisting of concentric circular bent columns, unknown in the bulk state. Starting from the walls this ring self-assembly propagates layer by layer towards the pore center in the supercooled domain of the bulk isotropic-columnar transition and thus allows one to switch on and off reversibly single, nanosized rings through small temperature variations. By establishing a Gibbs free energy phase diagram we trace the phase transition quantization to the discreteness of the layers' excess bend deformation energies in comparison to the thermal energy, even for this near room-temperature system. Monte Carlo simulations yielding spatially resolved nematic order parameters, density maps, and bond-orientational order parameters corroborate the universality and robustness of the confinement-induced columnar ring formation as well as its quantized nature.

Applying AFM-based nanofabrication for measuring the thickness of nanopatterns: the role of head groups in the vertical self-assembly of omega-functionalized n-alkanethiols.

PubMed

Kelley, Algernon T; Ngunjiri, Johnpeter N; Serem, Wilson K; Lawrence, Steve O; Yu, Jing-Jiang; Crowe, William E; Garno, Jayne C

2010-03-02

Molecules of n-alkanethiols with methyl head groups typically form well-ordered monolayers during solution self-assembly for a wide range of experimental conditions. However, we have consistently observed that, for either carboxylic acid or thiol-terminated n-alkanethiols, under certain conditions nanografted patterns are generated with a thickness corresponding precisely to a double layer. To investigate the role of head groups for solution self-assembly, designed patterns of omega-functionalized n-alkanethiols were nanografted with systematic changes in concentration. Nanografting is an in situ approach for writing patterns of thiolated molecules on gold surfaces by scanning with an AFM tip under high force, accomplished in dilute solutions of desired ink molecules. As the tip is scanned across the surface of a self-assembled monolayer under force, the matrix molecules are displaced from the surface and are immediately replaced with fresh molecules from solution to generate nanopatterns. In this report, side-by-side comparison of nanografted patterns is achieved for different matrix molecules using AFM images. The chain length and head groups (i.e., carboxyl, hydroxyl, methyl, thiol) were varied for the nanopatterns and matrix monolayers. Interactions such as head-to-head dimerization affect the vertical self-assembly of omega-functionalized n-alkanethiol molecules within nanografted patterns. At certain threshold concentrations, double layers were observed to form when nanografting with head groups of carboxylic acid and dithiols, whereas single layers were generated exclusively for nanografted patterns with methyl and hydroxyl groups, regardless of changes in concentration.

Extending the Diffuse Layer Model of Surface Acidity Constant Behavior: IV. Diffuse Layer Charge/Potential Relationships

EPA Science Inventory

Most current electrostatic surface complexation models describing ionic binding at the particle/water interface rely on the use of Poisson - Boltzmann (PB) theory for relating diffuse layer charge densities to diffuse layer electrostatic potentials. PB theory is known to contain ...

Self-assembling siloxane bilayer directly on SiO2 surface of micro-cantilevers for long-term highly repeatable sensing to trace explosives.

PubMed

Chen, Ying; Xu, Pengcheng; Li, Xinxin

2010-07-02

This paper presents a novel sensing layer modification technique for static micro-cantilever sensors that detect trace explosives by measuring specific adsorption-induced surface stress. For the first time, a method of directly modifying a siloxane sensing bilayer on an SiO(2) surface is proposed to replace the conventional self-assembled monolayers (SAMs) of thiols on Au to avoid the trouble from long-term unstable Au-S bonds. For modifying the long-term reliable sensing bilayer on the piezoresistor-integrated micro-cantilevers, a siloxane-head bottom layer is self-assembled directly on the SiO(2) cantilever surface, which is followed by grafting another explosive-sensing-group functionalized molecule layer on top of the siloxane layer. The siloxane-modified sensor has experimentally exhibited a highly resoluble response to 0.1 ppb TNT vapor. More importantly, the repeated detection results after 140 days show no obvious attenuation in sensing signal. Also observed experimentally, the specific adsorption of the siloxane sensing bilayer to TNT molecules causes a tensile surface stress on the cantilever. Herein the measured tensile surface stress is in contrast to the compressive surface stress normally measured from conventional cantilever sensors where the sensitive thiol-SAMs are modified on an Au surface. The reason for this newly observed phenomenon is discussed and preliminarily analyzed.

Biosensor Based on Self-Assembling Acetylcholinesterase on Carbon Nanotubes for Flow injection/Amperometric Detection of Organophosphate Pesticides and Nerve Agents

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

Liu, Guodong; Lin, Yuehe

A highly sensitive flow-injection amperometric biosensor for organophosphate pesticides and nerve agents based on self-assembly of acetylcholinesterase (AChE) on carbon nanotube (CNT)-modified glassy carbon (GC) electrode is described. AChE is immobilized on the negatively-charged CNT surface by alternatively assembling a cationic polydiallyldimethylammonium chloride (PDDA) layer and an AChE layer. Transmission electron microscopy images confirm the formation of layer-by-layer nanostructures on carboxyl functionalized CNTs. The unique sandwich-like structure (PDDA/AChE/PDDA) on the CNT surface formed by self-assembly provides a favorable microenvironment to keep the bioactivity of AChE and to prevent enzyme molecule leakage. The electrocatalytic activity of CNT leads to a greatlymore » improved electrochemical detection of the enzymatically generated thiocholine product, including a low oxidation overvoltage (+150 mV), higher sensitivity, and stability. The developed PDDA/AChE/PDDA/CNT/GC biosensor integrated into a flow injection system was used to monitor organophosphate pesticides and nerve agents, such as paraoxon. The sensor performance, including inhibition time and regeneration conditions, was optimized with respect to operating conditions. Under the optimal conditions, the biosensor was used to measure as low as 0.4 pM paraoxon with a 6-min inhibition time. The biosensor had excellent operational lifetime stability with no decrease in the activity of enzymes for more than 20 repeated measurements over a 1-week period. The developed biosensor system is an ideal tool for online monitoring of organophosphate pesticides and nerve agents.« less

Self-assembling of 2,3-phenyl/thienyl-substituted acrylic acids over polycrystalline gold

NASA Astrophysics Data System (ADS)

Csankó, K.; Kozma, G.; Valkai, L.; Kukovecz, Á.; Kónya, Z.; Sipos, P.; Pálinkó, I.

2013-07-01

Self-assembling layers were formed from sulfur-containing cinnamic acid analogues over polycrystalline Au surface. The horizontal organising forces were strong O-H⋯O and weaker C-H⋯S hydrogen bonds (the former interaction kept together the acid dimers serving as the fundamental unit, while the latter was crucial in the construction of the 2D layers), while the vertical organisation forces were provided by Au-S covalent bonds. Measurements by atomic force, scanning electron, infrared and Raman microscopies attested that the dimers were situated in a nearly perpendicular fashion to the Au surface providing a ˜30-40 nm thick organic "carpet" and out of this layer occasionally, peaks with height of ˜100-120 nm grew out. The outgrowth of these surface structures were most probably governed by the defects of the polycrystalline metal surface.

Transparent 1T-MoS2 nanofilm robustly anchored on substrate by layer-by-layer self-assembly and its ultra-high cycling stability as supercapacitors

NASA Astrophysics Data System (ADS)

Li, Danqin; Zhou, Weiqiang; Zhou, Qianjie; Ye, Guo; Wang, Tongzhou; Wu, Jing; Chang, Yanan; Xu, Jingkun

2017-09-01

Two-dimensional MoS2 materials have attracted more and more interest and been applied to the field of energy storage because of its unique physical, optical, electronic and electrochemical properties. However, there are no reports on high-stable transparent MoS2 nanofilms as supercapacitors electrode. Here, we describe a transparent 1T-MoS2 nanofilm electrode with super-long stability anchored on the indium tin oxide (ITO) glass by a simple alternate layer-by-layer (LBL) self-assembly of a highly charged cationic poly(diallyldimethylammonium chloride) (PDDA) and negative single-/few-layer 1T MoS2 nanosheets. The ITO/(PDDA/MoS2)20 electrode shows a transmittance of 51.6% at 550 nm and obviously exhibits excellent transparency by naked eye observation. Ultrasonic damage test validates that the (PDDA/MoS2)20 film with the average thickness about 50 nm is robustly anchored on ITO substrate. Additionally, the electrochemical results indicate that the ITO/(PDDA/MoS2)20 film shows areal capacitance of 1.1 mF cm-2 and volumetric capacitance of 220 F cm-3 at 0.04 mA cm-2, 130.6% retention of the original capacitance value after 5000 cycles. Further experiments indicate that the formation of transparent (PDDA/MoS2) x nanofilm by LBL self-assembly can be extended to other substrates, e.g., slide glass and flexible polyethylene terephthalate (PET). Thus, the easily available (PDDA/MoS2) x nanofilm electrode has great potential for application in transparent and/or flexible optoelectronic and electronics devices.

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.

Polyethylenimine/kappa carrageenan: Micro-arc oxidation coating for passivation of magnesium alloy.

PubMed

Golshirazi, A; Kharaziha, M; Golozar, M A

2017-07-01

The aim of this study was to combine micro-arc oxidation (MAO) and self-assembly technique to improve corrosion resistivity of AZ91 alloy. While a silicate-fluoride electrolyte was adopted for MAO treatment, polyethylenimine (PEI)/kappa carrageenan (KC) self-assembly coating was applied as the second coating layer. Resulted demonstrated the formation of forsterite-fluoride containing MAO coating on AZ91 alloy depending on the voltage and time of anodizing process. Addition of the second PEI/KC coating layer on MAO treated sample effectively enhanced the adhesive strength of MAO coated sample due to filling the pores with polymers and increase in the mechanical interlocking of coating to the substrate. Moreover, the corrosion evaluation considered by potentiodynamic polarization and electrochemical impedance spectroscopy confirmed that double layered PEI/KC:MAO coating presented superior resistance to corrosion attack. It is envisioned that the proposed double layered PEI/KC:MAO coating could be useful for biomedical applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Starch-based nanocapsules fabricated through layer-by-layer assembly for oral delivery of protein to lower gastrointestinal tract.

PubMed

Zhang, Yiping; Chi, Chengdeng; Huang, Xiaoyi; Zou, Qin; Li, Xiaoxi; Chen, Ling

2017-09-01

Anionic carboxymethyl starch (CMS) and cationic quaternary ammonium starch (QAS), were used to fabricate nanocapsules through electrostatic layer by layer (LbL) alternate deposition onto colloidal BSA particles. An ideal starch-based colloidal nanocapsule was achieved by adjusting the degree of substitution (DS) and weight average molecular molar mass (M w ) of CMS. The nanocapsules fabricated by CMS with lower DS or M w possessed more compact and stable core-shell structure, which favoured the BSA delivery from the upper gastrointestinal tract (GIT) to the colon. In particular, CMS/QAS nanocapsules constructed by CMS with lower DS and M w showed better colon-specific delivery and release performance in simulated GIT fluid after 7days' storage in different kinds of beverage (33.04%-46.35% in upper GIT, 52.70%-64.97% in colon, respectively). These findings demonstrated that CMS/QAS nanocapsules constructed by CMS with lower DS and M w can be further exploited as a potential oral delivery system for protein to colon. Copyright © 2017 Elsevier Ltd. All rights reserved.

Inhibiting surface crystallization of amorphous indomethacin by nanocoating.

PubMed

Wu, Tian; Sun, Ye; Li, Ning; de Villiers, Melgardt M; Yu, Lian

2007-04-24

An amorphous solid (glass) may crystallize faster at the surface than through the bulk, making surface crystallization a mechanism of failure for amorphous pharmaceuticals and other materials. An ultrathin coating of gold or polyelectrolytes inhibited the surface crystallization of amorphous indomethacin (IMC), an anti-inflammatory drug and model organic glass. The gold coating (10 nm) was deposited by sputtering, and the polyelectrolyte coating (3-20 nm) was deposited by an electrostatic layer-by-layer assembly of cationic poly(dimethyldiallyl ammonium chloride) (PDDA) and anionic sodium poly(styrenesulfonate) (PSS) in aqueous solution. The coating also inhibited the growth of existing crystals. The inhibition was strong even with one layer of PDDA. The polyelectrolyte coating still permitted fast dissolution of amorphous IMC and improved its wetting and flow. The finding supports the view that the surface crystallization of amorphous IMC is enabled by the mobility of a thin layer of surface molecules, and this mobility can be suppressed by a coating of only a few nanometers. This technique may be used to stabilize amorphous drugs prone to surface crystallization, with the aqueous coating process especially suitable for drugs of low aqueous solubility.

Enzyme-free Detection of Hydrogen Peroxide from Cerium Oxide Nanoparticles Immobilized on Poly(4-vinylpyridine) Self-Assembled Monolayers

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

Gaynor, James D.; Karakoti, Ajay S.; Inerbaev, Talgat

2013-05-02

A single layer of oxygen-deficient cerium oxide nanoparticles (CNPs) are immobilized on microscopic glass slide using poly(4-vinylpyridine) (PVP) self-assembled monolayers (SAMs). A specific colorimetric property of CNPs when reacted with hydrogen peroxide allows for the direct, single-step peroxide detection which can be used in medical diagnosis and explosives detection. Multiple PVP-CNP immobilized layers improve sensitivity of detection and the sensor can be regenerated for reuse.

Cell-Adhesive and Cell-Repulsive Zwitterionic Oligopeptides for Micropatterning and Rapid Electrochemical Detachment of Cells

PubMed Central

Kakegawa, Takahiro; Mochizuki, Naoto; Sadr, Nasser; Suzuki, Hiroaki

2013-01-01

In this study, we describe the development of oligopeptide-modified cell culture surfaces from which adherent cells can be rapidly detached by application of an electrical stimulus. An oligopeptide, CGGGKEKEKEK, was designed with a terminal cysteine residue to mediate binding to a gold surface via a gold–thiolate bond. The peptide forms a self-assembled monolayer through the electrostatic force between the sequence of alternating charged glutamic acid (E) and lysine (K) residues. The dense and electrically neutral oligopeptide zwitterionic layer of the modified surface was resistant to nonspecific adsorption of proteins and adhesion of cells, while the surface was altered to cell adhesive by the addition of a second oligopeptide (CGGGKEKEKEKGRGDSP) containing the RGD cell adhesion motif. Application of a negative electrical potential to this gold surface cleaved the gold–thiolate bond, leading to desorption of the oligopeptide layer, and rapid (within 2 min) detachment of virtually all cells. This approach was applicable not only to detachment of cell sheets but also for transfer of cell micropatterns to a hydrogel. This electrochemical approach of cell detachment may be a useful tool for tissue-engineering applications. PMID:22853640

Transgene Delivery using Poly(amino ether)-Gold Nanorod Assemblies

PubMed Central

Ramos, James; Rege, Kaushal

2012-01-01

Gold nanorods (GNRs) have emerged as promising nanomaterials for biosensing, imaging, photothermal treatment and therapeutic delivery for several diseases, including cancer. We have generated poly(amino ether)-functionalized gold nanorods (PAE-GNRs) using a layer-by-layer deposition approach; polymers from a poly(amino ether) library recently synthesized in our laboratory were employed to generate the PAE-GNR assemblies. PAE-GNR assemblies demonstrate long-term colloidal stability as well as the capacity to bind plasmid DNA by means of electrostatic interactions. Sub-toxic concentrations of PAE-GNRs were employed to deliver plasmid DNA to prostate cancer cells in vitro. PAE-GNRs generated using 1,4C-1,4Bis, a cationic polymer from our laboratory demonstrated significantly higher transgene expression and exhibited lower cytotoxicities when compared to similar assemblies generated using 25 kDa poly(ethylene imine) (PEI25k-GNRs), a current standard for polymer-mediated gene delivery. The roles of polyelectrolyte chemistry and zeta-potential in determining transgene expression efficacies of PAE-GNR assemblies were investigated. Our results indicate that stable and effective PAE-GNR assemblies are a promising engineered platform for transgene delivery. PAE-GNRs also have the potential to be used simultaneously for photothermal ablation, photothermally enhanced drug and gene delivery, and biological imaging, thus making them a powerful theranostic platform. PMID:22170455

Temperature Controlled Electrostatic Disorder and Polymorphism in Ultrathin Films of α-Sexithiophene

NASA Astrophysics Data System (ADS)

Hoffman, Benjamin; Jafari, Sara; McAfee, Terry; Apperson, Aubrey; O'Connor, Brendan; Dougherty, Daniel

Competing phases in well-ordered alpha-sexithiophene (α-6T) are shown to contribute to electrostatic disorder observed by differences in surface potential between mono- and bi-layer crystallites. Ultrathin films are of key importance to devices in which charge transport occurs in the first several monolayers nearest to a dielectric interface (e.g. thin film transistors) and complex structures in this regime impact the general electrostatic landscape. This study is comprised of 1.5 ML sample crystals grown via organic molecular beam deposition onto a temperature controlled hexamethyldisilazane (HMDS) passivated SiO2 substrate to produce well-ordered layer-by-layer type growth. Sample topography and surface potential were characterized simultaneously using Kelvin Probe Force Microscopy to then isolate contact potential differences by first and second layer α-6T regions. Films grown on 70° C, 120° C substrates are observed to have a bilayer with lower, higher potential than the monolayer, respectively. Resulting interlayer potential differences are a clear source of electrostatic disorder and are explained as subtle shifts in tilt-angles between layers relative to the substrate. These empirical results continue our understanding of how co-existing orientations contribute to the complex electrostatics influencing charge transport. NSF CAREER award DMR-1056861.

Three-Dimensional Self-Assembled Photonic Crystal Waveguide

NASA Astrophysics Data System (ADS)

Baek, Kang-Hyun

Photonic crystals (PCs), two- or three-dimensionally periodic, artificial, and dielectric structures, have a specific forbidden band for electromagnetic waves, referred to as photonic bandgap (PBG). The PBG is analogous to the electronic bandgap in natural crystal structures with periodic atomic arrangement. A well-defined and embedded planar, line, or point defect within the PCs causes a break in its structural periodicity, and introduces a state in the PBG for light localization. It offers various applications in integrated optics and photonics including optical filters, sharp bending light guides and very low threshold lasers. Using nanofabrication processes, PCs of the 2-D slab-type and 3-D layer-by-layer structures have been investigated widely. Alternatively, simple and low-cost self-assembled PCs with full 3-D PBG, inverse opals, have been suggested. A template with face centered cubic closed packed structure, opal, may initially be built by self-assembly of colloidal spheres, and is selectively removed after infiltrating high refractive index materials into the interstitials of spheres. In this dissertation, the optical waveguides utilizing the 3-D self-assembled PCs are discussed. The waveguides were fabricated by microfabrication technology. For high-quality colloidal silica spheres and PCs, reliable synthesis, self-assembly, and characterization techniques were developed. Its theoretical and experimental demonstrations are provided and correlated. They suggest that the self-assembled PCs with PBG are feasible for the applications in integrated optics and photonics.

Auroral-particle precipitation and trapping caused by electrostatic double layers in the ionosphere.

PubMed

Albert, R D; Lindstrom, P J

1970-12-25

Interpretation of high-resolution angular distribution measurements of the primary auroral electron flux detected by a rocket probe launched into a visible aurora from Fort Churchill in the fall of 1966 leads to the following conclusions. The auroral electron flux is nearly monoenergetic and has a quasi-trapped as well as a precipitating component. The quasi-trapped flux appears to be limited to a region defined by magnetic-mirror points and multiple electrostatic double layers in the ionosphere. The electrostatic field of the double-layer distribution enhances the aurora by lowering the magnetic-mirror points and supplying energy to the primary auroral electrons.

The Structures of Fibronectin Adsorbed on Polyelectrolyte Thin Films

NASA Astrophysics Data System (ADS)

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

2002-03-01

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

Three-input gate logic circuits on chemically assembled single-electron transistors with organic and inorganic hybrid passivation layers

PubMed Central

Majima, Yutaka; Hackenberger, Guillaume; Azuma, Yasuo; Kano, Shinya; Matsuzaki, Kosuke; Susaki, Tomofumi; Sakamoto, Masanori; Teranishi, Toshiharu

2017-01-01

Abstract Single-electron transistors (SETs) are sub-10-nm scale electronic devices based on conductive Coulomb islands sandwiched between double-barrier tunneling barriers. Chemically assembled SETs with alkanethiol-protected Au nanoparticles show highly stable Coulomb diamonds and two-input logic operations. The combination of bottom-up and top-down processes used to form the passivation layer is vital for realizing multi-gate chemically assembled SET circuits, as this combination enables us to connect conventional complementary metal oxide semiconductor (CMOS) technologies via planar processes. Here, three-input gate exclusive-OR (XOR) logic operations are demonstrated in passivated chemically assembled SETs. The passivation layer is a hybrid bilayer of self-assembled monolayers (SAMs) and pulsed laser deposited (PLD) aluminum oxide (AlOx), and top-gate electrodes were prepared on the hybrid passivation layers. Top and two-side-gated SETs showed clear Coulomb oscillation and diamonds for each of the three available gates, and three-input gate XOR logic operation was clearly demonstrated. These results show the potential of chemically assembled SETs to work as logic devices with multi-gate inputs using organic and inorganic hybrid passivation layers. PMID:28634499

Three-input gate logic circuits on chemically assembled single-electron transistors with organic and inorganic hybrid passivation layers.

PubMed

Majima, Yutaka; Hackenberger, Guillaume; Azuma, Yasuo; Kano, Shinya; Matsuzaki, Kosuke; Susaki, Tomofumi; Sakamoto, Masanori; Teranishi, Toshiharu

2017-01-01

Single-electron transistors (SETs) are sub-10-nm scale electronic devices based on conductive Coulomb islands sandwiched between double-barrier tunneling barriers. Chemically assembled SETs with alkanethiol-protected Au nanoparticles show highly stable Coulomb diamonds and two-input logic operations. The combination of bottom-up and top-down processes used to form the passivation layer is vital for realizing multi-gate chemically assembled SET circuits, as this combination enables us to connect conventional complementary metal oxide semiconductor (CMOS) technologies via planar processes. Here, three-input gate exclusive-OR (XOR) logic operations are demonstrated in passivated chemically assembled SETs. The passivation layer is a hybrid bilayer of self-assembled monolayers (SAMs) and pulsed laser deposited (PLD) aluminum oxide (AlO[Formula: see text]), and top-gate electrodes were prepared on the hybrid passivation layers. Top and two-side-gated SETs showed clear Coulomb oscillation and diamonds for each of the three available gates, and three-input gate XOR logic operation was clearly demonstrated. These results show the potential of chemically assembled SETs to work as logic devices with multi-gate inputs using organic and inorganic hybrid passivation layers.

Electrostatic interactions between diffuse soft multi-layered (bio)particles: beyond Debye-Hückel approximation and Deryagin formulation.

PubMed

Duval, Jérôme F L; Merlin, Jenny; Narayana, Puranam A L

2011-01-21

We report a steady-state theory for the evaluation of electrostatic interactions between identical or dissimilar spherical soft multi-layered (bio)particles, e.g. microgels or microorganisms. These generally consist of a rigid core surrounded by concentric ion-permeable layers that may differ in thickness, soft material density, chemical composition and degree of dissociation for the ionogenic groups. The formalism allows the account of diffuse interphases where distributions of ionogenic groups from one layer to the other are position-dependent. The model is valid for any number of ion-permeable layers around the core of the interacting soft particles and covers all limiting situations in terms of nature of interacting particles, i.e. homo- and hetero-interactions between hard, soft or entirely porous colloids. The theory is based on a rigorous numerical solution of the non-linearized Poisson-Boltzmann equation including radial and angular distortions of the electric field distribution within and outside the interacting soft particles in approach. The Gibbs energy of electrostatic interaction is obtained from a general expression derived following the method by Verwey and Overbeek based on appropriate electric double layer charging mechanisms. Original analytical solutions are provided here for cases where interaction takes place between soft multi-layered particles whose size and charge density are in line with Deryagin treatment and Debye-Hückel approximation. These situations include interactions between hard and soft particles, hard plate and soft particle or soft plate and soft particle. The flexibility of the formalism is highlighted by the discussion of few situations which clearly illustrate that electrostatic interaction between multi-layered particles may be partly or predominantly governed by potential distribution within the most internal layers. A major consequence is that both amplitude and sign of Gibbs electrostatic interaction energy may dramatically change depending on the interplay between characteristic Debye length, thickness of ion-permeable layers and their respective protolytic features (e.g. location, magnitude and sign of charge density). This formalism extends a recent model by Ohshima which is strictly limited to interaction between soft mono-shell particles within Deryagin and Debye-Hückel approximations under conditions where ionizable sites are completely dissociated.

Emergence of a Stern Layer from the Incorporation of Hydration Interactions into the Gouy-Chapman Model of the Electrical Double Layer.

PubMed

Brown, Matthew A; Bossa, Guilherme Volpe; May, Sylvio

2015-10-27

In one of the most commonly used phenomenological descriptions of the electrical double layer, a charged solid surface and a diffuse region of mobile ions are separated from each other by a thin charge-depleted Stern layer. The Stern layer acts as a capacitor that improves the classical Gouy-Chapman model by increasing the magnitude of the surface potential and limiting the maximal counterion concentration. We show that very similar Stern-like properties of the diffuse double layer emerge naturally from adding a nonelectrostatic hydration repulsion to the electrostatic Coulomb potential. The interplay of electrostatic attraction and hydration repulsion of the counterions and the surface leads to the formation of a diffuse counterion layer that remains well separated from the surface. In addition, hydration repulsions between the ions limit and control the maximal ion concentration and widen the width of the diffuse double layer. Our mean-field model, which we express in terms of electrostatic and hydration potentials, is physically consistent and conceptually similar to the classical Gouy-Chapman model. It allows the incorporation of ion specificity, accounts for hydration properties of charged surfaces, and predicts Stern layer properties, which we analyze in terms of the effective size of the hydrated counterions.

Calcium dependent formation of tubular assemblies by recombinant S-layer proteins in vivo and in vitro

NASA Astrophysics Data System (ADS)

Korkmaz, Nuriye; Ostermann, Kai; Rödel, Gerhard

2011-03-01

Surface layer proteins have the appealing property to self-assemble in nanosized arrays in solution and on solid substrates. In this work, we characterize the formation of assembly structures of the recombinant surface layer protein SbsC of Geobacillus stearothermophilus ATTC 12980, which was tagged with enhanced green fluorescent protein and expressed in the yeast Saccharomyces cerevisiae. The tubular structures formed by the protein in vivo are retained upon bursting the cells by osmotic shock; however, their average length is decreased. During dialysis, monomers obtained by treatment with chaotropic chemicals recrystallize again to form tube-like structures. This process is strictly dependent on calcium (Ca2 + ) ions, with an optimal concentration of 10 mM. Further increase of the Ca2 + concentration results in multiple non-productive nucleation points. We further show that the lengths of the S-layer assemblies increase with time and can be controlled by pH. After 48 h, the average length at pH 9.0 is 4.13 µm compared to 2.69 µm at pH 5.5. Successful chemical deposition of platinum indicates the potential of recrystallized mSbsC-eGFP structures for nanobiotechnological applications.

Layer-by-layer composite film of nickel phthalocyanine and montmorillonite clay for synergistic effect on electrochemical detection of dopamine

NASA Astrophysics Data System (ADS)

de Lucena, Nathalia C.; Miyazaki, Celina M.; Shimizu, Flávio M.; Constantino, Carlos J. L.; Ferreira, Marystela

2018-04-01

Dopamine (DA) abnormal levels are related to diseases which makes important the development of fast, reliable, low-cost and sensitive devices for diagnosis and pharmaceutical controls. Nanostructured film composite of sodium montmorillonite clay (Na+MMT) and nickel phthalocyanine (NiTsPc) was self-assembled by layer-by-layer (LbL) technique and applied as electrochemical sensor for DA in the presence of common natural interferents as ascorbic acid (AA) and uric acid (UA). Three different LbL architecture films were investigated: LbL films of clay (PEI/Na+MMT) and phthalocyanine (PEI/NiTsPc) in a bilayer structure with a conventional polyelectrolyte (PEI) and a composite film formed by both materials to verify the synergistic effect in the LbL film in a quadri-layer assembly (PEI/Na+MMT/PEI/NiTsPc). Structural characterization indicated molecular level interactions between the layers forming the LbL films. The ITO/(PEI/Na+MMT/PEI/NiTsPc)10 electrode exhibited a LOD of 1.0 μmol L-1 and linear range 5-150 μmol L-1.

Assembly of citrate gold nanoparticles on hydrophilic monolayers

NASA Astrophysics Data System (ADS)

Vikholm-Lundin, Inger; Rosqvist, Emil; Ihalainen, Petri; Munter, Tony; Honkimaa, Anni; Marjomäki, Varpu; Albers, Willem M.; Peltonen, Jouko

2016-08-01

Self-assembled monolayers (SAMs) as model surfaces were linked onto planar gold films thorough lipoic acid or disulfide groups. The molecules used were polyethylene glycol (EG-S-S), N-[tris-(hydroxymethyl)methyl]acrylamide polymers with and without lipoic acid (Lipa-pTHMMAA and pTHMMAA) and a lipoic acid triazine derivative (Lipa-MF). All the layers, but Lipa-MF with a primary amino group were hydroxyl terminated. The layers were characterized by contact angle measurements and atomic force microscopy, AFM. Citrate stabilized nanoparticles, AuNPs in water and phosphate buffer were allowed to assemble on the layers for 10 min and the binding was followed in real-time with surface plasmon resonance, SPR. The SPR resonance curves were observed to shift to higher angles and become increasingly damped, while also the peaks strongly broaden when large nanoparticles assembled on the surface. Both the angular shift and the damping of the curve was largest for nanoparticles assembling on the EG-S-S monolayer. High amounts of particles were also assembled on the pTHMMAA layer without the lipoic acid group, but the damping of the curve was considerably lower with a more even distribution of the particles. Topographical images confirmed that the highest number of particles were assembled on the polyethylene glycol monolayer. By increasing the interaction time more particles could be assembled on the surface.

Layer-by-Layer Assembly of a Self-Healing Anticorrosion Coating on Magnesium Alloys.

PubMed

Fan, Fan; Zhou, Chunyu; Wang, Xu; Szpunar, Jerzy

2015-12-16

Fabrication of self-healing anticorrosion coatings has attracted attention as it has the ability to extend the service life and prevent the substrate from corrosive attack. However, a coating system with a rapid self-healing ability and an improved corrosion resistance is rarely reported. In this work, we developed a self-healing anticorrosion coating on a magnesium alloy (AZ31). The coating comprises a cerium-based conversion layer, a graphene oxide layer, and a branched poly(ethylene imine) (PEI)/poly(acrylic acid) (PAA) multilayer. We incorporated the graphene oxide as corrosion inhibitors and used the PEI/PAA multilayers to provide the self-healing ability to the coating systems. X-ray diffraction (XRD) and Raman spectroscopy were used to characterize the composition of the multilayers, and scanning electron microscopy (SEM) was used to analyze the surface morphology. The electrochemical impedance spectroscopy (EIS) results illustrate the improved corrosion resistance of the coating. The proposed coating also has a rapid self-healing ability in the presence of water.

Onion-like microspheres with tricomponent from gelable triblock copolymers.

PubMed

Zhang, Ke; Gao, Lei; Chen, Yongming; Yang, Zhenzhong

2010-06-01

Onion-like functional microspheres with three alternate layers were obtained by aerosol-assisted self-assembly of a functional block copolymer, poly(3-(triethoxysilyl)propyl methacrylate)-block-polystyrene-block-poly(2-vinylpyridine) (PTEPM-b-PS-b-P2VP). Through self-gelation reaction occurred in the PTEPM layers, organic/inorganic hybrid functional spheres with highly ordered concentric curved lamellar structure were prepared. Using these hybrid onion-like microspheres as templates, gold ions were entrapped into the P2VP layers and then gold nanoparticles located in each P2VP layers were formed by a reduction. By dispersing in acidic water, the onion-like polymeric spheres were broken and, as a result, sandwich-like nanoplates with curved morphology were obtained. Copyright © 2010 Elsevier Inc. All rights reserved.

Tunable self-organization of nanocomposite multilayers

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

Chen, C. Q.; Pei, Y. T.; Shaha, K. P.

In this letter we report the controlled growth and microstructural evolution of self-assembled nanocomposite multilayers that are induced by surface ion-impingement. The nanoscale structures together with chemical composition, especially at the growing front, have been investigated with high-resolution transmission electron microscopy. Concurrent ion impingement of growing films produces an amorphous capping layer 3 nm in thickness where spatially modulated phase separation is initiated. It is shown that the modulation of multilayers as controlled by the self-organization of nanocrystallites below the capping layer, can be tuned through the entire film.

High-performance mussel-inspired adhesives of reduced complexity.

PubMed

Ahn, B Kollbe; Das, Saurabh; Linstadt, Roscoe; Kaufman, Yair; Martinez-Rodriguez, Nadine R; Mirshafian, Razieh; Kesselman, Ellina; Talmon, Yeshayahu; Lipshutz, Bruce H; Israelachvili, Jacob N; Waite, J Herbert

2015-10-19

Despite the recent progress in and demand for wet adhesives, practical underwater adhesion remains limited or non-existent for diverse applications. Translation of mussel-inspired wet adhesion typically entails catechol functionalization of polymers and/or polyelectrolytes, and solution processing of many complex components and steps that require optimization and stabilization. Here we reduced the complexity of a wet adhesive primer to synthetic low-molecular-weight catecholic zwitterionic surfactants that show very strong adhesion (∼50 mJ m(-2)) and retain the ability to coacervate. This catecholic zwitterion adheres to diverse surfaces and self-assembles into a molecularly smooth, thin (<4 nm) and strong glue layer. The catecholic zwitterion holds particular promise as an adhesive for nanofabrication. This study significantly simplifies bio-inspired themes for wet adhesion by combining catechol with hydrophobic and electrostatic functional groups in a small molecule.

Novel Quantum Dot Gate FETs and Nonvolatile Memories Using Lattice-Matched II-VI Gate Insulators

NASA Astrophysics Data System (ADS)

Jain, F. C.; Suarez, E.; Gogna, M.; Alamoody, F.; Butkiewicus, D.; Hohner, R.; Liaskas, T.; Karmakar, S.; Chan, P.-Y.; Miller, B.; Chandy, J.; Heller, E.

2009-08-01

This paper presents the successful use of ZnS/ZnMgS and other II-VI layers (lattice-matched or pseudomorphic) as high- k gate dielectrics in the fabrication of quantum dot (QD) gate Si field-effect transistors (FETs) and nonvolatile memory structures. Quantum dot gate FETs and nonvolatile memories have been fabricated in two basic configurations: (1) monodispersed cladded Ge nanocrystals (e.g., GeO x -cladded-Ge quantum dots) site-specifically self-assembled over the lattice-matched ZnMgS gate insulator in the channel region, and (2) ZnTe-ZnMgTe quantum dots formed by self-organization, using metalorganic chemical vapor-phase deposition (MOCVD), on ZnS-ZnMgS gate insulator layers grown epitaxially on Si substrates. Self-assembled GeO x -cladded Ge QD gate FETs, exhibiting three-state behavior, are also described. Preliminary results on InGaAs-on-InP FETs, using ZnMgSeTe/ZnSe gate insulator layers, are presented.

A pentacene monolayer trapped between graphene and a substrate.

PubMed

Zhang, Qicheng; Peng, Boyu; Chan, Paddy Kwok Leung; Luo, Zhengtang

2015-09-21

A self-assembled pentacene monolayer can be fabricated between the solid-solid interface of few-layered graphene (FLG) and the mica substrate, through a diffusion-spreading method. By utilizing a transfer method that allows us to sandwich pentacene between graphene and mica, followed by controlled annealing, we enabled the diffused pentacene to be trapped in the interfaces and led to the formation of a stable monolayer. We found that the formation of a monolayer is kinetically favored by using a 2D Ising lattice gas model for pentacene trapped between the graphene-substrate interfaces. This kinetic Monte Carlo simulation results indicate that, due to the graphene substrate enclosure, the spreading of the first layer proceeds faster than the second layer, as the kinetics favors the filling of voids by molecules from the second layer. This graphene assisted monolayer assembly method provides a new avenue for the fabrication of two-dimensional monolayer structures.

Simulation of plasma double-layer structures

NASA Technical Reports Server (NTRS)

Borovsky, J. E.; Joyce, G.

1982-01-01

Electrostatic plasma double layers are numerically simulated by means of a magnetized 2 1/2 dimensional particle in cell method. The investigation of planar double layers indicates that these one dimensional potential structures are susceptible to periodic disruption by instabilities in the low potential plasmas. Only a slight increase in the double layer thickness with an increase in its obliqueness to the magnetic field is observed. Weak magnetization results in the double layer electric field alignment of accelerated particles and strong magnetization results in their magnetic field alignment. The numerical simulations of spatially periodic two dimensional double layers also exhibit cyclical instability. A morphological invariance in two dimensional double layers with respect to the degree of magnetization implies that the potential structures scale with Debye lengths rather than with gyroradii. Electron beam excited electrostatic electron cyclotron waves and (ion beam driven) solitary waves are present in the plasmas adjacent to the double layers.

Novel Biocatalysts Based on S-Layer Self-Assembly of Geobacillus Stearothermophilus NRS 2004/3a: A Nanobiotechnological Approach

PubMed Central

Schäffer, Christina; Novotny, René; Küpcü, Seta; Zayni, Sonja; Scheberl, Andrea; Friedmann, Jacqueline; Sleytr, Uwe B.; Messner, Paul

2015-01-01

The crystalline cell-surface (S) layer sgsE of Geobacillus stearothermophilus NRS 2004/3a represents a natural protein self-assembly system with nanometer-scale periodicity that is evaluated as a combined carrier/patterning element for the conception of novel types of biocatalyst aiming at the controllable display of biocatalytic epitopes, storage stability, and reuse. The glucose-1-phosphate thymidylyltransferase RmlA is used as a model enzyme and chimeric proteins are constructed by translational fusion of rmlA to the C-terminus of truncated forms of sgsE (rSgsE 131–903, rSgsE331–903) and used for the construction of three principal types of biocatalysts: soluble (monomeric), self-assembled in aqueous solution, and recrystallized on negatively charged liposomes. Enzyme activity of the biocatalysts reaches up to 100% compared to sole RmlA cloned from the same bacterium. The S-layer portion of the biocatalysts confers significantly improved shelf life to the fused enzyme without loss of activity over more than three months, and also enables biocatalyst recycling. These nanopatterned composites may open up new functional concepts for biocatalytic applications in nanobiotechnology. PMID:17786898

Infrared light-induced protein crystallization. Structuring of protein interfacial water and periodic self-assembly

NASA Astrophysics Data System (ADS)

Kowacz, Magdalena; Marchel, Mateusz; Juknaité, Lina; Esperança, José M. S. S.; Romão, Maria João; Carvalho, Ana Luísa; Rebelo, Luís Paulo N.

2017-01-01

We show that a physical trigger, a non-ionizing infrared (IR) radiation at wavelengths strongly absorbed by liquid water, can be used to induce and kinetically control protein (periodic) self-assembly in solution. This phenomenon is explained by considering the effect of IR light on the structuring of protein interfacial water. Our results indicate that the IR radiation can promote enhanced mutual correlations of water molecules in the protein hydration shell. We report on the radiation-induced increase in both the strength and cooperativeness of H-bonds. The presence of a structured dipolar hydration layer can lead to attractive interactions between like-charged biomacromolecules in solution (and crystal nucleation events). Furthermore, our study suggests that enveloping the protein within a layer of structured solvent (an effect enhanced by IR light) can prevent the protein non-specific aggregation favoring periodic self-assembly. Recognizing the ability to affect protein-water interactions by means of IR radiation may have important implications for biological and bio-inspired systems.

