Functionalization of biodegradable magnesium alloy implants with alkylphosphonate self-assembled films.

PubMed

Grubač, Z; Metikoš-Huković, M; Babić, R; Rončević, I Škugor; Petravić, M; Peter, R

2013-05-01

Mg and Mg-alloys are promising materials for biodegradable implants. In order to slowdown the Mg-alloy (AZ91D) degradation and enhance its biocompatibility, the alloy surface was modified with alkylphosphonate self-assembling films. The binding configuration and the structural organization of alkylphosphonate monolayers on the Mg-alloy surface were investigated using contact angle measurements, FTIR, and XPS. Combination of FTIR and XPS data indicated the presence of several different bonding modes (mono-, di-, and tri dentate) of phosphonate head groups with the alloy surface. The existence of well organized and ordered self-assembled alkylphosphonate monolayers with good barrier protecting properties in a physiological solution is a key step in the development of biocompatible Mg-alloy implants. Copyright © 2013 Elsevier B.V. All rights reserved.

Chemoselective covalent coupling of oligonucleotide probes to self-assembled monolayers.

PubMed

Devaraj, Neal K; Miller, Gregory P; Ebina, Wataru; Kakaradov, Boyko; Collman, James P; Kool, Eric T; Chidsey, Christopher E D

2005-06-22

A chemoselective route to routinely and rapidly attach oligonucleotide probes to well-defined surfaces is presented. Cu(I) tris(benzyltriazolylmethyl)amine-catalyzed coupling of terminal acetylenes to azides on a self-assembled monolayer is used instead of traditional nucleophilic-electrophilic coupling reactions. The reaction proceeds well even in the presence of purposely introduced nucleophilic and electrophilic impurities. The density of oligonucleotide probes can be controlled by controlling the amount of azide functionality. Although most of our work was done on gold surfaces, this technique should be readily applicable to any surface on which an azide-containing monolayer can be assembled as we have preliminarily demonstrated by derivatizing azidotrimethoxysilane-modified glass slides with fluorescein-containing oligonucleotides.

Activated Carbon Fibers "Thickly Overgrown" by Ag Nanohair Through Self-Assembly and Rapid Thermal Annealing

NASA Astrophysics Data System (ADS)

Yan, Xuefeng; Xu, Sijun; Wang, Qiang; Fan, Xuerong

2017-11-01

Anisotropic nanomaterial-modified carbon fibers attract increasing attention because of their superior properties over traditional ones. In this study, activated carbon fibers (ACFs) "thickly overgrown" by Ag nanohair were prepared through self-assembly and rapid thermal annealing. Viscose fibers with well-dispersed silver nanoparticles (AgNPs) on surfaces were first prepared through self-assembly of hyperbranched poly(amino-amine) (HBPAA)-capped AgNPs on viscose surfaces. HBPAA endowed the AgNP surfaces with negative charges and abundant amino groups, allowing AgNPs to monodispersively self-assemble to fiber surfaces. Ag nanohair-grown ACFs were prepared by sequential pre-oxidation and carbonization. Because the carbonization furnace was open-ended, ACFs are immediately transferrable to the outside of the furnace. Therefore, the Ag liquid adsorbed by ACF pores squeezed out to form Ag nanowires through thermal contraction. FESEM characterization indicated that Ag nanohairs stood on ACF surface and grew from ACF caps. XPS and XRD characterization showed that Ag successfully assembled to fiber surfaces and retained its metallic state even after high-temperature carbonization. TG analysis suggested that Ag nanohair-grown ACFs maintained their excellent thermal stabilities. Finally, the fabricated ACFs showed excellent and durable antibacterial activities, and the developed method may provide a potential strategy for preparing metal nanowire-grown ACFs.

Disulfide-induced self-assembled targets: A novel strategy for the label free colorimetric detection of DNAs/RNAs via unmodified gold nanoparticles

NASA Astrophysics Data System (ADS)

Shokri, Ehsan; Hosseini, Morteza; Davari, Mehdi D.; Ganjali, Mohammad R.; Peppelenbosch, Maikel P.; Rezaee, Farhad

2017-04-01

A modified non-cross-linking gold-nanoparticles (Au-NPs) aggregation strategy has been developed for the label free colorimetric detection of DNAs/RNAs based on self-assembling target species in the presence of thiolated probes. Two complementary thiol- modified probes, each of which specifically binds at one half of the target introduced SH groups at both ends of dsDNA. Continuous disulfide bond formation at 3‧ and 5‧ terminals of targets leads to the self-assembly of dsDNAs into the sulfur- rich and flexible products with different lengths. These products have a high affinity for the surface of Au-NPs and efficiently protect the surface from salt induced aggregation. To evaluate the assay efficacy, a small part of the citrus tristeza virus (CTV) genome was targeted, leading to a detection limit of about 5 × 10-9 mol.L-1 over a linear ranged from 20 × 10-9 to 10 × 10-7 mol.L-1. This approach also exhibits good reproducibility and recovery levels in the presence of plant total RNA or human plasma total circulating RNA extracts. Self-assembled targets can be then sensitively distinguished from non-assembled or mismatched targets after gel electrophoresis. The disulfide reaction method and integrating self-assembled DNAs/RNAs targets with bare AuNPs as a sensitive indicator provide us a powerful and simple visual detection tool for a wide range of applications.

Monolayer Colloidal Crystals by Modified Air-Water Interface Self-Assembly Approach

PubMed Central

Ye, Xin; Huang, Jin; Zeng, Yong; Sun, Lai-Xi; Geng, Feng; Liu, Hong-Jie; Wang, Feng-Rui; Jiang, Xiao-Dong; Wu, Wei-Dong; Zheng, Wan-Guo

2017-01-01

Hexagonally ordered arrays of polystyrene (PS) microspheres were prepared by a modified air-water self-assembly method. A detailed analysis of the air-water interface self-assembly process was conducted. Several parameters affect the quality of the monolayer colloidal crystals, i.e., the colloidal microsphere concentration on the latex, the surfactant concentration, the polystyrene microsphere diameter, the microsphere polydispersity, and the degree of sphericity of polystyrene microspheres. An abrupt change in surface tension was used to improve the quality of the monolayer colloidal crystal. Three typical microstructures, i.e., a cone, a pillar, and a binary structure were prepared by reactive-ion etching using a high-quality colloidal crystal mask. This study provides insight into the production of microsphere templates with flexible structures for large-area patterned materials. PMID:28946664

Self-assembled monolayers of alendronate on Ti6Al4V alloy surfaces enhance osteogenesis in mesenchymal stem cells

NASA Astrophysics Data System (ADS)

Rojo, Luis; Gharibi, Borzo; McLister, Robert; Meenan, Brian J.; Deb, Sanjukta

2016-07-01

Phosphonates have emerged as an alternative for functionalization of titanium surfaces by the formation of homogeneous self-assembled monolayers (SAMs) via Ti-O-P linkages. This study presents results from an investigation of the modification of Ti6Al4V alloy by chemisorption of osseoinductive alendronate using a simple, effective and clean methodology. The modified surfaces showed a tailored topography and surface chemistry as determined by SEM microscopy and RAMAN spectroscopy. X-ray photoelectron spectroscopy revealed that an effective mode of bonding is created between the metal oxide surface and the phosphate residue of alendronate, leading to formation of homogenous drug distribution along the surface. In-vitro studies showed that alendronate SAMs induce differentiation of hMSC to a bone cell phenotype and promote bone formation on modified surfaces. Here we show that this novel method for the preparation of functional coatings on titanium-based medical devices provides osseoinductive bioactive molecules to promote enhanced integration at the site of implantation.

Self-assembled monolayers of alendronate on Ti6Al4V alloy surfaces enhance osteogenesis in mesenchymal stem cells

PubMed Central

Rojo, Luis; Gharibi, Borzo; McLister, Robert; Meenan, Brian J.; Deb, Sanjukta

2016-01-01

Phosphonates have emerged as an alternative for functionalization of titanium surfaces by the formation of homogeneous self-assembled monolayers (SAMs) via Ti-O-P linkages. This study presents results from an investigation of the modification of Ti6Al4V alloy by chemisorption of osseoinductive alendronate using a simple, effective and clean methodology. The modified surfaces showed a tailored topography and surface chemistry as determined by SEM microscopy and RAMAN spectroscopy. X-ray photoelectron spectroscopy revealed that an effective mode of bonding is created between the metal oxide surface and the phosphate residue of alendronate, leading to formation of homogenous drug distribution along the surface. In-vitro studies showed that alendronate SAMs induce differentiation of hMSC to a bone cell phenotype and promote bone formation on modified surfaces. Here we show that this novel method for the preparation of functional coatings on titanium-based medical devices provides osseoinductive bioactive molecules to promote enhanced integration at the site of implantation. PMID:27468811

Appropriate salt concentration of nanodiamond colloids for electrostatic self-assembly seeding of monosized individual diamond nanoparticles on silicon dioxide surfaces.

PubMed

Yoshikawa, Taro; Zuerbig, Verena; Gao, Fang; Hoffmann, René; Nebel, Christoph E; Ambacher, Oliver; Lebedev, Vadim

2015-05-19

Monosized (∼4 nm) diamond nanoparticles arranged on substrate surfaces are exciting candidates for single-photon sources and nucleation sites for ultrathin nanocrystalline diamond film growth. The most commonly used technique to obtain substrate-supported diamond nanoparticles is electrostatic self-assembly seeding using nanodiamond colloidal suspensions. Currently, monodisperse nanodiamond colloids, which have a narrow distribution of particle sizes centering on the core particle size (∼4 nm), are available for the seeding technique on different substrate materials such as Si, SiO2, Cu, and AlN. However, the self-assembled nanoparticles tend to form small (typically a few tens of nanometers or even larger) aggregates on all of those substrate materials. In this study, this major weakness of self-assembled diamond nanoparticles was solved by modifying the salt concentration of nanodiamond colloidal suspensions. Several salt concentrations of colloidal suspensions were prepared using potassium chloride as an inserted electrolyte and were examined with respect to seeding on SiO2 surfaces. The colloidal suspensions and the seeded surfaces were characterized by dynamic light scattering and atomic force microscopy, respectively. Also, the interaction energies between diamond nanoparticles in each of the examined colloidal suspensions were compared on the basis of the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. From these investigations, it became clear that the appropriate salt concentration suppresses the formation of small aggregates during the seeding process owing to the modified electrostatic repulsive interaction between nanoparticles. Finally, monosized (<10 nm) individual diamond nanoparticles arranged on SiO2 surfaces have been successfully obtained.