Radial dependence of self-organized criticality behavior in TCABR tokamak

NASA Astrophysics Data System (ADS)

dos Santos Lima, G. Z.; Iarosz, K. C.; Batista, A. M.; Guimarães-Filho, Z. O.; Caldas, I. L.; Kuznetsov, Y. K.; Nascimento, I. C.; Viana, R. L.; Lopes, S. R.

2011-03-01

In this work we present evidence of the self-organized criticality behavior of the plasma edge electrostatic turbulence in the tokamak TCABR. Analyzing fluctuation data measured by Langmuir probes, we verify the radial dependence of self-organized criticality behavior at the plasma edge and scrape-off layer. We identify evidence of this radial criticality in statistical properties of the laminar period distribution function, power spectral density, autocorrelation, and Hurst parameter for the analyzed fluctuations.

Self-Assembly of Janus Oligomers into Onion-like Vesicles with Layer-by-Layer Water Discharging Capability: A Minimalist Model.

PubMed

Arai, Noriyoshi; Yasuoka, Kenji; Zeng, Xiao Cheng

2016-08-23

A vesicle in a cell is an enclosed structure in which the interior fluid is encompassed by a lipid bilayer. Synthetic vesicles are known as the liposomes. Liposomes with a single phospholipid bilayer are called unilamellar liposomes; otherwise, they are called multilamellar liposomes or onion-like liposomes (vesicles). One prototype synthetic onion-like vesicle, namely, onion-like dendrimersomes, have been recently produced via the self-assembly of amphiphilic Janus dendrimers (Proc. Natl. Acad. Sci. U.S.A. 2016, 113, 1162). Herein, we show computer simulation evidence of another type of onion-like vesicle, namely, onion-like oligomersomes, via the self-assembly of amphiphilic Janus oligomers in water. Specifically, we investigate the minimum-sized oligomers (or minimalist model) that can give rise to the onion-like oligomersomes as well as the composition-dependent phase diagrams. Insights into the formation condition and formation process of the onion-like oligomersomes are obtained. We demonstrate that the discharge of the in-vesicle water is through the remarkable "peeling-one-onion-layer-at-a-time" fashion, a feature that can be utilized for a clinical dosing regimen. The ability to control the formation of onion-like oligomersomes by design can be exploited for applications in drug and gene delivery.

Investigation of the fabrication mechanism of self-assembled GaAs quantum rings grown by droplet epitaxy.

PubMed

Tong, C Z; Yoon, S F

2008-09-10

We have directly imaged the formation of a GaAs quantum ring (QR) using droplet epitaxy followed by annealing in arsenic ambient. Based on the atomic force micrograph measurement and the analysis of surface energy, we determine that the formation of self-assembled GaAs QRs is due to the gallium atom's diffusion and crystallization driven by the gradient of surface energy. The phenomenon that GaAs is etched by the gallium droplets is reported and analyzed. It has been demonstrated that the epitaxy layers, such as AlAs and InGaP, can be used as the etching stop layer and hence can be used to control the shape and height of the QRs.

Heparin-mimicking multilayer coating on polymeric membrane via LbL assembly of cyclodextrin-based supramolecules.

PubMed

Deng, Jie; Liu, Xinyue; Ma, Lang; Cheng, Chong; Shi, Wenbin; Nie, Chuanxiong; Zhao, Changsheng

2014-12-10

In this study, multifunctional and heparin-mimicking star-shaped supramolecules-deposited 3D porous multilayer films with improved biocompatibility were fabricated via a layer-by-layer (LbL) self-assembly method on polymeric membrane substrates. Star-shaped heparin-mimicking polyanions (including poly(styrenesulfonate-co-sodium acrylate; Star-PSS-AANa) and poly(styrenesulfonate-co-poly(ethylene glycol)methyl ether methacrylate; Star-PSS-EGMA)) and polycations (poly(methyl chloride-quaternized 2-(dimethylamino)ethyl methacrylate; Star-PMeDMA) were first synthesized by atom transfer radical polymerization (ATRP) from β-cyclodextrin (β-CD) based cores. Then assembly of 3D porous multilayers onto polymeric membrane surfaces was carried out by alternating deposition of the polyanions and polycations via electrostatic interaction. The surface morphology and composition, water contact angle, blood activation, and thrombotic potential as well as cell viability for the coated heparin-mimicking films were systematically investigated. The results of surface ATR-FTIR spectra and XPS spectra verified successful deposition of the star-shaped supramolecules onto the biomedical membrane surfaces; scanning electron microscopy (SEM) and atomic force microscopy (AFM) observations revealed that the modified substrate had 3D porous surface morphology, which might have a great biological influence on the biointerface. Furthermore, systematic in vitro investigation of protein adsorption, platelet adhesion, human platelet factor 4 (PF4, indicates platelet activation), activate partial thromboplastin time (APTT), thrombin time (TT), coagulation activation (thrombin-antithrombin III complex (TAT, indicates blood coagulant)), and blood-related complement activation (C3a and C5a, indicates inflammation potential) confirmed that the heparin-mimicking multilayer coated membranes exhibited ultralow blood component activations and excellent hemocompatibility. Meanwhile, after surface coating, endothelial cell viability was also promoted, which indicated that the heparin-mimicking multilayer coating might extend the application fields of polymeric membranes in biomedical fields.

Fabrication of Thickness-Controllable Micropatterned Polyelectrolyte-Film/Nanoparticle Surfaces by Using the Plasma Oxidation Method.

PubMed

Zhu, Chun-Tao; Ma, Sheng-Hua; Zhang, Ying; Wang, Xue-Jing; Lv, Peng; Han, Xiao-Jun

2016-04-05

We have demonstrated a novel way to form thickness-controllable polyelectrolyte-film/nanoparticle patterns by using a plasma etching technique to form, first, a patterned self-assembled monolayer surface, followed by layer-by-layer assembly of polyelectrolyte-films/nanoparticles. Octadecyltrimethoxysilane (ODS) and (3-aminopropyl)triethoxysilane (APTES) self-assembled monolayers (SAMs) were used for polyelectrolyte-film and nanoparticle patterning, respectively. The resolution of the proposed patterning method can easily reach approximately 2.5 μm. The height of the groove structure was tunable from approximately 2.5 to 150 nm. The suspended lipid membrane across the grooves was fabricated by incubating the patterned polyelectrolyte groove arrays in solutions of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) giant unilamellar vesicles (GUVs). The method demonstrated here reveals a new path to create patterned 2D or 3D structures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. Copyright © 2014 Elsevier B.V. All rights reserved.

Hybrid Lead Halide Layered Perovskites with Silsesquioxane Interlayers.

PubMed

Kataoka, Sho; Kaburagi, Wako; Mochizuki, Hiroyuki; Kamimura, Yoshihiro; Sato, Kazuhiko; Endo, Akira

2018-01-01

Hybrid organic-lead halide perovskites exhibit remarkable properties as semiconductors and light absorbers. Here, we report the formation of silsesquioxane-lead halide hybrid layered perovskites. We prepared silsesquioxane with a cubic cage-like structure and fabricated hybrid silsesquioxane-lead halide layered perovskites in a self-assembled manner. It is demonstrated that the silsesquioxane maintain their cage-like structure between lead halide perovskite layers. The silsesquioxane-lead halide perovskites also show excitonic absorption and emission in the visible light region similar to typical lead halide layered perovskites.

Characteristics of Reduced Graphene Oxide Quantum Dots for a Flexible Memory Thin Film Transistor.

PubMed

Kim, Yo-Han; Lee, Eun Yeol; Lee, Hyun Ho; Seo, Tae Seok

2017-05-17

Reduced graphene oxide quantum dot (rGOQD) devices in formats of capacitor and thin film transistor (TFT) were demonstrated and examined as the first trial to achieve nonambipolar channel property. In addition, through a gold nanoparticle (Au NP) layer embedded between the rGOQD active channel and dielectric layer, memory capacitor and TFT performances were realized by capacitance-voltage (C-V) hysteresis and gate program, erase, and reprogram biases. First, capacitor structure of the rGOQD memory device was constructed to examine memory charging effect featured in hysteretic C-V behavior with a 30 nm dielectric layer of cross-linked poly(vinyl alcohol). For the intervening Au NP charging layer, self-assembled monolayer (SAM) formation of the Au NP was executed to utilize electrostatic interaction by a dip-coating process under ambient environments with a conformal fabrication uniformity. Second, the rGOQD memory TFT device was also constructed in the same format of the Au NPs SAMs on a flexible substrate. Characteristics of the rGOQD TFT output showed novel saturation curves unlike typical graphene-based TFTs. However, The rGOQD TFT device reveals relatively low on/off ratio of 10 1 and mobility of 5.005 cm 2 /V·s. For the memory capacitor, the flat-band voltage shift (ΔV FB ) was measured as 3.74 V for ±10 V sweep, and for the memory TFT, the threshold voltage shift (ΔV th ) by the Au NP charging was detected as 7.84 V. In summary, it was concluded that the rGOQD memory device could accomplish an ideal graphene-based memory performance, which could have provided a wide memory window and saturated output characteristics.

Layer-by-Layer-Assembled AuNPs-Decorated First-Generation Poly(amidoamine) Dendrimer with Reduced Graphene Oxide Core as Highly Sensitive Biosensing Platform with Controllable 3D Nanoarchitecture for Rapid Voltammetric Analysis of Ultratrace DNA Hybridization.

PubMed

Jayakumar, Kumarasamy; Camarada, María Belén; Dharuman, Venkataraman; Rajesh, Rajendiran; Venkatesan, Rengarajan; Ju, Huangxian; Maniraj, Mahalingam; Rai, Abhishek; Barman, Sudipta Roy; Wen, Yangping

2018-06-27

The structure and electrochemical properties of layer-by-layer-assembled gold nanoparticles (AuNPs)-decorated first-generation (G1) poly(amidoamine) dendrimer (PD) with reduced graphene oxide (rGO) core as a highly sensitive and label-free biosensing platform with a controllable three-dimensional (3D) nanoarchitecture for the rapid voltammetric analysis of DNA hybridization at ultratrace levels were characterized. Mercaptopropinoic acid (MPA) was self-assembled onto Au substrate, then GG1PD formed by the covalent functionalization between the amino terminals of G1PD and carboxyl terminals of rGO was covalently linked onto MPA, and finally AuNPs were decorated onto GG1PD by strong physicochemical interaction between AuNPs and -OH of rGO in GG1PD, which was characterized through different techniques and confirmed by computational calculation. This 3D controllable thin-film electrode was optimized and evaluated using [Fe(CN) 6 ] 3-/4- as the redox probe and employed to covalently immobilize thiol-functionalized single-stranded DNA as biorecognition element to form the DNA nanobiosensor, which achieved fast, ultrasensitive, and high-selective differential pulse voltammetric analysis of DNA hybridization in a linear range from 1 × 10 -6 to 1 × 10 -13 g m -1 with a low detection limit of 9.07 × 10 -14 g m -1 . This work will open a new pathway for the controllable 3D nanoarchitecture of the layer-by-layer-assembled metal nanoparticles-functionalized lower-generation PD with two-dimensional layered nanomaterials as cores that can be employed as ultrasensitive and label-free nanobiodevices for the fast diagnosis of specific genome diseases in the field of biomedicine.

Layer-by-layer self-assembled multilayer films composed of graphene/polyaniline bilayers: high-energy electrode materials for supercapacitors.

PubMed

Sarker, Ashis K; Hong, Jong-Dal

2012-08-28

Multilayer assemblies of uniform ultrathin film electrodes with good electrical conductivity and very large surface areas were prepared for use as electrochemical capacitors. A layer-by-layer self-assembly approach was employed in an effort to improve the processability of highly conducting polyaniline (PANi) and chemically modified graphene. The electrochemical properties of the multilayer film (MF-) electrodes, including the sheet resistance, volumetric capacitance, and charge/discharge ratio, were determined by the morphological modification and the method used to reduce the graphene oxide (GO) to reduced graphene oxide (RGO) in the multilayer films. The PANi and GO concentrations could be modulated to control the morphology of the GO monolayer film in the multilayer assemblies. Optical ellipsometry was used to determine the thickness of the GO film in a single layer (1.32 nm), which agreed well with the literature value (~1.3 nm). Hydroiodic acid (HI), hydrazine, or pyrolysis were tested for the reduction of GO to RGO. HI was found to be the most efficient technique for reducing the GO to RGO in the multilayer assemblies while minimizing damage to the virgin state of the acid-doped PANi. Ultimately, the MF-electrode, which could be optimized by fine-tuning the nanostructure and selecting a suitable reduction method, exhibited an excellent volumetric capacitance, good cycling stability, and a rapid charge/discharge rate, which are required for supercapacitors. A MF-electrode composed of 15 PANi/RGO bilayers yielded a volumetric capacitance of 584 F/cm(3) at a current density of 3.0 A/cm(3). Although this value decreased exponentially as the current density increased, approaching a value of 170 F/cm(3) at 100 A/cm(3), this volumetric capacitance is one of the best yet reported for the other carbon-based materials. The intriguing features of the MF-electrodes composed of PANi/RGO multilayer films offer a new microdimensional design for high energy storage devices for use in small portable electronic devices.

Metamagnetism in hydrophobically induced carboxylate (phenylmalonate)-bridged copper(II) layers.

PubMed

Pasán, Jorge; Sanchiz, Joaquín; Ruiz-Pérez, Catalina; Campo, Javier; Lloret, Francesc; Julve, Miguel

2006-07-21

Self-assembly of copper(l) ions, phenylmalonate and pyrimidine yields the layered compound [Cu(pym)(Phmal)n (1) where intralayer ferro- and interlayer antiferromagnetic interactions occur with three-dimensional antiferromagnetic ordering at T(c) = 2.15 K.

Surface engineering of zirconium particles by molecular layer deposition: Significantly enhanced electrostatic safety at minimum loss of the energy density

NASA Astrophysics Data System (ADS)

Qin, Lijun; Yan, Ning; Hao, Haixia; An, Ting; Zhao, Fengqi; Feng, Hao

2018-04-01

Because of its high volumetric heat of oxidation, Zr powder is a promising high energy fuel/additive for rocket propellants. However, the application of Zr powder is restricted by its ultra-high electrostatic discharge sensitivity, which poses great hazards for handling, transportation and utilization of this material. By performing molecular layer deposition of polyimide using 1,2,4,5-benzenetetracarboxylic anhydride and ethylenediamine as the precursors, Zr particles can be uniformly encapsulated by thin layers of the polymer. The thicknesses of the encapsulation layers can be precisely controlled by adjusting the number of deposition cycle. High temperature annealing converts the polymer layer into a carbon coating. Results of thermal analyses reveal that the polymer or carbon coatings have little negative effect on the energy release process of the Zr powder. By varying the thickness of the polyimide or carbon coating, electrostatic discharge sensitivity of the Zr powder can be tuned in a wide range and its uncontrolled ignition hazard can be virtually eliminated. This research demonstrates the great potential of molecular layer deposition in effectively modifying the surface properties of highly reactive metal based energetic materials with minimum sacrifices of their energy densities.

Spore coat architecture of Clostridium novyi NT spores.

PubMed

Plomp, Marco; McCaffery, J Michael; Cheong, Ian; Huang, Xin; Bettegowda, Chetan; Kinzler, Kenneth W; Zhou, Shibin; Vogelstein, Bert; Malkin, Alexander J

2007-09-01

Spores of the anaerobic bacterium Clostridium novyi NT are able to germinate in and destroy hypoxic regions of tumors in experimental animals. Future progress in this area will benefit from a better understanding of the germination and outgrowth processes that are essential for the tumorilytic properties of these spores. Toward this end, we have used both transmission electron microscopy and atomic force microscopy to determine the structure of both dormant and germinating spores. We found that the spores are surrounded by an amorphous layer intertwined with honeycomb parasporal layers. Moreover, the spore coat layers had apparently self-assembled, and this assembly was likely to be governed by crystal growth principles. During germination and outgrowth, the honeycomb layers, as well as the underlying spore coat and undercoat layers, sequentially dissolved until the vegetative cell was released. In addition to their implications for understanding the biology of C. novyi NT, these studies document the presence of proteinaceous growth spirals in a biological organism.

A dielectric model of self-assembled monolayer interfaces by capacitive spectroscopy.

PubMed

Góes, Márcio S; Rahman, Habibur; Ryall, Joshua; Davis, Jason J; Bueno, Paulo R

2012-06-26

The presence of self-assembled monolayers at an electrode introduces capacitance and resistance contributions that can profoundly affect subsequently observed electronic characteristics. Despite the impact of this on any voltammetry, these contributions are not directly resolvable with any clarity by standard electrochemical means. A capacitive analysis of such interfaces (by capacitance spectroscopy), introduced here, enables a clean mapping of these features and additionally presents a means of studying layer polarizability and Cole-Cole relaxation effects. The resolved resistive term contributes directly to an intrinsic monolayer uncompensated resistance that has a linear dependence on the layer thickness. The dielectric model proposed is fully aligned with the classic Helmholtz plate capacitor model and additionally explains the inherently associated resistive features of molecular films.

Toward Three Dimensional Circuits Formed by Molten-Alloy Driven Self-Assembly

DTIC Science & Technology

2008-12-01

layers. Next, we deposited a lead-free, eutectic Bi-Sn alloy with a 138°C melting point shown in Fig. 2D). First, we evaporated 100nm of Au to...IEEE, 427-429. Chan, V. W. C., P. C. H. Chan, and M. Chan, 2001: Multiple layers of CMOS integrated circuits using recrystallized silicon film

Acetylene Gas-Sensing Properties of Layer-by-Layer Self-Assembled Ag-Decorated Tin Dioxide/Graphene Nanocomposite Film

PubMed Central

Jiang, Chuanxing; Yin, Nailiang; Yao, Yao; Shaymurat, Talgar; Zhou, Xiaoyan

2017-01-01

This paper demonstrates an acetylene gas sensor based on an Ag-decorated tin dioxide/reduced graphene oxide (Ag–SnO2/rGO) nanocomposite film, prepared by layer-by-layer (LbL) self-assembly technology. The as-prepared Ag–SnO2/rGO nanocomposite was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectrum. The acetylene sensing properties were investigated using different working temperatures and gas concentrations. An optimal temperature of 90 °C was determined, and the Ag–SnO2/rGO nanocomposite sensor exhibited excellent sensing behaviors towards acetylene, in terms of response, repeatability, stability and response/recovery characteristics, which were superior to the pure SnO2 and SnO2/rGO film sensors. The sensing mechanism of the Ag–SnO2/rGO sensor was attributed to the synergistic effect of the ternary nanomaterials, and the heterojunctions created at the interfaces between SnO2 and rGO. This work indicates that the Ag–SnO2/rGO nanocomposite is a good candidate for constructing a low-temperature acetylene sensor. PMID:28927021

Magnesium effects on CdSe self-assembled quantum dot formation on Zn xCd yMg 1-x-ySe layers

NASA Astrophysics Data System (ADS)

Noemi Perez-Paz, M.; Lu, Hong; Shen, Aidong; Jean Mary, F.; Akins, Daniel; Tamargo, Maria C.

2006-09-01

Optical and morphological studies are used to investigate the effects of chemical composition and, in particular, the magnesium content of the Zn xCd yMg 1-x-ySe barrier layers on the size, density and uniformity of CdSe self-assembled quantum dots (QDs). A reduction of the uncapped QD size, as well as a blue shift of the capped QD photoluminescence peak position by increasing Mg concentration in the Zn xCd yMg 1-x-ySe barrier has been demonstrated by changing the Mg cell temperature during growth. In addition, a more uniform and more densely packed QD layer has been observed with an increase of the MgSe fraction in the Zn xCd yMg 1-x-ySe barrier layer using three-dimensional topographic atomic force microscopy images of the surface of uncapped QDs. Results point to Mg as a chemical factor that induces QD formation, either by increasing the density of atomic steps or/and by changing the energy of the Zn xCd yMg 1-x-ySe surface.

FRET detection of Octamer-4 on a protein nanoarray made by size-dependent self-assembly

PubMed Central

Tran, Phat L.; Gamboa, Jessica R.; You, David J.

2010-01-01

An alternative approach for fabricating a protein array at nanoscale is suggested with a capability of characterization and/or localization of multiple components on a nanoarray. Fluorescent micro- and nanobeads each conjugated with different antibodies are assembled by size-dependent self-assembly (SDSA) onto nanometer wells that were created on a polymethyl methacrylate (PMMA) substrate by electron beam lithography (EBL). Antibody-conjugated beads of different diameters are added serially and electrostatically attached to corresponding wells through electrostatic attraction between the charged beads (confirmed by zeta potential analysis) and exposed p-doped silicon substrate underneath the PMMA layer. This SDSA method is enhanced by vibrated-wire-guide manipulation of droplets on the PMMA surface containing nanometer wells. Saturation rates of antibody-conjugated beads to the nanometer patterns are up to 97% under one component and 58–70% under two components nanoarrays. High-density arrays (up to 40,000 wells) could be fabricated, which can also be multi-component. Target detection utilizes fluorescence resonance energy transfer (FRET) from fluorescent beads to fluorescent-tagged secondary antibodies to Octamer-4 (Oct4), which eliminates the need for multiple steps of rinsing. The 100 nm green beads are covalently conjugated with anti-Oct4 to capture Oct4 peptides (39 kDa); where the secondary anti-Oct4 and F(ab)2 fragment of anti-gIgG tagged with phycoerythrin are then added to function as an indicator of Oct4 detection. FRET signals are detected through confocal microscopes, and further confirmed by Fluorolog3 spectrofluorometer. The success rates of detecting Oct4 are 32% and 14% of the beads in right place under one and two component nanoarrays, respectively. Ratiometric FRET is used to quantify the amount of Oct4 peptides per each bead, which is estimated about 2 molecules per bead. PMID:20652550

A three-dimensional flexible microprobe array for neural recording assembled through electrostatic actuation.

PubMed

Chen, Chang-Hsiao; Chuang, Shih-Chang; Su, Huan-Chieh; Hsu, Wei-Lun; Yew, Tri-Rung; Chang, Yen-Chung; Yeh, Shih-Rung; Yao, Da-Jeng

2011-05-07

We designed, fabricated and tested a novel three-dimensional flexible microprobe to record neural signals of a lateral giant nerve fiber of the escape circuit of an American crayfish. An electrostatic actuation folded planar probes into three-dimensional neural probes with arbitrary orientations for neuroscientific applications. A batch assembly based on electrostatic forces simplified the fabrication and was non-toxic. A novel fabrication for these three-dimensional flexible probes used SU-8 and Parylene technology. The mechanical strength of the neural probe was great enough to penetrate into a bio-gel. A flexible probe both decreased the micromotion and alleviated tissue encapsulation of the implant caused by chronic inflammation of tissue when an animal breathes or moves. The cortex consisted of six horizontal layers, and the neurons of the cortex were arranged in vertical structures; the three-dimensional microelectrode arrays were suitable to investigate the cooperative activity for neurons in horizontal separate layers and in vertical cortical columns. With this flexible probe we recorded neural signals of a lateral giant cell from an American crayfish. The response amplitude of action potentials was about 343 µV during 1 ms period; the average recorded data had a ratio of signal to noise as great as 30.22 ± 3.58 dB. The improved performance of this electrode made feasible the separation of neural signals according to their distinct shapes. The cytotoxicity indicated a satisfactory biocompatibility and non-toxicity of the flexible device fabricated in this work. © The Royal Society of Chemistry 2011

Self Assembly of Nano Metric Metallic Particles for Realization of Photonic and Electronic Nano Transistors

PubMed Central

Shahmoon, Asaf; Limon, Ofer; Girshevitz, Olga; Zalevsky, Zeev

2010-01-01

In this paper, we present the self assembly procedure as well as experimental results of a novel method for constructing well defined arrangements of self assembly metallic nano particles into sophisticated nano structures. The self assembly concept is based on focused ion beam (FIB) technology, where metallic nano particles are self assembled due to implantation of positive gallium ions into the insulating material (e.g., silica as in silicon on insulator wafers) that acts as intermediary layer between the substrate and the negatively charge metallic nanoparticles. PMID:20559513

Self assembly of nano metric metallic particles for realization of photonic and electronic nano transistors.

PubMed

Shahmoon, Asaf; Limon, Ofer; Girshevitz, Olga; Zalevsky, Zeev

2010-05-25

In this paper, we present the self assembly procedure as well as experimental results of a novel method for constructing well defined arrangements of self assembly metallic nano particles into sophisticated nano structures. The self assembly concept is based on focused ion beam (FIB) technology, where metallic nano particles are self assembled due to implantation of positive gallium ions into the insulating material (e.g., silica as in silicon on insulator wafers) that acts as intermediary layer between the substrate and the negatively charge metallic nanoparticles.

Ultrahigh PEMFC performance of a thin-film, dual-electrode assembly with tailored electrode morphology.

PubMed

Jung, Chi-Young; Kim, Tae-Hyun; Yi, Sung-Chul

2014-02-01

A dual-electrode membrane electrode assembly (MEA) for proton exchange membrane fuel cells with enhanced polarization under zero relative humidity (RH) is fabricated by introducing a phase-separated morphology in an agglomerated catalyst layer of Pt/C (platinum on carbon black) and Nafion. In the catalyst layer, a sufficient level of phase separation is achieved by dispersing the Pt catalyst and the Nafion dispersion in a mixed-solvent system (propane-1,2,3-triol/1-methyl-2-pyrrolidinone).The high polymer chain mobility results in improved water uptake and regular pore-size distribution with small pore diameters. The electrochemical performance of the dual-film electrode assembly with different levels of phase separation is compared to conventional electrode assemblies. As a result, good performance at 0 % RH is obtained because self-humidification is dramatically improved by attaching this dense and phase-separated catalytic overlayer onto the conventional catalyst layer. A MEA prepared using the thin-film, dual-layered electrode exhibits 39-fold increased RH stability and 28-fold improved start-up recovery time during the on-off operation relative to the conventional device. We demonstrate the successful operation of the dual-layered electrode comprised of discriminatively phase-separated agglomerates with an ultrahigh zero RH fuel-cell performance reaching over 95 % performance of a fully humidified MEA. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multilayers enzyme-coated carbon nanotubes as biolabel for ultrasensitive chemiluminescence immunoassay of cancer biomarker.

PubMed

Bi, Sai; Zhou, Hong; Zhang, Shusheng

2009-06-15

A novel and ultrasensitive chemiluminescence immunoassay (CLIA) method based on multiple enzyme layers assembled multiwall carbon nanotubes (MWCNTs) as signal amplification labels was developed by employing luminol-H(2)O(2)-HRP-bromophenol blue (BPB) enhanced chemiluminescence (CL) system for the detection of a cancer biomarker in human serum samples, as exemplified by the measurement of alpha-fetoprotein (AFP) as a model protein. In this study, horseradish peroxidase (HRP) was assembled onto MWCNTs templates layer-by-layer (LBL) through electrostatic interactions with polyion PDDA, and further conjugated with AFP secondary antibodies (Ab(2)) as the enzyme label. The resulting LBL assembly could maximize the ratio of HRP/Ab(2) which could amplify the sensitivity greatly. To the best of our knowledge, it was the first time for this strategy applied in CLIA to date. Under the optimum conditions of luminol-H(2)O(2)-HRP-BPB CL system and the sandwich immunoreactions, a linear range from 0.02 to 2.0 ng/mL (R=0.9980) was obtained with the detection limit of 8.0 pg/mL (3sigma) which was two orders of magnitude lower than standard ELISA method. Furthermore, accurate detection of AFP in human serum samples was also demonstrated by comparison to ELISA assays. From the above results, such signal amplification strategy proposed by the novel CNT-LBL enzyme label showed an excellent promise for ultrasensitive detection of cancer biomarkers in clinical laboratory.

Biocompatible magnetic and molecular dual-targeting polyelectrolyte hybrid hollow microspheres for controlled drug release.

PubMed

Du, Pengcheng; Zeng, Jin; Mu, Bin; Liu, Peng

2013-05-06

Well-defined biocompatible magnetic and molecular dual-targeting polyelectrolyte hybrid hollow microspheres have been accomplished via the layer-by-layer (LbL) self-assembly technique. The hybrid shell was fabricated by the electrostatic interaction between the polyelectrolyte cation, chitosan (CS), and the hybrid anion, citrate modified ferroferric oxide nanoparticles (Fe3O4-CA), onto the uniform polystyrene sulfonate microsphere templates. Then the magnetic hybrid core/shell composite particles were modified with a linear, functional poly(ethylene glycol) (PEG) monoterminated with a biotargeting molecule (folic acid (FA)). Afterward the dual targeting hybrid hollow microspheres were obtained after etching the templates by dialysis. The dual targeting hybrid hollow microspheres exhibit exciting pH response and stability in high salt-concentration media. Their pH-dependent controlled release of the drug molecule (anticancer drug, doxorubicin (DOX)) was also investigated in different human body fluids. As expected, the cell viability of the HepG2 cells which decreased more rapidly was treated by the FA modified hybrid hollow microspheres rather than the unmodified one in the in vitro study. The dual-targeting hybrid hollow microspheres demonstrate selective killing of the tumor cells. The precise magnetic and molecular targeting properties and pH-dependent controlled release offers promise for cancer treatment.

All-optical switching based on optical fibre long period gratings modified bacteriorhodopsin

NASA Astrophysics Data System (ADS)

Korposh, S.; James, S.; Partridge, M.; Sichka, M.; Tatam, R.

2018-05-01

All-optical switching using an optical fibre long-period gating (LPG) modified with bacteriorhodopsin (bR) is demonstrated. The switching process is based on the photo-induced RI change of bR, which in turn changes the phase matching conditions of the mode coupling by the LPG, leading to modulation of the propagating light. The effect was studied with an LPG immersed into a bR solution and with LPGs coated with the bR films, deposited onto the LPGs using the layer-by-layer electrostatic self-assembly (LbL) method. The dependence of the all-optical switching efficiency upon the concentration of the bR solution and on the grating period of the LPG was also studied. In addition, an in-fibre Mach-Zehnder interferometer (MZI) composed of a cascaded LPG pair separated by 30 mm and modified with bR was used to enhance the wavelength range of all-optical switching. The switching wavelength is determined by the grating period of the LPG. Switching efficiencies of 16% and 35% were observed when an LPG and an MZI were immersed into bR solutions, respectively. The switching time for devices coated with bR-films was within 1 s, 10 times faster than that observed for devices immersed into bR solution.

A surface-mediated siRNA delivery system developed with chitosan/hyaluronic acid-siRNA multilayer films through layer-by-layer self-assembly

NASA Astrophysics Data System (ADS)

Wu, Lijuan; Wu, Changlin; Liu, Guangwan; Liao, Nannan; Zhao, Fang; Yang, Xuxia; Qu, Hongyuan; Peng, Bo; Chen, Li; Yang, Guang

2016-12-01

siRNA delivery remains highly challenging because of its hydrophilic and anionic nature and its sensitivity to nuclease degradation. Effective siRNA loading and improved transfection efficiency into cells represents a key problem. In our study, we prepared Chitosan/Hyaluronic acid-siRNA multilayer films through layer-by-layer self-assembly, in which siRNAs can be effectively loaded and protected. The construction process was characterized by FTIR, 13C NMR (CP/MAS), UV-vis spectroscopy, and atomic force microscopy (AFM). We presented the controlled-release performance of the films during incubation in 1 M NaCl solution for several days through UV-vis spectroscopy and polyacrylamide gel electrophoresis (PAGE). Additionally, we verified the stability and integrity of the siRNA loaded on multilayer films. Finally, the biological efficacy of the siRNA delivery system was evaluated via cells adhesion and gene silencing analyses in eGFP-HEK 293T cells. This new type of surface-mediated non-viral multilayer films may have considerable potential in the localized and controlled-release delivery of siRNA in mucosal tissues, and tissue engineering application.

Multilayer Ferritin Array for Bionanobattery

NASA Technical Reports Server (NTRS)

Chu, Sang-Hyon (Inventor); Choi, Sang H. (Inventor); Kim, Jae-Woo (Inventor); Lillehei, Peter T. (Inventor); Park, Yeonjoon (Inventor); King, Glen C. (Inventor); Elliott, James R., Jr. (Inventor)

2009-01-01

A thin-film electrode for a bio-nanobattery is produced by consecutively depositing arrays of a ferritin protein on a substrate, employing a spin self-assembly procedure. By this procedure, a first ferritin layer is first formed on the substrate, followed by building a second, oppositely-charged ferritin layer on the top of the first ferritin layer to form a bilayer structure. Oppositely-charged ferritin layers are subsequently deposited on top of each other until a desired number of bilayer structures is produced. An ordered, uniform, stable and robust, thin-film electrode material of enhanced packing density is presented, which provides optimal charge density for the bio-nanobattery.

A fabrication guide for planar silicon quantum dot heterostructures

NASA Astrophysics Data System (ADS)

Spruijtenburg, Paul C.; Amitonov, Sergey V.; van der Wiel, Wilfred G.; Zwanenburg, Floris A.

2018-04-01

We describe important considerations to create top-down fabricated planar quantum dots in silicon, often not discussed in detail in literature. The subtle interplay between intrinsic material properties, interfaces and fabrication processes plays a crucial role in the formation of electrostatically defined quantum dots. Processes such as oxidation, physical vapor deposition and atomic-layer deposition must be tailored in order to prevent unwanted side effects such as defects, disorder and dewetting. In two directly related manuscripts written in parallel we use techniques described in this work to create depletion-mode quantum dots in intrinsic silicon, and low-disorder silicon quantum dots defined with palladium gates. While we discuss three different planar gate structures, the general principles also apply to 0D and 1D systems, such as self-assembled islands and nanowires.

Controlling the optical parameters of self-assembled silver films with wetting layers and annealing

NASA Astrophysics Data System (ADS)

Ciesielski, Arkadiusz; Skowronski, Lukasz; Trzcinski, Marek; Szoplik, Tomasz

2017-11-01

We investigated the influence of presence of Ni and Ge wetting layers as well as annealing on the permittivity of Ag films with thicknesses of 20, 35 and 65 nm. Most of the research on thin silver films deals with very small (<20 nm) or relatively large (≥50 nm) thicknesses. We studied the transition region (around 30 nm) from charge percolation pathways to fully continuous films and compared the values of optical parameters among silver layers with at least one fixed attribute (thickness, wetting and capping material, post-process annealing). Our study, based on atomic force microscopy, ellipsometric and X-ray photoelectron spectroscopy measurements, shows that utilizing a wetting layer is comparable to increasing the thickness of the silver film. Both operations decrease the roughness-to-thickness ratio, thus decreasing the scattering losses and both narrow the Lorentz-shaped interband transition peak. However, while increasing silver thickness increases absorption on the free carriers, the use of wetting layers influences the self-assembled internal structure of silver films in such a way, that the free carrier absorption decreases. Wetting layers also introduce additional contributions from effects like segregation or diffusion, which evolve in time and due to annealing.

Modeling and stabilization results for a charge or current-actuated active constrained layer (ACL) beam model with the electrostatic assumption

NASA Astrophysics Data System (ADS)

Özer, Ahmet Özkan

2016-04-01

An infinite dimensional model for a three-layer active constrained layer (ACL) beam model, consisting of a piezoelectric elastic layer at the top and an elastic host layer at the bottom constraining a viscoelastic layer in the middle, is obtained for clamped-free boundary conditions by using a thorough variational approach. The Rao-Nakra thin compliant layer approximation is adopted to model the sandwich structure, and the electrostatic approach (magnetic effects are ignored) is assumed for the piezoelectric layer. Instead of the voltage actuation of the piezoelectric layer, the piezoelectric layer is proposed to be activated by a charge (or current) source. We show that, the closed-loop system with all mechanical feedback is shown to be uniformly exponentially stable. Our result is the outcome of the compact perturbation argument and a unique continuation result for the spectral problem which relies on the multipliers method. Finally, the modeling methodology of the paper is generalized to the multilayer ACL beams, and the uniform exponential stabilizability result is established analogously.

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

PubMed

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

2012-01-01

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

Self-Functionalization Behind a Solution-Processed NiOx Film Used As Hole Transporting Layer for Efficient Perovskite Solar Cells.

PubMed

Ciro, John; Ramírez, Daniel; Mejía Escobar, Mario Alejandro; Montoya, Juan Felipe; Mesa, Santiago; Betancur, Rafael; Jaramillo, Franklin

2017-04-12

Fabrication of solution-processed perovskite solar cells (PSCs) requires the deposition of high quality films from precursor inks. Frequently, buffer layers of PSCs are formed from dispersions of metal oxide nanoparticles (NPs). Therefore, the development of trustable methods for the preparation of stable colloidal NPs dispersions is crucial. In this work, a novel approach to form very compact semiconducting buffer layers with suitable optoelectronic properties is presented through a self-functionalization process of the nanocrystalline particles by their own amorphous phase and without adding any other inorganic or organic functionalization component or surfactant. Such interconnecting amorphous phase composed by residual nitrate, hydroxide, and sodium ions, proved to be fundamental to reach stable colloidal dispersions and contribute to assemble the separate crystalline nickel oxide NPs in the final film, resulting in a very homogeneous and compact layer. A proposed mechanism behind the great stabilization of the nanoparticles is exposed. At the end, the self-functionalized nickel oxide layer exhibited high optoelectronic properties enabling perovskite p-i-n solar cells as efficient as 16.6% demonstrating the pertinence of the presented strategy to obtain high quality buffer layers processed in solution at room temperature.

Adsorption and self-assembly of M13 phage into directionally organized structures on C and SiO2 films.

PubMed

Moghimian, Pouya; Srot, Vesna; Rothenstein, Dirk; Facey, Sandra J; Harnau, Ludger; Hauer, Bernhard; Bill, Joachim; van Aken, Peter A

2014-09-30

A versatile method for the directional assembly of M13 phage using amorphous carbon and SiO2 thin films was demonstrated. A high affinity of the M13 phage macromolecules for incorporation into aligned structures on an amorphous carbon surface was observed at the concentration range, in which the viral nanofibers tend to disorder. In contrast, the viral particles showed less freedom to adopt an aligned orientation on SiO2 films when deposited in close vicinity. Here an interpretation of the role of the carbon surface in significant enhancement of adsorption and generation of viral arrays with a high orientational order was proposed in terms of surface chemistry and competitive electrostatic interactions. This study suggests the use of amorphous carbon substrates as a template for directional organization of a closely-packed and two-dimensional M13 viral film, which can be a promising route to mineralize a variety of smooth and homogeneous inorganic nanostructure layers.

Ultrasensitive electrochemical detection of tumor cells based on multiple layer CdS quantum dots-functionalized polystyrene microspheres and graphene oxide - polyaniline composite.

PubMed

Wang, Jidong; Wang, Xiaoyu; Tang, Hengshan; Gao, Zehua; He, Shengquan; Li, Jian; Han, Shumin

2018-02-15

In this work, a novel ultrasensitive electrochemical biosensor was developed for the detection of K562 cell by a signal amplification strategy based on multiple layer CdS QDs functionalized polystyrene microspheres(PS) as bioprobe and graphene oxide(GO) -polyaniline(PANI) composite as modified materials of capture electrode. Due to electrostatic force of different charge, CdS QDs were decorated on the surface of PS by PDDA (poly(diallyldimethyl-ammonium chloride)) through a layer-by-layer(LBL) assemble technology, in which the structure of multiple layer CdS QDs increased the detection signal intensity. Moreover, GO-PANI composite not only enhanced the electron transfer rate, but also increased tumor cells load ratio. The resulting electrochemical biosensor was used to detect K562 cells with a lower detection limit of 3 cellsmL -1 (S/N = 3) and a wider linear range from 10 to 1.0 × 10 7 cellsmL -1 . This sensor was also used for mannosyl groups on HeLa cells and Hct116 cells, which showed high specificity and sensitivity. This signal amplification strategy would provide a novel approach for detection, diagnosis and treatment for tumor cells. Copyright © 2017 Elsevier B.V. All rights reserved.

The expansion of polarization charge layers into magnetized vacuum - Theory and computer simulations

NASA Technical Reports Server (NTRS)

Galvez, Miguel; Borovsky, Joseph E.

1991-01-01

The formation and evolution of polarization charge layers on cylindrical plasma streams moving in vacuum are investigated using analytic theory and 2D electrostatic particle-in-cell computer simulations. It is shown that the behavior of the electron charge layer goes through three stages. An early time expansion is driven by electrostatic repulsion of electrons in the charge layer. At the intermediate stage, the simulations show that the electron-charge-layer expansion is halted by the positively charged plasma stream. Electrons close to the stream are pulled back to the stream and a second electron expansion follows in time. At the late stage, the expansion of the ion charge layer along the magnetic field lines accompanies the electron expansion to form an ambipolar expansion. It is found that the velocities of these electron-ion expansions greatly exceed the velocities of ambipolar expansions which are driven by plasma temperatures.

Self-assembly Columnar Structure in Active Layer of Bulk Heterojunction Solar Cell

NASA Astrophysics Data System (ADS)

Pan, Cheng; Segui, Jennifer; Yu, Yingjie; Li, Hongfei; Akgun, Bulent; Satijia, Sushil. K.; Gersappe, Dilip; Nam, Chang-Yong; Rafailovich, Miriam

2012-02-01

Bulk Heterojunction (BHJ) polymer solar cells are an area of intense interest due to their flexibility and relatively low cost. However, due to the disordered inner structure in active layer, the power conversion efficiency of BHJ solar cell is relatively low. Our research provides the method to produce ordered self-assembly columnar structure within active layer of bulk heterojunction (BHJ) solar cell by introducing polystyrene (PS) into the active layer. The blend thin film of polystyrene, poly (3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) at different ratio are spin coated on substrate and annealed in vacuum oven for certain time. Atomic force microscopy (AFM) images show uniform phase segregation on the surface of polymer blend thin film and highly ordered columnar structure is then proven by etching the film with ion sputtering. TEM cross-section technology is also used to investigate the column structure. Neutron reflectometry was taken to establish the confinement of PCBM at the interface of PS and P3HT. The different morphological structures formed via phase segregation will be correlated with the performance of the PEV cells to be fabricated at the BNL-CFN.

High-performance mussel-inspired adhesives of reduced complexity

PubMed Central

Ahn, B. Kollbe; Das, Saurabh; Linstadt, Roscoe; Kaufman, Yair; Martinez-Rodriguez, Nadine R.; Mirshafian, Razieh; Kesselman, Ellina; Talmon, Yeshayahu; Lipshutz, Bruce H.; Israelachvili, Jacob N.; Waite, J. Herbert

2015-01-01

Despite the recent progress in and demand for wet adhesives, practical underwater adhesion remains limited or non-existent for diverse applications. Translation of mussel-inspired wet adhesion typically entails catechol functionalization of polymers and/or polyelectrolytes, and solution processing of many complex components and steps that require optimization and stabilization. Here we reduced the complexity of a wet adhesive primer to synthetic low-molecular-weight catecholic zwitterionic surfactants that show very strong adhesion (∼50 mJ m−2) and retain the ability to coacervate. This catecholic zwitterion adheres to diverse surfaces and self-assembles into a molecularly smooth, thin (<4 nm) and strong glue layer. The catecholic zwitterion holds particular promise as an adhesive for nanofabrication. This study significantly simplifies bio-inspired themes for wet adhesion by combining catechol with hydrophobic and electrostatic functional groups in a small molecule. PMID:26478273

Construction and Self-Assembly of Single-Chain Polymer Nanoparticles via Coordination Association and Electrostatic Repulsion in Water.

PubMed

Zhu, Zhengguang; Xu, Na; Yu, Qiuping; Guo, Lei; Cao, Hui; Lu, Xinhua; Cai, Yuanli

2015-08-01

Simultaneous coordination-association and electrostatic-repulsion interactions play critical roles in the construction and stabilization of enzymatic function metal centers in water media. These interactions are promising for construction and self-assembly of artificial aqueous polymer single-chain nanoparticles (SCNPs). Herein, the construction and self-assembly of dative-bonded aqueous SCNPs are reported via simultaneous coordination-association and electrostatic-repulsion interactions within single chains of histamine-based hydrophilic block copolymer. The electrostatic-repulsion interactions are tunable through adjusting the imidazolium/imidazole ratio in response to pH, and in situ Cu(II)-coordination leads to the intramolecular association and single-chain collapse in acidic water. SCNPs are stabilized by the electrostatic repulsion of dative-bonded block and steric shielding of nonionic water-soluble block, and have a huge specific surface area of function metal centers accessible to substrates in acidic water. Moreover, SCNPs can assemble into micelles, networks, and large particles programmably in response to the solution pH. These unique media-sensitive phase-transformation behaviors provide a general, facile, and versatile platform for the fabrication of enzyme-inspired smart aqueous catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Manipulation and Investigation of Uniformly-Spaced Nanowire Array on a Substrate via Dielectrophoresis and Electrostatic Interaction.

PubMed

Choi, U Hyeok; Park, Ji Hun; Kim, Jaekyun

2018-06-21

Directed-assembly of nanowires on the dielectrics-covered parallel electrode structure is capable of producing uniformly-spaced nanowire array at the electrode gap due to dielectrophoretic nanowire attraction and electrostatic nanowire repulsion. Beyond uniformly-spaced nanowire array formation, the control of spacing in the array is beneficial in that it should be the experimental basis of the precise positioning of functional nanowires on a circuit. Here, we investigate the material parameters and bias conditions to modulate the nanowire spacing in the ordered array, where the nanowire array formation is readily attained due to the electrostatic nanowire interaction. A theoretical model for the force calculation and the simulation of the induced charge in the assembled nanowire verifies that the longer nanowires on thicker dielectric layer tend to be assembled with a larger pitch due to the stronger nanowire-nanowire electrostatic repulsion, which is consistent with the experimental results. It was claimed that the stronger dielectrophoretic force is likely to attract more nanowires that are suspended in solution at the electrode gap, causing them to be less-spaced. Thus, we propose a generic mechanism, competition of dielectrophoretic and electrostatic force, to determine the nanowire pitch in an ordered array. Furthermore, this spacing-controlled nanowire array offers a way to fabricate the high-density nanodevice array without nanowire registration.

Biomimetic Structural Materials: Inspiration from Design and Assembly.

PubMed

Yaraghi, Nicholas A; Kisailus, David

2018-04-20

Nature assembles weak organic and inorganic constituents into sophisticated hierarchical structures, forming structural composites that demonstrate impressive combinations of strength and toughness. Two such composites are the nacre structure forming the inner layer of many mollusk shells, whose brick-and-mortar architecture has been the gold standard for biomimetic composites, and the cuticle forming the arthropod exoskeleton, whose helicoidal fiber-reinforced architecture has only recently attracted interest for structural biomimetics. In this review, we detail recent biomimetic efforts for the fabrication of strong and tough composite materials possessing the brick-and-mortar and helicoidal architectures. Techniques discussed for the fabrication of nacre- and cuticle-mimetic structures include freeze casting, layer-by-layer deposition, spray deposition, magnetically assisted slip casting, fiber-reinforced composite processing, additive manufacturing, and cholesteric self-assembly. Advantages and limitations to these processes are discussed, as well as the future outlook on the biomimetic landscape for structural composite materials.

Biomimetic Structural Materials: Inspiration from Design and Assembly

NASA Astrophysics Data System (ADS)

Yaraghi, Nicholas A.; Kisailus, David

2018-04-01

Nature assembles weak organic and inorganic constituents into sophisticated hierarchical structures, forming structural composites that demonstrate impressive combinations of strength and toughness. Two such composites are the nacre structure forming the inner layer of many mollusk shells, whose brick-and-mortar architecture has been the gold standard for biomimetic composites, and the cuticle forming the arthropod exoskeleton, whose helicoidal fiber-reinforced architecture has only recently attracted interest for structural biomimetics. In this review, we detail recent biomimetic efforts for the fabrication of strong and tough composite materials possessing the brick-and-mortar and helicoidal architectures. Techniques discussed for the fabrication of nacre- and cuticle-mimetic structures include freeze casting, layer-by-layer deposition, spray deposition, magnetically assisted slip casting, fiber-reinforced composite processing, additive manufacturing, and cholesteric self-assembly. Advantages and limitations to these processes are discussed, as well as the future outlook on the biomimetic landscape for structural composite materials.

Identifying the Assembly Configuration and Fluorescence Spectra of Nanoscale Zinc-Tetraphenylporphyrin Aggregates with Scanning Tunneling Microscopy

PubMed Central

Zhang, Xiao-Lei; Jiang, Jian-Wei; Liu, Yi-Ting; Lou, Shi-Tao; Gao, Chun-Lei; Jin, Qing-Yuan

2016-01-01

ZnTPP (Zinc-Tetraphenylporphyrin) is one of the most common nanostructured materials, having high stability and excellent optoelectronic properties. In this paper, the fluorescence features of self-assembled ZnTPP monomers and aggregates on Au(111) surface are investigated in detail on the nanometer scale with scanning tunneling microscopy (STM). The formation of ZnTPP dimers is found in thick layers of a layer-by-layer molecular assembly on Au substrate with its specific molecular arrangement well characterized. Tip-induced luminescence shows a red shift from tilted dimers comparing with the behavior from monomers, which can be attributed to the change of vibrational states due to the intermolecular interaction and the increasing dielectric effect. The nanoscale configuration dependence of electroluminescence is demonstrated to provide a powerful tool aiding the design of functional molecular photoelectric devices. PMID:26948654

Methods for batch fabrication of cold cathode vacuum switch tubes

DOEpatents

Walker, Charles A [Albuquerque, NM; Trowbridge, Frank R [Albuquerque, NM

2011-05-10

Methods are disclosed for batch fabrication of vacuum switch tubes that reduce manufacturing costs and improve tube to tube uniformity. The disclosed methods comprise creating a stacked assembly of layers containing a plurality of adjacently spaced switch tube sub-assemblies aligned and registered through common layers. The layers include trigger electrode layer, cathode layer including a metallic support/contact with graphite cathode inserts, trigger probe sub-assembly layer, ceramic (e.g. tube body) insulator layer, and metallic anode sub-assembly layer. Braze alloy layers are incorporated into the stacked assembly of layers, and can include active metal braze alloys or direct braze alloys, to eliminate costs associated with traditional metallization of the ceramic insulator layers. The entire stacked assembly is then heated to braze/join/bond the stack-up into a cohesive body, after which individual switch tubes are singulated by methods such as sawing. The inventive methods provide for simultaneously fabricating a plurality of devices as opposed to traditional methods that rely on skilled craftsman to essentially hand build individual devices.

Layer-by-layer assembled biopolymer microcapsule with separate layer cavities generated by gas-liquid microfluidic approach.

PubMed

Wang, Yifeng; Zhou, Jing; Guo, Xuecheng; Hu, Qian; Qin, Chaoran; Liu, Hui; Dong, Meng; Chen, Yanjun

2017-12-01

In this work, a layer-by-layer (LbL) assembled biopolymer microcapsule with separate layer cavities is generated by a novel and convenient gas-liquid microfluidic approach. This approach exhibits combined advantages of microfluidic approach and LbL assembly method, and it can straightforwardly build LbL-assembled capsules in mild aqueous environments at room temperature. In particular, using this approach we can build the polyelectrolyte multilayer capsule with favorable cavities in each layer, and without the need for organic solvent, emulsifying agent, or sacrificial template. Various components (e.g., drugs, proteins, fluorescent dyes, and nanoparticles) can be respectively encapsulated in the separate layer cavities of the LbL-assembled capsules. Moreover, the encapsulated capsules present the ability as colorimetric sensors, and they also exhibit the interesting release behavior. Therefore, the LbL-assembled biopolymer capsule is a promising candidate for biomedical applications in targeted delivery, controlled release, and bio-detection. Copyright © 2017 Elsevier B.V. All rights reserved.

Polyfibroblast Phase 4: A Self-Healing and Galvanic Protection Additive

DTIC Science & Technology

2014-11-26

scratches. Designed to work with existing military grade primers, Polyfibroblast consists of microscopic, hollow zinc tubes filled with a moisture...barrier layer if corrosion commences before its self-assembly completes. Once the OTS passivation layer has formed, however, it forms an insulating ...silica nanopowder (10-20 nm diameter) replaces the conventional surfactant or hydrocolloid emulsifier. Isophorone diisocyanate (IPDI) in the OTS core

On the Impact of Electrostatic Correlations on the Double-Layer Polarization of a Spherical Particle in an Alternating Current Field.

PubMed

Alidoosti, Elaheh; Zhao, Hui

2018-05-15

At concentrated electrolytes, the ion-ion electrostatic correlation effect is considered an important factor in electrokinetics. In this paper, we compute, in theory and simulation, the dipole moment for a spherical particle (charged, dielectric) under the action of an alternating electric field using the modified continuum Poisson-Nernst-Planck (PNP) model by Bazant et al. [ Double Layer in Ionic Liquids: Overscreening Versus Crowding . Phys. Rev. Lett. 2011 , 106 , 046102 ] We investigate the dependency of the dipole moment in terms of frequency and its variation with such quantities like ζ-potential, electrostatic correlation length, and double-layer thickness. With thin electric double layers, we develop simple models through performing an asymptotic analysis of the modified PNP model. We also present numerical results for an arbitrary Debye screening length and electrostatic correlation length. From the results, we find a complicated impact of electrostatic correlations on the dipole moment. For instance, with increasing the electrostatic correlation length, the dipole moment decreases and reaches a minimum and then it goes up. This is because of initially decreasing of surface conduction and finally increasing due to the impact of ion-ion electrostatic correlations on ion's convection and migration. Also, we show that in contrast to the standard PNP model, the modified PNP model can qualitatively explain the data from the experimental results in multivalent electrolytes.

Assembly of the outermost spore layer: pieces of the puzzle are coming together.

PubMed

Stewart, George C

2017-05-01

Certain endospore-forming soil dwelling bacteria are important human, animal or insect pathogens. These organisms produce spores containing an outer layer, the exosporium. The exosporium is the site of interactions between the spore and the soil environment and between the spore and the infected host during the initial stages of infection. The composition and assembly process of the exosporium are poorly understood. This is partly due to the extreme stability of the exosporium that has proven to be refractive to existing methods to deconstruct the intact structure into its component parts. Although more than 20 proteins have been identified as exosporium-associated, their abundance, relationship to other proteins and the processes by which they are assembled to create the exosporium are largely unknown. In this issue of Molecular Microbiology, Terry, Jiang, and colleagues in Per Bullough's laboratory show that the ExsY protein is a major structural protein of the exosporium basal layer of B. cereus family spores and that it can self-assemble into complex structures that possess many of the structural features characteristic of the exosporium basal layer. The authors refined a model for exosporium assembly. Their findings may have implications for exosporium formation in other spore forming bacteria, including Clostridium species. © 2017 John Wiley & Sons Ltd.

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.

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.

Gold Nanoclusters@Ru(bpy)₃²⁺-Layered Double Hydroxide Ultrathin Film as a Cathodic Electrochemiluminescence Resonance Energy Transfer Probe.

PubMed

Yu, Yingchang; Lu, Chao; Zhang, Meining

2015-08-04

Herein, it is the first report that a cathodic electrochemiluminescence (ECL) resonance energy transfer (ERET) system is fabricated by layer-by-layer (LBL) electrostatic assembly of CoAl layered double hydroxide (LDH) nanosheets with a mixture of blue BSA-gold nanoclusters (AuNCs) and Ru(bpy)3(2+) (denoted as AuNCs@Ru) on an Au electrode. The possible ECL mechanism indicates that the appearance of CoAl-LDH nanosheets generates a long-range stacking order of the AuNCs@Ru on an Au electrode, facilitating the occurrence of the ERET between BSA-AuNC donors and Ru(bpy)3(2+) acceptors on the as-prepared AuNCs@Ru-LDH ultrathin films (UTFs). Furthermore, it is observed that the cathodic ECL intensity can be quenched efficiently in the presence of 6-mercaptopurine (6-MP) in a linear range of 2.5-100 nM with a detection limit of 1.0 nM. On the basis of these interesting phenomena, a facile cathodic ECL sensor has successfully distinguished 6-MP from other thiol-containing compounds (e.g., cysteine and glutathione) in human serum and urine samples. The proposed sensing scheme opens a way for employing the layered UTFs as a platform for the cathodic ECL of Ru(bpy)3(2+).

Enhanced vanadium redox flow battery performance using graphene nanoplatelets to decorate carbon electrodes

NASA Astrophysics Data System (ADS)

Sankar, Abhinandh; Michos, Ioannis; Dutta, Indrajit; Dong, Junhang; Angelopoulos, Anastasios P.

2018-05-01

Rotating Disk Electrode (RDE) measurements on model glassy carbon (GC) substrates and Cyclic Voltammetry on more practical commercial carbon supports are used to demonstrate that the kinetics of the positive VO2+/VO2+ redox reaction can be substantially enhanced by using electrostatic layer-by-layer assembly (LbL) to decorate their surface with graphene nanoplatelets (GNPs). An exchange current density, i0, is obtained that is more than two orders of magnitude greater than that observed with standard carbon supported Pt nanocatalyst with the deposition of only 20 GNP layers. Tafel slope analysis is compared to electron microscopy imaging to conclude that while faster redox kinetics is associated with an increase in the available active area, the prevalence of smaller GNPs and associated edge sites the can attenuate activity gains with increasing number of layers. Practical implementation to existing Vanadium Redox Flow Battery (VRFB) configurations was demonstrated through the application of a 370 nm (20 layer) LbL GNP coating on carbon felt (CF). The GNP coating yielded a 5% increase relative in voltage and overall efficiency of charge discharge curves obtained under typical VRFB cell operating conditions at 40 mA cm-2. Furthermore, a substantial increase in the discharge time is observed with this GNP coating on CF.

Molecular dynamics simulation of the diffusion of uranium species in clay pores.

PubMed

Liu, Xiao-yu; Wang, Lu-hua; Zheng, Zhong; Kang, Ming-liang; Li, Chun; Liu, Chun-li

2013-01-15

Molecular dynamics simulations were carried out to investigate the diffusive behavior of aqueous uranium species in montmorillonite pores. Three uranium species (UO(2)(2+), UO(2)CO(3), UO(2)(CO(3))(2)(2-)) were confirmed in both the adsorbed and diffuse layers. UO(2)(CO(3))(3)(4-) was neglected in the subsequent analysis due to its scare occurrence. The species-based diffusion coefficients in montmorillonite pores were then calculated, and compared with the water mobility and their diffusivity in aqueous solution/feldspar nanosized fractures. Three factors were considered that affected the diffusive behavior of the uranium species: the mobility of water, the self-diffusion coefficient of the aqueous species, and the electrostatic forces between the negatively charged surface and charged molecules. The mobility of U species in the adsorbed layer decreased in the following sequence: UO(2)(2+)>UO(2)CO(3)>UO(2)(CO(3))(2)(2-). In the diffuse layer, we obtained the highest diffusion coefficient for UO(2)(CO(3))(2)(2-) with the value of 5.48×10(-10) m(2) s(-1), which was faster than UO(2)(2+). For these two charged species, the influence of electrostatic forces on the diffusion of solutes in the diffuse layer is overwhelming, whereas the influence of self-diffusion and water mobility is minor. Our study demonstrated that the negatively charged uranyl carbonate complex must be addressed in the safety assessment of potential radioactive waste disposal systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Self-assembled virus-membrane complexes

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

Yang, Lihua; Liang, Hongjun; Angelini, Thomas

Anionic polyelectrolytes and cationic lipid membranes can self-assemble into lamellar structures ranging from alternating layers of membranes and polyelectrolytes to 'missing layer' superlattice structures. We show that these structural differences can be understood in terms of the surface-charge-density mismatch between the polyelectrolyte and membrane components by examining complexes between cationic membranes and highly charged M13 viruses, a system that allowed us to vary the polyelectrolyte diameter independently of the charge density. Such virus-membrane complexes have pore sizes that are about ten times larger in area than DNA-membrane complexes, and can be used to package and organize large functional molecules; correlatedmore » arrays of Ru(bpy){sub 3}{sup 2+} macroionic dyes have been directly observed within the virus-membrane complexes using an electron-density reconstruction. These observations elucidate fundamental design rules for rational control of self-assembled polyelectrolyte-membrane structures, which have applications ranging from non-viral gene therapy to biomolecular templates for nanofabrication.« less

Inkjet-Printed Biofunctional Thermo-Plasmonic Interfaces for Patterned Neuromodulation.

PubMed

Kang, Hongki; Lee, Gu-Haeng; Jung, Hyunjun; Lee, Jee Woong; Nam, Yoonkey

2018-02-27

Localized heat generation by the thermo-plasmonic effect of metal nanoparticles has great potential in biomedical engineering research. Precise patterning of the nanoparticles using inkjet printing can enable the application of the thermo-plasmonic effect in a well-controlled way (shape and intensity). However, a universally applicable inkjet printing process that allows good control in patterning and assembly of nanoparticles with good biocompatibility is missing. Here we developed inkjet-printing-based biofunctional thermo-plasmonic interfaces that can modulate biological activities. We found that inkjet printing of plasmonic nanoparticles on a polyelectrolyte layer-by-layer substrate coating enables high-quality, biocompatible thermo-plasmonic interfaces across various substrates (rigid/flexible, hydrophobic/hydrophilic) by induced contact line pinning and electrostatically assisted nanoparticle assembly. We experimentally confirmed that the generated heat from the inkjet-printed thermo-plasmonic patterns can be applied in micrometer resolution over a large area. Lastly, we demonstrated that the patterned thermo-plasmonic effect from the inkjet-printed gold nanorods can selectively modulate neuronal network activities. This inkjet printing process therefore can be a universal method for biofunctional thermo-plasmonic interfaces in various bioengineering applications.

Electrostatic interaction between an enzyme and electrodes in the electric double layer examined in a view of direct electron transfer-type bioelectrocatalysis.

PubMed

Sugimoto, Yu; Kitazumi, Yuki; Tsujimura, Seiya; Shirai, Osamu; Yamamoto, Masahiro; Kano, Kenji

2015-01-15

Effects of the electrode poential on the activity of an adsorbed enzyme has been examined by using copper efflux oxidase (CueO) as a model enzyme and by monitoring direct electron transfer (DET)-type bioelectrocatalysis of oxygen reduction. CueO adsorbed on bare Au electrodes at around the point of zero charge (E(pzc)) shows the highest DET activity, and the activity decreases as the adsorption potential (E(ad); at which the enzyme adsorbs) is far from E(pzc). We propose a model to explain the phenomena in which the electrostatic interaction between the enzyme and electrodes in the electric double layer affects the orientation and the stability of the adsorbed enzyme. The self-assembled monolayer of butanethiol on Au electrodes decreases the electric field in the outside of the inner Helmholtz plane and drastically diminishes the E(ad) dependence of the DET activity of CueO. When CueO is adsorbed on bare Au electrodes under open circuit potential and then is held at hold potentials (E(ho)) more positive than E(pzc), the DET activity of the CueO rapidly decreases with the hold time. The strong electric field with positive surface charge density on the metallic electrode (σ(M)) leads to fatal denaturation of the adsorbed CueO. Such denaturation effect is not so serious at E(ho)

Controlling the Mesostructure Formation within the Shell of Novel Cubic/Hexagonal Phase Cetyltrimethylammonium Bromide-Poly(acrylamide-acrylic acid) Capsules for pH Stimulated Release.

PubMed

Tangso, Kristian J; Patel, Hetika; Lindberg, Seth; Hartley, Patrick G; Knott, Robert; Spicer, Patrick T; Boyd, Ben J

2015-11-11

The self-assembly of ordered structures in mixtures of oppositely charged surfactant and polymer systems has been exploited in various cleaning and pharmaceutical applications and continue to attract much interest since their discovery in the late twentieth century. The ability to control the electrostatic and hydrophobic interactions that dictate the formation of liquid crystalline phases in these systems is advantageous in manipulation of structure and rendering them responsive to external stimuli. Nanostructured capsules comprised of the cationic surfactant, cetyltrimethylammonium bromide (CTAB), and the diblock copolymer poly(acrylamide-acrylic acid) (PAAm-AA) were prepared to assess their potential as pH responsive nanomaterials. Crossed-polarizing light microscopy (CPLM) and small-angle X-ray scattering (SAXS) identified coexisting Pm3n cubic and hexagonal phases at the surfactant-polymer interface. The hydrophobic and electrostatic interactions between the oppositely charged components were studied by varying temperature and solution pH, respectively, and were found to influence the liquid crystalline nanostructure formed. The lattice parameter of the mesophases and the fraction of cubic phase in the system decreased upon heating. Acidic conditions resulted in the loss of the highly ordered structures due to protonation of the carboxylic acid group, and subsequent reduction of attractive forces previously present between the oppositely charged molecules. The rate of release of the model hydrophilic drug, Rhodamine B (RhB), from nanostructured macro-sized capsules significantly increased when the pH of the solution was adjusted from pH 7 to pH 2. This allowed for immediate release of the compound of interest "on demand", opening new options for structured materials with increased functionality over typical layer-by-layer capsules.

Ionic Conductivity, Structural Deformation and Programmable Anisotropy of DNA Origami in Electric Field

PubMed Central

Li, Chen-Yu; Hemmig, Elisa A.; Kong, Jinglin; Yoo, Jejoong; Hernández-Ainsa, Silvia

2015-01-01

The DNA origami technique can enable functionalization of inorganic structures for single-molecule electric current recordings. Experiments have shown that several layers of DNA molecules—a DNA origami plate— placed on top of a solid-state nanopore is permeable to ions. Here, we report a comprehensive characterization of the ionic conductivity of DNA origami plates by means of all-atom molecular dynamics (MD) simulations and nanocapillary electric current recordings. Using the MD method, we characterize the ionic conductivity of several origami constructs, revealing the local distribution of ions, the distribution of the electrostatic potential and contribution of different molecular species to the current. The simulations determine the dependence of the ionic conductivity on the applied voltage, the number of DNA layers, the nucleotide content and the lattice type of the plates. We demonstrate that increasing the concentration of Mg2+ ions makes the origami plates more compact, reducing their conductivity. The conductance of a DNA origami plate on top of a solid-state nanopore is determined by the two competing effects: bending of the DNA origami plate that reduces the current and separation of the DNA origami layers that increases the current. The latter is produced by the electro-osmotic flow and is reversible at the time scale of a hundred nanoseconds. The conductance of a DNA origami object is found to depend on its orientation, reaching maximum when the electric field aligns with the direction of the DNA helices. Our work demonstrates feasibility of programming the electrical properties of a self-assembled nanoscale object using DNA. PMID:25623807

Ionic conductivity, structural deformation, and programmable anisotropy of DNA origami in electric field.

PubMed

Li, Chen-Yu; Hemmig, Elisa A; Kong, Jinglin; Yoo, Jejoong; Hernández-Ainsa, Silvia; Keyser, Ulrich F; Aksimentiev, Aleksei

2015-02-24

The DNA origami technique can enable functionalization of inorganic structures for single-molecule electric current recordings. Experiments have shown that several layers of DNA molecules, a DNA origami plate, placed on top of a solid-state nanopore is permeable to ions. Here, we report a comprehensive characterization of the ionic conductivity of DNA origami plates by means of all-atom molecular dynamics (MD) simulations and nanocapillary electric current recordings. Using the MD method, we characterize the ionic conductivity of several origami constructs, revealing the local distribution of ions, the distribution of the electrostatic potential and contribution of different molecular species to the current. The simulations determine the dependence of the ionic conductivity on the applied voltage, the number of DNA layers, the nucleotide content and the lattice type of the plates. We demonstrate that increasing the concentration of Mg(2+) ions makes the origami plates more compact, reducing their conductivity. The conductance of a DNA origami plate on top of a solid-state nanopore is determined by the two competing effects: bending of the DNA origami plate that reduces the current and separation of the DNA origami layers that increases the current. The latter is produced by the electro-osmotic flow and is reversible at the time scale of a hundred nanoseconds. The conductance of a DNA origami object is found to depend on its orientation, reaching maximum when the electric field aligns with the direction of the DNA helices. Our work demonstrates feasibility of programming the electrical properties of a self-assembled nanoscale object using DNA.

Design of five-layer gold nanoparticles self-assembled in a liquid open tubular column for ultrasensitive nano-LC-MS/MS proteomic analysis of 80 living cells.

PubMed

Shao, Xi; Zhang, Xiangmin

2017-04-01

In this work, for the first time, a liquid open tubular column modified by five-layer gold nanoparticles and linked with C 18 (GNPs@C 18 ) was designed and fabricated for nano-LC-MS/MS analysis of 80 living cells. Sixty nanometer gold nanoparticles were self-assembled layer by layer on the inner wall of a 20 μm id fused-silica capillary. C 18 was then linked on the gold nanoparticles to make the liquid open tubular column show hydrophobic character. Enough loading capacities for analysis of 80 living cells, ∼100 fmol for pk-10 and ∼30 fmol for insulin, were obtained with the 2 m × 20 μm id five-layer GNPs@C 18 open tubular column. The open tubular column was used in an online pretreatment and direct nano-LC-MS/MS analysis system to analyze 80 living HepG2 cells. In total, 650 proteins were identified in triplicate runs. The subcellular localization of the identified proteins showed that our system had no bias toward different cellular compartments. Protein copy number per cell of the identified proteins showed that the detection limit could reach 50 zmol and the abundance of the identified proteins could cover a dynamic range of 6 orders. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct optical imaging of nanoscale internal organization of polymer films

NASA Astrophysics Data System (ADS)

Suran, Swathi; Varma, Manoj

2018-02-01

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

New Strategies and Methods to Study Interactions between Tobacco Mosaic Virus Coat Protein and Its Inhibitors

PubMed Central

Li, Xiangyang; Chen, Zhuo; Jin, Linhong; Hu, Deyu; Yang, Song

2016-01-01

Studies of the targets of anti-viral compounds are hot topics in the field of pesticide research. Various efficient anti-TMV (Tobacco Mosaic Virus) compounds, such as Ningnanmycin (NNM), Antofine (ATF), Dufulin (DFL) and Bingqingxiao (BQX) are available. However, the mechanisms of the action of these compounds on targets remain unclear. To further study the mechanism of the action of the anti-TMV inhibitors, the TMV coat protein (TMV CP) was expressed and self-assembled into four-layer aggregate disks in vitro, which could be reassembled into infectious virus particles with TMV RNA. The interactions between the anti-TMV compounds and the TMV CP disk were analyzed by size exclusion chromatography, isothermal titration calorimetry and native-polyacrylamide gel electrophoresis methods. The results revealed that assembly of the four-layer aggregate disk was inhibited by NNM; it changed the four-layer aggregate disk into trimers, and affected the regular assembly of TMV CP and TMV RNA. The four-layer aggregate disk of TMV CP was little inhibited by ATF, DFL and BQX. Our results provide original data, as well as new strategies and methods, for research on the mechanism of action of anti-viral drugs. PMID:26927077

Model-based guiding pattern synthesis for robust assembly of contact layers using directed self-assembly

NASA Astrophysics Data System (ADS)

Mitra, Joydeep; Torres, Andres; Ma, Yuansheng; Pan, David Z.

2018-01-01

Directed self-assembly (DSA) has emerged as one of the most compelling next-generation patterning techniques for sub 7 nm via or contact layers. A key issue in enabling DSA as a mainstream patterning technique is the generation of grapho-epitaxy-based guiding pattern (GP) shapes to assemble the contact patterns on target with high fidelity and resolution. Current GP generation is mostly empirical, and limited to a very small number of via configurations. We propose the first model-based GP synthesis algorithm and methodology for on-target and robust DSA, on general via pattern configurations. The final postoptical proximity correction-printed GPs derived from our original synthesized GPs are resilient to process variations and continue to maintain the same DSA fidelity in terms of placement error and target shape.

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

Programmable Electrochemical Rectifier Based on a Thin-Layer Cell.

PubMed

Park, Seungjin; Park, Jun Hui; Hwang, Seongpil; Kwak, Juhyoun

2017-06-21

A programmable electrochemical rectifier based on thin-layer electrochemistry is described here. Both the rectification ratio and the response time of the device are programmable by controlling the gap distance of the thin-layer electrochemical cell, which is easily controlled using commercially available beads. One of the electrodes was modified using a ferrocene-terminated self-assembled monolayer to offer unidirectional charge transfers via soluble redox species. The thin-layer configuration provided enhanced mass transport, which was determined by the gap thickness. The device with the smallest gap thickness (∼4 μm) showed an unprecedented, high rectification ratio (up to 160) with a fast response time in a two-terminal configuration using conventional electronics.

Energy storage device including a redox-enhanced electrolyte

DOEpatents

Stucky, Galen; Evanko, Brian; Parker, Nicholas; Vonlanthen, David; Auston, David; Boettcher, Shannon; Chun, Sang-Eun; Ji, Xiulei; Wang, Bao; Wang, Xingfeng; Chandrabose, Raghu Subash

2017-08-08

An electrical double layer capacitor (EDLC) energy storage device is provided that includes at least two electrodes and a redox-enhanced electrolyte including two redox couples such that there is a different one of the redox couples for each of the electrodes. When charged, the charge is stored in Faradaic reactions with the at least two redox couples in the electrolyte and in a double-layer capacitance of a porous carbon material that comprises at least one of the electrodes, and a self-discharge of the energy storage device is mitigated by at least one of electrostatic attraction, adsorption, physisorption, and chemisorption of a redox couple onto the porous carbon material.

Ternary blend polymer solar cells with self-assembled structure for enhancing power conversion efficiency

NASA Astrophysics Data System (ADS)

Yang, Zhenhua; Li, Hongfei; Nam, Chang-Yong; Kisslinger, Kim; Satija, Sushil; Rafailovich, Miriam

Bulk heterojunction (BHJ) polymer solar cells are an area of intense interest due to their advantages such as mechanical flexibility. The active layer is typically spin coated from the solution of polythiophene derivatives (donor) and fullerenes (acceptor) and interconnected domains are formed because of phase separation. However, the power conversion efficiency (PCE) of BHJ solar cell is restricted by the disordered inner structures in the active layer, donor or acceptor domains isolated from electrodes. Here we report a self-assembled columnar structure formed by phase separation between (PCDTBT) and polystyrene (PS) for the active layer morphology optimization. The BHJ solar cell device based on this structure is promising for exhibiting higher performance due to the shorter carrier transportation pathway and larger interfacial area between donor and acceptor. The surface morphology is investigated with atomic force microscopy (AFM) and the columnar structure is studied by investigation of cross-section of the blend thin film of PCDTBT and PS under the transmission electron microscopy (TEM). The different morphological structures formed via phase segregation are correlated with the performance of the BHJ solar cells.

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.

Numerically simulated two-dimensional auroral double layers

NASA Technical Reports Server (NTRS)

Borovsky, J. E.; Joyce, G.

1983-01-01

A magnetized 2 1/2-dimensional particle-in-cell system which is periodic in one direction and bounded by reservoirs of Maxwellian plasma in the other is used to numerically simulate electrostatic plasma double layers. For the cases of both oblique and two-dimensional double layers, the present results indicate periodic instability, Debye length rather than gyroradii scaling, and low frequency electrostatic turbulence together with electron beam-excited electrostatatic electron-cyclotron waves. Estimates are given for the thickness of auroral doule layers, as well as the separations within multiple auroral arcs. Attention is given to the temporal modulation of accelerated beams, and the possibilities for ion precipitation and ion conic production by the double layer are hypothesized. Simulations which include the atmospheric backscattering of electrons imply the action of an ionospheric sheath which accelerates ionospheric ions upward.

Anti-Oxidative and Antibacterial Self-Healing Edible Polyelectrolyte Multilayer Film in Fresh-Cut Fruits.

PubMed

Liu, Xuefan; Han, Wei; Zhu, Yanxi; Xuan, Hongyun; Ren, Jiaoyu; Zhang, Jianhao; Ge, Liqin

2018-04-01

The consumption of fresh-cut fruits is limited because of the oxidation browning and pathogenic bacteria's growth on the fruit surface. Besides, crack of the fresh-keeping film may shorten the preservation time of fruit. In this work, polyelectrolyte multilayer (PEM) film was fabricated by layer-by-layer (LBL) electrostatic deposition method. The film was made by carboxy methylcellulose sodium (CMC) and chitosan (CS). The as-prepared PEM film had good anti-oxidative and antibacterial capability. It inhibited the growth of Gram-negative bacteria and the antibacterial rate was more than 95%. The stratified structure and linear increase of the absorbance in the film verified a linear increase of film thickness. The slight scratched film could self-heal rapidly after the stimulation of water whatever the layer number was. Moreover, the film could heal cracks whose width was far bigger than the thickness. The application of PEM film on fresh-cut apples showed that PEM film had good browning, weight loss and metabolic activity inhibition ability. These results showed that the PEM film is a good candidate as edible film in fresh-cut fruits applications.

Mussel-inspired nano-building block assemblies for mimicking extracellular matrix microenvironments with multiple functions.

PubMed

Wang, Zhenming; Jia, Zhanrong; Jiang, Yanan; Li, Pengfei; Han, Lu; Lu, Xiong; Ren, Fuzeng; Wang, Kefeng; Yuan, Huiping

2017-08-03

The assembly of nano-building blocks is an effective way to produce artificial extracellular matrix microenvironments with hierarchical micro/nano structures. However, it is hard to assemble different types of nano-building blocks, to form composite coatings with multiple functions, by traditional layer-by-layer (LbL) self-assembly methods. Inspired by the mussel adhesion mechanism, we developed polydopamine (PDA)-decorated bovine serum albumin microspheres (BSA-MS) and nano-hydroxyapatite (nano-HA), and assembled them to form bioactive coatings with micro/nano structures encapsulating bone morphogenetic protein-2 (BMP-2). First, PDA-decorated nano-HA (nano-pHA) was obtained by oxidative polymerization of dopamine on nano-HA. Second, BMP-2-encapsulated BSA microspheres were prepared through desolvation, and then were also decorated by PDA (pBSA-MS). Finally, the nano-pHA and pBSA-MS were assembled using the adhesive properties of PDA. Bone marrow stromal cell cultures and in vivo implantation, showed that the pHA/pBSA (BMP-2) coatings can promote cell adhesion, proliferation, and benefited for osteoinductivity. PDA decoration was also applied to assemble various functional nanoparticles, such as nano-HA, polystyrene, and Fe 3 O 4 nanoparticles. In summary, this study provides a novel strategy for the assembly of biofunctional nano-building blocks, which surpasses traditional LbL self-assembly of polyelectrolytes, and can find broad applications in bioactive agents delivery or multi-functional coatings.