Cell-free protein synthesis and assembly on a biochip

NASA Astrophysics Data System (ADS)

Heyman, Yael; Buxboim, Amnon; Wolf, Sharon G.; Daube, Shirley S.; Bar-Ziv, Roy H.

2012-06-01

Biologically active complexes such as ribosomes and bacteriophages are formed through the self-assembly of proteins and nucleic acids. Recapitulating these biological self-assembly processes in a cell-free environment offers a way to develop synthetic biodevices. To visualize and understand the assembly process, a platform is required that enables simultaneous synthesis, assembly and imaging at the nanoscale. Here, we show that a silicon dioxide grid, used to support samples in transmission electron microscopy, can be modified into a biochip to combine in situ protein synthesis, assembly and imaging. Light is used to pattern the biochip surface with genes that encode specific proteins, and antibody traps that bind and assemble the nascent proteins. Using transmission electron microscopy imaging we show that protein nanotubes synthesized on the biochip surface in the presence of antibody traps efficiently assembled on these traps, but pre-assembled nanotubes were not effectively captured. Moreover, synthesis of green fluorescent protein from its immobilized gene generated a gradient of captured proteins decreasing in concentration away from the gene source. This biochip could be used to create spatial patterns of proteins assembled on surfaces.

Densifying carbon nanotubes on assembly surface by the self-contraction of silk fibroin

NASA Astrophysics Data System (ADS)

Jiang, Chunyang; Yang, Xueqin; Zhao, Jingna; Li, Qingsong; Zhang, Ke-Qin; Zhang, Xiaohua; Li, Qingwen

2018-04-01

High densification of carbon nanotubes (CNTs) is important for high utilization efficiency of their superior properties in macroscopic assemblies. However, the conventional "top-down" compressing strategies have met problems to modify CNT assemblies at and below the micrometer scale. Here we report a molecular way to strap CNTs together via the self-contraction of silk fibroin (SF) during its drying process, resulting in a localized densification below the micrometer scale. Importantly, after the thermal removal of SF molecules, the densified assembly was well maintained. The SF-induced densification increased the average strength from 355 MPa to 960 MPa for CNT fibers, and from 1.45 GPa to 1.82 GPa for CNT ribbons, which contain much more CNTs on the surface.

Functionalized boron nitride nanotubes

DOEpatents

Sainsbury, Toby; Ikuno, Takashi; Zettl, Alexander K

2014-04-22

A plasma treatment has been used to modify the surface of BNNTs. In one example, the surface of the BNNT has been modified using ammonia plasma to include amine functional groups. Amine functionalization allows BNNTs to be soluble in chloroform, which had not been possible previously. Further functionalization of amine-functionalized BNNTs with thiol-terminated organic molecules has also been demonstrated. Gold nanoparticles have been self-assembled at the surface of both amine- and thiol-functionalized boron nitride Nanotubes (BNNTs) in solution. This approach constitutes a basis for the preparation of highly functionalized BNNTs and for their utilization as nanoscale templates for assembly and integration with other nanoscale materials.

Effect of molecular desorption on the electronic properties of self-assembled polarizable molecular monolayers.

PubMed

Wang, Gunuk; Jeong, Hyunhak; Ku, Jamin; Na, Seok-In; Kang, Hungu; Ito, Eisuke; Jang, Yun Hee; Noh, Jaegeun; Lee, Takhee

2014-04-01

We investigated the interfacial electronic properties of self-assembled monolayers (SAM)-modified Au metal surface at elevated temperatures. We observed that the work functions of the Au metal surfaces modified with SAMs changed differently under elevated-temperature conditions based on the type of SAMs categorized by three different features based on chemical anchoring group, molecular backbone structure, and the direction of the dipole moment. The temperature-dependent work function of the SAM-modified Au metal could be explained in terms of the molecular binding energy and the thermal stability of the SAMs, which were investigated with thermal desorption spectroscopic measurements and were explained with molecular modeling. Our study will aid in understanding the electronic properties at the interface between SAMs and metals in organic electronic devices if an annealing treatment is applied. Copyright © 2013 Elsevier Inc. All rights reserved.

Corrosion resistance and biocompatibility of magnesium alloy modified by alkali heating treatment followed by the immobilization of poly (ethylene glycol), fibronectin and heparin.

PubMed

Pan, Changjiang; Hu, Youdong; Hou, Yu; Liu, Tao; Lin, Yuebin; Ye, Wei; Hou, Yanhua; Gong, Tao

2017-01-01

In recent years, magnesium alloys are attracting more and more attention as a kind of biodegradable metallic biomaterials, however, their uncontrollable biodegradation speed in vivo and the limited surface biocompatibility hinder their clinical applications. In the present study, with the aim of improving the corrosion resistance and biocompatibility, the magnesium alloy (AZ31B) surface was modified by alkali heating treatment followed by the self-assembly of 3-aminopropyltrimethoxysilane (APTMS). Subsequently, poly (ethylene glycol) (PEG) and fibronectin or fibronectin/heparin complex were sequentially immobilized on the modified surface. The results of attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) confirmed that the above molecules were successfully immobilized on the magnesium alloy surface. An excellent hydrophilic surface was obtained after the alkali heating treatment while the hydrophilicity decreased to some degree after the self-assembly of APTMS, the surface hydrophilicity was gradually improved again after the immobilization of PEG, fibronectin or fibronectin/heparin complex. The corrosion resistance of the control magnesium alloy was significantly improved by the alkali heating treatment. The self-assembly of APTMS and the following immobilization of PEG further enhanced the corrosion resistance of the substrates, however, the grafting of fibronectin or fibronectin/heparin complex slightly lowered the corrosion resistance. As compared to the pristine magnesium alloy, the samples modified by the immobilization of PEG and fibronectin/heparin complex presented better blood compatibility according to the results of hemolysis assay and platelet adhesion as well as the activated partial thromboplastin time (APTT). In addition, the modified substrates had better cytocompatibility to endothelial cells due to the improved anticorrosion and the introduction of fibronectin. The substrates modified by fibronectin or fibronectin/heparin complex can significantly promote endothelial cell adhesion and proliferation. Taking all these results into consideration, the method of the present study can be used for the surface modification of the magnesium alloy to simultaneously impart it better corrosion resistance, favorable blood compatibility and good cytocompatibility to endothelial cells. Copyright © 2016 Elsevier B.V. All rights reserved.

Self-assembling layers created by membrane proteins on gold.

PubMed

Shah, D S; Thomas, M B; Phillips, S; Cisneros, D A; Le Brun, A P; Holt, S A; Lakey, J H

2007-06-01

Membrane systems are based on several types of organization. First, amphiphilic lipids are able to create monolayer and bilayer structures which may be flat, vesicular or micellar. Into these structures membrane proteins can be inserted which use the membrane to provide signals for lateral and orientational organization. Furthermore, the proteins are the product of highly specific self-assembly otherwise known as folding, which mostly places individual atoms at precise places in three dimensions. These structures all have dimensions in the nanoscale, except for the size of membrane planes which may extend for millimetres in large liposomes or centimetres on planar surfaces such as monolayers at the air/water interface. Membrane systems can be assembled on to surfaces to create supported bilayers and these have uses in biosensors and in electrical measurements using modified ion channels. The supported systems also allow for measurements using spectroscopy, surface plasmon resonance and atomic force microscopy. By combining the roles of lipids and proteins, highly ordered and specific structures can be self-assembled in aqueous solution at the nanoscale.

An Investigation of the Effects of Self-Assembled Monolayers on Protein Crystallisation

PubMed Central

Zhang, Chen-Yan; Shen, He-Fang; Wang, Qian-Jin; Guo, Yun-Zhu; He, Jin; Cao, Hui-Ling; Liu, Yong-Ming; Shang, Peng; Yin, Da-Chuan

2013-01-01

Most protein crystallisation begins from heterogeneous nucleation; in practice, crystallisation typically occurs in the presence of a solid surface in the solution. The solid surface provides a nucleation site such that the energy barrier for nucleation is lower on the surface than in the bulk solution. Different types of solid surfaces exhibit different surface energies, and the nucleation barriers depend on the characteristics of the solid surfaces. Therefore, treatment of the solid surface may alter the surface properties to increase the chance to obtain protein crystals. In this paper, we propose a method to modify the glass cover slip using a self-assembled monolayer (SAM) of functional groups (methyl, sulfydryl and amino), and we investigated the effect of each SAM on protein crystallisation. The results indicated that both crystallisation success rate in a reproducibility study, and crystallisation hits in a crystallisation screening study, were increased using the SAMs, among which, the methyl-modified SAM demonstrated the most significant improvement. These results illustrated that directly modifying the crystallisation plates or glass cover slips to create surfaces that favour heterogeneous nucleation can be potentially useful in practical protein crystallisation, and the utilisation of a SAM containing a functional group can be considered a promising technique for the treatment of the surfaces that will directly contact the crystallisation solution. PMID:23749116

Self-assembling Gold Nanoparticle Monolayers in a Three-phase System - Overcoming Ligand Size Limitations

NASA Astrophysics Data System (ADS)

Yang, Guang; Nanda, Jagjit; Wang, Boya; Chen, Gang; Hallinan, Daniel T., Jr.

An effective self-assembly technique was developed to prepare centimeter-scale monolayer gold nanoparticle (Au NP) films of long-range order with hydrophobic ligands. Aqueous Au NPs were entrapped in the organic/aqueous interface where the Au NP surface was in situ modified with different types of amine ligands, including amine-terminated polystyrene. The Au NPs then spontaneously relocated to the air/water interface to form an NP monolayer. The spontaneous formation of an Au NP film at the organic/water interface was due to the minimization of the system Helmholtz free energy. Self-assembled Au NP films has a hexagonal close packed structure. The interparticle spacing was dictated by the amine ligand length. Thus-assembled Au NP monolayers exhibit tunable surface plasma resonance and excellent spacial homogeneity of surface-enhanced Raman-scattering. The ``air/water/oil'' self-assembly method developed in this study not only benefits the fundamental understanding of NP ligand conformations, but is also promising to scale up the manufacture of plasmonic nanoparticle devices with precisely designed optical properties. This study was financially supported by start-up funding supplied by the Florida State University and the FAMU-FSU College of Engineering.