Diesel particulate filter with zoned resistive heater

DOEpatents

Gonze, Eugene V [Pinckney, MI

2011-03-08

A diesel particulate filter assembly comprises a diesel particulate filter (DPF) and a heater assembly. The DPF filters a particulate from exhaust produced by an engine. The heater assembly has a first metallic layer that is applied to the DPF, a resistive layer that is applied to the first metallic layer, and a second metallic layer that is applied to the resistive layer. The second metallic layer is etched to form a plurality of zones.

Fabrication of superhydrophilic and antireflective silica coatings on poly(methyl methacrylate) substrates

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

Geng, Zhi; Graduate University of Chinese Academy of Sciences; He, Junhui, E-mail: jhhe@mail.ipc.ac.cn

2012-06-15

Graphical abstract: Self-cleaning and antireflection properties were successfully achieved by assembling (PDDA/S-20){sub n} coatings on PMMA substrates followed by oxygen plasma treatment. Highlights: ► Porous silica coatings were created by layer-by-layer assembly on PMMA substrates. ► Silica coatings were treated by oxygen plasma. ► Porous silica coatings were highly antireflective and superhydrophilic on PMMA substrates. -- Abstract: Silica nanoparticles of ca. 20 nm in size were synthesized, from which hierarchically porous silica coatings were fabricated on poly(methyl methacrylate) (PMMA) substrates via layer-by-layer (LbL) assembly followed by oxygen plasma treatment. These porous silica coatings were highly transparent and superhydrophilic. The maximummore » transmittance reached as high as 99%, whereas that of the PMMA substrate is only 92%. After oxygen plasma treatment, the time for a water droplet to spread to a contact angle of lower than 5° decreased to as short as 0.5 s. Scanning and transmission electron microscopy were used to observe the morphology and structure of nanoparticles and coating surfaces. Transmission and reflection spectra were recorded on UV–vis spectrophotometer. Surface wettability was studied by a contact angle/interface system. The influence of mesopores on the transmittance and wetting properties of coatings was discussed on the basis of experimental observations.« less

Self-Assembled, Iridescent, Crustacean-Mimetic Nanocomposites with Tailored Periodicity and Layered Cuticular Structure.

PubMed

Wang, Baochun; Walther, Andreas

2015-11-24

Natural high-performance materials inspire the pursuit of ordered hard/soft nanocomposite structures at high fractions of reinforcements and with balanced molecular interactions. Herein, we develop a facile, waterborne self-assembly pathway to mimic the multiscale cuticle structure of the crustacean armor by combining hard reinforcing cellulose nanocrystals (CNCs) with soft poly(vinyl alcohol) (PVA). We show iridescent CNC nanocomposites with cholesteric liquid-crystal structure, in which different helical pitches and photonic band gaps can be realized by varying the CNC/PVA ratio. We further show that multilayered crustacean-mimetic materials with tailored periodicity and layered cuticular structure can be obtained by sequential preparation pathways. The transition from a cholesteric to a disordered structure occurs for a critical polymer concentration. Correspondingly, we find a transition from stiff and strong mechanical behavior to materials with increasing ductility. Crack propagation studies using scanning electron microscopy visualize the different crack growth and toughening mechanisms inside cholesteric nanocomposites as a function of the interstitial polymer content for the first time. Different extents of crack deflection, layered delamination, ligament bridging, and constrained microcracking can be observed. Drawing of highly plasticized films sheds light on the mechanistic details of the transition from a cholesteric/chiral nematic to a nematic structure. The study demonstrates how self-assembly of biobased CNCs in combination with suitable polymers can be used to replicate a hierarchical biological structure and how future design of these ordered multifunctional nanocomposites can be optimized by understanding mechanistic details of deformation and fracture.

Electrostatically Tuned Self-Assembly of Branched Amphiphilic Peptides

DOE PAGES

Ting, Christina L.; Frischknecht, Amalie L.; Stevens, Mark J.; ...

2014-06-19

Electrostatics plays an important role in the self-assembly of amphiphilic peptides. To develop a molecular understanding of the role of the electrostatic interactions, we develop a coarse-grained model peptide and apply self-consistent field theory to investigate the peptide assembly into a variety of aggregate nanostructures. We find that the presence and distribution of charged groups on the hydrophilic branches of the peptide can modify the molecular configuration from extended to collapsed. This change in molecular configuration influences the packing into spherical micelles, cylindrical micelles (nanofibers), or planar bilayers. The effects of charge distribution therefore has important implications for the designmore » and utility of functional materials based on peptides.« less

Hierarchical porous carbons with layer-by-layer motif architectures from confined soft-template self-assembly in layered materials

NASA Astrophysics Data System (ADS)

Wang, Jie; Tang, Jing; Ding, Bing; Malgras, Victor; Chang, Zhi; Hao, Xiaodong; Wang, Ya; Dou, Hui; Zhang, Xiaogang; Yamauchi, Yusuke

2017-06-01

Although various two-dimensional (2D) nanomaterials have been explored as promising capacitive materials due to their unique layered structure, their natural restacking tendency impedes electrolyte transport and significantly restricts their practical applications. Herein, we synthesize all-carbon layer-by-layer motif architectures by introducing 2D ordered mesoporous carbons (OMC) within the interlayer space of 2D nanomaterials. As a proof of concept, MXenes are selected as 2D hosts to design 2D-2D heterostructures. Further removing the metal elements from MXenes leads to the formation of all-carbon 2D-2D heterostructures consisting of alternating layers of MXene-derived carbon (MDC) and OMC. The OMC layers intercalated with the MDC layers not only prevent restacking but also facilitate ion diffusion and electron transfer. The performance of the obtained hybrid carbons as supercapacitor electrodes demonstrates their potential for upcoming electronic devices. This method allows to overcome the restacking and blocking of 2D nanomaterials by constructing ion-accessible OMC within the 2D host material.

Self-recovery of stressed nanomembranes

NASA Astrophysics Data System (ADS)

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

2005-03-01

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

Supramolecular self-assembly of graphene oxide and metal nanoparticles into stacked multilayers by means of a multitasking protein ring.

PubMed

Ardini, Matteo; Golia, Giordana; Passaretti, Paolo; Cimini, Annamaria; Pitari, Giuseppina; Giansanti, Francesco; Di Leandro, Luana; Ottaviano, Luca; Perrozzi, Francesco; Santucci, Sandro; Morandi, Vittorio; Ortolani, Luca; Christian, Meganne; Treossi, Emanuele; Palermo, Vincenzo; Angelucci, Francesco; Ippoliti, Rodolfo

2016-03-28

Graphene oxide (GO) is rapidly emerging worldwide as a breakthrough precursor material for next-generation devices. However, this requires the transition of its two-dimensional layered structure into more accessible three-dimensional (3D) arrays. Peroxiredoxins (Prx) are a family of multitasking redox enzymes, self-assembling into ring-like architectures. Taking advantage of both their symmetric structure and function, 3D reduced GO-based composites are hereby built up. Results reveal that the "double-faced" Prx rings can adhere flat on single GO layers and partially reduce them by their sulfur-containing amino acids, driving their stacking into 3D multi-layer reduced GO-Prx composites. This process occurs in aqueous solution at a very low GO concentration, i.e. 0.2 mg ml(-1). Further, protein engineering allows the Prx ring to be enriched with metal binding sites inside its lumen. This feature is exploited to both capture presynthesized gold nanoparticles and grow in situ palladium nanoparticles paving the way to straightforward and "green" routes to 3D reduced GO-metal composite materials.

Polyethylene-Glycol-Mediated Self-Assembly of Magnetite Nanoparticles at the Liquid/Vapor Interface

DOE PAGES

Vaknin, David; Wang, Wenjie; Islam, Farhan; ...

2018-03-23

It is shown that magnetite nanoparticles (MagNPs) grafted with polyethylene glycol (PEG) self-assemble and short-range-order as 2D films at surfaces of aqueous suspensions by manipulating salt concentrations. Synchrotron X-ray reflectivity and grazing-incidence small angle X-ray scattering studies reveal that K 2CO 3 induces the migration of the PEG-MagNPs to the liquid/vapor interface to form a Gibbs layer of monoparticle in thickness. As the salt concentration and/or nanoparticle concentration increase, the surface-adsorbed nanoparticles become more organized. And further increase in salt concentration leads to the growth of an additional incomplete nanoparticle layer contiguous to the first one at the vapor/liquid interfacemore » that remains intact.« less

Polyethylene-Glycol-Mediated Self-Assembly of Magnetite Nanoparticles at the Liquid/Vapor Interface

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

Vaknin, David; Wang, Wenjie; Islam, Farhan

It is shown that magnetite nanoparticles (MagNPs) grafted with polyethylene glycol (PEG) self-assemble and short-range-order as 2D films at surfaces of aqueous suspensions by manipulating salt concentrations. Synchrotron X-ray reflectivity and grazing-incidence small angle X-ray scattering studies reveal that K 2CO 3 induces the migration of the PEG-MagNPs to the liquid/vapor interface to form a Gibbs layer of monoparticle in thickness. As the salt concentration and/or nanoparticle concentration increase, the surface-adsorbed nanoparticles become more organized. And further increase in salt concentration leads to the growth of an additional incomplete nanoparticle layer contiguous to the first one at the vapor/liquid interfacemore » that remains intact.« less

Electrodynamic tailoring of self-assembled three-dimensional electrospun constructs

NASA Astrophysics Data System (ADS)

Reis, Tiago C.; Correia, Ilídio J.; Aguiar-Ricardo, Ana

2013-07-01

The rational design of three-dimensional electrospun constructs (3DECs) can lead to striking topographies and tailored shapes of electrospun materials. This new generation of materials is suppressing some of the current limitations of the usual 2D non-woven electrospun fiber mats, such as small pore sizes or only flat shaped constructs. Herein, we pursued an explanation for the self-assembly of 3DECs based on electrodynamic simulations and experimental validation. We concluded that the self-assembly process is driven by the establishment of attractive electrostatic forces between the positively charged aerial fibers and the already collected ones, which tend to acquire a negatively charged network oriented towards the nozzle. The in situ polarization degree is strengthened by higher amounts of clustered fibers, and therefore the initial high density fibrous regions are the preliminary motifs for the self-assembly mechanism. As such regions increase their in situ polarization electrostatic repulsive forces will appear, favoring a competitive growth of these self-assembled fibrous clusters. Highly polarized regions will evidence higher distances between consecutive micro-assembled fibers (MAFs). Different processing parameters - deposition time, electric field intensity, concentration of polymer solution, environmental temperature and relative humidity - were evaluated in an attempt to control material's design.The rational design of three-dimensional electrospun constructs (3DECs) can lead to striking topographies and tailored shapes of electrospun materials. This new generation of materials is suppressing some of the current limitations of the usual 2D non-woven electrospun fiber mats, such as small pore sizes or only flat shaped constructs. Herein, we pursued an explanation for the self-assembly of 3DECs based on electrodynamic simulations and experimental validation. We concluded that the self-assembly process is driven by the establishment of attractive electrostatic forces between the positively charged aerial fibers and the already collected ones, which tend to acquire a negatively charged network oriented towards the nozzle. The in situ polarization degree is strengthened by higher amounts of clustered fibers, and therefore the initial high density fibrous regions are the preliminary motifs for the self-assembly mechanism. As such regions increase their in situ polarization electrostatic repulsive forces will appear, favoring a competitive growth of these self-assembled fibrous clusters. Highly polarized regions will evidence higher distances between consecutive micro-assembled fibers (MAFs). Different processing parameters - deposition time, electric field intensity, concentration of polymer solution, environmental temperature and relative humidity - were evaluated in an attempt to control material's design. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr01668d

Expression of an endotoxin-free S-layer/allergen fusion protein in gram-positive Bacillus subtilis 1012 for the potential application as vaccines for immunotherapy of atopic allergy

PubMed Central

2011-01-01

Background Genetic fusion of the major birch pollen allergen (Bet v1) to bacterial surface-(S)-layer proteins resulted in recombinant proteins exhibiting reduced allergenicity as well as immunomodulatory capacity. Thus, S-layer/allergen fusion proteins were considered as suitable carriers for new immunotherapeutical vaccines for treatment of Type I hypersensitivity. Up to now, endotoxin contamination of the fusion protein which occurred after isolation from the gram-negative expression host E. coli had to be removed by an expensive and time consuming procedure. In the present study, in order to achieve expression of pyrogen-free, recombinant S-layer/allergen fusion protein and to study the secretion of a protein capable to self-assemble, the S-layer/allergen fusion protein rSbpA/Bet v1 was produced in the gram-positive organism Bacillus subtilis 1012. Results The chimaeric gene encoding the S-layer protein SbpA of Lysinibacillus sphaericus CCM 2177 as well as Bet v1 was cloned and expressed in B. subtilis 1012. For that purpose, the E. coli-B. subtilis shuttle vectors pHT01 for expression in the B. subtilis cytoplasm and pHT43 for secretion of the recombinant fusion protein into the culture medium were used. As shown by western blot analysis, immediately after induction of expression, B. subtilis 1012 was able to secret rSbpA/Bet v1 mediated by the signal peptide amyQ of Bacillus amyloliquefaciens. Electron microscopical investigation of the culture medium revealed that the secreted fusion protein was able to form self-assembly products in suspension but did not recrystallize on the surface of the B. subtilis cells. The specific binding mechanism between the N-terminus of the S-layer protein and a secondary cell wall polymer (SCWP), located in the peptidoglycan-containing sacculi of Ly. sphaericus CCM 2177, could be used for isolation and purification of the secreted fusion protein from the culture medium. Immune reactivity of rSbpA/Bet v1 could be demonstrated in immunoblotting experiments with Bet v1 specific IgE containing serum samples from patients suffering birch pollen allergy. Conclusions The impact of this study can be seen in the usage of a gram-positive organism for the production of pyrogen-free self-assembling recombinant S-layer/allergen fusion protein with great relevance for the development of vaccines for immunotherapy of atopic allergy. PMID:21310062

Improved Barrier Properties in Flexible Plastic Substrates

DTIC Science & Technology

2009-01-01

layer 2:1 sandwich is required to balance this charge deficit. The extra charge is provided by a layer of large cations, usually potassium or sodium...ions (K+).32,30 Each of the potassium ions in this interiayer is shared among 12 oxygen atoms and the electrostatic force between the potassium ion...layer. Potassium • Aluminum • Silicon • Oxygen {-* Hydroxyl pair b axfs" This tabulation giving the layer by layer population of elements

Matrix polyelectrolyte capsules based on polysaccharide/MnCO₃ hybrid microparticle templates.

PubMed

Wei, Qingrong; Ai, Hua; Gu, Zhongwei

2011-06-15

An efficient strategy for biomacromolecule encapsulation based on spontaneous deposition into polysaccharide matrix-containing capsules is introduced in this study. First, hybrid microparticles composed of manganese carbonate and ionic polysaccharides including sodium hyaluronate (HA), sodium alginate (SA) and dextran sulfate sodium (DS) with narrow size distribution were synthesized to provide monodisperse templates. Incorporation of polysaccharide into the hybrid templates was successful as verified by thermogravimetric analysis (TGA) and confocal laser scanning microscopy (CLSM). Matrix polyelectrolyte microcapsules were fabricated through layer-by-layer (LbL) self-assembly of oppositely charged polyelectrolytes (PEs) onto the hybrid particles, followed by removal of the inorganic part of the cores, leaving polysaccharide matrix inside the capsules. The loading and release properties of the matrix microcapsules were investigated using myoglobin as a model biomacromolecule. Compared to matrix-free capsules, the matrix capsules had a much higher loading capacity up to four times; the driving force is mostly due to electrostatic interactions between myoglobin and the polysaccharide matrix. From our observations, for the same kind of polysaccharide, a higher amount of polysaccharide inside the capsules usually led to better loading capacity. The release behavior of the loaded myoglobin could be readily controlled by altering the environmental pH. These matrix microcapsules may be used as efficient delivery systems for various charged water-soluble macromolecules with applications in biomedical fields. Copyright © 2010 Elsevier B.V. All rights reserved.

Improved attachment of mesenchymal stem cells on super-hydrophobic TiO2 nanotubes.

PubMed

Bauer, Sebastian; Park, Jung; von der Mark, Klaus; Schmuki, Patrik

2008-09-01

Self-organized layers of vertically orientated TiO(2) nanotubes providing defined diameters ranging from 15 up to 100nm were grown on titanium by anodic oxidation. These TiO(2) nanotube layers show super-hydrophilic behavior. After coating TiO(2) nanotube layers with a self-assembled monolayer (octadecylphosphonic acid) they showed a diameter-dependent wetting behavior ranging from hydrophobic (108+/-2 degrees ) up to super-hydrophobic (167+/-2 degrees ). Cell adhesion, spreading and growth of mesenchymal stem cells on the unmodified and modified nanotube layers were investigated and compared. We show that cell adhesion and proliferation are strongly affected in the super-hydrophobic range. Adsorption of extracellular matrix proteins as fibronectin, type I collagen and laminin, as well as bovine serum albumin, on the coated and uncoated surfaces showed a strong influence on wetting behavior and dependence on tube diameter.

Electrostatic repulsive out-of-plane actuator using conductive substrate.

PubMed

Wang, Weimin; Wang, Qiang; Ren, Hao; Ma, Wenying; Qiu, Chuankai; Chen, Zexiang; Fan, Bin

2016-10-07

A pseudo-three-layer electrostatic repulsive out-of-plane actuator is proposed. It combines the advantages of two-layer and three-layer repulsive actuators, i.e., fabrication requirements and fill factor. A theoretical model for the proposed actuator is developed and solved through the numerical calculation of Schwarz-Christoffel mapping. Theoretical and simulated results show that the pseudo-three-layer actuator offers higher performance than the two-layer and three-layer actuators with regard to the two most important characteristics of actuators, namely, driving force and theoretical stroke. Given that the pseudo-three-layer actuator structure is compatible with both the parallel-plate actuators and these two types of repulsive actuators, a 19-element two-layer repulsive actuated deformable mirror is operated in pseudo-three-layer electrical connection mode. Theoretical and experimental results demonstrate that the pseudo-three-layer mode produces a larger displacement of 0-4.5 μm for a dc driving voltage of 0-100 V, when compared with that in two-layer mode.

Electrostatic repulsive out-of-plane actuator using conductive substrate

PubMed Central

Wang, Weimin; Wang, Qiang; Ren, Hao; Ma, Wenying; Qiu, Chuankai; Chen, Zexiang; Fan, Bin

2016-01-01

A pseudo-three-layer electrostatic repulsive out-of-plane actuator is proposed. It combines the advantages of two-layer and three-layer repulsive actuators, i.e., fabrication requirements and fill factor. A theoretical model for the proposed actuator is developed and solved through the numerical calculation of Schwarz-Christoffel mapping. Theoretical and simulated results show that the pseudo-three-layer actuator offers higher performance than the two-layer and three-layer actuators with regard to the two most important characteristics of actuators, namely, driving force and theoretical stroke. Given that the pseudo-three-layer actuator structure is compatible with both the parallel-plate actuators and these two types of repulsive actuators, a 19-element two-layer repulsive actuated deformable mirror is operated in pseudo-three-layer electrical connection mode. Theoretical and experimental results demonstrate that the pseudo-three-layer mode produces a larger displacement of 0–4.5 μm for a dc driving voltage of 0–100 V, when compared with that in two-layer mode. PMID:27713542

Green synthesis of layered 1T-MoS2/reduced graphene oxide nanocomposite with excellent catalytic performances for 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Meng, Nannan; Cheng, Jian; Zhou, Yifeng; Nie, Wangyan; Chen, Pengpeng

2017-02-01

A green and facile process was developed to prepare layered octahedral phase MoS2/reduced graphene oxide (1T-MoS2/RGO) nanocomposite by a Vitamin C-assisted self-assemble method, in which graphene oxide (GO) and LiMoS2 were used as starting materials. Catalytic performances of 1T-MoS2/RGO were evaluated by hydrogenation of 4-nitrophenol (4-NP). It was demonstrated that the prepared 1T-MoS2/RGO nanocomposite presented excellent catalytic performance and cycling stability for 4-NP reduction, which made it a promising noble-metal-free catalyst. Additionally, broadening work suggested some other RGO-based metal nanocomposite with well-defined porous structure could be also generated via this facile self-assembly method.

Extending the Solvation-Layer Interface Condition Continum Electrostatic Model to a Linearized Poisson-Boltzmann Solvent.

PubMed

Molavi Tabrizi, Amirhossein; Goossens, Spencer; Mehdizadeh Rahimi, Ali; Cooper, Christopher D; Knepley, Matthew G; Bardhan, Jaydeep P

2017-06-13

We extend the linearized Poisson-Boltzmann (LPB) continuum electrostatic model for molecular solvation to address charge-hydration asymmetry. Our new solvation-layer interface condition (SLIC)/LPB corrects for first-shell response by perturbing the traditional continuum-theory interface conditions at the protein-solvent and the Stern-layer interfaces. We also present a GPU-accelerated treecode implementation capable of simulating large proteins, and our results demonstrate that the new model exhibits significant accuracy improvements over traditional LPB models, while reducing the number of fitting parameters from dozens (atomic radii) to just five parameters, which have physical meanings related to first-shell water behavior at an uncharged interface. In particular, atom radii in the SLIC model are not optimized but uniformly scaled from their Lennard-Jones radii. Compared to explicit-solvent free-energy calculations of individual atoms in small molecules, SLIC/LPB is significantly more accurate than standard parametrizations (RMS error 0.55 kcal/mol for SLIC, compared to RMS error of 3.05 kcal/mol for standard LPB). On parametrizing the electrostatic model with a simple nonpolar component for total molecular solvation free energies, our model predicts octanol/water transfer free energies with an RMS error 1.07 kcal/mol. A more detailed assessment illustrates that standard continuum electrostatic models reproduce total charging free energies via a compensation of significant errors in atomic self-energies; this finding offers a window into improving the accuracy of Generalized-Born theories and other coarse-grained models. Most remarkably, the SLIC model also reproduces positive charging free energies for atoms in hydrophobic groups, whereas standard PB models are unable to generate positive charging free energies regardless of the parametrized radii. The GPU-accelerated solver is freely available online, as is a MATLAB implementation.

Growth and characterization of organic layers deposited on porous-patterned Si surface

NASA Astrophysics Data System (ADS)

Gorbach, Tamara Ya.; Smertenko, Petro S.; Olkhovik, G. P.; Wisz, Grzegorz

2017-01-01

The organic layers with the thickness from a few nanometers up to few micrometers have been deposited from the chemical solution at room temperature on porous patterned Si surfaces using two medical solutions: thiamine diphosphide (pH=1÷2) and metamizole sodium (pH=6÷7). Based on evolution of morphology, structural and compositional features obtained by scanning electron microscopy, X-ray analysis, reflectance high energy electron diffraction the grown mechanisms in thin organic layers are discussed in the terms of terrace-step-kink model whereas self-organized assemblies evaluated more thick layers. Transport mechanism features and possible photovoltaic properties are discussed on the base of differential current-voltage characteristics.

The Self-Assembly of Nanogold for Optical Metamaterials

NASA Astrophysics Data System (ADS)

Nidetz, Robert A.

2011-12-01

Optical metamaterials are an emerging field that enables manipulation of light like never before. Producing optical metamaterials requires sub-wavelength building blocks. The focus here was to develop methods to produce building blocks for metamaterials from nanogold. Electron-beam lithography was used to define an aminosilane patterned chemical template in order to electrostatically self-assemble citrate-capped gold nanoparticles. Equilibrium self-assembly was achieved in 20 minutes by immersing chemical templates into gold nanoparticle solutions. The number of nanoparticles that self-assembled on an aminosilane dot was controlled by manipulating the diameters of the dots and nanoparticles. Adding salt to the nanoparticle solution enabled the nanoparticles to self-assemble in greater numbers on the same sized dot. However, the preparation of the nanoparticle solution containing salt was sensitive to spikes in the salt concentration which led to aggregation of the nanoparticles and non-specific deposition. Gold nanorods were also electrostatically self-assembled. Polyelectrolyte-coated gold nanorods were patterned with limited success. A polyelectrolyte chemical template also patterned gold nanorods, but the gold nanorods preferred to pattern on the edges of the pattern. Ligand-exchanged gold nanorods displayed the best self-assembly, but suffered from slow kinetics. Self-assembled gold nanoparticles were cross-linked with poly(diallyldimethylammonium chloride). The poly(diallyldimethylammonium chloride) allowed additional nanoparticles to pattern on top of the already patterned nanoparticles. Cross-linked nanoparticles were lifted-off of the substrate by sonication in a sodium hydroxide solution. The presence of van der Waals forces and/or amine bonding prevent the nanogold from lifting-off without sonication. A good-solvent evaporation process was used to self-assemble poly(styrene) coated gold nanoparticles into spherical microbead assemblies. The use of larger nanoparticles and larger poly(styrene) ligands resulted in larger and smaller assemblies, respectively. Stirring the solution resulted in a wider size distribution of microbead assemblies due to the stirring's shear forces. Two undeveloped methods to self-assemble nanogold were investigated. One method used block-copolymer thin films as chemical templates to direct the electrostatic self-assembly of nanogold. Another method used gold nanorods that are passivated with different ligands on different faces. The stability of an alkanethiol ligand in different acids and bases was investigated to determine which materials could be used to produce Janus nanorods.

Rapid growing clay coatings to reduce the fire threat of furniture.

PubMed

Kim, Yeon Seok; Li, Yu-Chin; Pitts, William M; Werrel, Martin; Davis, Rick D

2014-02-12

Layer-by-layer (LbL) assembly coatings reduce the flammability of textiles and polyurethane foam but require extensive repetitive processing steps to produce the desired coating thickness and nanoparticle fire retardant content that translates into a fire retardant coating. Reported here is a new hybrid bi-layer (BL) approach to fabricate fire retardant coatings on polyurethane foam. Utilizing hydrogen bonding and electrostatic attraction along with the pH adjustment, a fast growing coating with significant fire retardant clay content was achieved. This hybrid BL coating exhibits significant fire performance improvement in both bench scale and real scale tests. Cone calorimetry bench scale tests show a 42% and 71% reduction in peak and average heat release rates, respectively. Real scale furniture mockups constructed using the hybrid LbL coating reduced the peak and average heat release rates by 53% and 63%, respectively. This is the first time that the fire safety in a real scale test has been reported for any LbL technology. This hybrid LbL coating is the fastest approach to develop an effective fire retardant coating for polyurethane foam.

Lanthanide-integrated supramolecular polymeric nanoassembly with multiple regulation characteristics for multidrug-resistant cancer therapy.

PubMed

Jin, Weihong; Wang, Qiwen; Wu, Min; Li, Yang; Tang, Guping; Ping, Yuan; Chu, Paul K

2017-06-01

Cancer treatment can in principle be enhanced by the synergistic effects of chemo- and nucleic acid-based combination therapies but the lack of efficient drug nanocarriers and occurrence of multidrug resistance (MDR) are major obstacles adversely affecting the effectiveness. Herein, a lanthanide-integrated supramolecular polymeric nanoassembly that delivers anticancer drugs and siRNA for more effective cancer therapy is described. This nanotherapeutic system is prepared by loading adamantane-modified doxorubicin (Dox) into polyethylenimine-crosslinked-γ-cyclodextrin (PC) through the supramolecular assembly to form the interior Dox-loaded PC (PCD) followed by electrostatically driven self-assembly of siRNA and PCD to produce the PCD/siRNA nanocomplexes. The PCD/siRNA nanocomplex is further decorated with the exterior neodymium (Nd)-integrated PC (Nd-PC) layer to obtain the PCD/siRNA/Nd-PC nanoassembly in which the interior PC serves as an efficient carrier for simultaneous delivery of Dox and siRNA to the human breast cancer cell line, Dox-resistant MCF-7 (MCF-7/ADR) both in vitro and in vivo. The exterior Nd-PC layer improves the drug sensitivity to the MCF-7/ADR cells as a result of the improved nanoassembly uptake, reduced drug efflux, and enhanced apoptosis, as evidenced by multiple regulation of a series of intracellular proteins related to MDR. Furthermore, in vivo delivery of the PCD/siRNA/Nd-PC nanoassembly is demonstrated to inhibit tumor growth in the mouse model with MCF-7/ADR tumor xenografts as a result of reduced angiogenesis and increased necrosis at the tumor site. This study reveals a simple and universal strategy to transform polymer-based nanoassemblies into advanced organic-inorganic nanotherapeutics suitable for cancer MDR therapy. Copyright © 2017 Elsevier Ltd. All rights reserved.

Monolithically self-assembled organic active materials integrated with thermoelectric for large spectrum solar harvesting system (Presentation Recording)

NASA Astrophysics Data System (ADS)

Busani, Tito L.; Lavrova, Olga; Erdman, Matthew; Martinez, Julio; Dawson, Noel M.

2015-10-01

We designed and studied a radial junction composed by a photovoltaic and thermoelectric array based on ZnO and CdTe nanowires surrounded by an absorbing organic self assembled in order to efficiently convert UV-visible and IR energy into electricity. The hot anode of n-type ZnO nanowires was fabricated using a thermal process on pre-seeded layer and results to be crystalline with a transmittance up to 92 % and a bandgap of ~ 3.32 eV. Conductivity measurements reveal diode-like behavior for the ZnO nanowires. The organic layer was deposited between the anode and cathode at room temperature The organic layer is composed of oppositely charged porphyrin metal (Zn(II) and Sn(IV)(OH)2) derivatives that are separately water soluble, but when combined form a virtually insoluble solid. The electron donor/acceptor properties (energy levels, band gaps) of the solid can be controlled by the choice of metals and the nature of the peripheral substituent groups of the porphyrin ring. A defect free sub nanometer deposition was achieved using a layer-by-layer deposition onto both ZnO and Bi2Te3 nanowires. The highly thermoelectric structure, which acts as a cold cathode, is composed of p-type Bi2Te3 nanowires with a thermoelectric efficiency (ZT) between ~0.7 to 1, values that are twice that expected for bulk Bi2Te3. Optoelectronic and structural properties shows that with 6 nm of organic layer it is possible to form a 3% efficient solar device with an enhanced thermo electric effected with a temperature gradient of 300 C.

Fabrication of textured SnO2 transparent conductive films using self-assembled Sn nanospheres

NASA Astrophysics Data System (ADS)

Fukumoto, Michitaka; Nakao, Shoichiro; Hirose, Yasushi; Hasegawa, Tetsuya

2018-06-01

We present a novel method to fabricate textured surfaces on transparent conductive SnO2 films by processing substrates through a bottom-up technique with potential for industrially scalable production. The substrate processing consists of three steps: deposition of precursor Sn films on glass substrates, formation of a self-assembled Sn nanosphere layer with reductive annealing, and conversion of Sn to SnO2 by oxidative annealing. Ta-doped SnO2 films conformally deposited on the self-assembled nanospherical SnO2 templates exhibited attractive optical and electrical properties, namely, enhanced haze values and low sheet resistances, for applications as transparent electrodes in photovoltaics.

A simple model for the prediction of the discrete stiffness states of a homogeneous electrostatically tunable multi-layer beam

NASA Astrophysics Data System (ADS)

Bergamini, A.; Christen, R.; Motavalli, M.

2007-04-01

The adaptive modification of the mechanical properties of structures has been described as a key to a number of new or enhanced technologies, ranging from prosthetics to aerospace applications. Previous work reported the electrostatic tuning of the bending stiffness of simple sandwich structures by modifying the shear stress transfer parameters at the interface between faces and the compliant core of the sandwich. For this purpose, the choice of a sandwich structure presented considerable experimental advantages, such as the ability to obtain a large increase in stiffness by activating just two interfaces between the faces and the core of the beam. The hypothesis the development of structures with tunable bending stiffness is based on, is that by applying a normal stress at the interface between two layers of a multi-layer structure it is possible to transfer shear stresses from one layer to the other by means of adhesion or friction forces. The normal stresses needed to generate adhesion or friction can be generated by an electrostatic field across a dielectric layer interposed between the layers of a structure. The shear stress in the cross section of the structure (e.g. a beam) subjected to bending forces is transferred in full, if sufficiently large normal stresses and an adequate friction coefficient at the interface are given. Considering beams with a homogeneous cross-section, in which all layers are made of the same material and have the same width, eliminates the need to consider parameters such as the shear modulus of the material and the shear stiffness of the core, thus making the modelling work easier and the results more readily understood. The goal of the present work is to describe a numerical model of a homogeneous multi-layer beam. The model is validated against analytical solutions for the extreme cases of interaction at the interface (no friction and a high level of friction allowing for full shear stress transfer). The obtained model is used to better understand the processes taking place at the interfaces between layers, demonstrate the existence of discrete stiffness states and to find guidance for the selection of suitable dielectric layers for the generation of the electrostatic normal stresses needed for the shear stress transfer at the interface.

A new self-assembled layer-by-layer glucose biosensor based on chitosan biopolymer entrapped enzyme with nitrogen doped graphene.

PubMed

Barsan, Madalina M; David, Melinda; Florescu, Monica; Ţugulea, Laura; Brett, Christopher M A

2014-10-01

The layer-by-layer (LbL) technique has been used for the construction of a new enzyme biosensor. Multilayer films containing glucose oxidase, GOx, and nitrogen-doped graphene (NG) dispersed in the biocompatible positively-charged polymer chitosan (chit(+)(NG+GOx)), together with the negatively charged polymer poly(styrene sulfonate), PSS(-), were assembled by alternately immersing a gold electrode substrate in chit(+)(NG+GOx) and PSS(-) solutions. Gravimetric monitoring during LbL assembly by an electrochemical quartz microbalance enabled investigation of the adsorption mechanism and deposited mass for each monolayer. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the LbL modified electrodes, in order to establish the contribution of each monolayer to the overall electrochemical properties of the biosensor. The importance of NG in the biosensor architecture was evaluated by undertaking a comparative study without NG in the chit layer. The GOx biosensor's analytical properties were evaluated by fixed potential chronoamperometry and compared with similar reported biosensors. The biosensor operates at a low potential of -0.2V vs., Ag/AgCl, exhibiting a high sensitivity of 10.5 μA cm(-2) mM(-1), and a detection limit of 64 μM. This study shows a simple approach in developing new biosensor architectures, combining the advantages of nitrogen-doped graphene with the LbL technique for enzyme immobilization. Copyright © 2014 Elsevier B.V. All rights reserved.

Transparent superwetting nanofilms with enhanced durability at model physiological condition

PubMed Central

Hwangbo, Sunghee; Heo, Jiwoong; Lin, Xiangde; Choi, Moonhyun; Hong, Jinkee

2016-01-01

There have been many studies on superwetting surfaces owing to the variety of their potential applications. There are some drawbacks to developing these films for biomedical applications, such as the fragility of the microscopic roughness feature that is vital to ensure superwettability. But, there are still only a few studies that have shown an enhanced durability of nanoscale superwetting films at certain extreme environment. In this study, we fabricated intrinsically stable superwetting films using the organosilicate based layer-by-layer (LbL) self-assembly method in order to control nano-sized roughness of the multilayer structures. In order to develop mechanically and chemically robust surfaces, we successfully introduced polymeric silsesquioxane as a building block for LbL assembly with desired fashion. Even in the case that the superhydrophobic outer layers were damaged, the films maintained their superhydrophobicity because of the hydrophobic nature of their inner layers. As a result, we successfully fabricated superwetting nano-films and evaluated their robustness and stability. PMID:26764164

Interactions regulating the head-to-tail directed assembly of biological Janus rods

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

Greene, A. C.; Bachand, M.; Gomez, A.

We can generalize the directed, head-to-tail self-assembly of microtubule filaments in the context of Janus colloidal rods. Specifically, their assembly at the tens of micron-length scale involves a careful balance between long-range electrostatic repulsion and short-range attractive forces. We show that the addition of counterion salts increases the rate of directed assembly by screening the electrostatic forces and enhancing the effectiveness of short-range interactions at the microtubule ends.

Interactions regulating the head-to-tail directed assembly of biological Janus rods

DOE PAGES

Greene, A. C.; Bachand, M.; Gomez, A.; ...

2017-03-31

We can generalize the directed, head-to-tail self-assembly of microtubule filaments in the context of Janus colloidal rods. Specifically, their assembly at the tens of micron-length scale involves a careful balance between long-range electrostatic repulsion and short-range attractive forces. We show that the addition of counterion salts increases the rate of directed assembly by screening the electrostatic forces and enhancing the effectiveness of short-range interactions at the microtubule ends.

Directed self-assembly of nanogold using a chemically modified nanopatterned surface

NASA Astrophysics Data System (ADS)

Nidetz, Robert; Kim, Jinsang

2012-02-01

Electron-beam lithography (EBL) was used to define an aminosilane nanopatterned surface in order to electrostatically self-assemble gold nanoparticles (Au NPs). The chemically modified nanopatterned surfaces were immersed into a Au NP solution to allow the Au NPs to self-assemble. Equilibrium self-assembly was achieved in only 20 min. The number of Au NPs that self-assembled on an aminosilane dot was controlled by manipulating the diameters of both the Au NPs and the dots. Adding salt to the Au NP solution enabled the Au NPs to self-assemble in greater numbers on the same sized dot. However, the preparation of the Au NP solution containing salt was sensitive to spikes in the salt concentration. These spikes led to aggregation of the Au NPs and non-specific deposition of Au NPs on the substrate. The Au NP patterned surfaces were immersed in a sodium hydroxide solution in order to lift-off the patterned Au NPs, but no lift-off was observed without adequate physical agitation. The van der Waals forces are too strong to allow for lift-off despite the absence of electrostatic forces.

Self assembly of magnetic nanoparticles at silicon surfaces.

PubMed

Theis-Bröhl, Katharina; Gutfreund, Philipp; Vorobiev, Alexei; Wolff, Max; Toperverg, Boris P; Dura, Joseph A; Borchers, Julie A

2015-06-21

Neutron reflectometry was used to study the assembly of magnetite nanoparticles in a water-based ferrofluid close to a silicon surface. Under three conditions, static, under shear and with a magnetic field, the depth profile is extracted. The particles have an average diameter of 11 nm and a volume density of 5% in a D2O-H2O mixture. They are surrounded by a 4 nm thick bilayer of carboxylic acid for steric repulsion. The reflectivity data were fitted to a model using a least square routine based on the Parratt formalism. From the scattering length density depth profiles the following behavior is concluded: the fits indicate that excess carboxylic acid covers the silicon surface and almost eliminates the water in the densely packed wetting layer that forms close to the silicon surface. Under constant shear the wetting layer persists but a depletion layer forms between the wetting layer and the moving ferrofluid. Once the flow is stopped, the wetting layer becomes more pronounced with dense packing and is accompanied by a looser packed second layer. In the case of an applied magnetic field the prolate particles experience a torque and align with their long axes along the silicon surface which leads to a higher particle density.

Power module assembly with reduced inductance

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

Ward, Terence G.; Stancu, Constantin C.; Jaksic, Marko

A power module assembly has a plurality of electrically conducting layers, including a first layer and a third layer. One or more electrically insulating layers are operatively connected to each of the plurality of electrically conducting layers. The electrically insulating layers include a second layer positioned between and configured to electrically isolate the first and the third layers. The first layer is configured to carry a first current flowing in a first direction. The third layer is configured to carry a second current flowing in a second direction opposite to the first direction, thereby reducing an inductance of the assembly.more » The electrically insulating layers may include a fourth layer positioned between and configured to electrically isolate the third layer and a fifth layer. The assembly results in a combined substrate and heat sink structure. The assembly eliminates the requirements for connections between separate substrate and heat sink structures.« less

Electrostatic Repulsion-Induced Desorption of Dendritic Viologen-Arranged Molecules Anchored on a Gold Surface through a Gold-Thiolate Bond Leading to a Tunable Molecular Template.

PubMed

Kawauchi, Takehiro; Kojima, Takahiro; Sakaguchi, Hiroshi; Iyoda, Tomokazu

2018-06-05

We investigated the adsorption and desorption behavior of self-assembled monolayers (SAMs) on gold derived from dendritic viologen-arranged molecules with an ω-mercaptodecyl group (A n, n (dendritic generation) = 0-3) at the apex of the dendritic structure in polar solvents. The adsorption of the dendritic molecules occurred quickly and saturated within a few minutes in an acetonitrile/ethanol (1/1, v/v) mixture at a concentration of 2 mM. Atomic force microscopy images of the SAMs showed flat surfaces regardless of the dendritic generation because the peripheral viologen units were closely packed at the surface of the molecular layer. Individual A3 molecules immobilized on the substrate were observed by scanning tunneling microscopy measurements of a mixed SAM with decanethiol. The desorption behaviors of dendritic molecules from the A n-SAMs in several solvents such as water were also investigated. The spontaneous desorption of the A n-SAM occurred more rapidly than that of a conventional n-alkanethiol SAM. However, the desorption was inhibited by adding electrolytes such as NaNO 3 due to the shielding effect on the electrostatic repulsion between the dendritic molecules. These results indicate that the surface density of the dendritic molecules can be controlled through the desorption.

Aggrecan nanoscale solid-fluid interactions are a primary determinant of cartilage dynamic mechanical properties.

PubMed

Nia, Hadi Tavakoli; Han, Lin; Bozchalooi, Iman Soltani; Roughley, Peter; Youcef-Toumi, Kamal; Grodzinsky, Alan J; Ortiz, Christine

2015-03-24

Poroelastic interactions between interstitial fluid and the extracellular matrix of connective tissues are critical to biological and pathophysiological functions involving solute transport, energy dissipation, self-stiffening and lubrication. However, the molecular origins of poroelasticity at the nanoscale are largely unknown. Here, the broad-spectrum dynamic nanomechanical behavior of cartilage aggrecan monolayer is revealed for the first time, including the equilibrium and instantaneous moduli and the peak in the phase angle of the complex modulus. By performing a length scale study and comparing the experimental results to theoretical predictions, we confirm that the mechanism underlying the observed dynamic nanomechanics is due to solid-fluid interactions (poroelasticity) at the molecular scale. Utilizing finite element modeling, the molecular-scale hydraulic permeability of the aggrecan assembly was quantified (kaggrecan = (4.8 ± 2.8) × 10(-15) m(4)/N·s) and found to be similar to the nanoscale hydraulic permeability of intact normal cartilage tissue but much lower than that of early diseased tissue. The mechanisms underlying aggrecan poroelasticity were further investigated by altering electrostatic interactions between the molecule's constituent glycosaminoglycan chains: electrostatic interactions dominated steric interactions in governing molecular behavior. While the hydraulic permeability of aggrecan layers does not change across species and age, aggrecan from adult human cartilage is stiffer than the aggrecan from newborn human tissue.

Titanium modified with layer-by-layer sol-gel tantalum oxide and an organodiphosphonic acid: a coating for hydroxyapatite growth.

PubMed

Arnould, C; Volcke, C; Lamarque, C; Thiry, P A; Delhalle, J; Mekhalif, Z

2009-08-15

Titanium and its alloys are widely used in surgical implants due to their appropriate properties like corrosion resistance, biocompatibility, and load bearing. Unfortunately when metals are used for orthopedic and dental implants there is the possibility of loosening over a long period of time. Surface modification is a good way to counter this problem. A thin tantalum oxide layer obtained by layer-by-layer (LBL) sol-gel deposition on top of a titanium surface is expected to improve biocorrosion resistance in the body fluid, biocompatibility, and radio-opacity. This elaboration step is followed by a modification of the tantalum oxide surface with an organodiphosphonic acid self-assembled monolayer, capable of chemically binding to the oxide surface, and also improving hydroxyapatite growth. The different steps of this proposed process are characterized by surfaces techniques like contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM).

Bottom-up photonic crystal approach with top-down defect and heterostructure fine-tuning.

PubMed

Ding, Tao; Song, Kai; Clays, Koen; Tung, Chen-Ho

2010-03-16

We combine the most efficient (chemical) approach toward three-dimensional photonic crystals with the most convenient (physical) technique for creating non-close-packed crystalline structures. Self-assembly of colloidal particles in artificial opals is followed by a carefully tuned plasma etching treatment. By covering the resulting top layer of more open structure with original dense opal, embedded defect layers and heterostructures can be conveniently designed for advanced photonic band gap and band edge engineering.

Combination Growth Factor Therapy via Electrostatically Assembled Wound Dressings Improves Diabetic Ulcer Healing In Vivo.

PubMed

Almquist, Benjamin D; Castleberry, Steven A; Sun, Julia B; Lu, Alice Y; Hammond, Paula T

2015-10-01

Chronic skin ulcerations are a common complication of diabetes mellitus, affecting up to one in four diabetic individuals. Despite the prevalence of these wounds, current pharmacologic options for treating them remain limited. Growth factor-based therapies have displayed a mixed ability to drive successful healing, which may be due to nonoptimal delivery strategies. Here, a method for coating commercially available nylon dressings using the layer-by-layer process is described to enable both sustained release and independent control over the release kinetics of vascular endothelial growth factor 165 and platelet-derived growth factor BB. It is shown that the use of strategically spaced diffusion barriers formed spontaneously by disulfide bonds enables independent control over the release rates of incorporated growth factors, and that in vivo these dressings improve several aspects of wound healing in db/db mice. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Three-stage nucleation and growth of Ge self-assembled quantum dots grown on partially relaxed SiGe buffer layers

NASA Astrophysics Data System (ADS)

Kim, H. J.; Zhao, Z. M.; Xie, Y. H.

2003-11-01

Three-stage nucleation and growth of Ge self-assembled quantum dots (SAQDs) on a relaxed SiGe buffer layer has been studied. Plastic relaxation of the SiGe buffer layer is associated with a network of buried 60° dislocations leading to an undulating strain field. As a result, the surface possesses three different types of sites for the nucleation and growth of Ge SAQDs: over the intersection of two perpendicular buried dislocations, over a single dislocation line, and in the region beyond one diffusion length away from any dislocation. Ge SAQDs are observed to nucleate exclusively over the dislocation intersections first, followed by over single dislocation lines, and finally in the region far away from dislocations. By increasing the Ge coverage at a slow rate, the prenucleation stage at the various sites is observed. It appears that the varying strain field has a significant effect on both the diffusion of Ge adatoms before SAQD nucleation, as well as the shape evolution of the SAQDs after they form. Moreover, two distinctly different self-assembly mechanisms are observed at different sites. There exist denuded zones free of Ge SAQDs adjacent to dislocation lines. The width of the denuded zone can be used to make direct determination of the Ge adatom diffusion lengths. The partially relaxed substrate provides a useful experimental vehicle for the in-depth understanding of the formation mechanism of SAQDs grown epitaxially in the Stranski-Krastanov growth mode.

Highly scalable, closed-loop synthesis of drug-loaded, layer-by-layer nanoparticles.

PubMed

Correa, Santiago; Choi, Ki Young; Dreaden, Erik C; Renggli, Kasper; Shi, Aria; Gu, Li; Shopsowitz, Kevin E; Quadir, Mohiuddin A; Ben-Akiva, Elana; Hammond, Paula T

2016-02-16

Layer-by-layer (LbL) self-assembly is a versatile technique from which multicomponent and stimuli-responsive nanoscale drug carriers can be constructed. Despite the benefits of LbL assembly, the conventional synthetic approach for fabricating LbL nanoparticles requires numerous purification steps that limit scale, yield, efficiency, and potential for clinical translation. In this report, we describe a generalizable method for increasing throughput with LbL assembly by using highly scalable, closed-loop diafiltration to manage intermediate purification steps. This method facilitates highly controlled fabrication of diverse nanoscale LbL formulations smaller than 150 nm composed from solid-polymer, mesoporous silica, and liposomal vesicles. The technique allows for the deposition of a broad range of polyelectrolytes that included native polysaccharides, linear polypeptides, and synthetic polymers. We also explore the cytotoxicity, shelf life and long-term storage of LbL nanoparticles produced using this approach. We find that LbL coated systems can be reliably and rapidly produced: specifically, LbL-modified liposomes could be lyophilized, stored at room temperature, and reconstituted without compromising drug encapsulation or particle stability, thereby facilitating large scale applications. Overall, this report describes an accessible approach that significantly improves the throughput of nanoscale LbL drug-carriers that show low toxicity and are amenable to clinically relevant storage conditions.

Infrared spectroscopy of large scale single layer graphene on self assembled organic monolayer

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

Woo Kim, Nak; Youn Kim, Joo; Lee, Chul

2014-01-27

We study the effect of self-assembled monolayer (SAM) organic molecule substrate on large scale single layer graphene using infrared transmission measurement on Graphene/SAM/SiO{sub 2}/Si composite samples. From the Drude weight of the chemically inert CH{sub 3}-SAM, the electron-donating NH{sub 2}-SAM, and the SAM-less graphene, we determine the carrier density doped into graphene by the three sources—the SiO{sub 2} substrate, the gas-adsorption, and the functional group of the SAM's—separately. The SAM-treatment leads to the low carrier density N ∼ 4 × 10{sup 11} cm{sup −2} by blocking the dominant SiO{sub 2}- driven doping. The carrier scattering increases by the SAM-treatment rather than decreases. However, the transportmore » mobility is nevertheless improved due to the reduced carrier doping.« less

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

PubMed

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

2018-06-01

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

A novel multi-actuation CMOS RF MEMS switch

NASA Astrophysics Data System (ADS)

Lee, Chiung-I.; Ko, Chih-Hsiang; Huang, Tsun-Che

2008-12-01

This paper demonstrates a capacitive shunt type RF MEMS switch, which is actuated by electro-thermal actuator and electrostatic actuator at the same time, and than latching the switching status by electrostatic force only. Since thermal actuators need relative low voltage compare to electrostatic actuators, and electrostatic force needs almost no power to maintain the switching status, the benefits of the mechanism are very low actuation voltage and low power consumption. Moreover, the RF MEMS switch has considered issues for integrated circuit compatible in design phase. So the switch is fabricated by a standard 0.35um 2P4M CMOS process and uses wet etching and dry etching technologies for postprocess. This compatible ability is important because the RF characteristics are not only related to the device itself. If a packaged RF switch and a packaged IC wired together, the parasitic capacitance will cause the problem for optimization. The structure of the switch consists of a set of CPW transmission lines and a suspended membrane. The CPW lines and the membrane are in metal layers of CMOS process. Besides, the electro-thermal actuators are designed by polysilicon layer of the CMOS process. So the RF switch is only CMOS process layers needed for both electro-thermal and electrostatic actuations in switch. The thermal actuator is composed of a three-dimensional membrane and two heaters. The membrane is a stacked step structure including two metal layers in CMOS process, and heat is generated by poly silicon resistors near the anchors of membrane. Measured results show that the actuation voltage of the switch is under 7V for electro-thermal added electrostatic actuation.

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.

pH-programmable self-assembly of plasmonic nanoparticles: hydrophobic interaction versus electrostatic repulsion.

PubMed

Li, Weikun; Kanyo, Istvan; Kuo, Chung-Hao; Thanneeru, Srinivas; He, Jie

2015-01-21

We report a general strategy to conceptualize a new design for the pH-programmable self-assembly of plasmonic gold nanoparticles (AuNPs) tethered by random copolymers of poly(styrene-co-acrylic acid) (P(St-co-AA)). It is based on using pH as an external stimulus to reversibly change the surface charge of polymer tethers and to control the delicate balance of interparticle attractive and repulsive interactions. By incorporating -COOH moieties locally within PSt hydrophobic segments, the change in the ionization degree of -COOH moieties can dramatically disrupt the hydrophobic attraction within a close distance. pH acts as a key parameter to control the deprotonation of -COOH moieties and "programs" the assembled nanostructures of plasmonic nanoparticles in a stepwise manner. At a higher solution pH where -COOH groups of polymer tethers became highly deprotonated, electrostatic repulsion dominated the self-assembly and favored the formation of end-to-end, anisotropic assemblies, e.g. 1-D single-line chains. At a lower pH, the less deprotonated -COOH groups led to the decrease of electrostatic repulsion and the side-to-side aggregates, e.g. clusters and multi-line chains of AuNPs, became favorable. The pH-programmable self-assembly allowed us to engineer a "manual" program for a sequential self-assembly by changing the pH of the solution. We demonstrated that the two-step pH-programmable assembly could generate more sophisticated "multi-block" chains using two differently sized AuNPs. Our strategy offers a general means for the programmable design of plasmonic nanoparticles into the specific pre-ordained nanostructures that are potentially useful for the precise control over their plasmon coupling.

Flower-like ZnO nanorod arrays grown on HF-etched Si (111): constraining relation between ZnO seed layer and Si (111)

NASA Astrophysics Data System (ADS)

Brahma, Sanjaya; Liu, C.-W.; Huang, R.-J.; Chang, S.-J.; Lo, K.-Y.

2015-11-01

We demonstrate the formation of self-assembled homogenous flower-like ZnO nanorods over a ZnO seed layer deposited on a HF-etched Si (111) substrate. The typical flower-like morphology of ZnO nanorod arrays is ascribed to the formation of the island-like seed layer which is deposited by the drop method followed by annealing at 300 °C. The island-like ZnO seed layer consists of larger ZnO grains, and is built by constraining of the Si (111) surface due to pattern matching. Pattern matching of Si with ZnO determines the shape and size of the seed layer and this controls the final morphology of ZnO nanorods to be either flower like or vertically aligned. The high quality of the island-like ZnO seed layer enhances the diameter and length of ZnO nanorods. Besides, while the amorphous layer formed during the annealing process would influence the strained ZnO grain, that subsequent amorphous layer will not block the constraining between the ZnO grain and the substrate.

Evaluation of molecular dynamics simulation methods for ionic liquid electric double layers.

PubMed

Haskins, Justin B; Lawson, John W

2016-05-14

We investigate how systematically increasing the accuracy of various molecular dynamics modeling techniques influences the structure and capacitance of ionic liquid electric double layers (EDLs). The techniques probed concern long-range electrostatic interactions, electrode charging (constant charge versus constant potential conditions), and electrolyte polarizability. Our simulations are performed on a quasi-two-dimensional, or slab-like, model capacitor, which is composed of a polarizable ionic liquid electrolyte, [EMIM][BF4], interfaced between two graphite electrodes. To ensure an accurate representation of EDL differential capacitance, we derive new fluctuation formulas that resolve the differential capacitance as a function of electrode charge or electrode potential. The magnitude of differential capacitance shows sensitivity to different long-range electrostatic summation techniques, while the shape of differential capacitance is affected by charging technique and the polarizability of the electrolyte. For long-range summation techniques, errors in magnitude can be mitigated by employing two-dimensional or corrected three dimensional electrostatic summations, which led to electric fields that conform to those of a classical electrostatic parallel plate capacitor. With respect to charging, the changes in shape are a result of ions in the Stern layer (i.e., ions at the electrode surface) having a higher electrostatic affinity to constant potential electrodes than to constant charge electrodes. For electrolyte polarizability, shape changes originate from induced dipoles that soften the interaction of Stern layer ions with the electrode. The softening is traced to ion correlations vertical to the electrode surface that induce dipoles that oppose double layer formation. In general, our analysis indicates an accuracy dependent differential capacitance profile that transitions from the characteristic camel shape with coarser representations to a more diffuse profile with finer representations.

Biomimetic polymers of plant cutin: an approach from molecular modeling.

PubMed

San-Miguel, Miguel A; Oviedo, Jaime; Heredia-Guerrero, Jose Alejandro; Heredia, Antonio; Benitez, Jose Jesus

2014-07-01

Biomimetics of materials is based on adopting and reproducing a model in nature with a well-defined functionality optimized through evolution. An example is barrier polymers that protect living tissues from the environment. The protecting layer of fruits, leaves, and non-lignified stems is the plant cuticle. The cuticle is a complex system in which the cutin is the main component. Cutin is a biopolyester made of polyhydroxylated carboxylic acids of 16 and 18 carbon atoms. The biosynthesis of cutin in plants is not well understood yet, but a direct chemical route involving the self-assembly of either molecules or molecular aggregates has been proposed. In this work, we present a combined study using experimental and simulation techniques on self-assembled layers of monomers selectively functionalized with hydroxyl groups. Our results demonstrate that the number and position of the hydroxyl groups are critical for the interaction between single molecules and the further rearrangement. Also, the presence of lateral hydroxyl groups reinforces lateral interactions and favors the bi-dimensional growth (2D), while terminal hydroxyl groups facilitate the formation of a second layer caused by head-tail interactions. The balance of 2D/3D growth is fundamental for the plant to create a protecting layer both large enough in 2D and thick enough in 3D.

Investigation of microstructure and properties of ultrathin graded ZrNx self-assembled diffusion barrier in deep nano-vias prepared by plasma ion immersion implantation

NASA Astrophysics Data System (ADS)

Zou, Jianxiong; Liu, Bo; Lin, Liwei; Lu, Yuanfu; Dong, Yuming; Jiao, Guohua; Ma, Fei; Li, Qiran

2018-01-01

Ultrathin graded ZrNx self-assembled diffusion barriers with controllable stoichiometry was prepared in Cu/p-SiOC:H interfaces by plasma immersion ion implantation (PIII) with dynamic regulation of implantation fluence. The fundamental relationship between the implantation fluence of N+ and the stoichiometry and thereby the electrical properties of the ZrNx barrier was established. The optimized fluence of a graded ZrN thin film with gradually decreased Zr valence was obtained with the best electrical performance as well. The Cu/p-SiOC:H integration is thermally stable up to 500 °C due to the synergistic effect of Cu3Ge and ZrNx layers. Accordingly, the PIII process was verified in a 100-nm-thick Cu dual-damascene interconnect, in which the ZrNx diffusion barrier of 1 nm thick was successfully self-assembled on the sidewall without barrier layer on the via bottom. In this case, the via resistance was reduced by approximately 50% in comparison with Ta/TaN barrier. Considering the results in this study, ultrathin ZrNx conformal diffusion barrier can be adopted in the sub-14 nm technology node.

Preparation and characterization of the nanoporous ultrathin multilayer films based on molybdenum polyoxometalate (Mo 38) n

NASA Astrophysics Data System (ADS)

Wang, L.; Jiang, M.; Wang, E. B.; Duan, L. Y.; Hao, N.; Lan, Y.; Xu, L.; Li, Z.

2003-11-01

Ultrathin multilayer films of the wheel-shaped molybdenum polyoxometalate cluster (Mo 38) n and poly(allylamine hydrochloride)(PAH) have been prepared by the layer-by-layer (LbL) self-assembly method. The ((Mo 38) n/PAH) m multilayer films have been characterized by X-ray photoelectron spectra (XPS) and atomic force microscopy (AFM). UV-VIS measurements reveal regular film growth with each (Mo 38) n adsorption. The electrochemistry behavior of the film at room temperature was investigated.

Surfactant-free carnauba wax dispersion and its use for layer-by-layer assembled protective surface coatings on wood

NASA Astrophysics Data System (ADS)

Lozhechnikova, Alina; Bellanger, Hervé; Michen, Benjamin; Burgert, Ingo; Österberg, Monika

2017-02-01

Protection from liquid water and UV radiation are equally important, and a sophisticated approach is needed when developing surface coatings that preserve the natural and well-appreciated aesthetic appearance of wood. In order to prevent degradation and prolong the service life of timber, a protective coating was assembled using carnauba wax particles and zinc oxide nanoparticles via layer-by-layer deposition in water. For this purpose, a facile sonication route was developed to produce aqueous wax dispersion without any surfactants or stabilizers. The suspension was stable above pH 4 due to the electrostatic repulsion between the negatively charged wax particles. The particle size could be controlled by the initial wax concentration with average particle sizes ranging from 260 to 360 nm for 1 and 10 g/L, respectively. The deposition of wax particles onto the surface of spruce wood introduced additional roughness to the wood surface at micron level, while zinc oxide provided nano roughness and UV-absorbing properties. In addition to making wood superhydrophobic, this novel multilayer coating enhanced the natural moisture buffering capability of spruce. Moreover, wood surfaces prepared in this fashion showed a significant reduction in color change after exposure to UV light. A degradation of the wax through photocatalytic activity of the ZnO particles was measured by FTIR, indicating that further studies are required to achieve long-term stability. Nevertheless, the developed coating showed a unique combination of superhydrophobicity and excellent moisture buffering ability and some UV protection, all achieved using an environmentally friendly coating process, which is beneficial to retain the natural appearance of wood and improve indoor air quality and comfort.

Self-Assembled Multilayer Structure and Enhanced Thermochromic Performance of Spinodally Decomposed TiO2-VO2 Thin Film.

PubMed

Sun, Guangyao; Zhou, Huaijuan; Cao, Xun; Li, Rong; Tazawa, Masato; Okada, Masahisa; Jin, Ping

2016-03-23

Composite films of VO2-TiO2 were deposited on sapphire (11-20) substrate by cosputtering method. Self-assembled well-ordered multilayer structure with alternating Ti- and V-rich epitaxial thin layer was obtained by thermal annealing via a spinodal decomposition mechanism. The structured thermochromic films demonstrate superior optical modulation upon phase transition, with significantly reduced transition temperature. The results provide a facile and novel approach to fabricate smart structures with excellent performance.

Phosphorene-directed self-assembly of asymmetric PS-b-PMMA block copolymer for perpendicularly-oriented sub-10 nm PS nanopore arrays

NASA Astrophysics Data System (ADS)

Zhang, Ziming; Zheng, Lu; Khurram, Muhammad; Yan, Qingfeng

2017-10-01

Few-layer black phosphorus, also known as phosphorene, is a new two-dimensional material which is of enormous interest for applications, mainly in electronics and optoelectronics. Herein, we for the first time employ phosphorene for directing the self-assembly of asymmetric polystyrene-block-polymethylmethacrylate (PS-b-PMMA) block copolymer (BCP) thin film to form the perpendicular orientation of sub-10 nm PS nanopore arrays in a hexagonal fashion normal to the interface. We experimentally demonstrate that none of the PS and PMMA blocks exhibit preferential affinity to the phosphorene-modified surface. Furthermore, the perpendicularly-oriented PS nanostructures almost stay unchanged with the variation of number of layers of few-layer phosphorene nanoflakes between 15-30 layers. Differing from the neutral polymer brushes which are widely used for chemical modification of the silicon substrate, phosphorene provides a novel physical way to control the interfacial interactions between the asymmetric PS-b-PMMA BCP thin film and the silicon substrate. Based on our results, it is possible to build a new scheme for producing sub-10 nm PS nanopore arrays oriented perpendicularly to the few-layer phosphorene nanoflakes. Furthermore, the nanostructural microdomains could serve as a promising nanolithography template for surface patterning of phosphorene nanoflakes.

Three-dimensional textures and defects of soft material layering revealed by thermal sublimation.

PubMed

Yoon, Dong Ki; Kim, Yun Ho; Kim, Dae Seok; Oh, Seong Dae; Smalyukh, Ivan I; Clark, Noel A; Jung, Hee-Tae

2013-11-26

Layering is found and exploited in a variety of soft material systems, ranging from complex macromolecular self-assemblies to block copolymer and small-molecule liquid crystals. Because the control of layer structure is required for applications and characterization, and because defects reveal key features of the symmetries of layered phases, a variety of techniques have been developed for the study of soft-layer structure and defects, including X-ray diffraction and visualization using optical transmission and fluorescence confocal polarizing microscopy, atomic force microscopy, and SEM and transmission electron microscopy, including freeze-fracture transmission electron microscopy. Here, it is shown that thermal sublimation can be usefully combined with such techniques to enable visualization of the 3D structure of soft materials. Sequential sublimation removes material in a stepwise fashion, leaving a remnant layer structure largely unchanged and viewable using SEM, as demonstrated here using a lamellar smectic liquid crystal.

Langmuir-Blodgett Thin Films of Diketopyrrolopyrrole-Based Amphiphiles.

PubMed

Lo, Chi Kin; Wang, Cheng-Yin; Oosterhout, Stefan D; Zheng, Zilong; Yi, Xueping; Fuentes-Hernandez, Canek; So, Franky; Coropceanu, Veaceslav; Brédas, Jean-Luc; Toney, Michael F; Kippelen, Bernard; Reynolds, John R

2018-04-11

We report on two π-conjugated donor-acceptor-donor (D-A-D) molecules of amphiphilic nature, aiming to promote intermolecular ordering and carrier mobility in organic electronic devices. Diketopyrrolopyrrole was selected as the acceptor moiety that was disubstituted with nonpolar and polar functional groups, thereby providing the amphiphilic structures. This structural design resulted in materials with a strong intermolecular order in the solid state, which was confirmed by differential scanning calorimetry and polarized optical microscopy. Langmuir-Blodgett (LB) films of ordered mono- and multilayers were transferred onto glass and silicon substrates, with layer quality, coverage, and intermolecular order controlled by layer compression pressure on the LB trough. Organic field-effect transistors and organic photovoltaics devices with active layers consisting of the amphiphilic conjugated D-A-D-type molecules were constructed to demonstrate that the LB technique is an effective layer-by-layer deposition approach to fabricate self-assembled, ordered thin films.

Langmuir–Blodgett Thin Films of Diketopyrrolopyrrole-Based Amphiphiles

DOE PAGES

Lo, Chi Kin; Wang, Cheng -Yin; Oosterhout, Stefan D.; ...

2018-03-30

Here, we report on two π-conjugated donor–acceptor–donor (D–A–D) molecules of amphiphilic nature, aiming to promote intermolecular ordering and carrier mobility in organic electronic devices. Diketopyrrolopyrrole was selected as the acceptor moiety that was disubstituted with nonpolar and polar functional groups, thereby providing the amphiphilic structures. This structural design resulted in materials with a strong intermolecular order in the solid state, which was confirmed by differential scanning calorimetry and polarized optical microscopy. Langmuir–Blodgett (LB) films of ordered mono- and multilayers were transferred onto glass and silicon substrates, with layer quality, coverage, and intermolecular order controlled by layer compression pressure on themore » LB trough. Organic field-effect transistors and organic photovoltaics devices with active layers consisting of the amphiphilic conjugated D–A–D-type molecules were constructed to demonstrate that the LB technique is an effective layer-by-layer deposition approach to fabricate self-assembled, ordered thin films.« less

Self-assembled nanolaminate coatings (SV)

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

Fan, H.

2012-03-01

Sandia National Laboratories (Sandia) and Lockheed Martin Aeronautics (LM Aero) are collaborating to develop affordable, self-assembled, nanocomposite coatings and associated fabrication processes that will be tailored to Lockheed Martin product requirements. The purpose of this project is to develop a family of self-assembled coatings with properties tailored to specific performance requirements, such as antireflective (AR) optics, using Sandia-developed self-assembled techniques. The project met its objectives by development of a simple and economic self-assembly processes to fabricate multifunctional coatings. Specifically, materials, functionalization methods, and associated coating processes for single layer and multiple layers coatings have been developed to accomplish high reflectivemore » coatings, hydrophobic coatings, and anti-reflective coatings. Associated modeling and simulations have been developed to guide the coating designs for optimum optical performance. The accomplishments result in significant advantages of reduced costs, increased manufacturing freedom/producibility, improved logistics, and the incorporation of new technology solutions not possible with conventional technologies. These self-assembled coatings with tailored properties will significantly address LMC's needs and give LMC a significant competitive lead in new engineered materials. This work complements SNL's LDRD and BES programs aimed at developing multifunctional nanomaterials for microelectronics and optics as well as structure/property investigations of self-assembled nanomaterials. In addition, this project will provide SNL with new opportunities to develop and apply self-assembled nanocomposite optical coatings for use in the wavelength ranges of 3-5 and 8-12 micrometers, ranges of vital importance to military-based sensors and weapons. The SANC technologies will be applied to multiple programs within the LM Company including the F-35, F-22, ADP (Future Strike Bomber, UAV, UCAV, etc.). The SANC technologies will establish LMA and related US manufacturing capability for commercial and military applications therefore reducing reliance on off-shore development and production of related critical technologies. If these technologies are successfully licensed, production of these coatings in manufactory will create significant technical employment opportunities.« less

Hybrid nanomaterial of α-Co(OH)2 nanosheets and few-layer graphene as an enhanced electrode material for supercapacitors.

PubMed

Cheng, J P; Liu, L; Ma, K Y; Wang, X; Li, Q Q; Wu, J S; Liu, F

2017-01-15

Supercapacitor with metal hydroxide nanosheets as electrode can have high capacitance. However, the cycling stability and high rate capacity is low due to the low electrical conductivity. Here, the exfoliated α-Co(OH) 2 nanosheets with high capacitance has been assembled on few-layer graphene with high electric conductivity by a facile yet effective and scalable solution method. Exfoliated hydrotalcite-like α-Co(OH) 2 nanosheets and few-layer graphene suspensions were prepared by a simple ultrasonication in formamide and N-methyl-2-pyrrolidone, respectively. Subsequently, a hybrid was made by self-assembly of α-Co(OH) 2 and few-layer graphene when the two dispersions were mixed at room temperature. The hybrid material provided a high specific capacitance of 567.1F/g at 1A/g, while a better rate capability and better stability were achieved compared to that mad of pristine and single exfoliated α-Co(OH) 2 . When the hybrid nanocomposite was used as a positive electrode and activated carbon was applied as negative electrode to assembly an asymmetric capacitor, an energy density of 21.2Wh/kg at a power density of 0.41kW/kg within a potential of 1.65V was delivered. The high electrochemical performance and facile solution-based synthesis method suggested that the hybrid of exfoliated α-Co(OH) 2 /few-layer graphene could be a potential electrode material for electrochemical capacitor. Copyright © 2016 Elsevier Inc. All rights reserved.

Preparation of a self-humidifying membrane electrode assembly for fuel cell and its performance analysis

NASA Astrophysics Data System (ADS)

Wang, Cheng; Mao, Zongqiang; Xu, Jingming; Xie, Xiaofeng; Yang, Lizhai

2003-10-01

A novel nano-porous material SiO2-gel was prepared. After being purified by H2O2, then protonized by H2SO4 and desiccated in vacuum, the SiO2-gel, mixed with Nafion solution, was coated between an electrode and a solid electrolyte, which made a new type of self-humidifying membrane electrode assembly. The SiO2 powder was characterized by FTIR, BET and XRD. The surface of the electrodes was characterized by SEM and EDS. The performances of the self-humidifying membrane electrodes were analyzed by polarization discharge and AC impedance under the operation modes of external humidification and self-humidification respectively. Experimental-results indicated that the SiO2 powder held super-hydrophilicity, and the layer of SiO2 and Nafion polymer between electrode and solid electrolyte expanded three-dimension electrochemistry reac-tion area, maintained stability of catalyst layer and enhanced back-diffusion of water from cathode to anode, so the PEM Fuel cell can generate electricity at self-humidification mode. The power density of single PEM fuel cell reached 1.5 W/cm2 under 0.2 Mpa, 70°C and dry hydrogen and oxygen.

Dynamical Generation of Quasi-Stationary Alfvenic Double Layers and Charge Holes and Unified Theory of Quasi-Static and Alfvenic Auroral Arc Formation

NASA Astrophysics Data System (ADS)

Song, Y.; Lysak, R. L.

2015-12-01

Parallel E-fields play a crucial role for the acceleration of charged particles, creating discrete aurorae. However, once the parallel electric fields are produced, they will disappear right away, unless the electric fields can be continuously generated and sustained for a fairly long time. Thus, the crucial question in auroral physics is how to generate such a powerful and self-sustained parallel electric fields which can effectively accelerate charge particles to high energy during a fairly long time. We propose that nonlinear interaction of incident and reflected Alfven wave packets in inhomogeneous auroral acceleration region can produce quasi-stationary non-propagating electromagnetic plasma structures, such as Alfvenic double layers (DLs) and Charge Holes. Such Alfvenic quasi-static structures often constitute powerful high energy particle accelerators. The Alfvenic DL consists of localized self-sustained powerful electrostatic electric fields nested in a low density cavity and surrounded by enhanced magnetic and mechanical stresses. The enhanced magnetic and velocity fields carrying the free energy serve as a local dynamo, which continuously create the electrostatic parallel electric field for a fairly long time. The generated parallel electric fields will deepen the seed low density cavity, which then further quickly boosts the stronger parallel electric fields creating both Alfvenic and quasi-static discrete aurorae. The parallel electrostatic electric field can also cause ion outflow, perpendicular ion acceleration and heating, and may excite Auroral Kilometric Radiation.

Graphene quantum blisters: A tunable system to confine charge carriers

NASA Astrophysics Data System (ADS)

Abdullah, H. M.; Van der Donck, M.; Bahlouli, H.; Peeters, F. M.; Van Duppen, B.

2018-05-01

Due to Klein tunneling, electrostatic confinement of electrons in graphene is not possible. This hinders the use of graphene for quantum dot applications. Only through quasi-bound states with finite lifetime has one achieved to confine charge carriers. Here, we propose that bilayer graphene with a local region of decoupled graphene layers is able to generate bound states under the application of an electrostatic gate. The discrete energy levels in such a quantum blister correspond to localized electron and hole states in the top and bottom layers. We find that this layer localization and the energy spectrum itself are tunable by a global electrostatic gate and that the latter also coincides with the electronic modes in a graphene disk. Curiously, states with energy close to the continuum exist primarily in the classically forbidden region outside the domain defining the blister. The results are robust against variations in size and shape of the blister which shows that it is a versatile system to achieve tunable electrostatic confinement in graphene.

Controlling the electronic properties of van der Waals heterostructures by applying electrostatic design

NASA Astrophysics Data System (ADS)

Winkler, Christian; Harivyasi, Shashank S.; Zojer, Egbert

2018-07-01

Van der Waals heterostructures based on the heteroassembly of 2D materials represent a recently developed class of materials with promising properties especially for optoelectronic applications. The alignment of electronic energy bands between consecutive layers of these heterostructures crucially determines their functionality. In the present paper, relying on dispersion-corrected density-functional theory calculations, we present electrostatic design as a promising tool for manipulating this band alignment. The latter is achieved by inserting a layer of aligned polar molecules between consecutive transition-metal dichalcogenide (TMD) sheets. As a consequence, collective electrostatic effects induce a shift of as much as 0.3 eV in the band edges of successive TMD layers. Building on that, the proposed approach can be used to design electronically more complex systems, like quantum cascades or quantum wells, or to change the type of band lineup between type II and type I.

Amplified amperometric aptasensor for selective detection of protein using catalase-functional DNA-PtNPs dendrimer as a synergetic signal amplification label.

PubMed

Zhang, Juan; Yuan, Yali; biXie, Shun; Chai, Yaqin; Yuan, Ruo

2014-10-15

In this work, we present a new strategy to construct an electrochemical aptasensor for sensitive detection of platelet-derived growth factor BB (PDGF-BB) based on the synergetic amplification of a three-dimensional (3D) nanoscale catalase (CAT) enzyme-functional DNA-platinum nanoparticles (PtNPs) dendrimer through autonomous layer-by-layer assembly. Firstly, polyamidoaminedendrimer (PAMAM) with a hyper-branched and three-dimensional structure was served as nanocarriers to coimmobilize a large number of PDGF-BB binding aptamer (PBA II) and ssDNA 1 (S1) to form PBA II-PAMAM-S1 bioconjugate. In the presence of PDGF-BB, the bioconjugate was self-assembled on the electrode by sandwich assay. Following that, the carried S1 propagated a chain reaction of hybridization events between CAT-PtNPs-S1 and CAT-PtNPs-ssDNA 2 (S2) to form a 3D nanoscale CAT-functional PtNPs-DNA dendrimer, which successfully immobilized substantial CAT enzyme and PtNPs with superior catalysis activity. In this process, the formed negatively charged double-helix DNA could cause the intercalation of hexaammineruthenium(III) chloride (RuHex) into the groove via electrostatic interactions. Thus, numerous RuHex redox probes and CAT were decorated inside/outside of the dendrimer. In the presence of H2O2 in electrolytic cell, the synergistic reaction of CAT and PtNPs towards electrocatalysis could further amplify electrochemical signal. Under optimal condition, the CAT-PtNPs-DNA dendrimer-based sensing system presented a linear dependence between the reduction peak currents and logarithm of PDGF-BB concentrations in the range of 0.00005-35 nM with a relatively low detection limit of 0.02 pM. Copyright © 2014 Elsevier B.V. All rights reserved.

Supramolecular self-assembly of graphene oxide and metal nanoparticles into stacked multilayers by means of a multitasking protein ring

NASA Astrophysics Data System (ADS)

Ardini, Matteo; Golia, Giordana; Passaretti, Paolo; Cimini, Annamaria; Pitari, Giuseppina; Giansanti, Francesco; Leandro, Luana Di; Ottaviano, Luca; Perrozzi, Francesco; Santucci, Sandro; Morandi, Vittorio; Ortolani, Luca; Christian, Meganne; Treossi, Emanuele; Palermo, Vincenzo; Angelucci, Francesco; Ippoliti, Rodolfo

2016-03-01

Graphene oxide (GO) is rapidly emerging worldwide as a breakthrough precursor material for next-generation devices. However, this requires the transition of its two-dimensional layered structure into more accessible three-dimensional (3D) arrays. Peroxiredoxins (Prx) are a family of multitasking redox enzymes, self-assembling into ring-like architectures. Taking advantage of both their symmetric structure and function, 3D reduced GO-based composites are hereby built up. Results reveal that the ``double-faced'' Prx rings can adhere flat on single GO layers and partially reduce them by their sulfur-containing amino acids, driving their stacking into 3D multi-layer reduced GO-Prx composites. This process occurs in aqueous solution at a very low GO concentration, i.e. 0.2 mg ml-1. Further, protein engineering allows the Prx ring to be enriched with metal binding sites inside its lumen. This feature is exploited to both capture presynthesized gold nanoparticles and grow in situ palladium nanoparticles paving the way to straightforward and ``green'' routes to 3D reduced GO-metal composite materials.Graphene oxide (GO) is rapidly emerging worldwide as a breakthrough precursor material for next-generation devices. However, this requires the transition of its two-dimensional layered structure into more accessible three-dimensional (3D) arrays. Peroxiredoxins (Prx) are a family of multitasking redox enzymes, self-assembling into ring-like architectures. Taking advantage of both their symmetric structure and function, 3D reduced GO-based composites are hereby built up. Results reveal that the ``double-faced'' Prx rings can adhere flat on single GO layers and partially reduce them by their sulfur-containing amino acids, driving their stacking into 3D multi-layer reduced GO-Prx composites. This process occurs in aqueous solution at a very low GO concentration, i.e. 0.2 mg ml-1. Further, protein engineering allows the Prx ring to be enriched with metal binding sites inside its lumen. This feature is exploited to both capture presynthesized gold nanoparticles and grow in situ palladium nanoparticles paving the way to straightforward and ``green'' routes to 3D reduced GO-metal composite materials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08632a

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.