Low-temperature poly(oxymethylene) direct bonding via self-assembled monolayer

NASA Astrophysics Data System (ADS)

Fu, Weixin; Ma, Bo; Kuwae, Hiroyuki; Shoji, Shuichi; Mizuno, Jun

2018-02-01

A direct bonding of poly(oxymethylene) (POM) was feasible at 100 °C by using self-assembled monolayer (SAM) as a surface modification method. (3-aminopropyl)triethoxysilane (APTES) and (3-glycidyloxypropyl)trimethoxysilane (GOPTS) were used in our work. X-ray photoelectron spectroscopy showed that both APTES and GOPTS modified the POM surface successfully. Bonding strength evaluation revealed that surface modification was affected by pretreatment (VUV/O3) process time. In addition, the bonding condition with highest strength had an average strength of 372 kPa. This technology is expected to be used in packaging for micro-/nano-electromechanical systems, such as biomedical devices.

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.

Self-Assembled N-Heterocyclic Carbene-Based Carboxymethylated Dextran Monolayers on Gold as a Tunable Platform for Designing Affinity-Capture Biosensor Surfaces.

PubMed

Li, Zhijun; Munro, Kim; Narouz, Mina R; Lau, Andrew; Hao, Hongxia; Crudden, Cathleen M; Horton, J Hugh

2018-05-30

Sensor surfaces play a predominant role in the development of optical biosensor technologies for the analysis of biomolecular interactions. Thiol-based self-assembled monolayers (SAMs) on gold have been widely used as linker layers for sensor surfaces. However, the degradation of the thiol-gold bond can limit the performance and durability of such surfaces, directly impacting their performance and cost-effectiveness. To this end, a new family of materials based on N-heterocyclic carbenes (NHCs) has emerged as an alternative for surface modification, capable of self-assembling onto a gold surface with higher affinity and superior stability as compared to the thiol-based systems. Here we demonstrate three applications of NHC SAMs supporting a dextran layer as a tunable platform for developing various affinity-capture biosensor surfaces. We describe the development and testing of NHC-based dextran biosensor surfaces modified with each of streptavidin, nitrilotriacetic acid, and recombinant Protein A. These affinity-capture sensor surfaces enable oriented binding of ligands for optimal performance in biomolecular assays. Together, the intrinsic high stability and flexible design of the NHC biosensing platforms show great promise and open up exciting possibilities for future biosensing applications.

Self-assembled Monolayer Mediated Surface Environment Modification of Poly(vinylpyrrolidone)-Coated Hollow Au-Ag Nanoshells for Enhanced Loading of Hydrophobic Drug and Efficient Multimodal Therapy.

PubMed

Jang, Hongje; Kim, Dong-Eun; Min, Dal-Hee

2015-06-17

Hollow Au-Ag bimetallic nanoshell possessing hydrophobic interior space and hydrophilic exterior surface was prepared and its application as a chemo-thermo-gene therapeutic agent based on its high payload of multiple drugs having different water solubility was demonstrated. The multifunctional drug delivery system is based on the hydrophobic interior created by the self-assembled monolayer (SAM) of hexanethiol onto the inner surface of the hollow metallic nanoshells whereas the outer surface was mostly coated by hydrophilic biocompatible polymer. The nanoshells having surface environment modified by hexanethiol SAMs provided high capacity both for hydrophilic DNAzyme (Dz) to induce gene silencing and for hydrophobic SN38 (7-ethyl-10-hydroxycamptothecin), anticancer drug. The release of the loaded Dz and SN38 was independently triggered by an acidic environment and by photothermal temperature elevation upon irradiation, respectively. The chemo-thermo-gene multitherapy based on the present nanoshells having modified surface environment showed high efficacy in quantitative cell-based assays using Huh7 human liver cell containing hepatitis C viral NS3 gene replicon RNA.

Mirror-finished superhydrophobic aluminum surfaces modified by anodic alumina nanofibers and self-assembled monolayers

NASA Astrophysics Data System (ADS)

Nakajima, Daiki; Kikuchi, Tatsuya; Natsui, Shungo; Suzuki, Ryosuke O.

2018-05-01

We demonstrate mirror-finished superhydrophobic aluminum surfaces fabricated via the formation of anodic alumina nanofibers and subsequent modification with self-assembled monolayers (SAMs). High-density anodic alumina nanofibers were formed on the aluminum surface via anodizing in a pyrophosphoric acid solution. The alumina nanofibers became tangled and bundled by further anodizing at low temperature because of their own weight, and the aluminum surface was completely covered by the long falling nanofibers. The nanofiber-covered aluminum surface exhibited superhydrophilic behavior, with a contact angle measuring less than 10°. As the nanofiber-covered aluminum surface was modified with n-alkylphosphonic acid SAMs, the water contact angle drastically shifted to superhydrophobicity, measuring more than 150°. The contact angle increased with the applied voltage during pyrophosphoric acid anodizing, the anodizing time, and the number of carbon atoms contained in the SAM molecules modified on the alumina nanofibers. By optimizing the anodizing and SAM-modification conditions, superhydrophobic behavior could be achieved with only a brief pyrophosphoric acid anodizing period of 3 min and subsequent simple immersion in SAM solutions. The superhydrophobic aluminum surface exhibited a high reflectance, measuring approximately 99% across most of the visible spectrum, similar to that of an electropolished aluminum surface. Therefore, our mirror-finished superhydrophobic aluminum surface based on anodic alumina nanofibers and SAMs can be used as a reflective mirror in various optical applications such as concentrated solar power systems.

Self-assembly of fatty acids on hydroxylated Al surface and effects of their stability on wettability and nanoscale organization.

PubMed

Liascukiene, Irma; Steffenhagen, Marie; Asadauskas, Svajus J; Lambert, Jean-François; Landoulsi, Jessem

2014-05-27

The self-assembly of fatty acids (FA) on the surfaces of inorganic materials is a relevant way to control their wetting properties. While the mechanism of adsorption on model flat substrate is well described in the literature, interfacial processes remain poorly documented on nanostructured surfaces. In this study, we report the self-assembly of a variety of FA on a hydroxylated Al surface which exhibits a random nanoscale organization. Our results revealed a peculiar fingerprint due to the FA self-assembly which consists in the formation of aligned nanopatterns in a state of hierarchical nanostructuration, regardless of the molecular structure of the FA (chain length, level of unsaturation). After a significant removal of adsorbed FA using UV/O3 treatment, a complete wetting was reached, and a noticeable disturbance of the surface morphology was observed, evidencing the pivotal role of FA molecules to maintain these nanostructures. The origin of wetting properties was investigated prior to and after conditioning of FA-modified samples taking into account key parameters, namely the surface roughness and its composition. For this purpose, the Wenzel roughness, defined as the third moment of power spectral density, was used, as it is sensitive to high spatial frequency and thus to the obtained hierarchical level of nanostructuration. Our results revealed that no correlation can be made between water contact angles (θ(w)) and the Wenzel roughness. By contrast, θ(w) strongly increased with the amount of -CHx- groups exhibited by adsorbed FA. These findings suggest that the main origin of hydrophobization is the presence of self-assembled molecules and that the surface roughness has only a small contribution to the wettability.

Fiber Surface Modification Technology for Fiber-Optic Localized Surface Plasmon Resonance Biosensors

PubMed Central

Zhang, Qiang; Xue, Chenyang; Yuan, Yanling; Lee, Junyang; Sun, Dong; Xiong, Jijun

2012-01-01

Considerable studies have been performed on the development of optical fiber sensors modified by gold nanoparticles based on the localized surface plasmon resonance (LSPR) technique. The current paper presents a new approach in fiber surface modification technology for biosensors. Star-shaped gold nanoparticles obtained through the seed-mediated solution growth method were found to self-assemble on the surface of tapered optical fibers via amino- and mercapto-silane coupling agents. Transmitted power spectra of 3-aminopropyltrimethoxy silane (APTMS)-modified fiber were obtained, which can verify that the silane coupling agent surface modification method is successful. Transmission spectra are characterized in different concentrations of ethanol and gentian violet solutions to validate the sensitivity of the modified fiber. Assembly using star-shaped gold nanoparticles and amino/mercapto silane coupling agent are analyzed and compared. The transmission spectra of the gold nanoparticles show that the nanoparticles are sensitive to the dielectric properties of the surrounding medium. After the fibers are treated in t-dodecylmercaptan to obtain their transmission spectra, APTMS-modified fiber becomes less sensitive to different media, except that modified by 3-mercaptopropyltrimethoxy silane (MPTMS). Experimental results of the transmission spectra show that the surface modified by the gold nanoparticles using MPTMS is firmer compared to that obtained using APTMS. PMID:22736974

Adsorption at air-water and oil-water interfaces and self-assembly in aqueous solution of ethoxylated polysorbate nonionic surfactants.

PubMed

Penfold, Jeffrey; Thomas, Robert K; Li, Peixun X; Petkov, Jordan T; Tucker, Ian; Webster, John R P; Terry, Ann E

2015-03-17

The Tween nonionic surfactants are ethoxylated sorbitan esters, which have 20 ethylene oxide groups attached to the sorbitan headgroup and a single alkyl chain, lauryl, palmityl, stearyl, or oleyl. They are an important class of surfactants that are extensively used in emulsion and foam stabilization and in applications associated with foods, cosmetics and pharmaceuticals. A range of ethoxylated polysorbate surfactants, with differing degrees of ethoxylation from 3 to 50 ethylene oxide groups, have been synthesized and characterized by neutron reflection, small-angle neutron scattering, and surface tension. In conjunction with different alkyl chain groups, this provides the opportunity to modify their surface properties, their self-assembly in solution, and their interaction with macromolecules, such as proteins. Adsorption at the air-water and oil-water interfaces and solution self-assembly of the range of ethoxylated polysorbate surfactants synthesized are presented and discussed.

Lipid membrane-assisted condensation and assembly of amphiphilic Janus particles

DOE PAGES

Chambers, Mariah; Mallory, Stewart Anthony; Malone, Heather; ...