Electron Debye scale Kelvin-Helmholtz instability: Electrostatic particle-in-cell simulations

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

Lee, Sang-Yun; Lee, Ensang, E-mail: eslee@khu.ac.kr; Kim, Khan-Hyuk

2015-12-15

In this paper, we investigated the electron Debye scale Kelvin-Helmholtz (KH) instability using two-dimensional electrostatic particle-in-cell simulations. We introduced a velocity shear layer with a thickness comparable to the electron Debye length and examined the generation of the KH instability. The KH instability occurs in a similar manner as observed in the KH instabilities in fluid or ion scales producing surface waves and rolled-up vortices. The strength and growth rate of the electron Debye scale KH instability is affected by the structure of the velocity shear layer. The strength depends on the magnitude of the velocity and the growth ratemore » on the velocity gradient of the shear layer. However, the development of the electron Debye scale KH instability is mainly determined by the electric field generated by charge separation. Significant mixing of electrons occurs across the shear layer, and a fraction of electrons can penetrate deeply into the opposite side fairly far from the vortices across the shear layer.« less

Transition metal partially supported graphene: Magnetism and oscillatory electrostatic potentials

DOE PAGES

Liu, Xiaojie; Wang, Cai-Zhuang

2017-08-07

Using first-principles calculations here, we show that Mn and Cr layers under graphene exhibit almost zero magnetic moment due to anti-ferromagnetic order, while ferromagnetic coupling in Fe, Co, and Ni leads to large magnetic moment. The transition metal partially supported graphene, with a mixture of supported and pristine areas, exhibits an oscillatory electrostatic potential, thus alternating the electric field across the supported and pristine areas. Such an effect can be utilized to control mass transport and nanostructure self-organization on graphene at the atomic level.

Transition metal partially supported graphene: Magnetism and oscillatory electrostatic potentials

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

Liu, Xiaojie; Wang, Cai-Zhuang

Using first-principles calculations here, we show that Mn and Cr layers under graphene exhibit almost zero magnetic moment due to anti-ferromagnetic order, while ferromagnetic coupling in Fe, Co, and Ni leads to large magnetic moment. The transition metal partially supported graphene, with a mixture of supported and pristine areas, exhibits an oscillatory electrostatic potential, thus alternating the electric field across the supported and pristine areas. Such an effect can be utilized to control mass transport and nanostructure self-organization on graphene at the atomic level.

S-layer fusion protein as a tool functionalizing emulsomes and CurcuEmulsomes for antibody binding and targeting

PubMed Central

Ucisik, Mehmet H.; Küpcü, Seta; Breitwieser, Andreas; Gelbmann, Nicola; Schuster, Bernhard; Sleytr, Uwe B.

2015-01-01

Selective targeting of tumor cells by nanoparticle-based drug delivery systems is highly desirable because it maximizes the drug concentration at the desired target while simultaneously protecting the surrounding healthy tissues. Here, we show a design for smart nanocarriers based on a biomimetic approach that utilizes the building principle of virus envelope structures. Emulsomes and CurcuEmulsomes comprising a tripalmitin solid core surrounded by phospholipid layers are modified by S-layer proteins that self-assemble into a two-dimensional array to form a surface layer. One significant advantage of this nanoformulation is that it increases the solubility of the lipophilic anti-cancer agent curcumin in the CurcuEmulsomes by a factor of 2700. In order to make the emulsomes specific for IgG, the S-layer protein is fused with two protein G domains. This S-layer fusion protein preserves its recrystallization characteristics, forming an ordered surface layer (square lattice with 13 nm unit-by-unit distance). The GG domains are presented in a predicted orientation and exhibit a selective binding affinity for IgG. PMID:25734967

Nanoengineered Plasmonic Hybrid Systems for Bio-nanotechnology

NASA Astrophysics Data System (ADS)

Leong, Kirsty

Plasmonic hybrid systems are fabricated using a combination of lithography and layer-by-layer directed self-assembly approaches to serve as highly sensitive nanosensing devices. This layer-by-layer directed self-assembly approach is utilized as a hybrid methodology to control the organization of quantum dots (QDs), nanoparticles, and biomolecules onto inorganic nanostructures with site-specific attachment and functionality. Here, surface plasmon-enhanced nanoarrays are fabricated where the photoluminescence of quantum dots and conjugated polymer nanoarrays are studied. This study was performed by tuning the localized surface plasmon resonance and the distance between the emitter and the metal surface using genetically engineered polypeptides as binding agents and biotin-streptavidin binding as linker molecules. In addition, these nanoarrays were also chemically modified to support the immobilization and label-free detection of DNA using surface enhanced Raman scattering. The surface of the nanoarrays was chemically modified using an acridine containing molecule which can act as an intercalating agent for DNA. The self-assembled monolayer (SAM) showed the ability to immobilize and intercalate DNA onto the surface. This SAM system using surface enhanced Raman scattering (SERS) serves as a highly sensitive methodology for the immobilization and label-free detection of DNA applicable into a wide range of bio-diagnostic platforms. Other micropatterned arrays were also fabricated using a combination of soft lithography and surface engineering. Selective single cell patterning and adhesion was achieved through chemical modifications and surface engineering of poly(dimethylsiloxane) surface. The surface of each microwell was functionally engineered with a SAM which contained an aldehyde terminated fused-ring aromatic thiolated molecule. Cells were found to be attracted and adherent to the chemically modified microwells. By combining soft lithography and surface engineering, a simple methodology produced single cell arrays on biocompatible substrates. Thus the design of plasmonic devices relies heavily on the nature of the plasmonic interactions between nanoparticles in the devices which can potentially be fabricated into lab-on-a-chip devices for multiplex sensing capabilities.

First-Principles Study of the Self-Assembled Pentacene Molecules on Metal Surfaces

NASA Astrophysics Data System (ADS)

Lee, Kyuho; Han, Myung-Joon; Yu, Jaejun

2003-03-01

Oriented thin films of organic semiconducting small molecules have received considerable attention as active semiconductors for device applications such as Schottky diodes and thin-film transistors (TFTs). Among these organic materials, pentacene has been found to have the highest mobilities for hole transport. Understanding the formation of self-organized ad-layers of pentacene would contribute to the fabrication of nanostructures and possibly highly oriented pentacene layers by epitaxy for use in electronic devices. To understand the ordering patterns of pentacene ad-layers on metal surfaces, we investigated the energetics between pentacene molecules with and without metal substrates and analyzed its electronic structure. We used a self-consistent first-principles calculation method based on the density functional theory (DFT) within local density approximation (LDA). The localized pseudo-atomic orbitals (PAO) are employed for a real-space numerical basis set, which was suggested by Sankey and Niklewski, and the Troullier-Martins-type pseudo-potential is used. As results, we found that the ordering patterns can be explained by the energetics between pentacene molecules, and the metal substrates appears not to influence too much on the interaction between pentacenes. To investigate the nature of the self-assembled structure, we calculated the total energies of various configurations for the molecule pattern, e.g., side-by-side and head-to-head ordering or on-top stacking. Depending on its direction, extremely different interaction character between two pentacenes is found and explained by its electronic structure analysis.

Monolayers and multilayers of conjugated polymers as nanosized electronic components.

PubMed

Zotti, Gianni; Vercelli, Barbara; Berlin, Anna

2008-09-01

Conjugated polymers (CPs) are interesting materials for preparing devices based on nanoscopic molecular architectures because they exhibit electrical, electronic, magnetic, and optical properties similar to those of metals or semiconductors while maintaining the flexibility and ease of processing of polymers. The production of well-defined mono- and multilayers of CPs on electrodes with nanometer-scale, one-dimensional resolution remains, however, an important challenge. In this Account, we describe the preparation and conductive properties of nanometer-sized CP molecular structures formed on electrode surfaces--namely, self-assembled monolayer (SAM), brush-type, and self-assembled multilayer CPs--and in combination with gold nanoparticles (AuNPs). We have electrochemically polymerized SAMs of carboxyalkyl-functionalized terthiophenes aligned either perpendicular or parallel to the electrode surface. Anodic coupling of various pyrrole- and thiophene-based monomers in solution with the oligothiophene-based SAMs produced brush-like films. Microcontact printing of these SAMs produced patterns that, after heterocoupling, exhibited large height enhancements, as measured using atomic force microscopy (AFM). We have employed layer-by-layer self-assembly of water-soluble polythiophene-based polyelectrolytes to form self-assembled multilayers. The combination of isostructural polycationic and polyanionic polythiophenes produced layers of chains aligned parallel to the substrate plane. These stable, robust, and dense layers formed with high regularity on the preformed monolayers, with minimal interchain penetration. Infrared reflection/adsorption spectroscopy and X-ray diffraction analyses revealed unprecedented degrees of order. Deposition of soluble polypyrroles produced molecular layers that, when analyzed using a gold-coated AFM tip, formed gold-polymer-gold junctions that were either ohmic or rectifying, depending of the layer sequence. We also describe the electronic conduction of model alpha,omega-capped sexithiophenes featuring a range of electron donor/acceptor units and lengths of additional conjugation. The sexithiophene cores exhibit redox-type conductivity, developing at the neutral/cation and cation/dication levels with values depending the nature of the substitution and the redox system. Extending the conjugation beyond the sexithiophene frame introduces further oxidation processes displaying enhanced conductivity. Finally, we discuss the ability of CP-based monolayers to coordinate AuNPs. Although thiophene- and pyrrole-based oligomers aggregate toluene-soluble AuNPs, alkyl substitution inhibits the aggregation process through steric restraint. Consequently, we investigated the interactions between AuNPs and polypyrrole or polythiophene monolayers, including those formed from star-shaped molecules. The hindered aggregation provided by alkyl substituents allowed us to adsorb thiol-functionalized oligothiophenes and oligopyrroles directly onto preformed AuNPs. Novel materials incorporating AuNPs of the same size but bearing different conjugated ends or bridges have great promise for applications in electrocatalysis, electroanalysis, and organic electronics.

PAMAM-Based Dendrimers with Different Alkyl Chains Self-Assemble on Silica Surfaces: Controllable Layer Structure and Molecular Aggregation.

PubMed

Zhang, Minghui; Yang, Hui; Wang, Shujuan; Zhang, Wei; Hou, Qingfeng; Guo, Donghong; Liu, Fanghui; Chen, Ting; Wu, Xu; Wang, Jinben

2018-06-20

Amphiphilic poly(amidoamine) (PAMAM) dendrimers are a well-known dendritic family due to their remarkable ability to self-assemble on solid surface. However, the relationship between molecular conformation (or adsorption kinetics) of a self-assembled layer and molecular amphiphilicity of such kind of dendrimer is still lacking, which limits the development of modulating self-assembling structures and surface functionality. With this in mind, we synthesized a series of amphiphilic PAMAM-based dendrimers, denoted as G 1 C n , with different alkyl chains ( n = 8, 12, and 16), and investigated the molecular aggregation on silica surfaces by means of quartz crystal microbalance with dissipation, atomic force microscopy, and contact angle. After rinsing, remaining adsorption amounts of G 1 C 12 were higher than those of G 1 C 8 at high concentrations, suggesting that G 1 C 12 adlayers were more stable due to the stronger intermolecular hydrophobic interactions, whereas it preferred to adopt the intramolecular hydrophobic interactions for G 1 C 16 , with low adsorption amounts and unstable adlayers. Bilayer-like structures were inferred in G 1 C 8 and G 1 C 12 adlayers with loose conformation, whereas monolayer structures were likely to exist in the sparse adsorption film of G 1 C 16 . Our results provided more detailed understanding of the effect of molecular structure on the self-assembled structures of amphiphilic dendrimers on solid surfaces, shedding light on the controlled microstructure and wettability of functional surface by modulating the length of hydrophobic chains of dendrimers and a potential application of dendrimer-substrate combinations.

Infrared Focal Plane Arrays Based on Semiconductor Quantum Dots

DTIC Science & Technology

2002-01-01

an ensemble of self -assembled InAs/GaAs or InAs/InP quantum dots (QDs) are typically in the range of 10-30 monolayers [1]. Here, we report on InAs...photoconductive properties of QDIPs based on self organized InAs quantum dots grown on In.52Al.48As/InP(100), using the MBE technique. Dr. Gendry grew the...composed of 10 layers of self assembled InAs dots, separated by 500 Å thick InAlAs (lattice matched to the semi-insulating InP substrate) barrier

Asymmetric organic-inorganic hybrid membrane formation via block copolymer-nanoparticle co-assembly.

PubMed

Gu, Yibei; Dorin, Rachel M; Wiesner, Ulrich

2013-01-01

A facile method for forming asymmetric organic-inorganic hybrid membranes for selective separation applications is developed. This approach combines co-assembly of block copolymer (BCP) and inorganic nanoparticles (NPs) with non-solvent induced phase separation. The method is successfully applied to two distinct molar mass BCPs with different fractions of titanium dioxide (TiO2) NPs. The resulting hybrid membranes exhibit structural asymmetry with a thin nanoporous surface layer on top of a macroporous fingerlike support layer. Key parameters that dictate membrane surface morphology include the fraction of inorganics used and the length of time allowed for surface layer development. The resulting membranes exhibit both good selectivity and high permeability (3200 ± 500 Lm(-2) h(-1) bar(-1)). This fast and straightforward synthesis method for asymmetric hybrid membranes provides a new self-assembly platform upon which multifunctional and high-performance organic-inorganic hybrid membranes can be formed.

Multi-layer electrode with nano-Li4Ti5O12 aggregates sandwiched between carbon nanotube and graphene networks for high power Li-ion batteries.

PubMed

Choi, Jin-Hoon; Ryu, Won-Hee; Park, Kyusung; Jo, Jeong-Dai; Jo, Sung-Moo; Lim, Dae-Soon; Kim, Il-Doo

2014-12-05

Self-aggregated Li4Ti5O12 particles sandwiched between graphene nanosheets (GNSs) and single-walled carbon nanotubes (SWCNTs) network are reported as new hybrid electrodes for high power Li-ion batteries. The multi-layer electrodes are fabricated by sequential process comprising air-spray coating of GNSs layer and the following electrostatic spray (E-spray) coating of well-dispersed colloidal Li4Ti5O12 nanoparticles, and subsequent air-spray coating of SWCNTs layer once again. In multi-stacked electrodes of GNSs/nanoporous Li4Ti5O12 aggregates/SWCNTs networks, GNSs and SWCNTs serve as conducting bridges, effectively interweaving the nanoporous Li4Ti5O12 aggregates, and help achieve superior rate capability as well as improved mechanical stability of the composite electrode by holding Li4Ti5O12 tightly without a binder. The multi-stacked electrodes deliver a specific capacity that maintains an impressively high capacity of 100 mA h g(-1) at a high rate of 100C even after 1000 cycles.

The effect of layer-by-layer chitosan-hyaluronic acid coating on graft-to-bone healing of a poly(ethylene terephthalate) artificial ligament.

PubMed

Li, Hong; Ge, Yunsheng; Zhang, Pengyun; Wu, Lingxiang; Chen, Shiyi

2012-01-01

Surface coating with an organic layer-by-layer self-assembled template of chitosan and hyaluronic acid on a poly(ethylene terephthalate) (PET) artificial ligament was designed for the promotion and enhancement of graft-to-bone healing after artificial ligament implantation in a bone tunnel. The results of in vitro culturing of MC3T3-E1 mouse osteoblastic cells supported the hypothesis that the layer-by-layer coating of chitosan and hyaluronic acid could promote the cell compatibility of grafts and could promote osteoblast proliferation. A rabbit extra-articular tendon-to-bone healing model was used to evaluate the effect of this kind of surface-modified stainless artificial ligament in vivo. The final results proved that this organic compound coating could significantly promote and enhance new bone formation at the graft-bone interface histologically and, correspondingly, the experimental group with coating had significantly higher biomechanical properties compared with controls at 8 weeks (P < 0.05).

Debye ring diffraction elucidation of 2D photonic crystal self-assembly and ordering at the air-water interface.

PubMed

Smith, N L; Coukouma, A; Dubnik, S; Asher, S A

2017-12-06

We fabricate 2D photonic crystals (2DPC) by spreading a dispersion of charged colloidal particles (diameters = 409, 570, and 915 nm) onto the surface of electrolyte solutions using a needle tip flow method. When the interparticle electrostatic interaction potential is large, particles self-assemble into highly ordered hexagonal close packed (hcp) monolayers. Ordered 2DPC efficiently forward diffract monochromatic light to produce a Debye ring on a screen parallel to the 2DPC. The diameter of the Debye ring is inversely proportional to the 2DPC particle spacing, while the Debye ring brightness and thickness depends on the 2DPC ordering. The Debye ring thickness increases as the 2DPC order decreases. The Debye ring ordering measurements of 2DPC attached to glass slides track measurements of the 2D pair correlation function order parameter calculated from SEM micrographs. The Debye ring method was used to investigate the 2DPC particle spacing, and ordering at the air-solution interface of NaCl solutions, and for 2DPC arrays attached to glass slides. Surprisingly, the 2DPC ordering does not monotonically decrease as the salt concentration increases. This is because of chloride ion adsorption onto the anionic particle surfaces. This adsorption increases the particle surface charge and compensates for the decreased Debye length of the electric double layer when the NaCl concentration is below a critical value.

Optical and structural properties of protein/gold hybrid bio-nanofilms prepared by layer-by-layer method.

PubMed

Pál, Edit; Hornok, Viktória; Sebok, Dániel; Majzik, Andrea; Dékány, Imre

2010-08-01

Lysozyme/gold thin layers were prepared by layer-by-layer (LbL) self-assembly method. The build-up of the films was followed by UV-vis-absorbance spectra, quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) techniques. The structural property of films was examined by X-ray diffraction (XRD) measurements, while their morphology was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). It was found that gold nanoparticles (NPs) had cubic crystalline structure, the primary particles form aggregates in the thin layer due to the presence of lysozyme molecules. The UV-vis measurements prove change in particle size while the colour of the film changes from wine-red to blue. The layer thickness of films was determined using the above methods and the loose, porous structure of the films explains the difference in the results. The vapour adsorption property of hybrid layers was also studied by QCM using different saturated vapours and ammonia gas. The lysozyme/Au films were most sensitive for ammonia gas among the tested gases/vapours due to the strongest interaction between the functional groups of the protein. Copyright 2010 Elsevier B.V. All rights reserved.

Real-Time Observation of Atomic Layer Deposition Inhibition: Metal Oxide Growth on Self-Assembled Alkanethiols

DOE PAGES

Avila, Jason R.; DeMarco, Erica J.; Emery, Jonathan D.; ...

2014-07-21

Through in-situ quartz crystal microbalance (QCM) monitoring we resolve the growth of a self-assembled monolayer (SAM) and subsequent metal oxide deposition with high resolution. Here, we introduce the fitting of mass deposited during each atomic layer deposition (ALD) cycle to an analytical island-growth model that enables quantification of growth inhibition, nucleation density, and the uninhibited ALD growth rate. A long-chain alkanethiol was self-assembled as a monolayer on gold-coated quartz crystals in order to investigate its effectiveness as a barrier to ALD. Compared to solution-loading, vapor-loading is observed to produce a SAM with equal or greater inhibition-ability in minutes vs. days.more » The metal oxide growth temperature and the choice of precursor also significantly affect the nucleation density, which ranges from 0.001 to 1 sites/nm 2. Finally, we observe a minimum 100 cycle inhibition of an oxide ALD process, ZnO, under moderately optimized conditions.« less

All-nanoparticle self-assembly ZnO/TiO₂ heterojunction thin films with remarkably enhanced photoelectrochemical activity.

PubMed

Yuan, Sujun; Mu, Jiuke; Mao, Ruiyi; Li, Yaogang; Zhang, Qinghong; Wang, Hongzhi

2014-04-23

The multilaminated ZnO/TiO2 heterojunction films were successfully deposited on conductive substrates including fluorine-doped tin oxide (FTO) glass and flexible indium tin oxide coated poly(ethylene terephthalate) via the layer-by-layer (LBL) self assembly method from the oxide colloids without using any polyelectrolytes. The positively charged ZnO nanoparticles and the negatively charged TiO2 nanoparticles were directly used as the components in the consecutive deposition process to prepare the heterojunction thin films by varying the thicknesses. Moreover, the crystal growth of both oxides could be efficiently inhibited by the good connection between ZnO and TiO2 nanoparticles even after calcination at 500 °C, especially for ZnO which was able to keep the crystallite size under 25 nm. The as-prepared films were used as the working electrodes in the three-electrode photoelectrochemical cells. Because the well-contacted nanoscale heterojunctions were formed during the LBL self-assembling process, the ZnO/TiO2 all-nanoparticle films deposited on both substrates showed remarkably enhanced photoelectrochemical properties compared to that of the well-established TiO2 LBL thin films with similar thicknesses. The photocurrent response collected from the ZnO/TiO2 electrode on the FTO glass substrate was about five times higher than that collected from the TiO2 electrode. Owing to the absence of the insulating layer of dried polyelectrolytes, the ZnO/TiO2 all-nanoparticle heterojunction films were expected to be used in the photoelectrochemical device before calcination.

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

DOE PAGES

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

2016-07-05

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

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

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

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

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

Studies of Low-Current Back-Discharge in Point-Plane Geometry with Dielectric Layer

NASA Astrophysics Data System (ADS)

Jaworek, Anatol; Rajch, Eryk; Krupa, Andrzej; Czech, Tadeusz; Lackowski, Marcin

2006-01-01

The paper presents results of spectroscopic investigations of back-discharges generated in the point-plane electrode geometry in ambient air at atmospheric pressure, with the plane electrode covered with a dielectric layer. Fly ash from an electrostatic precipitator of a coal-fired power plant was used as the dielectric layer in these investigations. The discharges for positive and negative polarities of the needle electrode were studied by measuring optical emission spectra at two regions of the discharge: near the needle electrode and dielectric layer surface. The visual forms of the discharge were recorded and correlated with the current-voltage characteristics and optical emission spectra. The back-arc discharge was of particular interest in these studies due to its detrimental effects it causes in electrostatic precipitators.

Nanocomposites for ultra high density information storage, devices including the same, and methods of making the same

DOEpatents

Goyal, Amit; Shin, Junsoo

2014-04-01

A nanocomposite article that includes a single-crystal or single-crystal-like substrate and heteroepitaxial, phase-separated layer supported by a surface of the substrate and a method of making the same are described. The heteroepitaxial layer can include a continuous, non-magnetic, crystalline, matrix phase, and an ordered, magnetic magnetic phase disposed within the matrix phase. The ordered magnetic phase can include a plurality of self-assembled crystalline nanostructures of a magnetic material. The phase-separated layer and the single crystal substrate can be separated by a buffer layer. An electronic storage device that includes a read-write head and a nanocomposite article with a data storage density of 0.75 Tb/in.sup.2 is also described.

Electrostatically assisted fabrication of silver-dielectric core/shell nanoparticles thin film capacitor with uniform metal nanoparticle distribution and controlled spacing.

PubMed

Li, Xue; Niitsoo, Olivia; Couzis, Alexander

2016-03-01

An electrostatically-assisted strategy for fabrication of thin film composite capacitors with controllable dielectric constant (k) has been developed. The capacitor is composed of metal-dielectric core/shell nanoparticle (silver/silica, Ag@SiO2) multilayer films, and a backfilling polymer. Compared with the simple metal particle-polymer mixtures where the metal nanoparticles (NP) are randomly dispersed in the polymer matrix, the metal volume fraction in our capacitor was significantly increased, owing to the densely packed NP multilayers formed by the electrostatically assisted assembly process. Moreover, the insulating layer of silica shell provides a potential barrier that reduces the tunneling current between neighboring Ag cores, endowing the core/shell nanocomposites with a stable and relatively high dielectric constant (k) and low dielectric loss (D). Our work also shows that the thickness of the SiO2 shell plays a dominant role in controlling the dielectric properties of the nanocomposites. Control over metal NP separation distance was realized not only by variation the shell thickness of the core/shell NPs but also by introducing a high k nanoparticle, barium strontium titanate (BST) of relatively smaller size (∼8nm) compared to 80-160nm of the core/shell Ag@SiO2 NPs. The BST assemble between the Ag@SiO2 and fill the void space between the closely packed core/shell NPs leading to significant enhancement of the dielectric constant. This electrostatically assisted assembly method is promising for generating multilayer films of a large variety of NPs over large areas at low cost. Copyright © 2015 Elsevier Inc. All rights reserved.

Self-assembled graphene hydrogel via a one-step hydrothermal process.

PubMed

Xu, Yuxi; Sheng, Kaixuan; Li, Chun; Shi, Gaoquan

2010-07-27

Self-assembly of two-dimensional graphene sheets is an important strategy for producing macroscopic graphene architectures for practical applications, such as thin films and layered paperlike materials. However, construction of graphene self-assembled macrostructures with three-dimensional networks has never been realized. In this paper, we prepared a self-assembled graphene hydrogel (SGH) via a convenient one-step hydrothermal method. The SGH is electrically conductive, mechanically strong, and thermally stable and exhibits a high specific capacitance. The high-performance SGH with inherent biocompatibility of carbon materials is attractive in the fields of biotechnology and electrochemistry, such as drug-delivery, tissue scaffolds, bionic nanocomposites, and supercapacitors.

Biocolloids with ordered urease multilayer shells as enzymatic reactors.

PubMed

Lvov, Y; Caruso, F

2001-09-01

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

Electrostatically Directed Self-Assembly of Ultrathin Supramolecular Polymer Microcapsules

PubMed Central

Parker, Richard M; Zhang, Jing; Zheng, Yu; Coulston, Roger J; Smith, Clive A; Salmon, Andrew R; Yu, Ziyi; Scherman, Oren A; Abell, Chris

2015-01-01

Supramolecular self-assembly offers routes to challenging architectures on the molecular and macroscopic scale. Coupled with microfluidics it has been used to make microcapsules—where a 2D sheet is shaped in 3D, encapsulating the volume within. In this paper, a versatile methodology to direct the accumulation of capsule-forming components to the droplet interface using electrostatic interactions is described. In this approach, charged copolymers are selectively partitioned to the microdroplet interface by a complementary charged surfactant for subsequent supramolecular cross-linking via cucurbit[8]uril. This dynamic assembly process is employed to selectively form both hollow, ultrathin microcapsules and solid microparticles from a single solution. The ability to dictate the distribution of a mixture of charged copolymers within the microdroplet, as demonstrated by the single-step fabrication of distinct core–shell microcapsules, gives access to a new generation of innovative self-assembled constructs. PMID:26213532

Layer-by-layer assembly of two-dimensional materials into wafer-scale heterostructures

NASA Astrophysics Data System (ADS)

Kang, Kibum; Lee, Kan-Heng; Han, Yimo; Gao, Hui; Xie, Saien; Muller, David A.; Park, Jiwoong

2017-10-01

High-performance semiconductor films with vertical compositions that are designed to atomic-scale precision provide the foundation for modern integrated circuitry and novel materials discovery. One approach to realizing such films is sequential layer-by-layer assembly, whereby atomically thin two-dimensional building blocks are vertically stacked, and held together by van der Waals interactions. With this approach, graphene and transition-metal dichalcogenides--which represent one- and three-atom-thick two-dimensional building blocks, respectively--have been used to realize previously inaccessible heterostructures with interesting physical properties. However, no large-scale assembly method exists at present that maintains the intrinsic properties of these two-dimensional building blocks while producing pristine interlayer interfaces, thus limiting the layer-by-layer assembly method to small-scale proof-of-concept demonstrations. Here we report the generation of wafer-scale semiconductor films with a very high level of spatial uniformity and pristine interfaces. The vertical composition and properties of these films are designed at the atomic scale using layer-by-layer assembly of two-dimensional building blocks under vacuum. We fabricate several large-scale, high-quality heterostructure films and devices, including superlattice films with vertical compositions designed layer-by-layer, batch-fabricated tunnel device arrays with resistances that can be tuned over four orders of magnitude, band-engineered heterostructure tunnel diodes, and millimetre-scale ultrathin membranes and windows. The stacked films are detachable, suspendable and compatible with water or plastic surfaces, which will enable their integration with advanced optical and mechanical systems.

Layer-by-layer assembly of two-dimensional materials into wafer-scale heterostructures.

PubMed

Kang, Kibum; Lee, Kan-Heng; Han, Yimo; Gao, Hui; Xie, Saien; Muller, David A; Park, Jiwoong

2017-10-12

High-performance semiconductor films with vertical compositions that are designed to atomic-scale precision provide the foundation for modern integrated circuitry and novel materials discovery. One approach to realizing such films is sequential layer-by-layer assembly, whereby atomically thin two-dimensional building blocks are vertically stacked, and held together by van der Waals interactions. With this approach, graphene and transition-metal dichalcogenides-which represent one- and three-atom-thick two-dimensional building blocks, respectively-have been used to realize previously inaccessible heterostructures with interesting physical properties. However, no large-scale assembly method exists at present that maintains the intrinsic properties of these two-dimensional building blocks while producing pristine interlayer interfaces, thus limiting the layer-by-layer assembly method to small-scale proof-of-concept demonstrations. Here we report the generation of wafer-scale semiconductor films with a very high level of spatial uniformity and pristine interfaces. The vertical composition and properties of these films are designed at the atomic scale using layer-by-layer assembly of two-dimensional building blocks under vacuum. We fabricate several large-scale, high-quality heterostructure films and devices, including superlattice films with vertical compositions designed layer-by-layer, batch-fabricated tunnel device arrays with resistances that can be tuned over four orders of magnitude, band-engineered heterostructure tunnel diodes, and millimetre-scale ultrathin membranes and windows. The stacked films are detachable, suspendable and compatible with water or plastic surfaces, which will enable their integration with advanced optical and mechanical systems.

Multi-layer assemblies with predetermined stress profile and method for producing same

NASA Technical Reports Server (NTRS)

Heuer, Arthur H. (Inventor); Kahn, Harold (Inventor); Yang, Jie (Inventor); Phillips, Stephen M. (Inventor)

2003-01-01

Multi-layer assemblies of polysilicon thin films having predetermined stress characteristics and techniques for forming such assemblies are disclosed. In particular, a multi-layer assembly of polysilicon thin films may be produced that has a stress level of zero, or substantially so. The multi-layer assemblies comprise at least one constituent thin film having a tensile stress and at least one constituent thin film having a compressive stress. The thin films forming the multi-layer assemblies may be disposed immediately adjacent to one another without the use of intermediate layers between the thin films. Multi-layer assemblies exhibiting selectively determinable overall bending moments are also disclosed. Selective production of overall bending moments in microstructures enables manufacture of such structures with a wide array of geometrical configurations.

Effect of the ordered interfacial water layer in protein complex formation: A nonlocal electrostatic approach

NASA Astrophysics Data System (ADS)

Rubinstein, A.; Sabirianov, R. F.; Mei, W. N.; Namavar, F.; Khoynezhad, A.

2010-08-01

Using a nonlocal electrostatic approach that incorporates the short-range structure of the contacting media, we evaluated the electrostatic contribution to the energy of the complex formation of two model proteins. In this study, we have demonstrated that the existence of an ordered interfacial water layer at the protein-solvent interface reduces the charging energy of the proteins in the aqueous solvent, and consequently increases the electrostatic contribution to the protein binding (change in free energy upon the complex formation of two proteins). This is in contrast with the finding of the continuum electrostatic model, which suggests that electrostatic interactions are not strong enough to compensate for the unfavorable desolvation effects.

Effect of the ordered interfacial water layer in protein complex formation: A nonlocal electrostatic approach.

PubMed

Rubinstein, A; Sabirianov, R F; Mei, W N; Namavar, F; Khoynezhad, A

2010-08-01

Using a nonlocal electrostatic approach that incorporates the short-range structure of the contacting media, we evaluated the electrostatic contribution to the energy of the complex formation of two model proteins. In this study, we have demonstrated that the existence of an ordered interfacial water layer at the protein-solvent interface reduces the charging energy of the proteins in the aqueous solvent, and consequently increases the electrostatic contribution to the protein binding (change in free energy upon the complex formation of two proteins). This is in contrast with the finding of the continuum electrostatic model, which suggests that electrostatic interactions are not strong enough to compensate for the unfavorable desolvation effects.

Laser-induced atomic assembling of periodic layered nanostructures of silver nanoparticles in fluoro-polymer film matrix

NASA Astrophysics Data System (ADS)

Bagratashvili, V. N.; Rybaltovsky, A. O.; Minaev, N. V.; Timashev, P. S.; Firsov, V. V.; Yusupov, V. I.

2010-05-01

Fluorinated acrylic polymer (FAP) films have been impregnated with silver precursor (Ag(hfac)COD) by supercritical fluid technique and next irradiated with laser (λ = 532 nm). Laser-chemically reduced Ag atoms have been assembled into massifs of Ag nanoparticles (3 - 8 nm) in FAP/Ag(hfac)COD films matrix in the form of periodic layered nanostructures (horizontal to film surface) with unexpectedly short period (90 - 180 nm). The wavelet analysis of TEM images reveals the existence of even shorter-period structures in such films. Photolysis with non-coherent light or pyrolysis of FAP/Ag(hfac)COD film results in formation of Ag nanoparticles massifs but free of any periodic nanoparticle assemblies. Our interpretation of the observed effect of laser formation of short-period nano-sized Ag nanoparticle assemblies is based on self-enhanced interference process in the course of modification of optical properties of film.

Biomolecule nanoparticle-induced nanocomposites with resistive switching nonvolatile memory properties

NASA Astrophysics Data System (ADS)

Ko, Yongmin; Ryu, Sook Won; Cho, Jinhan

2016-04-01

Resistive switching behavior-based memory devices are considered promising candidates for next-generation data storage because of their simple structure configuration, low power consumption, and rapid operating speed. Here, the resistive switching nonvolatile memory properties of Fe2O3 nanocomposite (NC) films prepared from the thermal calcination of layer-by-layer (LbL) assembled ferritin multilayers were successfully investigated. For this study, negatively charged ferritin nanoparticles were alternately deposited onto the Pt-coated Si substrate with positively charged poly(allylamine hydrochloride) (PAH) by solution-based electrostatic LbL assembly, and the formed multilayers were thermally calcinated to obtain a homogeneous transition metal oxide NC film through the elimination of organic components, including the protein shell of ferritin. The formed memory device exhibits a stable ON/OFF current ratio of approximately 103, with nanosecond switching times under an applied external bias. In addition, these reversible switching properties were kept stable during the repeated cycling tests of above 200 cycles and a test period of approximately 105 s under atmosphere. These solution-based approaches can provide a basis for large-area inorganic nanoparticle-based electric devices through the design of bio-nanomaterials at the molecular level.

Tunable Optical Polymer Systems (TOPS)

DTIC Science & Technology

2001-05-01

pixelation o1 displays is done. One team member has combined this work with self-assembling layers so that it is possible to make three-dimensional...I THERMOCHROMISM I ELECTROCHEMILUMINESCENCE (ECL) I MAGNETOCHROMISM I TUNABLE ELECTROLUMINESCENCE (EL) PROTONIC BAND GAP (PBG) SELECTIVE...via Selective Reflection • Chiral-nematic liquid crystalline film as a helical stack of quasinematic layers , illustrated below with a LH structure

The robust bio-immobilization based on pulsed plasma polymerization of cyclopropylamine and glutaraldehyde coupling chemistry

NASA Astrophysics Data System (ADS)

Manakhov, Anton; Makhneva, Ekaterina; Skládal, Petr; Nečas, David; Čechal, Jan; Kalina, Lukáš; Eliáš, Marek; Zajíčková, Lenka

2016-01-01

The performance of immunosensing devices crucially depends on the methodology of antibody or antigen immobilization on the sensor surface. Hence, the stable intermediate layers capable of specific and reproducible binding of antibodies are required. Herein, we introduce the amine rich (NHx concentration of 6 at.%) layers prepared by pulsed plasma polymerization of cyclopropylamine (CPA) for functionalization of the quartz crystal microbalance (QCM) surface by the antibody specific to human serum albumin. In these layers the amine groups serve as anchor for the antibody binding. The sensitivity of QCM sensors prepared in this way surpasses the one for the previously reported sensors functionalized by the thiol-based self-assembled monolayers by the factor of 2. Our results thus show that CPA plasma polymers have a significant potential for further development of the active layers for biosensing applications.

Passivation of Black Phosphorus via Self-Assembled Organic Monolayers by van der Waals Epitaxy.

PubMed

Zhao, Yinghe; Zhou, Qionghua; Li, Qiang; Yao, Xiaojing; Wang, Jinlan

2017-02-01

An effective passivation approach to protect black phosphorus (BP) from degradation based on multi-scale simulations is proposed. The self-assembly of perylene-3,4,9,10-tetracarboxylic dianhydride monolayers via van der Waals epitaxy on BP does not break the original electronic properties of BP. The passivation layer thickness is only 2 nm. This study opens up a new pathway toward fine passivation of BP. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of Layer-by-Layer Polyelectrolyte Deposition and EDC/NHS Activated Heparin Immobilization onto Silk Fibroin Fabric

PubMed Central

Elahi, M. Fazley; Guan, Guoping; Wang, Lu; King, Martin W.

2014-01-01

To enhance the hemocompatibility of silk fibroin fabric as biomedical material, polyelectrolytes architectures have been assembled through the layer-by-layer (LbL) technique on silk fibroin fabric (SFF). In particular, 1.5 and 2.5 bilayer of oppositely charged polyelectrolytes were assembled onto SFF using poly(allylamine hydrochloride) (PAH) as polycationic polymer and poly(acrylic acid) (PAA) as polyanionic polymer with PAH topmost. Low molecular weight heparin (LMWH) activated with 1-ethyl-3-(dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) was then immobilized on its surface. Alcian Blue staining, toluidine blue assay and X-ray photoelectron spectroscopy (XPS) confirmed the presence of heparin on modified SFF surfaces. The surface morphology of the modified silk fibroin fabric surfaces was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM), and obtained increased roughness. Negligible hemolytic effect and a higher concentration of free hemoglobin by a kinetic clotting time test ensured the improved biological performance of the modified fibroin fabric. Overall, the deposition of 2.5 bilayer was found effective in terms of biological and surface properties of the modified fibroin fabric compared to 1.5 bilayer self-assembly technique. Therefore, this novel approach to surface modification may demonstrate long term patency in future in vivo animal trials of small diameter silk fibroin vascular grafts. PMID:28788601

Soft Ultraviolet (UV) Photopatterning and Metallization of Self-Assembled Monolayers (SAMs) Formed from the Lipoic Acid Ester of α-Hydroxy-1-acetylpyrene: The Generality of Acid-Catalyzed Removal of Thiol-on-Gold SAMs using Soft UV Light.

PubMed

Pukenas, Laurynas; Prompinit, Panida; Nishitha, Boda; Tate, Daniel J; Singh, N D Pradeep; Wälti, Christoph; Evans, Stephen D; Bushby, Richard J

2017-05-31

Under a layer of 0.1 M HCl in isopropanol, soft ultraviolet (UV) (365 nm) photolysis of the thiol-on-gold self-assembled monolayer (SAM) derived from the lipoic acid ester of α-hydroxy-1-acetylpyrene results in the expected removal of the acetylpyrene protecting group. When photolyzing through a mask, this can be used to produce a patterned surface and, at a controlled electrochemical potential, it is then possible to selectively and reversibly electrodeposit copper on the photolyzed regions. Rather surprisingly, under these photolysis conditions, there is not only the expected photodeprotection of the ester but also partial removal of the lipoic acid layer which has been formed. In further studies, it is shown that this type of acid-catalyzed photoremoval of SAM layers by soft UV is a rather general phenomenon and results in the partial removal of the thiol-on-gold SAM layers derived from other ω-thiolated carboxylic acids. However, this phenomenon is chain-length dependent. Under conditions in which there is a ∼60% reduction in the thickness of the SAM derived from dithiobutyric acid, the SAM derived from mercaptoundecanoic acid is almost unaffected. The process by which the shorter-chain SAM layers are partially removed is not fully understood because these compounds do not absorb significantly in the 365 nm region of the spectrum! Significantly, this study shows that acid catalysis photolysis of thiol-on-gold SAMs needs to be used with caution.