2016-01-01

Amphiphilic Janus particles self-assemble into complex metastructures, but little is known about how their assembly might be modified by weak interactions with a nearby biological membrane surface. Here, we report an integrated experimental and molecular dynamics simulation study to investigate the self-assembly of amphiphilic Janus particles on a lipid membrane. We created an experimental system in which Janus particles are allowed to self-assemble in the same medium where zwitterionic lipids form giant unilamellar vesicles (GUVs). Janus particles spontaneously concentrated on the inner leaflet of the GUVs. They exhibited biased orientation and heterogeneous rotational dynamics as revealed by single particle rotationalmore » tracking. The combined experimental and simulation results show that Janus particles concentrate on the lipid membranes due to weak particle–lipid attraction, whereas the biased orientation of particles is driven predominantly by inter-particle interactions. Furthermore, this study demonstrates the potential of using lipid membranes to influence the self-assembly of Janus particles.« less

Determination of low levels of cadmium ions by the under potential deposition on a self-assembled monolayer on gold electrode.

PubMed

Noyhouzer, Tomer; Mandler, Daniel

2011-01-17

The electrochemical determination of low levels of Cd using a self-assembled monolayer (SAM) modified Au electrode is reported. Determination was based on the stripping of Cd, which was deposited by under potential deposition (UPD). A series of short alkanethiol SAMs bearing different end groups, i.e., sulfonate, carboxylate and ammonium, were examined. Lowest level of detection (ca. 50 ngL(-1)) was achieved with a 3-mercaptopropionic acid (MPA) monolayer using subtractive anodic square wave voltammetry (SASV). Additional surface methods, namely, reductive desorption and X-ray photoelectron spectroscopy, were applied to determine the interfacial structure of the electrodeposited Cd on the modified electrodes. We conclude that the deposited Cd forms a monoatomic layer, which bridges between the gold surface and the alkanethiol monolayer associating with both the gold and the sulfur atoms. Copyright © 2010 Elsevier B.V. All rights reserved.

Controlled doping by self-assembled dendrimer-like macromolecules

NASA Astrophysics Data System (ADS)

Wu, Haigang; Guan, Bin; Sun, Yingri; Zhu, Yiping; Dan, Yaping

2017-02-01

Doping via self-assembled macromolecules might offer a solution for developing single atom electronics by precisely placing individual dopants at arbitrary location to meet the requirement for circuit design. Here we synthesize dendrimer-like polyglycerol macromolecules with each carrying one phosphorus atom in the core. The macromolecules are immobilized by the coupling reagent onto silicon surfaces that are pre-modified with a monolayer of undecylenic acid. Nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) are employed to characterize the synthesized macromolecules and the modified silicon surfaces, respectively. After rapid thermal annealing, the phosphorus atoms carried by the macromolecules diffuse into the silicon substrate, forming dopants at a concentration of 1017 cm-3. Low-temperature Hall effect measurements reveal that the ionization process is rather complicated. Unlike the widely reported simple ionization of phosphorus dopants, nitrogen and carbon are also involved in the electronic activities in the monolayer doped silicon.

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

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.

Characterization of Self-Assembled Monolayers on a Ruthenium Surface

PubMed Central

2017-01-01

We have modified and stabilized the ruthenium surface by depositing a self-assembled monolayer (SAM) of 1-hexadecanethiol on a polycrystalline ruthenium thin film. The growth mechanism, dynamics, and stability of these monolayers were studied. SAMs, deposited under ambient conditions, on piranha-cleaned and piranha + H2SO4 cleaned substrates were compared to monolayers formed on H-radical-cleaned Ru surfaces. We found that alkanethiols on H-radical-cleaned Ru formed densely packed monolayers that remained stable when kept in a nitrogen atmosphere. X-ray photoelectron spectroscopy (XPS) shows a distinct sulfur peak (BE = 162.3 eV), corresponding to metal–sulfur bonding. When exposed to ambient conditions, the SAM decayed over a period of hours. PMID:28585831

Interactions of doxorubicin with self-assembled monolayer-modified electrodes: electrochemical, surface plasmon resonance (SPR), and gravimetric studies.

PubMed

Nieciecka, Dorota; Krysinski, Pawel

2011-02-01

We present the results on the partitioning of doxorubicin (DOX), a potent anticancer drug, through the model membrane system, self-assembled monolayers (SAMs) on gold electrodes. The monolayers were formed from alkanethiols of comparable length with different ω-terminal groups facing the aqueous electrolyte: the hydrophobic -CH(3) groups for the case of dodecanethiol SAMs or hydrophilic -OH groups of mercaptoundecanol SAMs. The electrochemical experiments combined with the surface plasmon resonance (SPR) and gravimetric studies show that doxorubicin is likely adsorbed onto the surface of hydrophilic monolayer, while for the case of the hydrophobic one the drug mostly penetrates the monolayer moiety. The adsorption of the drug hinders further penetration of doxorubicin into the monolayer moiety.

Self-assembling triblock proteins for biofunctional surface modification

NASA Astrophysics Data System (ADS)

Fischer, Stephen E.

Despite the tremendous promise of cell/tissue engineering, significant challenges remain in engineering functional scaffolds to precisely regulate the complex processes of tissue growth and development. As the point of contact between the cells and the scaffold, the scaffold surface plays a major role in mediating cellular behaviors. In this dissertation, the development and utility of self-assembling, artificial protein hydrogels as biofunctional surface modifiers is described. The design of these recombinant proteins is based on a telechelic triblock motif, in which a disordered polyelectrolyte central domain containing embedded bioactive ligands is flanked by two leucine zipper domains. Under moderate conditions of temperature and pH, the leucine zipper end domains form amphiphilic alpha-helices that reversibly associate into homo-trimeric aggregates, driving hydrogel formation. Moreover, the amphiphilic nature of these helical domains enables surface adsorption to a variety of scaffold materials to form biofunctional protein coatings. The nature and stability of these coatings in various solution conditions, and their interaction with mammalian cells is the primary focus of this dissertation. In particular, triblock protein coatings functionalized with cell recognition sequences are shown to produce well-defined surfaces with precise control over ligand density. The impact of this is demonstrated in multiple cell types through ligand density-dependent cell-substrate interactions. To improve the stability of these physically self-assembled coatings, two covalent crosslinking strategies are described---one in which a zero-length chemical crosslinker (EDC) is utilized and a second in which disulfide bonds are engineered into the recombinant proteins. These targeted crosslinking approaches are shown to increase the stability of surface adsorbed protein layers with minimal effect on the presentation of many bioactive ligands. Finally, to demonstrate the versatility of the triblock protein hydrogels, and the ease of introducing multiple functionalities to a substrate surface, a surface coating is tailored for neural stem cell culture in order to improve proliferation on the scaffold, while maintaining the stem cell phenotype. These studies demonstrate the unique advantages of genetic engineering over traditional techniques for surface modification. In addition to their unmatched sequence fidelity, recombinant proteins can easily be modified with bioactive ligands and their organization into coherent, supramolecular structures mimics natural self-assembly processes.

pH-Sensitive Reversible Programmed Targeting Strategy by the Self-Assembly/Disassembly of Gold Nanoparticles.

PubMed

Ma, Jinlong; Hu, Zhenpeng; Wang, Wei; Wang, Xinyu; Wu, Qiang; Yuan, Zhi

2017-05-24

A reversible programmed targeting strategy could achieve high tumor accumulation due to its long blood circulation time and high cellular internalization. Here, targeting ligand-modified poly(ethylene glycol) (PEG-ligand), dibutylamines (Bu), and pyrrolidinamines (Py) were introduced on the surface of gold nanoparticles (Au NPs) for reversible shielding/deshielding of the targeting ligands by pH-responsive self-assembly. Hydrophobic interaction and steric repulsion are the main driving forces for the self-assembly/disassembly of Au NPs. The precise self-assembly (pH ≥ 7.2) and disassembly (pH ≤ 6.8) of Au NPs with different ligands could be achieved by fine-tuning the modifying molar ratio of Bu and Py (R m ), which followed the formula R m = 1/(-0.0013X 2 + 0.0323X + 1), in which X is the logarithm of the partition coefficient of the targeting ligand. The assembled/disassembled behavior of Au NPs at pH 7.2 and 6.8 was confirmed by transmission electron microscopy and dynamic light scattering. Enzyme-linked immunosorbent assays and cellular uptake studies showed that the ligands could be buried inside the assembly and exposed when disassembled. More importantly, this process was reversible, which provides the possibility of prolonging blood circulation by shielding ligands associated with the NPs that were effused from tumor tissue.

Polycatenar Ligand Control of the Synthesis and Self-Assembly of Colloidal Nanocrystals.

PubMed

Diroll, Benjamin T; Jishkariani, Davit; Cargnello, Matteo; Murray, Christopher B; Donnio, Bertrand

2016-08-24

Hydrophobic colloidal nanocrystals are typically synthesized and manipulated with commercially available ligands, and surface functionalization is therefore typically limited to a small number of molecules. Here, we report the use of polycatenar ligands derived from polyalkylbenzoates for the direct synthesis of metallic, chalcogenide, pnictide, and oxide nanocrystals. Polycatenar molecules, branched structures bearing diverging chains in which the terminal substitution pattern, functionality, and binding group can be independently modified, offer a modular platform for the development of ligands with targeted properties. Not only are these ligands used for the direct synthesis of monodisperse nanocrystals, but nanocrystals coated with polycatenar ligands self-assemble into softer bcc superlattices that deviate from conventional harder close-packed structures (fcc or hcp) formed by the same nanocrystals coated with commercial ligands. Self-assembly experiments demonstrate that the molecular structure of polycatenar ligands encodes interparticle spacings and attractions, engineering self-assembly, which is tunable from hard sphere to soft sphere behavior.

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

NASA Astrophysics Data System (ADS)

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

2010-11-01

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

Organosilane self-assembled layers (SAMs) and hybrid silicate magnesium-rich primers for the corrosion protection of aluminum alloy 2024 T3

NASA Astrophysics Data System (ADS)

Wang, Duhua

Although current chromate coatings function very well in corrosion protection for aircraft alloys, such as aluminum alloy 2024 T3, the U.S. Environmental Protection Agency is planning to totally ban the use of chromates as coating materials in the next decade or so because of their extremely toxic effect. For this purpose, both self-assembled layers and silicate magnesium-rich primers were tested to provide the corrosion protection for aluminum alloy. The long-term goal of this research is to develop a coating system to replace the current chromate coating for aircraft corrosion protection. Aluminum alloy 2024 T3 substrates were modified with self-assembled monolayer or multilayer thin films from different alkylsilane compounds. Mono-functional silanes, such as octadecyltrichlorosilane (C18SiCl3), can form a mixed hydrophobic monolayer or multilayer thin film on the aluminum oxide surface to provide a barrier to water and other electrolytes, so the corrosion resistance of the SAMs modified surface was increased significantly. On the other hand, the bi-functional silane self-assembly could attach the aluminum surface through the silicon headgroup while using its functional tailgroup to chemically bond the polymer coating, thus improving the adhesion between the aluminum substrate and coating substantially, and seems to contribute more to corrosion protection of aluminum substrate. Organosilanes were also combined with tetraethyl orthosilicate (TEOS) in propel ratios to form a sol-gel binder to make silicate magnesium-rich primers. Analogue to the inorganic zinc-rich coatings, the silicate magnesium-rich primers also showed excellent adhesion and solvent resistance. The sacrificial magnesium pigments and the chemically inert silicate binder both contribute to the anti-corrosion properties. Future studies will be focused on the formula optimization for better toughness, chemical resistance and anticorrosion performance.

Calculation of Quasi-Particle Energies of Aromatic Self-Assembled Monolayers on Au(111).

PubMed

Li, Yan; Lu, Deyu; Galli, Giulia

2009-04-14

We present many-body perturbation theory calculations of the electronic properties of phenylene diisocyanide self-assembled monolayers (SAMs) on a gold surface. Using structural models obtained within density functional theory (DFT), we have investigated how the SAM molecular energies are modified by self-energy corrections and how they are affected by the presence of the surface. We have employed a combination of GW (G = Green's function; W = screened Coulomb interaction) calculations of the SAM quasi-particle energies and a semiclassical image potential model to account for surface polarization effects. We find that it is essential to include both quasi-particle corrections and surface screening in order to provide a reasonable estimate of the energy level alignment at a SAM-metal interface. In particular, our results show that within the GW approximation the energy distance between phenylene diisocyanide SAM energy levels and the gold surface Fermi level is much larger than that found within DFT, e.g., more than double in the case of low packing densities of the SAM.

Self-assembled biomimetic superhydrophobic CaCO3 coating inspired from fouling mineralization in geothermal water.

PubMed

Wang, Gong G; Zhu, Li Q; Liu, Hui C; Li, Wei P

2011-10-18

Inspired from fouling self-mineralization in geothermal water, a novel biomimetic cactuslike CaCO(3) coating with superhydrophobic features is reported in this letter. The structure, morphologies, and phases of the CaCO(3) coating were characterized by X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, and infrared spectrophotometry. After prenucleation treatment, a continuous cactuslike CaCO(3) coating with hierarchical nano- and microstructures was self-assembled on stainless steel surfaces after immersion in simulated geothermal water at 50 °C for 48 h. After being modified with a low-surface-energy monolayer of sodium stearate, the as-prepared coating exhibited superhydrophobic properties with a water contact angle of 158.9° and a sliding angle of 2°. Therefore, this work might open up a new application field of geothermal resources and provide insight into designing multidimensional structures with functional applications, including superhydrophobic surfaces. © 2011 American Chemical Society

Self-Assembled Monolayers for Dental Implants

PubMed Central

Correa-Uribe, Alejandra

2018-01-01

Implant-based therapy is a mature approach to recover the health conditions of patients affected by edentulism. Thousands of dental implants are placed each year since their introduction in the 80s. However, implantology faces challenges that require more research strategies such as new support therapies for a world population with a continuous increase of life expectancy, to control periodontal status and new bioactive surfaces for implants. The present review is focused on self-assembled monolayers (SAMs) for dental implant materials as a nanoscale-processing approach to modify titanium surfaces. SAMs represent an easy, accurate, and precise approach to modify surface properties. These are stable, well-defined, and well-organized organic structures that allow to control the chemical properties of the interface at the molecular scale. The ability to control the composition and properties of SAMs precisely through synthesis (i.e., the synthetic chemistry of organic compounds with a wide range of functional groups is well established and in general very simple, being commercially available), combined with the simple methods to pattern their functional groups on complex geometry appliances, makes them a good system for fundamental studies regarding the interaction between surfaces, proteins, and cells, as well as to engineering surfaces in order to develop new biomaterials. PMID:29552036

A novel fullerene lipoic acid derivative: Synthesis and preparation of self-assembled monolayers on gold

NASA Astrophysics Data System (ADS)

Viana, A. S.; Leupold, S.; Eberle, C.; Shokati, T.; Montforts, F.-P.; Abrantes, L. M.

2007-11-01

Synthesis and preparation of self-assembled monolayers of a novel fullerene lipoic acid derivative on gold are reported. The presence of densely packed SAMs was confirmed by ellipsometry and cyclic voltammetry. The electrochemical response of the modified electrode in organic media exhibits the first two redox peaks characteristic of the extended π-electron system of fullerene. C 60 surface coverage (1.4 × 10 -10 mol cm -2) has been electrochemically determined by the redox process of the adsorbed fullerene moiety and by reductive desorption of the SAM in strong alkaline solution. Electrochemical data indicate that all four sulphur atoms are involved in the self-assembly process, providing an increase of SAM stability in comparison to mono or di-thiolated appended molecules. Visualisation of discrete fullerene molecules by scanning tunnelling microscopy supplied further evidence for gold modification and molecular distribution on the surface. Mixed monolayers of hexanethiol and fullerene derivatives in a proportion of 1:2 have been also studied with the purpose of controlling the amount and distribution of fullerene units on the gold surface.

Surface modification of poly(L-lactic acid) to improve its cytocompatibility via assembly of polyelectrolytes and gelatin.

PubMed

Lin, Yuan; Wang, Luling; Zhang, Peibiao; Wang, Xin; Chen, Xuesi; Jing, Xiabin; Su, Zhaohui

2006-03-01

Poly(L-lactide) (PLLA) surface was modified via aminolysis by poly(allylamine hydrochloride) (PAH) at high pH and subsequent electrostatic self-assembly of poly(sodium styrenesulfonate) (PSS) and PAH, and the process was monitored by X-ray photoelectron spectroscopy (XPS) and contact angle measurement. These modified PLLAs were then used as charged substrates for further incorporation of gelatin to improve their cytocompatibility. The amphoteric nature of the gelatin was exploited and the gelatin was adsorbed to the negatively charged PLLA/PSS and positively charged PLLA/PAH at pH=3.4 and 7.4, respectively. XPS and water contact angle data indicated that the gelatin adsorption at pH=3.4 resulted in much higher surface coverage by gelatin than at pH=7.4. All the modified PLLA surfaces became more hydrophilic than the virgin PLLA. Chondrocyte culture was used to test the cell attachment, cell morphology and cell viability on the modified PLLA substrates. The results showed that the PAH and PSS modified PLLA exhibited better cytocompatibility than virgin PLLA, and the incorporation of the gelatin on these modified PLLA substrates further improved their cytocompatibility, with the PLLA/PSS substrate treated with the gelatin at pH=3.4 being the best, exceeding the chondrocyte compatibility of the tissue culture polystyrene.

Self-assembled structures of hydroxyapatite in the biomimetic coating on a bioinert ceramic substrate.

PubMed

Chakraborty, Jui; Sarkar, Soumi Dey; Chatterjee, Saradiya; Sinha, Mithlesh Kumar; Basu, Debabrata

2008-10-15

The tribological properties of alumina ceramic are excellent due in part to a high wettability because of the hydrophilic surface and fluid film lubrication that minimizes the adhesive wear. Such surfaces are further modified with bioactive glass/ceramic coating to promote direct bone apposition in orthopedic applications. The present communication reports the biomimetic coating of calcium hydroxyapatite (HAp) on dense (2-3% porosity) alumina (alpha-Al(2)O(3)) substrate (1cm x 1cm x 0.5 cm), at 37 degrees C. After a total period of 6 days immersion in simulated body fluid (SBF), at 37 degrees C, linear self-assembled porous (pore size: approximately 0.2 microm) structures (length: approximately 375.39 microm and width: 5-6 microm) of HAp were obtained. The phenomenon has been demonstrated by self-assembly and diffusion-limited aggregation (DLA) principles. Structural and compositional characterization of the coating was carried out using SEM with EDX facility, XRD and FT-IR data.

Method of making gold thiolate and photochemically functionalized microcantilevers

DOEpatents

Boiadjiev, Vassil I [Knoxville, TN; Brown, Gilbert M [Knoxville, TN; Pinnaduwage, Lal A [Knoxville, TN; Thundat, Thomas G [Knoxville, TN; Bonnesen, Peter V [Knoxville, TN; Goretzki, Gudrun [Nottingham, GB

2009-08-25

Highly sensitive sensor platforms for the detection of specific reagents, such as chromate, gasoline and biological species, using microcantilevers and other microelectromechanical systems (MEMS) whose surfaces have been modified with photochemically attached organic monolayers, such as self-assembled monolayers (SAM), or gold-thiol surface linkage are taught. The microcantilever sensors use photochemical hydrosilylation to modify silicon surfaces and gold-thiol chemistry to modify metallic surfaces thereby enabling individual microcantilevers in multicantilever array chips to be modified separately. Terminal vinyl substituted hydrocarbons with a variety of molecular recognition sites can be attached to the surface of silicon via the photochemical hydrosilylation process. By focusing the activating UV light sequentially on selected silicon or silicon nitride hydrogen terminated surfaces and soaking or spotting selected metallic surfaces with organic thiols, sulfides, or disulfides, the microcantilevers are functionalized. The device and photochemical method are intended to be integrated into systems for detecting specific agents including chromate groundwater contamination, gasoline, and biological species.

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.

Mussel-inspired bioceramics with self-assembled Ca-P/polydopamine composite nanolayer: preparation, formation mechanism, improved cellular bioactivity and osteogenic differentiation of bone marrow stromal cells.