Transfer Printing Method to Obtain Polarized Light Emission in Organic Light-Emitting Device

NASA Astrophysics Data System (ADS)

Noh, Hee Yeon; Park, Chang-sub; Park, Ji-Sub; Kang, Shin-Won; Kim, Hak-Rin

2012-06-01

We demonstrate a transfer printing method to obtain polarized light emission in organic light-emitting devices (OLEDs). On a rubbed self-assembled monolayer (SAM), a spin-coated liquid crystalline light-emissive polymer is aligned along the rubbing direction because of the anisotropic interfacial intermolecular interaction. Owing to the low surface energy of the SAM surface, the light-emissive layer was easily transferred to a patterned poly(dimethylsiloxane) (PDMS) stamp surface without degrading the ordering. Finally, a polarized light-emissive OLED device was prepared by transferring the patterned light-emissive layer to the charge transport layer of the OLED structure.

Large-scale, thick, self-assembled, nacre-mimetic brick-walls as fire barrier coatings on textiles

NASA Astrophysics Data System (ADS)

Das, Paramita; Thomas, Helga; Moeller, Martin; Walther, Andreas

2017-01-01

Highly loaded polymer/clay nanocomposites with layered structures are emerging as robust fire retardant surface coatings. However, time-intensive sequential deposition processes, e.g. layer-by-layer strategies, hinders obtaining large coating thicknesses and complicates an implementation into existing technologies. Here, we demonstrate a single-step, water-borne approach to prepare thick, self-assembling, hybrid fire barrier coatings of sodium carboxymethyl cellulose (CMC)/montmorillonite (MTM) with well-defined, bioinspired brick-wall nanostructure, and showcase their application on textile. The coating thickness on the textile is tailored using different concentrations of CMC/MTM (1-5 wt%) in the coating bath. While lower concentrations impart conformal coatings of fibers, thicker continuous coatings are obtained on the textile surface from highest concentration. Comprehensive fire barrier and fire retardancy tests elucidate the increasing fire barrier and retardancy properties with increasing coating thickness. The materials are free of halogen and heavy metal atoms, and are sourced from sustainable and partly even renewable building blocks. We further introduce an amphiphobic surface modification on the coating to impart oil and water repellency, as well as self-cleaning features. Hence, our study presents a generic, environmentally friendly, scalable, and one-pot coating approach that can be introduced into existing technologies to prepare bioinspired, thick, fire barrier nanocomposite coatings on diverse surfaces.

Self-consistent electrostatic simulations of reforming double layers in the downward current region of the aurora

NASA Astrophysics Data System (ADS)

Gunell, H.; Andersson, L.; De Keyser, J.; Mann, I.

2015-10-01

The plasma on a magnetic field line in the downward current region of the aurora is simulated using a Vlasov model. It is found that an electric field parallel to the magnetic fields is supported by a double layer moving toward higher altitude. The double layer accelerates electrons upward, and these electrons give rise to plasma waves and electron phase-space holes through beam-plasma interaction. The double layer is disrupted when reaching altitudes of 1-2 Earth radii where the Langmuir condition no longer can be satisfied due to the diminishing density of electrons coming up from the ionosphere. During the disruption the potential drop is in part carried by the electron holes. The disruption creates favourable conditions for double layer formation near the ionosphere and double layers form anew in that region. The process repeats itself with a period of approximately 1 min. This period is determined by how far the double layer can reach before being disrupted: a higher disruption altitude corresponds to a longer repetition period. The disruption altitude is, in turn, found to increase with ionospheric density and to decrease with total voltage. The current displays oscillations around a mean value. The period of the oscillations is the same as the recurrence period of the double layer formations. The oscillation amplitude increases with increasing voltage, whereas the mean value of the current is independent of voltage in the 100 to 800 V range covered by our simulations. Instead, the mean value of the current is determined by the electron density at the ionospheric boundary.

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-I collagen. These cells also showed active proliferation on the nanoparticle substrates. Cells attached on TiO2 substrates showed faster rate of spreading compared with the other types of nanoparticle coatings. Mesenchymal stem cells (MSCs) were used as a second cell type to support and elaborate on the results obtained with the HDFs. Increasing surface roughness was observed with increasing number of layers of TiO2. Tests with a higher number of layers of TiO2, showed an increased attachment, proliferation and faster spreading of the MSCs on a larger number of layers of TiO2.

The underlying micro-mechanism of performance enhancement of non-polar n-ZnO/p-AlGaN ultraviolet light emitting diode with i-ZnO inserted layer

NASA Astrophysics Data System (ADS)

Jiang, Fan; Chen, Jingwen; Bi, Han; Li, Luying; Jing, Wenkui; Zhang, Jun; Dai, Jiangnan; Che, Renchao; Chen, Changqing; Gao, Yihua

2018-01-01

Non-polar a-plane n-ZnO/p-AlGaN and n-ZnO/i-ZnO/p-AlGaN heterojunction film light-emitting diodes (LEDs) are fabricated with good crystalline quality. The optical measurements show obvious performance enhancement with i-ZnO layer insertion. Off-axis electron holography reveals a potential drop of ˜1.5 V across the heterojunctions with typical p-n junction characteristics. It is found that the electrostatic potentials are inclined and the corresponding electrostatic fields are opposite to each other in n-ZnO and p-AlGaN regions. The electrostatic fields are mainly attributed to strain induced piezoelectric polarizations. After an insertion of an i-ZnO layer into the p-n heterojunction, comparatively flat electrostatic potential generates in the intrinsic ZnO region and contributes to faster movements of the injected electrons and holes, making the i-ZnO layer more conductive to the radiative recombination with enhanced exciton recombination possibilities and at last the LED performance enhancement.

Graded porous inorganic materials derived from self-assembled block copolymer templates.

PubMed

Gu, Yibei; Werner, Jörg G; Dorin, Rachel M; Robbins, Spencer W; Wiesner, Ulrich

2015-03-19

Graded porous inorganic materials directed by macromolecular self-assembly are expected to offer unique structural platforms relative to conventional porous inorganic materials. Their preparation to date remains a challenge, however, based on the sparsity of viable synthetic self-assembly pathways to control structural asymmetry. Here we demonstrate the fabrication of graded porous carbon, metal, and metal oxide film structures from self-assembled block copolymer templates by using various backfilling techniques in combination with thermal treatments for template removal and chemical transformations. The asymmetric inorganic structures display mesopores in the film top layers and a gradual pore size increase along the film normal in the macroporous sponge-like support structure. Substructure walls between macropores are themselves mesoporous, constituting a structural hierarchy in addition to the pore gradation. Final graded structures can be tailored by tuning casting conditions of self-assembled templates as well as the backfilling processes. We expect that these graded porous inorganic materials may find use in applications including separation, catalysis, biomedical implants, and energy conversion and storage.

Polyelectrolyte multilayers: preparation and applications

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Ultrathin TiO2 layer coated-CdS spheres core-shell nanocomposite with enhanced visible-light photoactivity.

PubMed

Chen, Zhang; Xu, Yi-Jun

2013-12-26

Development of various strategies for controllable fabrication of core-shell nanocomposites (CSNs) with highly active photocatalytic performance has been attracting ever-increasing research attention. In particular, control of the ultrathin layer TiO2 shell in constructing CSNs in an aqueous phase is a significant but technologically challenging issue. Here, this paper demonstrates the interface assembly synthesis of CdS nanospheres@TiO2 core-shell photocatalyst via the electrostatic interaction of negatively charged water-stable titania precursor with positively charged CdS nanospheres (CdS NSPs), followed by the formation of the ultrathin-layer TiO2 shell through a facile refluxing process in aqueous phase. The as-formed CdS NSPs@TiO2 core-shell nanohybrid exhibits a high visible-light-driven photoactivity for selective transformation and reduction of heavy metal ions. The ultrathin TiO2 layer coated on CdS NSPs results in excellent light transmission property, enhanced adsorption capacity, and improved transfer of charge carriers and lifespan of photoinduced electron-hole pairs, which would prominently contribute to the significant photoactivity enhancement. It is anticipated that this facile aqueous-phase synthesis strategy could be extended to design a variety of more efficient CSN photocatalysts with controllable morphology toward target applications in diverse photoredox processes.

Via patterning in the 7-nm node using immersion lithography and graphoepitaxy directed self-assembly

NASA Astrophysics Data System (ADS)

Doise, Jan; Bekaert, Joost; Chan, Boon Teik; Hori, Masafumi; Gronheid, Roel

2017-04-01

Insertion of a graphoepitaxy directed self-assembly process as a via patterning technology into integrated circuit fabrication is seriously considered for the 7-nm node and beyond. At these dimensions, a graphoepitaxy process using a cylindrical block copolymer that enables hole multiplication can alleviate costs by extending 193-nm immersion-based lithography and significantly reducing the number of masks that would be required per layer. To be considered for implementation, it needs to be proved that this approach can achieve the required pattern quality in terms of defects and variability using a representative, aperiodic design. The patterning of a via layer from an actual 7-nm node logic layout is demonstrated using immersion lithography and graphoepitaxy directed self-assembly in a fab-like environment. The performance of the process is characterized in detail on a full 300-mm wafer scale. The local variability in an edge placement error of the obtained patterns (4.0 nm 3σ for singlets) is in line with the recent results in the field and significantly less than of the prepattern (4.9 nm 3σ for singlets). In addition, it is expected that pattern quality can be further improved through an improved mask design and optical proximity correction. No major complications for insertion of the graphoepitaxy directed self-assembly into device manufacturing were observed.

Hard Pd Nanorods in the Soft Surfactant Mixture of CTAB and Pluronics: Seedless Synthesis and Their Self-Assembly.

PubMed

Song, Hyon-Min; Zink, Jeffrey I

2018-04-10

Seedless synthesis of Pd nanorods and their self-assembly into the layered smectic ordering are described. Aqueous Pluronic triblock copolymers (14.3-35.7%) are used as a soft template along with cetyltrimethylammonium bromide for inducing one-dimensional growth of Pd nanorods. Pluronic triblock copolymers are probably the most used polymer surfactants, and they are composed of poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO triblocks. Neither pH adjustment nor AgNO 3 and other additives, such as poly(vinyl pyrrolidone) and ethylene glycol, are required to obtain Pd nanorods. Sonochemical synthesis at 43 °C, followed by thermal annealing for 1 h at 65 °C produces Pd nanorods with the aspect ratio from 3.1 (17.9%, Pluronic L-64) to 6.7 (35.7%, Pluronic P-123). Two-dimensional self-assembly of the nanorods is observed, and both nematic ordering between the mesogens and smectic ordering between the layers is identified. Micellar hydrophobic PPO with hydrated PEO coronas are known to self-assemble into many crystalline orders, including cubic, hexagonal, lamellar, and inverse hexagonal mesophases, which extend into cylindrical micelles with increasing temperature. Relatively small size of Pluronic copolymers with regard to general polymers, but rather large size of their micelles and their tendency to organize into crystalline mesophases are thought to contribute to the anisotropic growth of Pd nanorods.

Dynamic self-assembly of charged colloidal strings and walls in simple fluid flows.

PubMed

Abe, Yu; Zhang, Bo; Gordillo, Leonardo; Karim, Alireza Mohammad; Francis, Lorraine F; Cheng, Xiang

2017-02-22

Colloidal particles can self-assemble into various ordered structures in fluid flows that have potential applications in biomedicine, materials synthesis and encryption. These dynamic processes are also of fundamental interest for probing the general principles of self-assembly under non-equilibrium conditions. Here, we report a simple microfluidic experiment, where charged colloidal particles self-assemble into flow-aligned 1D strings with regular particle spacing near a solid boundary. Using high-speed confocal microscopy, we systematically investigate the influence of flow rates, electrostatics and particle polydispersity on the observed string structures. By studying the detailed dynamics of stable flow-driven particle pairs, we quantitatively characterize interparticle interactions. Based on the results, we construct a simple model that explains the intriguing non-equilibrium self-assembly process. Our study shows that the colloidal strings arise from a delicate balance between attractive hydrodynamic coupling and repulsive electrostatic interaction between particles. Finally, we demonstrate that, with the assistance of transverse electric fields, a similar mechanism also leads to the formation of 2D colloidal walls.

Stabilization of Ag nanostructures by tuning their Fermi levels

NASA Astrophysics Data System (ADS)

Tani, Tadaaki; Kan, Ryota; Yamano, Yuka; Uchida, Takayuki

2018-05-01

The oxidation of Ag nanostructures has been studied as a key step for their degradation under the guiding principle in the previous paper that they are stable when their Fermi level is lower than those of their surroundings. The drop of the Fermi level of a thin Ag layer was caused by the formation of self-assembled monolayers (SAMs) of certain organic compounds including those of photographic interest and a monolayer of AgI, and attributed to the formation of dielectric layers, whose positive charges were closer to the Ag layer than negative charges. A consideration is given on further examinations needed to realize the above guiding principle in individual devices.

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.

Postassembly chemical modification of a highly ordered organosilane multilayer: new insights into the structure, bonding, and dynamics of self-assembling silane monolayers.

PubMed

Wen, Ke; Maoz, Rivka; Cohen, Hagai; Sagiv, Jacob; Gibaud, Alain; Desert, Anne; Ocko, Benjamin M

2008-03-01

Experimental evidence derived from a comprehensive study of a self-assembled organosilane multilayer film system undergoing a process of postassembly chemical modification that affects interlayer-located polar groups of the constituent molecules while preserving its overall molecular architecture allows a quantitative evaluation of both the degree of intralayer polymerization and that of interlayer covalent bonding of the silane headgroups in a highly ordered layer assembly of this type. The investigated system consists of a layer-by-layer assembled multilayer of a bifunctional n-alkyl silane with terminal alcohol group that is in situ converted, via a wet chemical oxidation process conducted on the entire multilayer, to the corresponding carboxylic acid function. A combined chemical-structural analysis of data furnished by four different techniques, Fourier transform infrared spectroscopy (FTIR), synchrotron X-ray scattering, X-ray photoelectron spectroscopy (XPS), and contact angle measurements, demonstrates that the highly ordered 3D molecular arrangement of the initial alcohol-silane multilayer stack is well preserved upon virtually quantitative conversion of the alcohol to carboxylic acid and the concomitant irreversible cleavage of interlayer covalent bonds. Thus, the correlation of quantitative chemical and structural data obtained from such unreacted and fully reacted film samples offers an unprecedented experimental framework within which it becomes possible to differentiate between intralayer and interlayer covalent bonding. In addition, the use of a sufficiently thick multilayer effectively eliminates the interfering contributions of the underlying silicon oxide substrate to both the X-ray scattering and XPS data. The present findings contribute a firm experimental basis to the elucidation of the self-assembly mechanism, the molecular organization, and the modes and dynamics of intra- and interlayer bonding prevailing in highly ordered organosilane films; with further implications for the rational exploitation of some of the unique options such supramolecular surface entities can offer in the advancement of a chemical nanofabrication methodology.

Effect of TiO2 modification with amino-based self-assembled monolayer on inverted organic solar cell

NASA Astrophysics Data System (ADS)

Tozlu, Cem; Mutlu, Adem; Can, Mustafa; Havare, Ali Kemal; Demic, Serafettin; Icli, Sıddık

2017-11-01

The effects of surface modification of titanium dioxide (TiO2) on the performance of inverted type organic solar cells (i-OSCs) was investigated in this study. A series of benzoic acid derivatized self-assembled monolayer (SAM) molecules of 4‧-[(hexyloxy)phenyl]amino-3,5-biphenyl dicarboxylic acid (CT17) and 4‧-[1-naphthyl (phenyl)amino]biphenyl-4-carboxylic acid (CT19) were utilized to modify the interface between TiO2 buffer layer and poly-3 hexylthiophene (P3HT):[6,6]-phenyl C61 butyric acid methyl ester (PC61BM) active layer having the device structure of ITO/TiO2/SAM/P3HT:PC61BM/MoO3/Ag. The work function and surface wetting properties of TiO2 buffer layer served as electron transporting layer between ITO and PC61BM active layer were tuned by SAM method. The solar cell of the SAM modified devices exhibited better performance. The power conversion efficiency (PCE) of i-OSCs devices with bare TiO2 electrodes enhanced from 2.00% to 2.21% and 2.43% with CT17 and CT19 treated TiO2 electrodes, respectively. The open circuit voltage (Voc) of the SAM treated TiO2 devices reached to 0.60 V and 0.61 V, respectively, while the Voc of untreated TiO2 was 0.57 V. The water contact angle of i-OSCs with CT17 and CT19 SAMs was also higher than the value of the unmodified TiO2 electrode. These results show that inserting a monolayer at the interface between organic and inorganic layers is an useful alternative method to improve the performance of i-OSCs.

Tunable PhoXonic Band Gap Materials from Self-Assembly of Block Copolymers and Colloidal Nanocrystals (NBIT Phase II)

DTIC Science & Technology

2013-12-12

their application in sensors and as displays. We found that the thermochromic behavior of a lamellar block copolymer poly(styrene-b-2-vinylpyridine...the solution pH. The findings of this work provide the basis for understanding and controlling the properties of thermochromic block copolymers...by the glassy PS layers . The glassy layers completely constrain the lateral expansion of the P2VP gel block and the dislocation defect network that

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

PubMed

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

2014-11-20

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

Self-assembly preparation of SiO2@Ni-Al layered double hydroxide composites and their enhanced electrorheological characteristics

PubMed Central

Ji, Xuqiang; Zhang, Wenling; Shan, Lei; Tian, Yu; Liu, Jingquan

2015-01-01

The core-shell structured SiO2@Ni-Al layered double hydroxide (LDH) composites were prepared via self-assembly of Ni-Al LDH on the surface of SiO2 spheres. Only coating a layer of ultrathin Ni-Al LDH sheet, the resulting SiO2@Ni-Al LDH composites exhibit significantly enhanced electrorheological (ER) characteristics compared to conventional bare SiO2 spheres. The monodispersed SiO2 spheres with average diameters of 260 nm were synthesized by the hydrolysis of tetraethyl orthosilicate (TEOS), while the shell part, Ni-Al LDH sheet was prepared by the hydrothermal procedure. The morphology of the samples was investigated via scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure of the samples was characterized by X-ray diffraction (XRD). The species and distribution of elements in samples were confirmed by X-ray photoelectron spectroscopy (XPS), Energy dispersive analysis of X-ray (EDX) and elemental mapping in STEM. Subsequently, the ER characteristics of the composites dispersed in insulating oil were characterized by a rotational rheometer. The electric field-stimulated rheological performances (yield stress, viscosity, modulus, etc.) were observed under an external electric field, which is different from the Newtonian state in the free electric field. PMID:26670467

Self-assembly preparation of SiO2@Ni-Al layered double hydroxide composites and their enhanced electrorheological characteristics

NASA Astrophysics Data System (ADS)

Ji, Xuqiang; Zhang, Wenling; Shan, Lei; Tian, Yu; Liu, Jingquan

2015-12-01

The core-shell structured SiO2@Ni-Al layered double hydroxide (LDH) composites were prepared via self-assembly of Ni-Al LDH on the surface of SiO2 spheres. Only coating a layer of ultrathin Ni-Al LDH sheet, the resulting SiO2@Ni-Al LDH composites exhibit significantly enhanced electrorheological (ER) characteristics compared to conventional bare SiO2 spheres. The monodispersed SiO2 spheres with average diameters of 260 nm were synthesized by the hydrolysis of tetraethyl orthosilicate (TEOS), while the shell part, Ni-Al LDH sheet was prepared by the hydrothermal procedure. The morphology of the samples was investigated via scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure of the samples was characterized by X-ray diffraction (XRD). The species and distribution of elements in samples were confirmed by X-ray photoelectron spectroscopy (XPS), Energy dispersive analysis of X-ray (EDX) and elemental mapping in STEM. Subsequently, the ER characteristics of the composites dispersed in insulating oil were characterized by a rotational rheometer. The electric field-stimulated rheological performances (yield stress, viscosity, modulus, etc.) were observed under an external electric field, which is different from the Newtonian state in the free electric field.

Research Update: Programmable tandem repeat proteins inspired by squid ring teeth

NASA Astrophysics Data System (ADS)

Pena-Francesch, Abdon; Domeradzka, Natalia E.; Jung, Huihun; Barbu, Benjamin; Vural, Mert; Kikuchi, Yusuke; Allen, Benjamin D.; Demirel, Melik C.

2018-01-01

Cephalopods have evolved many interesting features that can serve as inspiration. Repetitive squid ring teeth (SRT) proteins from cephalopods exhibit properties such as strength, self-healing, and biocompatibility. These proteins have been engineered to design novel adhesives, self-healing textiles, and the assembly of 2d-layered materials. Compared to conventional polymers, repetitive proteins are easy to modify and can assemble in various morphologies and molecular architectures. This research update discusses the molecular biology and materials science of polypeptides inspired by SRT proteins, their properties, and perspectives for future applications.

Assembly and Function of the Bacillus anthracis S-Layer.

PubMed

Missiakas, Dominique; Schneewind, Olaf

2017-09-08

Bacillus anthracis, the anthrax agent, is a member of the Bacillus cereus sensu lato group, which includes invasive pathogens of mammals or insects as well as nonpathogenic environmental strains. The genes for anthrax pathogenesis are located on two large virulence plasmids. Similar virulence plasmids have been acquired by other B. cereus strains and enable the pathogenesis of anthrax-like diseases. Among the virulence factors of B. anthracis is the S-layer-associated protein BslA, which endows bacilli with invasive attributes for mammalian hosts. BslA surface display and function are dependent on the bacterial S-layer, whose constituents assemble by binding to the secondary cell wall polysaccharide (SCWP) via S-layer homology (SLH) domains. B. anthracis and other pathogenic B. cereus isolates harbor genes for the secretion of S-layer proteins, for S-layer assembly, and for synthesis of the SCWP. We review here recent insights into the assembly and function of the S-layer and the SCWP.

Mn-doped Ge self-assembled quantum dots via dewetting of thin films

NASA Astrophysics Data System (ADS)

Aouassa, Mansour; Jadli, Imen; Bandyopadhyay, Anup; Kim, Sung Kyu; Karaman, Ibrahim; Lee, Jeong Yong

2017-03-01

In this study, we demonstrate an original elaboration route for producing a Mn-doped Ge self-assembled quantum dots on SiO2 thin layer for MOS structure. These magnetic quantum dots are elaborated using dewetting phenomenon at solid state by Ultra-High Vacuum (UHV) annealing at high temperature of an amorphous Ge:Mn (Mn: 40%) nanolayer deposed at very low temperature by high-precision Solid Source Molecular Beam Epitaxy on SiO2 thin film. The size of quantum dots is controlled with nanometer scale precision by varying the nominal thickness of amorphous film initially deposed. The magnetic properties of the quantum-dots layer have been investigated by superconducting quantum interference device (SQUID) magnetometry. Atomic force microscopy (AFM), x-ray energy dispersive spectroscopy (XEDS) and transmission electron microscopy (TEM) were used to examine the nanostructure of these materials. Obtained results indicate that GeMn QDs are crystalline, monodisperse and exhibit a ferromagnetic behavior with a Curie temperature (TC) above room temperature. They could be integrated into spintronic technology.

Effect of the ordered interfacial water layer in protein complex formation: a non-local electrostatic approach

NASA Astrophysics Data System (ADS)

Rubinstein, Alexander; Sabirianov, Renat

2011-03-01

Using a non-local electrostatic approach that incorporates the short-range structure of the contacting media, we evaluated the electrostatic contribution to the energy of the complex formation of two model proteins. In this study, we have demonstrated that the existence of an low-dielectric interfacial water layer at the protein-solvent interface reduces the charging energy of the proteins in the aqueous solvent, and consequently increases the electrostatic contribution to the protein binding (change in free energy upon the complex formation of two proteins). This is in contrast with the finding of the continuum electrostatic model, which suggests that electrostatic interactions are not strong enough to compensate for the unfavorable desolvation effects.

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).

Interface reconstruction with emerging charge ordering in hexagonal manganite

PubMed Central

Xu, Changsong; Han, Myung-Geun; Bao, Shanyong; Nan, Cewen; Bellaiche, Laurent

2018-01-01

Multiferroic materials, which simultaneously have multiple orderings, hold promise for use in the next generation of memory devices. We report a novel self-assembled MnO double layer forming at the interface between a multiferroic YMnO3 film and a c-Al2O3 substrate. The crystal structures and the valence states of this MnO double layer were studied by atomically resolved scanning transmission electron microscopy and spectroscopy, as well as density functional theory (DFT) calculations. A new type of charge ordering has been identified within this MnO layer, which also contributes to a polarization along the [001] direction. DFT calculations further establish the occurrence of multiple couplings between charge and lattice in this novel double layer, in addition to the polarization in nearby YMnO3 single layer. The interface reconstruction reported here creates a new playground for emergent physics, such as giant ferroelectricity and strong magnetoelectric coupling, in manganite systems. PMID:29795782

Programming Cells for Dynamic Assembly of Inorganic Nano-Objects with Spatiotemporal Control.

PubMed

Wang, Xinyu; Pu, Jiahua; An, Bolin; Li, Yingfeng; Shang, Yuequn; Ning, Zhijun; Liu, Yi; Ba, Fang; Zhang, Jiaming; Zhong, Chao

2018-04-01

Programming living cells to organize inorganic nano-objects (NOs) in a spatiotemporally precise fashion would advance new techniques for creating ordered ensembles of NOs and new bio-abiotic hybrid materials with emerging functionalities. Bacterial cells often grow in cellular communities called biofilms. Here, a strategy is reported for programming dynamic biofilm formation for the synchronized assembly of discrete NOs or hetero-nanostructures on diverse interfaces in a dynamic, scalable, and hierarchical fashion. By engineering Escherichia coli to sense blue light and respond by producing biofilm curli fibers, biofilm formation is spatially controlled and the patterned NOs' assembly is simultaneously achieved. Diverse and complex fluorescent quantum dot patterns with a minimum patterning resolution of 100 µm are demonstrated. By temporally controlling the sequential addition of NOs into the culture, multilayered heterostructured thin films are fabricated through autonomous layer-by-layer assembly. It is demonstrated that biologically dynamic self-assembly can be used to advance a new repertoire of nanotechnologies and materials with increasing complexity that would be otherwise challenging to produce. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Manipulating polymers and composites from the nanoscopic to microscopic length scales

NASA Astrophysics Data System (ADS)

Gupta, Suresh

2008-10-01

This thesis focuses on the manipulation of polymers and composites on length scales ranging from the nanoscopic to microscopic. In particular, on the microscopic length scale electric fields were used to produce instabilities at the air surface and at polymer interfaces that lead to novel three dimensional structures and patterns. On the nanoscopic length scale, the interaction of ligands attached to nanoparticles and polymer matrix were used to induce self-assembly processes that, in turn, lead to systems that self-heal, self-corral, or are patterned. For manipulation at the micron length scale, electrohydrodynamic instabilities were used in trilayer system composed of a layer of poly(methyl methacrylate) (PMMA), a second layer of polystyrene (PS) and a third layer of air. Dewetting of the polymer at the substrate at the polymer/polymer interface under an applied electric field was used to generate novel three dimensional structures. Also, electrohydrodynamic instabilities were used to pattern thin polymer films in conjunction with ultrasonic vibrations and patterned upper electrodes. Self-assembly processes involving polymers and nanoparticles offer a unique means of generating pattern materials or materials that self heal. Simple polymer/nanoparticle composites were investigated. Here, in the absence of interactions between the poly(ethylene oxide) ligands attached to the nanoparticles and PMMA polymer matrix, the opportunity to generate self-healing systems was opened. The size of the nanoparticle was varied and the effect on diffusion of nanoparticle in the polymer matrix was studied. CdSe nanorods were also assembled on a substrate templated with or guided by microphase separated diblock copolymers. The nanorods were incorporated in the diblock copolymer thin films by spin coating the co-solution of nanorods and polymer, surface adsorption of nanorods on to the patterned diblock copolymer films and surface reconstruction of PS/PMMA diblock copolymer thin film. Further, the interactions between the PMMA polymer matrix and the tri n-octyl phosphine oxide ligands attached to an anisotropic nanoparticle, i.e. nanorods, were used to influence the dispersion of the nanorods in the polymer. This led to a novel assembly, termed self-corralling where under an applied electric field highly oriented, highly ordered arrays of nanorods form. Further, self corralling of nanorods was directed by chemically patterned substrates.

Bottom-up Fabrication of Multilayer Stacks of 3D Photonic Crystals from Titanium Dioxide.

PubMed

Kubrin, Roman; Pasquarelli, Robert M; Waleczek, Martin; Lee, Hooi Sing; Zierold, Robert; do Rosário, Jefferson J; Dyachenko, Pavel N; Montero Moreno, Josep M; Petrov, Alexander Yu; Janssen, Rolf; Eich, Manfred; Nielsch, Kornelius; Schneider, Gerold A

2016-04-27

A strategy for stacking multiple ceramic 3D photonic crystals is developed. Periodically structured porous films are produced by vertical convective self-assembly of polystyrene (PS) microspheres. After infiltration of the opaline templates by atomic layer deposition (ALD) of titania and thermal decomposition of the polystyrene matrix, a ceramic 3D photonic crystal is formed. Further layers with different sizes of pores are deposited subsequently by repetition of the process. The influence of process parameters on morphology and photonic properties of double and triple stacks is systematically studied. Prolonged contact of amorphous titania films with warm water during self-assembly of the successive templates is found to result in exaggerated roughness of the surfaces re-exposed to ALD. Random scattering on rough internal surfaces disrupts ballistic transport of incident photons into deeper layers of the multistacks. Substantially smoother interfaces are obtained by calcination of the structure after each infiltration, which converts amorphous titania into the crystalline anatase before resuming the ALD infiltration. High quality triple stacks consisting of anatase inverse opals with different pore sizes are demonstrated for the first time. The elaborated fabrication method shows promise for various applications demanding broadband dielectric reflectors or titania photonic crystals with a long mean free path of photons.

Assembly of purple membranes on polyelectrolyte films.

PubMed

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

2009-05-05

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

Required Equipment for Photo-Switchable Donor-Acceptor (D-A) Dyad Interfacial Self-Assembled Monolayers for Organic Photovoltaic Cells

DTIC Science & Technology

2014-01-24

Interfacial Tuning via Electron-Blocking/Hole-Transport Layers and Indium Tin Oxide Surface Treatment in Bulk- Heterojunction Organic Photovoltaic Cells...devices Figure 3 shows the compounds we prepared to assemble on gold (Au) surfaces. Results of TPA-C60 dyads (1 and 2) self-assembled on Au electrodes...surface hydroxyl groups, respectively, we decided to prepare compounds 5-7 to attach as SAMs, see Figure 5. Difficulties and unexpected problems

Electrostatic MEMS devices with high reliability

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

Goldsmith, Charles L; Auciello, Orlando H; Sumant, Anirudha V

The present invention provides for an electrostatic microelectromechanical (MEMS) device comprising a dielectric layer separating a first conductor and a second conductor. The first conductor is moveable towards the second conductor, when a voltage is applied to the MEMS device. The dielectric layer recovers from dielectric charging failure almost immediately upon removal of the voltage from the MEMS device.

Influence of Geometries on the Assembly of Snowman-Shaped Janus Nanoparticles.

PubMed

Kang, Chengjun; Honciuc, Andrei

2018-04-24

The self-assembly of micro/nanoparticles into suprastructures is a promising way to develop reconfigurable materials and to gain insights into the fundamental question of how matter organizes itself. The geometry of particles, especially those deviating from perfectly spherical shapes, is of significant importance in colloidal assembly because it influences the particle "recognition", determines the particle packing, and ultimately dictates the formation of assembled suprastructures. In order to organize particles into desired structures, it is of vital importance to understand the relationship between the shape of the colloidal building blocks and the assembled suprastructures. This fundamental issue is an enduring topic in the assembly of molecular surfactants, but it remained elusive in colloidal assembly. To address this issue, we use snowman-shaped Janus nanoparticles (JNPs) as a model to systematically study the effect of colloidal geometries on their assembled suprastructures. Ten types of JNPs with identical chemical compositions but with different geometries were synthesized. Specifically, the synthesized JNPs differ in their lobe size ratios, phase separation degrees, and overall sizes. We show that by altering these parameters, both finite suprastructures, such as capsules with different curvatures, and nonfinite suprastructures, including free-standing single-layered or double-layered JNPs sheets, can be obtained via self-assembly. All these different types of suprastructures are constituted by highly oriented and hexagonally packed JNPs. These findings demonstrate the significance of geometries in colloidal assembly, such that slightly changing the building block geometries could result in a large variety of very different assembled structures, without altering the chemistry of the particles.

Can a novel silver nano coating reduce infections and maintain cell viability in vitro?

PubMed

Qureshi, Ammar T; Landry, Jace P; Dasa, Vinod; Janes, Marlene; Hayes, Daniel J

2014-03-01

Herein we report a facile layer-by-layer method for creating an antimicrobial coating composed of silver nanoparticles on medical grade titanium test discs. Nanoscale silver nanoparticle layers are attached to the titanium orthopedic implant material via aminopropyltriethoxy silane crosslinker that reacts with neighboring silane moieties to create an interconnected network. A monolayer of silane, followed by a monolayer of silver nanoparticles would form one self-assembled layer and this process can be repeated serially, resulting in increased silver nanoparticles deposition. The release rate of silver ion increases predictably with increasing numbers of layers and at appropriate thicknesses these coatings demonstrate 3-4 log reduction of viable Escherichia coli and Staphylococcus aureus bacteria. Increasing the thickness of the coatings resulted in reduced bacterial colonization as determined by fluorescent staining and image analysis. Interestingly, the cytotoxicity of murine 3T3 cells as quantified by fluorescent staining and flow cytometry, was minimal and did not vary significantly with the coating thickness. Additionally, these coatings are mechanically stable and resist delamination by orthogonal stress test. This simple layer-by-layer coating technique may provide a cost-effective and biocompatible method for reducing microbial colonization of implantable orthopedic devices.

The role of electrostatics and temperature on morphological transitions of hydrogel nanostructures self-assembled by peptide amphiphiles via molecular dynamics simulations.

PubMed

Fu, Iris W; Markegard, Cade B; Chu, Brian K; Nguyen, Hung D

2013-10-01

Smart biomaterials that are self-assembled from peptide amphiphiles (PA) are known to undergo morphological transitions in response to specific physiological stimuli. The design of such customizable hydrogels is of significant interest due to their potential applications in tissue engineering, biomedical imaging, and drug delivery. Using a novel coarse-grained peptide/polymer model, which has been validated by comparison of equilibrium conformations from atomistic simulations, large-scale molecular dynamics simulations are performed to examine the spontaneous self-assembly process. Starting from initial random configurations, these simulations result in the formation of nanostructures of various sizes and shapes as a function of the electrostatics and temperature. At optimal conditions, the self-assembly mechanism for the formation of cylindrical nanofibers is deciphered involving a series of steps: (1) PA molecules quickly undergo micellization whose driving force is the hydrophobic interactions between alkyl tails; (2) neighboring peptide residues within a micelle engage in a slow ordering process that leads to the formation of β-sheets exposing the hydrophobic core; (3) spherical micelles merge together through an end-to-end mechanism to form cylindrical nanofibers that exhibit high structural fidelity to the proposed structure based on experimental data. As the temperature and electrostatics vary, PA molecules undergo alternative kinetic mechanisms, resulting in the formation of a wide spectrum of nanostructures. A phase diagram in the electrostatics-temperature plane is constructed delineating regions of morphological transitions in response to external stimuli. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vertical Diaphragm Electrostatic Actuator for a High Density Ink Jet Printer Head

NASA Astrophysics Data System (ADS)

Norimatsu, Takayuki; Tanaka, Shuji; Esashi, Masayoshi

This paper describes the design, fabrication process and preliminary evaluation of an electrostatic ink jet printer head with vertical diaphragms in deep trenches. By adopting the novel structure where an ink cavity is surrounded by the vertical diaphragm, the footprint of each unit (40 μm × 500 μm) becomes approximately one fifth as small as that of a conventional one. Such small footprint is advantageous in cost, resolution and printing speed. To make the vertical diaphragms, a 0.5 μm thick sacrificial thermally-oxidized layer and a 4.5 μm thick poly-silicon layer are sequentially formed in deep-reactive-ion-etched trenches, and then the sacrificial layer is etched away by fluoric acid. The nozzles are fabricated on a Pyrex glass substrate by femtosecond laser ablation, and the nozzle outside is covered with a water repellant Au/Pt/Ti layer. Impedance measurement found that the electrostatic gaps were in contact or closely approaching. This could be because the diaphragms buckled by compressive stress induced in low pressure chemical vapor deposition (LPCVD). Ink ejection was tried using commercially-available blue ink, but failed. The nozzles were covered with the ink, because the water repellant finish of the nozzle outside was not good.

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.

Characterization of self assembly layers of octadecanephosphonic acid by polarisation modulation FT-IRRA spectroscopy mapping

NASA Astrophysics Data System (ADS)

Steiner, G.; Sablinskas, V.; Savchuk, O.; Bariseviciute, R.; Jähne, E.; Adler, H. J.; Salzer, R.

2003-12-01

Self assembly layers were studied by a polarization modulation FT-spectroscopy mapping technique. The optical lay out is based on polarization modulation FT infrared reflection absorption spectroscopy (PM-FT-IRRAS). Here we report for the first time on a PM-FT-IRRAS mapping instrument. Octadecanephosphonic acid adsorbed on a patterned aluminum/gold surface was investigated. The nature of chemical bonding at particular surface areas was evaluated by principal component analysis. The most prominent features of the PM-FT-IRRA spectra are the P-O and PO stretching vibrations. It is shown that octadecanephosphonic acid is adsorbed both on Al 2O 3 and on Au. Moreover, PM-FT-IRRAS maps reveal areas of non-equivalent structural features. Lateral dimensions of these areas are in the micrometer range. Such non-equivalencies may control the inhibition potential of SAMs on ignoble metals, hence become crucial to the quality of products as biosensors or microelectronic components.

Controlled tuning of the radiative lifetime in InAs self-assembled quantum dots through vertical ordering

NASA Astrophysics Data System (ADS)

Colocci, M.; Vinattieri, A.; Lippi, L.; Bogani, F.; Rosa-Clot, M.; Taddei, S.; Bosacchi, A.; Franchi, S.; Frigeri, P.

1999-01-01

Multilayer structures of InAs quantum dots have been studied by means of photoluminescence techniques. A strong increase of the radiative lifetime with increasing number of stacked dot layers has been observed at low temperatures. Moreover, a strong temperature dependence of the radiative lifetime, which is not present in the single layer samples, has been found in the multistacked structures. The observed effects are nicely explained as a consequence of the electronic coupling between electrons and holes induced by vertical ordering.