PubMed

Wu, Chengtie; Han, Pingping; Liu, Xiaoguo; Xu, Mengchi; Tian, Tian; Chang, Jiang; Xiao, Yin

2014-01-01

The nanostructured surface of biomaterials plays an important role in improving their in vitro cellular bioactivity as well as stimulating in vivo tissue regeneration. Inspired by the mussel's adhesive versatility, which is thought to be due to the plaque-substrate interface being rich in 3,4-dihydroxy-l-phenylalamine (DOPA) and lysine amino acids, in this study we developed a self-assembly method to prepare a uniform calcium phosphate (Ca-P)/polydopamine composite nanolayer on the surface of β-tricalcium phosphate (β-TCP) bioceramics by soaking β-TCP bioceramics in Tris-dopamine solution. It was found that the addition of dopamine, reaction temperature and reaction time are three key factors inducing the formation of a uniform Ca-P/polydopamine composite nanolayer. The formation mechanism of a Ca-P/polydopamine composite nanolayer involved two important steps: (i) the addition of dopamine to Tris-HCl solution decreases the pH value and accelerates Ca and P ionic dissolution from the crystal boundaries of β-TCP ceramics; (ii) dopamine is polymerized to form self-assembled polydopamine film and, at the same time, nanosized Ca-P particles are mineralized with the assistance of polydopamine, in which the formation of polydopamine occurs simultaneously with Ca-P mineralization (formation of nanosized microparticles composed of calcium phosphate-based materials), and finally a self-assembled Ca-P/polydopamine composite nanolayer forms on the surface of the β-TCP ceramics. Furthermore, the formed self-assembled Ca-P/polydopamine composite nanolayer significantly enhances the surface roughness and hydrophilicity of β-TCP ceramics, and stimulates the attachment, proliferation, alkaline phosphate (ALP) activity and bone-related gene expression (ALP, OCN, COL1 and Runx2) of human bone marrow stromal cells. Our results suggest that the preparation of self-assembled Ca-P/polydopamine composite nanolayers is a viable method to modify the surface of biomaterials by significantly improving their surface physicochemical properties and cellular bioactivity for bone regeneration application. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Modular Self-Assembly of Protein Cage Lattices for Multistep Catalysis

DOE PAGES

Uchida, Masaki; McCoy, Kimberly; Fukuto, Masafumi; ...

2017-11-13

The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here, we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy: the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from anmore » amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme-packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. As a result, this study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales and exhibits properties and function that arise from the interaction between individual building blocks.« less

Modular Self-Assembly of Protein Cage Lattices for Multistep Catalysis

PubMed Central

Uchida, Masaki; McCoy, Kimberly; Fukuto, Masafumi; Yang, Lin; Yoshimura, Hideyuki; Miettinen, Heini M.; LaFrance, Ben; Patterson, Dustin P.; Schwarz, Benjamin; Karty, Jonathan A.; Prevelige, Peter E.; Lee, Byeongdu; Douglas, Trevor

2018-01-01

The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy; the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from an amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles, and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. This study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales, and exhibits properties and function that arise from the interaction between individual building blocks. PMID:29131580

Modular Self-Assembly of Protein Cage Lattices for Multistep Catalysis

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

Uchida, Masaki; McCoy, Kimberly; Fukuto, Masafumi

The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here, we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy: the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from anmore » amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme-packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. As a result, this study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales and exhibits properties and function that arise from the interaction between individual building blocks.« less

“Click” Synthesis of Dextran Macrostructures for Combinatorial-Designed Self-Assembled Nanoparticles Encapsulating Diverse Anticancer Therapeutics

PubMed Central

Abeylath, Sampath C.; Amiji, Mansoor

2011-01-01

With the non-specific toxicity of anticancer drugs to healthy tissues upon systemic administration, formulations capable of enhanced selectivity in delivery to the tumor mass and cells are highly desirable. Based on the diversity of the drug payloads, we have investigated a combinatorial-designed strategy where the nano-sized formulations are tailored based on the physicochemical properties of the drug and the delivery needs. Individually functionalized C2 to C12 lipid-, thiol-, and poly(ethylene glycol) (PEG)-modified dextran derivatives were synthesized via “click” chemistry from O-pentynyl dextran and relevant azides. These functionalized dextrans in combination with anticancer drugs form nanoparticles by self-assembling in aqueous medium having PEG surface functionalization and intermolecular disulfide bonds. Using anticancer drugs with logP values ranging from −0.5 to 3.0, the optimized nanoparticles formulations were evaluated for preliminary cellular delivery and cytotoxic effects in SKOV3 human ovarian adenocarcinoma cells. The results show that with the appropriate selection of lipid-modified dextran, one can effectively tailor the self-assembled nano-formulation for intended therapeutic payload. PMID:21978947

Ordered CdSe nanoparticles within self-assembled block copolymer domains on surfaces.

PubMed

Zou, Shan; Hong, Rui; Emrick, Todd; Walker, Gilbert C

2007-02-13

Hierarchical, high-density, ordered patterns were fabricated on Si substrates by self-assembly of CdSe nanoparticles within approximately 20-nm-thick diblock copolymer films in a controlled manner. Surface-modified CdSe nanoparticles formed well-defined structures within microphase-separated polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) domains. Trioctylphosphine oxide (TOPO)-coated CdSe nanoparticles were incorporated into PS domains and polyethylene glycol-coated CdSe nanoparticles were located primarily in the P2VP domains. Nearly close-packed CdSe nanoparticles were clearly identified within the highly ordered patterns on Si substrates by scanning electron microscopy (SEM). Contact angle measurements together with SEM results indicate that TOPO-CdSe nanoparticles were partially placed at the air/copolymer interface.

Spiropyran-Decorated SiO₂-Pt Janus Micromotor: Preparation and Light-Induced Dynamic Self-Assembly and Disassembly.

PubMed

Zhang, Qilu; Dong, Renfeng; Chang, Xueyi; Ren, Biye; Tong, Zhen

2015-11-11

The controlled self-assembly of self-propelled Janus micromotors may give the micromotors some potential applications in many fields. In this work, we design a kind of SiO2-Pt Janus catalytic micromotor functionalized by spiropyran (SP) moieties on the surface of the SiO2 hemisphere. The spiropyran-modified SiO2-Pt Janus micromotor exhibits autonomous self-propulsion in the presence of hydrogen peroxide fuel in N,N-dimethylformamide (DMF)/H2O (1:1 in volume) mixture. We demonstrate that the self-propelled Janus micromotors can dynamically assemble into multiple motors because of the electrostatic attractions and π-π stacking between MC molecules induced by UV light irradiation (λ = 365 nm) and also quickly disassemble into mono motors when the light is switched to green light (λ = 520 nm) for the first time. Furthermore, the assembled Janus motors can move together automatically with different motion patterns propelled by the hydrogen peroxide fuels upon UV irradiation. The work provides a new approach not only to the development of the potential application of Janus motors but also to the fundamental science of reversible self-assembly and disassembly of Janus micromotors.

Stacking the Deck: Leveraging Surface Interactions to Tune Interfacial Electronic Structure

NASA Astrophysics Data System (ADS)

Maughan, Bret; Eads, Calley; Zahl, Percy; Sutter, Peter; Monti, Oliver

We present results from a series of experiments aimed at understanding and controlling molecular interactions in phthalocyanine (Pc) thin-films on Cu(110) to tailor the interfacial electronic structure. Using low-temperature scanning tunneling microscopy (LT-STM), we identify interactions that drive surface-molecule coupling, molecular self-assembly and thin-film order. We provide evidence that interactions with native Cu adatoms play a pivotal role in self-assembly of Pc systems, along with anisotropic nanoribbon growth dynamics, supported by an agent-based kinetic Monte Carlo (AB-KMC) simulation. We show further that self-assembled nanoribbon length can be controlled using surface diffusion barriers and that ordered 2D thin-film growth is promoted by diminishing surface-molecule interactions that otherwise dominate native Cu(110) interfaces. Altogether, this detailed structural understanding allows us to interpret interfacial electronic structure and dynamics, uncovered through ultraviolet (UPS) and two-photon photoemission (2PPE) spectroscopy experiments, in molecular configuration-specific detail. In all, our understanding of interfacial processes guides strategic modifications to both surface and molecule to harness interfacial interactions and thereby modify the collective electronic structure of the interface. NSF No. CHE-1213243 and No. CHE-1565497, Arizona TRIF, DOE/BNL Cntrct No. DE-SC0012704, and DOE No. DE-SC0016343.

Surface Functionalization of Diamond Films by Photoreaction of Elemental Sulfur and Their Surface Properties

NASA Astrophysics Data System (ADS)

Nakamura, Takako; Ohana, Tsuguyori

2012-08-01

A useful method for direct sulfurization of diamond film surfaces by photoreaction of elemental sulfur was developed. The introduction of thiol groups onto the diamond films was confirmed by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, and scanning electron microscopy (SEM) analyses. The sulfur-modified diamond films attached to gold nanoparticles by self-assembly. The degrees of thiol group introduction and gold attachment were found to depend on photoirradiation time by monitoring by XPS. The gold-modified diamond film was observed to act as a surface-enhanced Raman scattering substrate for measurement of picric acid.

Reducing Staphylococcus aureus biofilm formation on stainless steel 316L using functionalized self-assembled monolayers

PubMed Central

Kruszewski, Kristen M; Nistico, Laura; Longwell, Mark J; Hynes, Matthew J; Maurer, Joshua A

2013-01-01

Stainless steel 316L (SS316L) is a common material used in orthopedic implants. Bacterial colonization of the surface and subsequent biofilm development can lead to refractory infection of the implant. Since the greatest risk of infection occurs perioperatively, strategies that reduce bacterial adhesion during this time are important. As a strategy to limit bacterial adhesion and biofilm formation on SS316L, self-assembled monolayers (SAMs) were used to modify the SS316L surface. SAMs with long alkyl chains terminated with hydrophobic (-CH3) or hydrophilic (oligoethylene glycol) tail groups were used to form coatings and in an orthogonal approach, SAMs were used to immobilize gentamicin or vancomycin on SS316L for the first time to form an “active” antimicrobial coating to inhibit early biofilm development. Modified SS316L surfaces were characterized using surface infrared spectroscopy, contact angles, MALDI-TOF mass spectrometry and atomic force microscopy. The ability of SAM-modified SS316L to retard biofilm development by Staphylococcus aureus was functionally tested using confocal scanning laser microscopy with COMSTAT image analysis, scanning electron microscopy and colony forming unit analysis. Neither hydrophobic nor hydrophilic SAMs reduced biofilm development. However, gentamicin-linked and vancomycin-linked SAMs significantly reduced S. aureus biofilm formation for up to 24 and 48 hours, respectively. PMID:23498233

Reducing Staphylococcus aureus biofilm formation on stainless steel 316L using functionalized self-assembled monolayers.

PubMed

Kruszewski, Kristen M; Nistico, Laura; Longwell, Mark J; Hynes, Matthew J; Maurer, Joshua A; Hall-Stoodley, Luanne; Gawalt, Ellen S

2013-05-01

Stainless steel 316L (SS316L) is a common material used in orthopedic implants. Bacterial colonization of the surface and subsequent biofilm development can lead to refractory infection of the implant. Since the greatest risk of infection occurs perioperatively, strategies that reduce bacterial adhesion during this time are important. As a strategy to limit bacterial adhesion and biofilm formation on SS316L, self-assembled monolayers (SAMs) were used to modify the SS316L surface. SAMs with long alkyl chains terminated with hydrophobic (-CH3) or hydrophilic (oligoethylene glycol) tail groups were used to form coatings and in an orthogonal approach, SAMs were used to immobilize gentamicin or vancomycin on SS316L for the first time to form an "active" antimicrobial coating to inhibit early biofilm development. Modified SS316L surfaces were characterized using surface infrared spectroscopy, contact angles, MALDI-TOF mass spectrometry and atomic force microscopy. The ability of SAM-modified SS316L to retard biofilm development by Staphylococcus aureus was functionally tested using confocal scanning laser microscopy with COMSTAT image analysis, scanning electron microscopy and colony forming unit analysis. Neither hydrophobic nor hydrophilic SAMs reduced biofilm development. However, gentamicin-linked and vancomycin-linked SAMs significantly reduced S. aureus biofilm formation for up to 24 and 48 h, respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

Effects of self-assembled monolayer structural order, surface homogeneity and surface energy on pentacene morphology and thin film transistor device performance.

PubMed

Hutchins, Daniel Orrin; Weidner, Tobias; Baio, Joe; Polishak, Brent; Acton, Orb; Cernetic, Nathan; Ma, Hong; Jen, Alex K-Y

2013-01-04

A systematic study of six phosphonic acid (PA) self-assembled monolayers (SAMs) with tailored molecular structures is performed to evaluate their effectiveness as dielectric modifying layers in organic field-effect transistors (OFETs) and determine the relationship between SAM structural order, surface homogeneity, and surface energy in dictating device performance. SAM structures and surface properties are examined by near edge X-ray absorption fine structure (NEXAFS) spectroscopy, contact angle goniometry, and atomic force microscopy (AFM). Top-contact pentacene OFET devices are fabricated on SAM modified Si with a thermally grown oxide layer as a dielectric. For less ordered methyl- and phenyl-terminated alkyl ~(CH 2 ) 12 PA SAMs of varying surface energies, pentacene OFETs show high charge carrier mobilities up to 4.1 cm 2 V -1 s -1 . It is hypothesized that for these SAMs, mitigation of molecular scale roughness and subsequent control of surface homogeneity allow for large pentacene grain growth leading to high performance pentacene OFET devices. PA SAMs that contain bulky terminal groups or are highly crystalline in nature do not allow for a homogenous surface at a molecular level and result in charge carrier mobilities of 1.3 cm 2 V -1 s -1 or less. For all molecules used in this study, no causal relationship between SAM surface energy and charge carrier mobility in pentacene FET devices is observed.

Effects of self-assembled monolayer structural order, surface homogeneity and surface energy on pentacene morphology and thin film transistor device performance

PubMed Central

Hutchins, Daniel Orrin; Weidner, Tobias; Baio, Joe; Polishak, Brent; Acton, Orb; Cernetic, Nathan; Ma, Hong; Jen, Alex K.-Y.

2013-01-01

A systematic study of six phosphonic acid (PA) self-assembled monolayers (SAMs) with tailored molecular structures is performed to evaluate their effectiveness as dielectric modifying layers in organic field-effect transistors (OFETs) and determine the relationship between SAM structural order, surface homogeneity, and surface energy in dictating device performance. SAM structures and surface properties are examined by near edge X-ray absorption fine structure (NEXAFS) spectroscopy, contact angle goniometry, and atomic force microscopy (AFM). Top-contact pentacene OFET devices are fabricated on SAM modified Si with a thermally grown oxide layer as a dielectric. For less ordered methyl- and phenyl-terminated alkyl ~(CH2)12 PA SAMs of varying surface energies, pentacene OFETs show high charge carrier mobilities up to 4.1 cm2 V−1 s−1. It is hypothesized that for these SAMs, mitigation of molecular scale roughness and subsequent control of surface homogeneity allow for large pentacene grain growth leading to high performance pentacene OFET devices. PA SAMs that contain bulky terminal groups or are highly crystalline in nature do not allow for a homogenous surface at a molecular level and result in charge carrier mobilities of 1.3 cm2 V−1 s−1 or less. For all molecules used in this study, no causal relationship between SAM surface energy and charge carrier mobility in pentacene FET devices is observed. PMID:24086795

Direct organocatalytic enantioselective functionalization of SiOx surfaces.

PubMed

Parkin, John David; Chisholm, Ross; Frost, Aileen B; Bailey, Richard G; Smith, Andrew David; Hähner, Georg

2018-06-05

Traditional methods to prepare chiral surfaces involve either the adsorption of a chiral molecule onto an achiral surface, or adsorption of a species that forms a chiral template creating lattices with long range order. To date only limited alternative strategies to prepare chiral surfaces have been studied. In this manuscript a "bottom up" approach is developed that allows the preparation of chiral surfaces by direct enantioselective organocatalysis on a functionalized Si-oxide supported self-assembled monolayer (SAM). The efficient catalytic generation of enantiomerically enriched organic surfaces is achieved using a commercially available homogeneous isothiourea catalyst (HyperBTM) that promotes an enantioselective Michael-lactonization process upon a Si-oxide supported self-assembled monolayer functionalized with a reactive trifluoroenone group. Chiral atomic force microscopy (chi-AFM) is used to probe the enantiomeric enrichment of the organic films by measurement of the force distributions arising from interaction of D- or L-cysteine modified AFM tips and the organic films. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscale silicon substrate patterns from self-assembly of cylinder forming poly(styrene)-block-poly(dimethylsiloxane) block copolymer on silane functionalized surfaces.

PubMed

Borah, Dipu; Cummins, Cian; Rasappa, Sozaraj; Watson, Scott M D; Pike, Andrew R; Horrocks, Benjamin R; Fulton, David A; Houlton, Andrew; Liontos, George; Ntetsikas, Konstantinos; Avgeropoulos, Apostolos; Morris, Michael A

2017-01-27

Poly(styrene)-block-poly(dimethylsiloxane) (PS-b-PDMS) is an excellent block copolymer (BCP) system for self-assembly and inorganic template fabrication because of its high Flory-Huggins parameter (χ ∼ 0.26) at room temperature in comparison to other BCPs, and high selective etch contrast between PS and PDMS block for nanopatterning. In this work, self-assembly in PS-b-PDMS BCP is achieved by combining hydroxyl-terminated poly(dimethylsiloxane) (PDMS-OH) brush surfaces with solvent vapor annealing. As an alternative to standard brush chemistry, we report a simple method based on the use of surfaces functionalized with silane-based self-assembled monolayers (SAMs). A solution-based approach to SAM formation was adopted in this investigation. The influence of the SAM-modified surfaces upon BCP films was compared with polymer brush-based surfaces. The cylinder forming PS-b-PDMS BCP and PDMS-OH polymer brush were synthesized by sequential living anionic polymerization. It was observed that silane SAMs provided the appropriate surface chemistry which, when combined with solvent annealing, led to microphase segregation in the BCP. It was also demonstrated that orientation of the PDMS cylinders may be controlled by judicious choice of the appropriate silane. The PDMS patterns were successfully used as an on-chip etch mask to transfer the BCP pattern to underlying silicon substrate with sub-25 nm silicon nanoscale features. This alternative SAM/BCP approach to nanopattern formation shows promising results, pertinent in the field of nanotechnology, and with much potential for application, such as in the fabrication of nanoimprint lithography stamps, nanofluidic devices or in narrow and multilevel interconnected lines.

Nanoscale silicon substrate patterns from self-assembly of cylinder forming poly(styrene)-block-poly(dimethylsiloxane) block copolymer on silane functionalized surfaces

NASA Astrophysics Data System (ADS)

Borah, Dipu; Cummins, Cian; Rasappa, Sozaraj; Watson, Scott M. D.; Pike, Andrew R.; Horrocks, Benjamin R.; Fulton, David A.; Houlton, Andrew; Liontos, George; Ntetsikas, Konstantinos; Avgeropoulos, Apostolos; Morris, Michael A.

2017-01-01

Poly(styrene)-block-poly(dimethylsiloxane) (PS-b-PDMS) is an excellent block copolymer (BCP) system for self-assembly and inorganic template fabrication because of its high Flory-Huggins parameter (χ ˜ 0.26) at room temperature in comparison to other BCPs, and high selective etch contrast between PS and PDMS block for nanopatterning. In this work, self-assembly in PS-b-PDMS BCP is achieved by combining hydroxyl-terminated poly(dimethylsiloxane) (PDMS-OH) brush surfaces with solvent vapor annealing. As an alternative to standard brush chemistry, we report a simple method based on the use of surfaces functionalized with silane-based self-assembled monolayers (SAMs). A solution-based approach to SAM formation was adopted in this investigation. The influence of the SAM-modified surfaces upon BCP films was compared with polymer brush-based surfaces. The cylinder forming PS-b-PDMS BCP and PDMS-OH polymer brush were synthesized by sequential living anionic polymerization. It was observed that silane SAMs provided the appropriate surface chemistry which, when combined with solvent annealing, led to microphase segregation in the BCP. It was also demonstrated that orientation of the PDMS cylinders may be controlled by judicious choice of the appropriate silane. The PDMS patterns were successfully used as an on-chip etch mask to transfer the BCP pattern to underlying silicon substrate with sub-25 nm silicon nanoscale features. This alternative SAM/BCP approach to nanopattern formation shows promising results, pertinent in the field of nanotechnology, and with much potential for application, such as in the fabrication of nanoimprint lithography stamps, nanofluidic devices or in narrow and multilevel interconnected lines.