Fabrication and notable optical nonlinearities of ultrathin composite films derived from water-soluble Keggin-type polyoxometalates and water-insoluble phthalocyanine.

PubMed

Shehzad, Farooq Khurum; Qu, Ningning; Zhou, Yunshan; Zhang, Lijuan; Ji, Huanyao; Shi, Zonghai; Li, Jiaqi; Hassan, Sadaf Ul

2016-11-28

Composite films with the general formula (POM/CuTAPc) n derived from water-soluble Keggin-type polyoxometalates (POMs = H 5 PMo 10 V 2 O 40 , H 4 SiW 12 O 40 , H 3 PMo 12 O 40 and H 3 PW 12 O 40 ) and water-insoluble 4,9,16,23-copper tetraaminophthalocyanine (denoted CuTAPc) are successfully fabricated by a layer-by-layer self-assembly technique and systematically characterized. The structure of the polyoxometalate anions in the multilayers is kept intact; the deposition amounts of POM and CuTAPc remain constant in every adsorption cycle of the composite film assembly process. The nonlinear optical properties of the composite films were studied by a Z-scan technique at a wavelength of 532 nm and a pulse width of 7 ns. The results not only show that the composite films exhibit notable optical nonlinear self-defocusing behavior and a saturated absorption effect with the nonlinear optical absorption co-efficient β, refractive index n 2 , and third-order NLO susceptibility χ (3) of the films increasing with the increase in number of layers of the films, but also reveal importantly that the discrepancy of LUMO levels between CuTAPc and POMs is proportional to their third-order NLO response.

Low stress polysilicon film and method for producing same

NASA Technical Reports Server (NTRS)

Heuer, Arthur H. (Inventor); Kahn, Harold (Inventor); Yang, Jie (Inventor)

2001-01-01

Multi-layer assemblies of polysilicon thin films having predetermined stress characteristics and techniques for forming such assemblies are disclosed. In particular, a multi-layer assembly of polysilicon thin film may be produced that has a stress level of zero, or substantially so. The multi-layer assemblies comprise at least one constituent thin film having a tensile stress and at least one constituent thin film having a compressive stress. The thin films forming the multi-layer assemblies may be disposed immediately adjacent to one another without the use of intermediate layers between the thin films.

Low stress polysilicon film and method for producing same

NASA Technical Reports Server (NTRS)

Heuer, Arthur H. (Inventor); Kahn, Harold (Inventor); Yang, Jie (Inventor)

2002-01-01

Multi-layer assemblies of polysilicon thin films having predetermined stress characteristics and techniques for forming such assemblies are disclosed. In particular, a multi-layer assembly of polysilicon thin film may be produced that has a stress level of zero, or substantially so. The multi-layer assemblies comprise at least one constituent thin film having a tensile stress and at least one constituent thin film having a compressive stress. The thin films forming the multi-layer assemblies may be disposed immediately adjacent to one another without the use of intermediate layers between the thin films.

Ammonia gas sensors based on chemically reduced graphene oxide sheets self-assembled on Au electrodes

PubMed Central

2014-01-01

We present a useful ammonia gas sensor based on chemically reduced graphene oxide (rGO) sheets by self-assembly technique to create conductive networks between parallel Au electrodes. Negative graphene oxide (GO) sheets with large sizes (>10 μm) can be easily electrostatically attracted onto positive Au electrodes modified with cysteamine hydrochloride in aqueous solution. The assembled GO sheets on Au electrodes can be directly reduced into rGO sheets by hydrazine or pyrrole vapor and consequently provide the sensing devices based on self-assembled rGO sheets. Preliminary results, which have been presented on the detection of ammonia (NH3) gas using this facile and scalable fabrication method for practical devices, suggest that pyrrole-vapor-reduced rGO exhibits much better (more than 2.7 times with the concentration of NH3 at 50 ppm) response to NH3 than that of rGO reduced from hydrazine vapor. Furthermore, this novel gas sensor based on rGO reduced from pyrrole shows excellent responsive repeatability to NH3. Overall, the facile electrostatic self-assembly technique in aqueous solution facilitates device fabrication, the resultant self-assembled rGO-based sensing devices, with miniature, low-cost portable characteristics and outstanding sensing performances, which can ensure potential application in gas sensing fields. PMID:24917701

Self-catalyzed growth of S layers via an amorphous-to-crystalline transition limited by folding kinetics.

PubMed

Chung, Sungwook; Shin, Seong-Ho; Bertozzi, Carolyn R; De Yoreo, James J

2010-09-21

The importance of nonclassical, multistage crystallization pathways is increasingly evident from theoretical studies on colloidal systems and experimental investigations of proteins and biomineral phases. Although theoretical predictions suggest that proteins follow these pathways as a result of fluctuations that create unstable dense-liquid states, microscopic studies indicate these states are long-lived. Using in situ atomic force microscopy to follow 2D assembly of S-layer proteins on supported lipid bilayers, we have obtained a molecular-scale picture of multistage protein crystallization that reveals the importance of conformational transformations in directing the pathway of assembly. We find that monomers with an extended conformation first form a mobile adsorbed phase, from which they condense into amorphous clusters. These clusters undergo a phase transition through S-layer folding into crystalline clusters composed of compact tetramers. Growth then proceeds by formation of new tetramers exclusively at cluster edges, implying tetramer formation is autocatalytic. Analysis of the growth kinetics leads to a quantitative model in which tetramer creation is rate limiting. However, the estimated barrier is much smaller than expected for folding of isolated S-layer proteins, suggesting an energetic rationale for this multistage pathway.

Self-assembly of self-limiting monodisperse supraparticles from polydisperse nanoparticles

NASA Astrophysics Data System (ADS)

Xia, Yunsheng; Nguyen, Trung Dac; Yang, Ming; Lee, Byeongdu; Santos, Aaron; Podsiadlo, Paul; Tang, Zhiyong; Glotzer, Sharon C.; Kotov, Nicholas A.

2011-09-01

Nanoparticles are known to self-assemble into larger structures through growth processes that typically occur continuously and depend on the uniformity of the individual nanoparticles. Here, we show that inorganic nanoparticles with non-uniform size distributions can spontaneously assemble into uniformly sized supraparticles with core-shell morphologies. This self-limiting growth process is governed by a balance between electrostatic repulsion and van der Waals attraction, which is aided by the broad polydispersity of the nanoparticles. The generic nature of the interactions creates flexibility in the composition, size and shape of the constituent nanoparticles, and leads to a large family of self-assembled structures, including hierarchically organized colloidal crystals.

Preparation of Flame Retardant Polyacrylonitrile Fabric Based on Sol-Gel and Layer-by-Layer Assembly

PubMed Central

Ren, Yuanlin; Huo, Tongguo; Qin, Yiwen; Liu, Xiaohui

2018-01-01

This paper aims to develop a novel method, i.e., sol-gel combined with layer-by-layer assembly technology, to impart flame retardancy on polyacrylonitrile (PAN) fabrics. Silica-sol was synthesized via the sol-gel process and acted as cationic solution, and phytic acid (PA) was used as the anionic medium. Flame-retardant-treated PAN fabric (FR-PAN) could achieve excellent flame retardancy with 10 bilayer (10BL) coating through layer-by-layer assembly. The structure of the fabrics was characterized by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The thermal stability and flame retardancy were evaluated by thermogravimetric (TG) analysis, cone calorimetry (CC) and limiting oxygen index (LOI). The LOI value of the coated fabric was up to 33.2 vol % and the char residue at 800 °C also increased to 57 wt %. Cone calorimetry tests revealed that, compared to the control fabric, the peak of heat release rate (PHRR) and total heat release (THR) of FR-PAN decreased by 66% and 73%, respectively. These results indicated that sol-gel combined with layer-by-layer assembly technique could impart PAN fabric with satisfactory flame-retardant properties, showing an efficient flame retardant strategy for PAN fabric. PMID:29570646

Preparation of Flame Retardant Polyacrylonitrile Fabric Based on Sol-Gel and Layer-by-Layer Assembly.

PubMed

Ren, Yuanlin; Huo, Tongguo; Qin, Yiwen; Liu, Xiaohui

2018-03-23

This paper aims to develop a novel method, i.e., sol-gel combined with layer-by-layer assembly technology, to impart flame retardancy on polyacrylonitrile (PAN) fabrics. Silica-sol was synthesized via the sol-gel process and acted as cationic solution, and phytic acid (PA) was used as the anionic medium. Flame-retardant-treated PAN fabric (FR-PAN) could achieve excellent flame retardancy with 10 bilayer (10BL) coating through layer-by-layer assembly. The structure of the fabrics was characterized by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The thermal stability and flame retardancy were evaluated by thermogravimetric (TG) analysis, cone calorimetry (CC) and limiting oxygen index (LOI). The LOI value of the coated fabric was up to 33.2 vol % and the char residue at 800 °C also increased to 57 wt %. Cone calorimetry tests revealed that, compared to the control fabric, the peak of heat release rate (PHRR) and total heat release (THR) of FR-PAN decreased by 66% and 73%, respectively. These results indicated that sol-gel combined with layer-by-layer assembly technique could impart PAN fabric with satisfactory flame-retardant properties, showing an efficient flame retardant strategy for PAN fabric.

Dynamic simulations of many-body electrostatic self-assembly

NASA Astrophysics Data System (ADS)

Lindgren, Eric B.; Stamm, Benjamin; Maday, Yvon; Besley, Elena; Stace, A. J.

2018-03-01

Two experimental studies relating to electrostatic self-assembly have been the subject of dynamic computer simulations, where the consequences of changing the charge and the dielectric constant of the materials concerned have been explored. One series of calculations relates to experiments on the assembly of polymer particles that have been subjected to tribocharging and the simulations successfully reproduce many of the observed patterns of behaviour. A second study explores events observed following collisions between single particles and small clusters composed of charged particles derived from a metal oxide composite. As before, observations recorded during the course of the experiments are reproduced by the calculations. One study in particular reveals how particle polarizability can influence the assembly process. This article is part of the theme issue `Modern theoretical chemistry'.

In Vitro Characterization of the Two-Stage Non-Classical Reassembly Pathway of S-Layers

PubMed Central

Breitwieser, Andreas; Iturri, Jagoba; Toca-Herrera, Jose-Luis; Sleytr, Uwe B.; Pum, Dietmar

2017-01-01

The recombinant bacterial surface layer (S-layer) protein rSbpA of Lysinibacillus sphaericus CCM 2177 is an ideal model system to study non-classical nucleation and growth of protein crystals at surfaces since the recrystallization process may be separated into two distinct steps: (i) adsorption of S-layer protein monomers on silicon surfaces is completed within 5 min and the amount of bound S-layer protein sufficient for the subsequent formation of a closed crystalline monolayer; (ii) the recrystallization process is triggered—after washing away the unbound S-layer protein—by the addition of a CaCl2 containing buffer solution, and completed after approximately 2 h. The entire self-assembly process including the formation of amorphous clusters, the subsequent transformation into crystalline monomolecular arrays, and finally crystal growth into extended lattices was investigated by quartz crystal microbalance with dissipation (QCM-D) and atomic force microscopy (AFM). Moreover, contact angle measurements showed that the surface properties of S-layers change from hydrophilic to hydrophobic as the crystallization proceeds. This two-step approach is new in basic and application driven S-layer research and, most likely, will have advantages for functionalizing surfaces (e.g., by spray-coating) with tailor-made biological sensing layers. PMID:28216572

Hierarchical nanoparticle assemblies formed by decorating breath figures.

PubMed

Böker, Alexander; Lin, Yao; Chiapperini, Kristen; Horowitz, Reina; Thompson, Mike; Carreon, Vincent; Xu, Ting; Abetz, Clarissa; Skaff, Habib; Dinsmore, A D; Emrick, Todd; Russell, Thomas P

2004-05-01

The combination of two self-assembly processes on different length scales leads to the formation of hierarchically structured nanoparticle arrays. Here, the formation of spherical cavities, or 'breath figures'-made by the condensation of micrometre-sized water droplets on the surface of a polymer solution-that self-assemble into a well-ordered hexagonal array, is combined with the self-assembly of CdSe nanoparticles at the polymer solution-water droplet interface. Complete evaporation of the solvent and water confines the particle assembly to an array of spherical cavities and allows for ex situ investigation. Fluorescence confocal, transmission electron and scanning electron microscope images show the preferential segregation of the CdSe nanoparticles to the polymer solution-water interface where they form a 5-7-nm-thick layer, thus functionalizing the walls of the holes. This process opens a new route to fabricating highly functionalized ordered microarrays of nanoparticles, potentially useful in sensory, separation membrane or catalytic applications.

Rotational superstructure in van der Waals heterostructure of self-assembled C 60 monolayer on the WSe 2 surface

DOE PAGES

Santos, Elton J. G.; Scullion, Declan; Chu, Ximo S.; ...

2017-08-23

Hybrid van der Waals (vdW) heterostructures composed of two-dimensional (2D) layered materials and self-assembled organic molecules are promising systems for electronic and optoelectronic applications with enhanced properties and performance. Control of molecular assembly is therefore paramount to fundamentally understand the nucleation, ordering, alignment, and electronic interaction of organic molecules with 2D materials. Here, we report the formation and detailed study of highly ordered, crystalline monolayers of C 60 molecules self-assembled on the surface of WSe 2 in well-ordered arrays with large grain sizes (~5 μm). Using high-resolution scanning tunneling microscopy (STM), we observe a periodic 2 × 2 superstructure inmore » the C 60 monolayer and identify four distinct molecular appearances. Using vdW-corrected ab initio density functional theory (DFT) simulations, we determine that the interplay between vdW and Coulomb interactions as well as adsorbate–adsorbate and adsorbate–substrate interactions results in specific rotational arrangements of the molecules forming the superstructure. The orbital ordering through the relative positions of bonds in adjacent molecules creates a charge redistribution that links the molecule units in a long-range network. Furthermore, this rotational superstructure extends throughout the self-assembled monolayer and opens a pathway towards engineering aligned hybrid organic/inorganic vdW heterostructures with 2D layered materials in a precise and controlled way.« less

Rotational superstructure in van der Waals heterostructure of self-assembled C 60 monolayer on the WSe 2 surface

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

Santos, Elton J. G.; Scullion, Declan; Chu, Ximo S.

Hybrid van der Waals (vdW) heterostructures composed of two-dimensional (2D) layered materials and self-assembled organic molecules are promising systems for electronic and optoelectronic applications with enhanced properties and performance. Control of molecular assembly is therefore paramount to fundamentally understand the nucleation, ordering, alignment, and electronic interaction of organic molecules with 2D materials. Here, we report the formation and detailed study of highly ordered, crystalline monolayers of C 60 molecules self-assembled on the surface of WSe 2 in well-ordered arrays with large grain sizes (~5 μm). Using high-resolution scanning tunneling microscopy (STM), we observe a periodic 2 × 2 superstructure inmore » the C 60 monolayer and identify four distinct molecular appearances. Using vdW-corrected ab initio density functional theory (DFT) simulations, we determine that the interplay between vdW and Coulomb interactions as well as adsorbate–adsorbate and adsorbate–substrate interactions results in specific rotational arrangements of the molecules forming the superstructure. The orbital ordering through the relative positions of bonds in adjacent molecules creates a charge redistribution that links the molecule units in a long-range network. Furthermore, this rotational superstructure extends throughout the self-assembled monolayer and opens a pathway towards engineering aligned hybrid organic/inorganic vdW heterostructures with 2D layered materials in a precise and controlled way.« less

Self-assembled iron oxide nanoparticle multilayer: x-ray and polarized neutron reflectivity.

PubMed

Mishra, D; Benitez, M J; Petracic, O; Badini Confalonieri, G A; Szary, P; Brüssing, F; Theis-Bröhl, K; Devishvili, A; Vorobiev, A; Konovalov, O; Paulus, M; Sternemann, C; Toperverg, B P; Zabel, H

2012-02-10

We have investigated the structure and magnetism of self-assembled, 20 nm diameter iron oxide nanoparticles covered by an oleic acid shell for scrutinizing their structural and magnetic correlations. The nanoparticles were spin-coated on an Si substrate as a single monolayer and as a stack of 5 ML forming a multilayer. X-ray scattering (reflectivity and grazing incidence small-angle scattering) confirms high in-plane hexagonal correlation and a good layering property of the nanoparticles. Using polarized neutron reflectivity we have also determined the long range magnetic correlations parallel and perpendicular to the layers in addition to the structural ones. In a field of 5 kOe we determine a magnetization value of about 80% of the saturation value. At remanence the global magnetization is close to zero. However, polarized neutron reflectivity reveals the existence of regions in which magnetic moments of nanoparticles are well aligned, while losing order over longer distances. These findings confirm that in the nanoparticle assembly the magnetic dipole-dipole interaction is rather strong, dominating the collective magnetic properties at room temperature.

Engineering Globular Protein Vesicles through Tunable Self-Assembly of Recombinant Fusion Proteins

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

Jang, Yeongseon; Choi, Won Tae; Heller, William T.

Vesicles assembled from folded, globular proteins have potential for functions different from traditional lipid or polymeric vesicles. However, they also present challenges in understanding the assembly process and controlling vesicle properties. From detailed investigation of the assembly behavior of recombinant fusion proteins, this work reports a simple strategy to engineer protein vesicles containing functional, globular domains. This is achieved through tunable self-assembly of recombinant globular fusion proteins containing leucine zippers and elastin-like polypeptides. The fusion proteins form complexes in solution via high affinity binding of the zippers, and transition through dynamic coacervates to stable hollow vesicles upon warming. The thermalmore » driving force, which can be tuned by protein concentration or temperature, controls both vesicle size and whether vesicles are single or bi-layered. Lastly, these results provide critical information to engineer globular protein vesicles via self-assembly with desired size and membrane structure.« less

Engineering Globular Protein Vesicles through Tunable Self-Assembly of Recombinant Fusion Proteins

DOE PAGES

Jang, Yeongseon; Choi, Won Tae; Heller, William T.; ...

2017-07-27

Vesicles assembled from folded, globular proteins have potential for functions different from traditional lipid or polymeric vesicles. However, they also present challenges in understanding the assembly process and controlling vesicle properties. From detailed investigation of the assembly behavior of recombinant fusion proteins, this work reports a simple strategy to engineer protein vesicles containing functional, globular domains. This is achieved through tunable self-assembly of recombinant globular fusion proteins containing leucine zippers and elastin-like polypeptides. The fusion proteins form complexes in solution via high affinity binding of the zippers, and transition through dynamic coacervates to stable hollow vesicles upon warming. The thermalmore » driving force, which can be tuned by protein concentration or temperature, controls both vesicle size and whether vesicles are single or bi-layered. Lastly, these results provide critical information to engineer globular protein vesicles via self-assembly with desired size and membrane structure.« less

Reliable aluminum contact formation by electrostatic bonding

NASA Astrophysics Data System (ADS)

Kárpáti, T.; Pap, A. E.; Radnóczi, Gy; Beke, B.; Bársony, I.; Fürjes, P.

2015-07-01

The paper presents a detailed study of a reliable method developed for aluminum fusion wafer bonding assisted by the electrostatic force evolving during the anodic bonding process. The IC-compatible procedure described allows the parallel formation of electrical and mechanical contacts, facilitating a reliable packaging of electromechanical systems with backside electrical contacts. This fusion bonding method supports the fabrication of complex microelectromechanical systems (MEMS) and micro-opto-electromechanical systems (MOEMS) structures with enhanced temperature stability, which is crucial in mechanical sensor applications such as pressure or force sensors. Due to the applied electrical potential of  -1000 V the Al metal layers are compressed by electrostatic force, and at the bonding temperature of 450 °C intermetallic diffusion causes aluminum ions to migrate between metal layers.

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

PubMed

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

2016-04-12

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

Low-cost zinc-plated photoanode for fabric-type dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Kong, Lingfeng; Bao, Yunna; Guo, Wanwan; Cheng, Li; Du, Jun; Liu, Renlong; Wang, Yundong; Fan, Xing; Tao, Changyuan

2016-02-01

Fabric-type flexible solar cells have been recently proposed as a very promising power source for wearable electronics. To increase the photocurrent of fabric-type flexible solar cells, low-cost zinc-plated wire and mesh photoanodes are assembled for the first time through a mild wet process. Given the protection of the compact protection layer, the DSSC device could benefit from the low work function of Zn and self-repairing behavior on the Zn/ZnO interface. An evident current increase by ∼6 mA/cm2 could be observed after coating a layer of metal Zn on various metal substrates, such as traditional stainless steel wire. Given the self-repairing behavior on Zn/ZnO interface, the Zn layer can help to improve the interfacial carrier transfer, leading to better photovoltaic performance, for both liquid-type and solid-type cells.

Mechanics of evolving thin film structures

NASA Astrophysics Data System (ADS)

Liang, Jim

In the Stranski-Krastanov system, the lattice mismatch between the film and the substrate causes the film to break into islands. During annealing, both the surface energy and the elastic energy drive the islands to coarsen. Motivated by several related studies, we suggest that stable islands should form when a stiff ceiling is placed at a small gap above the film. We show that the role of elasticity is reversed: with the ceiling, the total elastic energy stored in the system increases as the islands coarsen laterally. Consequently, the islands select an equilibrium size to minimize the combined elastic energy and surface energy. In lithographically-induced self-assembly, when a two-phase fluid confined between parallel substrates is subjected to an electric field, one phase can self-assemble into a triangular lattice of islands in another phase. We describe a theory of the stability of the island lattice. The islands select the equilibrium diameter to minimize the combined interface energy and electrostatic energy. Furthermore, we study compressed SiGe thin film islands fabricated on a glass layer, which itself lies on a silicon wafer. Upon annealing, the glass flows, and the islands relax. A small island relaxes by in-plane expansion. A large island, however, wrinkles at the center before the in-plane relaxation arrives. The wrinkles may cause significant tensile stress in the island, leading to fracture. We model the island by the von Karman plate theory and the glass layer by the Reynolds lubrication theory. Numerical simulations evolve the in-plane expansion and the wrinkles simultaneously. We determine the critical island size, below which in-plane expansion prevails over wrinkling. Finally, in devices that integrate dissimilar materials in small dimensions, crack extension in one material often accompanies inelastic deformation in another. We analyze a channel crack advancing in an elastic film under tension, while an underlayer creeps. We use a two-dimensional shear lag model to approximate the three-dimensional fracture process. Based on the computational results, we propose new experiments to measure fracture toughness and creep laws in small structures. Similarly, we study delayed crack initiation, steady crack growth, and transient crack growth when the underlayer is viscoelastic.

Drying bacterial biosaline patterns capable of vital reanimation upon rehydration: novel hibernating biomineralogical life formations.

PubMed

Gómez Gómez, José María; Medina, Jesús; Hochberg, David; Mateo-Martí, Eva; Martínez-Frías, Jesús; Rull, Fernando

2014-07-01

Water is the fundamental molecule for life on Earth. Thus, the search for hibernating life-forms in waterless environments is an important research topic for astrobiology. To date, however, the organizational patterns containing microbial life in extremely dry places, such as the deserts of Earth, the Dry Valleys of Antarctica, or Mars analog regolith, have been poorly characterized. Here, we report on the formation of bacterial biosaline self-organized drying patterns formed over plastic surfaces. These emerge during the evaporation of sessile droplets of aqueous NaCl salt 0.15 M solutions containing Escherichia coli cells. In the present study, scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS) analyses indicated that the bacterial cells and the NaCl in these biosaline formations are organized in a two-layered characteristic 3-D architectural morphology. A thin filmlike top layer formed by NaCl conjugated to, and intermingled with, "mineralized" bacterial cells covers a bottom layer constructed by the bulk of the nonmineralized bacterial cells; both layers have the same morphological pattern. In addition, optical microscopic time-lapsed movies show that the formation of these patterns is a kinetically fast process that requires the coupled interaction between the salt and the bacterial cells. Apparently, this mutual interaction drives the generative process of self-assembly that underlies the drying pattern formation. Most notably, the bacterial cells inside these drying self-assembled patterns enter into a quiescent suspended anhydrobiotic state resistant to complete desiccation and capable of vital reanimation upon rehydration. We propose that these E. coli biosaline drying patterns represent an excellent experimental model for understanding different aspects of anhydrobiosis phenomena in bacteria as well as for revealing the mechanisms of bacterially induced biomineralization, both highly relevant topics for the search of life in extraterrestrial locations.

Orientation of surfactant self-assembled aggregates on graphite

NASA Astrophysics Data System (ADS)

Sammalkorpi, Maria; Hynninen, Antti-Pekka; Panagiotopoulos, Athanassios Z.; Haataja, Mikko

2007-03-01

Micellar aggregates on surfaces can provide a self-healing corrosion protection or lubrication layer. It has been observed experimentally that on a single crystal surface this layer often consists of oriented hemi-cylindrical micelles which are aligned with the underlying crystal lattice (``orientation effect''). A key feature of this self-assembly process is the interplay between detergent--detergent and detergent--surface interactions. Since the dimensions of the detergent molecules and the unit cell of the surface are typically quite different, the origins of this orientation effect remain unclear. Here we address the question and present the results of Molecular Dynamics simulations of sodium dodecyl sulfate (SDS) self-aggregation on graphite. We employ both single-molecule and multi-molecule simulations of SDS to unravel the origins of the orientation effect. We report that the underlying graphite surface is sufficient to impose orientational bias on individual SDS molecules diffusing on the surface. This produces collective effects that give rise to the oriented hemi-micelles.

Optical phenomena and antifrosting property on biomimetics slippery fluid-infused antireflective films via layer-by-layer comparison with superhydrophobic and antireflective films.

PubMed

Manabe, Kengo; Nishizawa, Shingo; Kyung, Kyu-Hong; Shiratori, Seimei

2014-08-27

Sophisticated material interfaces generated by natural life forms such as lotus leaves and Nepenthes pitcher plants have exceptional abilities to resolve challenges in wide areas of industry and medicine. The nano- and microstructures inspired by these natural materials can repel various liquids and form self-cleaning coatings. In particular, slippery liquid-infused surfaces are receiving remarkable interest as transparent, nonfouling, and antifrosting synthetic surfaces for solar cells and optical devices. Here we focus on the transparency of lubricant-infused texture on antireflective films fabricated by layer-by-layer self-assembly that decrease light scattering, which is important to maintain device properties. A slippery fluid-infused antireflective film composed of chitin nanofibers less than 50 nm in diameter prevented light scattering at the long-wavelength side by Rayleigh scattering to achieve 97.2% transmittance. Moreover, films composed of the same materials demonstrated three different morphologies: superhydrophilicity with antireflection, superhydrophobicity, and omniphobicity, mimicking the biological structures of moth eyes, lotus leaves, and pitcher plants, respectively. The effect of thermal changes on the ability of each film to prevent frost formation was investigated. The slippery fluid-infused antireflective film showed effective antifrosting behavior.

Microgravity

NASA Image and Video Library

2000-12-15

NASA is looking to biological techniques that are millions of years old to help it develop new materials and technologies for the 21st century. Sponsored by NASA, Jeffrey Brinker of the University of New Mexico is studying how multiple elements can assemble themselves into a composite material that is clear, tough, and impermeable. His research is based on the model of how an abalone builds the nacre, also called mother-of-pearl, inside its shell. Strong thin coatings, or lamellae, in Brinker's research are formed when objects are dip-coated. Evaporation drives the self-assembly of molecular aggregates (micelles) of surfactant, soluble silica, and organic monomers and their further self-organization into layered organic and inorganic assemblies.

Large area polysilicon films with predetermined stress characteristics and method for producing same

NASA Technical Reports Server (NTRS)

Heuer, Arthur H. (Inventor); Kahn, Harold (Inventor); Yang, Jie (Inventor); Phillips, Stephen M. (Inventor)

2002-01-01

Multi-layer assemblies of polysilicon thin films having predetermined stress characteristics and techniques for forming such assemblies are disclosed. In particular, a multi-layer assembly of polysilicon thin films may be produced that has a stress level of zero, or substantially so. The multi-layer assemblies comprise at least one constituent thin film having a tensile stress and at least one constituent thin film having a compressive stress. The thin films forming the multi-layer assemblies may be disposed immediately adjacent to one another without the use of intermediate layers between the thin films. Multi-layer assemblies exhibiting selectively determinable overall bending moments are also disclosed. Selective production of overall bending moments in microstructures enables manufacture of such structures with a wide array of geometrical configurations.

Biosensing for the Environment and Defence: Aqueous Uranyl Detection Using Bacterial Surface Layer Proteins

PubMed Central

Conroy, David J.R.; Millner, Paul A.; Stewart, Douglas I.; Pollmann, Katrin

2010-01-01

The fabrication of novel uranyl (UO22+) binding protein based sensors is reported. The new biosensor responds to picomolar levels of aqueous uranyl ions within minutes using Lysinibacillus sphaericus JG-A12 S-layer protein tethered to gold electrodes. In comparison to traditional self assembled monolayer based biosensors the porous bioconjugated layer gave greater stability, longer electrode life span and a denser protein layer. Biosensors responded specifically to UO22+ ions and showed minor interference from Ni2+, Cs+, Cd2+ and Co2+. Chemical modification of JG-A12 protein phosphate and carboxyl groups prevented UO22+ binding, showing that both moieties are involved in the recognition to UO22+. PMID:22399904

Theoretical insights into aggregation-induced helicity modulation of a perylene bisimide derivative.

PubMed

Liang, Lijun; Li, Xin

2018-02-12

Formation of helical chiroptical self-assemblies via noncovalent interaction is a widely observed phenomenon in nature, the mechanism of which remains insufficiently understood. Employing an amphiphilic perylene-sugar dyad molecule (PBI-HAG) as an example, we report that the modulatable supramolecular helicity may emerge from an aggregating process that is dominated by competition between two types of noncovalent interaction: hydrogen bonding and π-π stacking. The interplay between these two driving forces, which is greatly affected by the solvent environment, determines the morphology the supramolecular assembly of PBI-HAGs. In particular, a non-layered supramolecular structure was formed in octane owing to stabilization effects of intermolecular hydrogen bonds, whereas a layered supramolecular structure was formed in water because of energetically favorable π-π stacking of aromatic rings. The formation of distinct supramolecular architectures in different solvents was reinforced by simulated circular dichroism spectra, which show opposite signals consistent with experimental observations. The results of this study could help us understand aggregation-induced supramolecular chirality of noncovalent self-assemblies. Graphical abstract Left Typical structures of amphiphilic perylene-sugar dyad (PBI-HAG) aggregates in different octane and water. Right Simulated CD and UV-Vis spectra of core PBIs aggregates in octane and water.

The role of surface charging during the coadsorption of mercaptohexanol to DNA layers on gold: direct observation of desorption and layer reorientation.

PubMed

Arinaga, K; Rant, U; Tornow, M; Fujita, S; Abstreiter, G; Yokoyama, N

2006-06-20

We study the coadsorption of mercaptohexanol onto preimmobilized oligonucleotide layers on gold. Monitoring the position of the DNA relative to the surface by optical means directly shows the mercaptohexanol-induced desorption of DNA and the reorientation of surface-tethered strands in situ and in real time. By simultaneously recording the electrochemical electrode potential, we are able to demonstrate that changes in the layer conformation are predominantly of electrostatic origin and can be reversed by applying external bias to the substrate.

Molecular dynamics simulations of structural transformation of perfluorooctane sulfonate (PFOS) at water/rutile interfaces.

PubMed

He, Guangzhi; Zhang, Meiyi; Zhou, Qin; Pan, Gang

2015-09-01

Concentration and salinity conditions are the dominant environmental factors affecting the behavior of perfluorinated compounds (PFCs) on the surfaces of a variety of solid matrices (suspended particles, sediments, and natural minerals). However, the mechanism has not yet been examined at molecular scales. Here, the structural transformation of perfluorooctane sulfonate (PFOS) at water/rutile interfaces induced by changes of the concentration level of PFOS and salt condition was investigated using molecular dynamics (MD) simulations. At low and intermediate concentrations all PFOS molecules directly interacted with the rutile (110) surface mainly by the sulfonate headgroups through electrostatic attraction, yielding a typical monolayer structure. As the concentration of PFOS increased, the molecules aggregated in a complex multi-layered structure, where an irregular assembling configuration was adsorbed on the monolayer structure by the van der Waals interactions between the perfluoroalkyl chains. When adding CaCl2 to the system, the multi-layered structure changed to a monolayer again, indicating that the addition of CaCl2 enhanced the critical concentration value to yield PFOS multilayer assemblies. The divalent Ca(2+) substituted for monovalent K(+) as the bridging counterion in PFOS adsorption. MD simulation may trigger wide applications in study of perfluorinated compounds (PFCs) from atomic/molecular scale. Copyright © 2015 Elsevier Ltd. All rights reserved.

Direct Loading and Tunable Release of Antibiotics from Polyelectrolyte Multilayers To Reduce Bacterial Adhesion and Biofilm Formation.

PubMed

Wang, Bailiang; Jin, Tingwei; Xu, Qingwen; Liu, Huihua; Ye, Zi; Chen, Hao

2016-05-18

Bacteria adhesion on the surface of biomaterials and following biofilm formation are important problems in biomedical applications. The charged antibiotics with small molar mass can hardly deposit alternately with polymers into multilayered films to load the drug. Herein, the (poly(acrylic acid)-gentamicin/poly(ethylenimine))n ((PAA-GS/PEI)n) multilayer film was designed and constructed via a layer-by-layer self-assembly method. Low molar mass GS cations were first combined with polyanion PAA and self-assembled with PEI to form multilayer films showing exponential growth behavior. The GS dosage could be adjusted by changing the layer number of films. Furthermore, the thermal cross-linking method was used to control the release rate of GS in PBS buffer. Owing to the diffusion of GS, a zone of inhibition of about 7.0 mm showed the efficient disinfection activity of the multilayer film. It could also be seen from the biofilm inhibition assay that the multilayer film effectively inhibited bacterial adhesion and biofilm formation. As the drug loading dosage was 160 μg/cm(2), the multilayer films showed very low cytotoxicity against human lens epithelial cells. The present work provides an easy way to load GS into multilayer films which can be applied to surface modification of implants and biomedical devices.

Optical manipulation of electron spin in quantum dot systems

NASA Astrophysics Data System (ADS)

Villas-Boas, Jose; Ulloa, Sergio; Govorov, Alexander

2006-03-01

Self-assembled quantum dots (QDs) are of particular interest for fundamental physics because of their similarity with atoms. Coupling two of such dots and addressing them with polarized laser light pulses is perhaps even more interesting. In this paper we use a multi-exciton density matrix formalism to model the spin dynamics of a system with single or double layers of QDs. Our model includes the anisotropic electron-hole exchange in the dots, the presence of wetting layer states, and interdot tunneling [1]. Our results show that it is possible to switch the spin polarization of a single self-assembled quantum dot under elliptically polarized light by increasing the laser intensity. In the nonlinear mechanism described here, intense elliptically polarized light creates an effective exchange channel between the exciton spin states through biexciton states, as we demonstrate by numerical and analytical methods. We further show that the effect persists in realistic ensembles of dots, and we propose alternative ways to detect it. We also extend our study to a double layer of quantum dots, where we find a competition between Rabi frequency and tunneling oscillations. [1] J. M. Villas-Boas, S. E. Ulloa, and A. O. Govorov, Phys. Rev. Lett. 94, 057404 (2005); Phys. Rev. B 69, 125342 (2004).

Adsorption of hyaluronic acid on solid supports: role of pH and surface chemistry in thin film self-assembly.

PubMed

Choi, Jae-Hyeok; Kim, Seong-Oh; Linardy, Eric; Dreaden, Erik C; Zhdanov, Vladimir P; Hammond, Paula T; Cho, Nam-Joon

2015-06-15

Owing to its biocompatibility, resistance to biofouling, and desirable physicochemical and biological properties, hyaluronic acid (HA) has been widely used to modify the surface of various materials. The role of various physicochemical factors in HA adsorption remains, however, to be clarified. Herein, we employed quartz crystal microbalance with dissipation (QCM-D) in order to investigate HA adsorption at different pH conditions onto three substrates-silicon oxide, amine-terminated self-assembled monolayer (SAM) on gold, and carboxylic acid-terminated SAM on gold. The QCM-D experiments indicated specific pH conditions where either strong or weak HA adsorption occurs. The morphology of the adsorbed HA layers was investigated by atomic force microscopy (AFM), and we identified that strong HA adsorption produced a complete, homogenous and smooth HA layer, while weak HA adsorption resulted in rough and inhomogeneous HA layers. The observed specifics of the kinetics of HA adsorption, including a short initial linear phase and subsequent long non-linear phase, were described by using a mean-field kinetic model taking HA diffusion limitations and reconfiguration in the adsorbed state into account. The findings extend the physicochemical background of design strategies for improving the use of passive HA adsorption for surface modification applications. Copyright © 2015 Elsevier Inc. All rights reserved.

Role of indium tin oxide electrode on the microstructure of self-assembled WO3-BiVO4 hetero nanostructures

NASA Astrophysics Data System (ADS)

Song, Haili; Li, Chao; Van, Chien Nguyen; Dong, Wenxia; Qi, Ruijuan; Zhang, Yuanyuan; Huang, Rong; Chu, Ying-Hao; Duan, Chun-Gang

2017-11-01

Self-assembled WO3-BiVO4 nanostructured thin films were grown on a (001) yttrium stabilized zirconia (YSZ) substrate by the pulsed laser deposition method with and without the indium tin oxide (ITO) bottom electrode. Their microstructures including surface morphologies, crystalline phases, epitaxial relationships, interface structures, and composition distributions were investigated by scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray energy dispersive spectroscopy. In both samples, WO3 formed nanopillars embedded into the monoclinic BiVO4 matrix with specific orientation relationships. In the sample with the ITO bottom electrode, an atomically sharp BiVO4/ITO interface was formed and the orthorhombic WO3 nanopillars were grown on a relaxed BiVO4 buffer layer with a mixed orthorhombic and hexagonal WO3 transition layer. In contrast, a thin amorphous layer appears at the interfaces between the thin film and the YSZ substrate in the sample without the ITO electrode. In addition, orthorhombic Bi2WO6 lamellar nanopillars were formed between WO3 and BiVO4 due to interdiffusion. Such a WO3-Bi2WO6-BiVO4 double heterojunction photoanode may promote the photo-generated charge separation and further improve the photoelectrochemical water splitting properties.

Improving Fire Resistance of Cotton Fabric through Layer-by-Layer Assembled Graphene Multilayer Nanocoating

NASA Astrophysics Data System (ADS)

Jang, Wonjun; Chung, Il Jun; Kim, Junwoo; Seo, Seongmin; Park, Yong Tae; Choi, Kyungwho

2018-05-01

In this study, thin films containing poly(vinyl alcohol) (PVA) and graphene nanoplatelets (GNPs), stabilized with poly(4-styrene-sulfonic acid) (PSS), were assembled by a simple and cost-effective layer-by-layer (LbL) technique in order to introduce the anti-flammability to cotton. These antiflammable layers were characterized by using UV-vis spectrometry and quartz crystal microbalance as a function of the number of bilayers deposited. Scanning electron microscopy was used to visualize the morphology of the thin film coatings on the cotton fabric. The graphene-polymer thin films introduced anti-flammable properties through thermally stable carbonaceous layers at a high temperature. The thermal stability and flame retardant property of graphene-coated cotton was demonstrated by thermogravimetric analysis, cone calorimetry, and vertical flame test. The results indicate that LbL-assembled graphene-polymer thin films can be applied largely in the field of flame retardant.