Self-assembly of proglycinin and hybrid proglycinin synthesized in vitro from cDNA

PubMed Central

Dickinson, Craig D.; Floener, Liliane A.; Lilley, Glenn G.; Nielsen, Niels C.

1987-01-01

An in vitro system was developed that results in the self-assembly of subunit precursors into complexes that resemble those found naturally in the endoplasmic reticulum. Subunits of glycinin, the predominant seed protein of soybeans, were synthesized from modified cDNAs using a combination of the SP6 transcription and the rabbit reticulocyte translation systems. Subunits produced from plasmid constructions that encoded either Gy4 or Gy5 gene products, but modified such that their signal sequences were absent, self-assembled into trimers equivalent in size to those precursors found in the endoplasmic reticulum. In contrast, proteins synthesized in vitro from Gy4 constructs failed to self-assemble when the signal sequence was left intact (e.g., preproglycinin) or when the coding sequence was modified to remove 27 amino acids from an internal hydrophobic region, which is highly conserved among the glycinin subunits. Various hybrid subunits were also produced by trading portions of Gy4 and Gy5 cDNAs and all self-assembled in our system. The in vitro assembly system provides an opportunity to study the self-assembly of precursors and to probe for regions important for assembly. It will also be helpful in attempts to engineer beneficial nutritional changes into this important food protein. Images PMID:16593868

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.

Surface charge dependent separation of modified and hybrid ferritin in native PAGE: Impact of lysine 104.

PubMed

Subhadarshanee, Biswamaitree; Mohanty, Abhinav; Jagdev, Manas Kumar; Vasudevan, Dileep; Behera, Rabindra K

2017-10-01

Preparation of modified and hybrid ferritin provides a great opportunity to understand the mechanisms of iron loading/unloading, protein self-assembly, size constrained nanomaterial synthesis and targeted drug delivery. However, the large size (M.W.=490kDa) has been limiting the separation of different modified and/or hybrid ferritin nanocages from each other in their intact assembled form and further characterization. Native polyacrylamide gel electrophoresis (PAGE) separates proteins on the basis of both charge and mass, while maintaining their overall native structure and activity. Altering surface charge distribution by substitution of amino acid residues located at the external surface of ferritin (K104E & D40A) affected the migration rate in native PAGE while internal modification had little effect. Crystal structures confirmed that ferritin nanocages made up of subunits with single amino acid substitutions retain the overall structure of ferritin nanocage. Taking advantage of K104E migration behavior, formation of hybrid ferritins with subunits of wild type (WT) and K104E were confirmed and separated in native PAGE. Cage integrity and iron loading ability (ferritin activity) were also tested. The migration pattern of hybrid ferritins in native PAGE depends on the subunit ratio (WT: K104E) in the ferritin cage. Our work shows that native PAGE can be exploited in nanobiotechnology, by analyzing modifications of large proteins like ferritin. Native PAGE, a simple, straight-forward technique, can be used to analyze small modification (by altering external surface charge) in large proteins like ferritin, without disintegrating its self-assembled nanocage structure. In doing so, native PAGE can complement the information obtained from mass spectrometry. The confirmation and separation of modified and hybrid ferritin protein nanocages in native PAGE, opens up various prospects of bio-conjugation, which can be useful in targeted drug delivery, nanobiotechnology and in understanding nature's idea of synthesizing hybrid ferritins in different human tissues. Copyright © 2017 Elsevier B.V. All rights reserved.

Cellular membrane enrichment of self-assembling D-peptides for cell surface engineering.

PubMed

Wang, Huaimin; Wang, Youzhi; Han, Aitian; Cai, Yanbin; Xiao, Nannan; Wang, Ling; Ding, Dan; Yang, Zhimou

2014-06-25

We occasionally found that several self-assembling peptides containing D-amino acids would be preferentially enriched in cellular membranes at self-assembled stages while distributed evenly in the cytoplasma of cells at unassembled stages. Self-assembling peptides containing only Lamino acids distributed evenly in cytoplasma of cells at both self-assembled and unassembled stages. The self-assembling peptides containing D-amino acids could therefore be applied for engineering cell surface with peptides. More importantly, by integrating a protein binding peptide (a PDZ domain binding hexapeptide of WRESAI) with the self-assembling peptide containing D-amino acids, protein could also be introduced to the cell surface. This study not only provided a novel approach to engineer cell surface, but also highlighted the unusual properties and potential applications of self-assembling peptides containing D-amino acids in regenerative medicine, drug delivery, and tissue engineering.

Chemically modified electrodes by nucleophilic substitution of chlorosilylated platinum oxide surfaces

NASA Astrophysics Data System (ADS)

Chen, Chun-Hsien; Hutchison, James H.; Postlethwaite, Timothy A.; Richardson, John N.; Murray, R. W.

1994-07-01

Chlorosilylated platinum oxide electrode surfaces can be generated by reaction of SiCl4 vapor with an electrochemically prepared monolayer of platinum oxide. A variety of nucleophilic agents (such as alcohols, amines, thiols, and Grignard reagents) can be used to displace chloride and thereby functionalize the metal surface. Electroactive surfaces prepared with ferrocene methanol as the nucleophile show that derivatization by small molecules can achieve coverages on the order of a full monolayer. Surfaces modified with long-chain alkyl groups efficiently block electrode reactions of redox probes dissolved in the contacting solution, but other electrochemical (double layer capacitance and surface coverage) and contact angle measurements suggest that these molecule films are not highly ordered, self-assembled monolayers.

Comparison of Zirconium Phosphonate-Modified Surfaces for Immobilizing Phosphopeptides and Phosphate-Tagged Proteins.

PubMed

Forato, Florian; Liu, Hao; Benoit, Roland; Fayon, Franck; Charlier, Cathy; Fateh, Amina; Defontaine, Alain; Tellier, Charles; Talham, Daniel R; Queffélec, Clémence; Bujoli, Bruno

2016-06-07

Different routes for preparing zirconium phosphonate-modified surfaces for immobilizing biomolecular probes are compared. Two chemical-modification approaches were explored to form self-assembled monolayers on commercially available primary amine-functionalized slides, and the resulting surfaces were compared to well-characterized zirconium phosphonate monolayer-modified supports prepared using Langmuir-Blodgett methods. When using POCl3 as the amine phosphorylating agent followed by treatment with zirconyl chloride, the result was not a zirconium-phosphonate monolayer, as commonly assumed in the literature, but rather the process gives adsorbed zirconium oxide/hydroxide species and to a lower extent adsorbed zirconium phosphate and/or phosphonate. Reactions giving rise to these products were modeled in homogeneous-phase studies. Nevertheless, each of the three modified surfaces effectively immobilized phosphopeptides and phosphopeptide tags fused to an affinity protein. Unexpectedly, the zirconium oxide/hydroxide modified surface, formed by treating the amine-coated slides with POCl3/Zr(4+), afforded better immobilization of the peptides and proteins and efficient capture of their targets.

Amphiphilic invertible polymers: Self-assembly into functional materials driven by environment polarity

NASA Astrophysics Data System (ADS)

Hevus, Ivan

Stimuli-responsive polymers adapt to environmental changes by adjusting their chain conformation in a fast and reversible way. Responsive polymeric materials have already found use in electronics, coatings industry, personal care, and bio-related areas. The current work aims at the development of novel responsive functional polymeric materials by manipulating environment-dependent self-assembly of a new class of responsive macromolecules strategically designed in this study,—amphiphilic invertible polymers (AIPs). Environment-dependent micellization and self-assembly of three different synthesized AIP types based on poly(ethylene glycol) as a hydrophilic fragment and varying hydrophobic constituents was demonstrated in polar and nonpolar solvents, as well as on the surfaces and interfaces. With increasing concentration, AIP micelles self-assemble into invertible micellar assemblies composed of hydrophilic and hydrophobic domains. Polarity-responsive properties of AIPs make invertible micellar assemblies functional in polar and nonpolar media including at interfaces. Thus, invertible micellar assemblies solubilize poorly soluble substances in their interior in polar and nonpolar solvents. In a polar aqueous medium, a novel stimuli-responsive mechanism of drug release based on response of AIP-based drug delivery system to polarity change upon contact with the target cell has been established using invertible micellar assemblies loaded with curcumin, a phytochemical drug. In a nonpolar medium, invertible micellar assemblies were applied simultaneously as nanoreactors and stabilizers for size-controlled synthesis of silver nanoparticles stable in both polar and nonpolar media. The developed amphiphilic nanosilver was subsequently used as seeds to promote anisotropic growth of CdSe semiconductor nanoparticles that have potential in different applications ranging from physics to medicine. Amphiphilic invertible polymers were shown to adsorb on the surface of silica nanoparticles strongly differing in polarity. AIP modified silica nanoparticles are able to adsolubilize molecules of poorly water-soluble 2-naphthol into the adsorbed polymer layer. The adsolubilization ability of adsorbed invertible macromolecules makes AIP-modified silica nanoparticles potentially useful in wastewater treatment or biomedical applications. Finally, the invertible micellar assemblies were used as functional additives to improve the appearance of electrospun silicon wires based on cyclohexasilane, a liquid silicon precursor. AIP-assisted fabrication of silicon wires from the liquid cyclohexasilane precursor has potential as a scalable method for developing electronic functional materials.

Atomic force measurements of 16-mercaptohexadecanoic acid and its salt with CH 3, OH, and CONHCH 3 functionalized self-assembled monolayers

NASA Astrophysics Data System (ADS)

Morales-Cruz, Angel L.; Tremont, Rolando; Martínez, Ramón; Romañach, Rodolfo; Cabrera, Carlos R.

2005-03-01

Chemical and mechanical properties of different compounds can be elucidated by measuring fundamental forces such as adhesion, attraction and repulsion, between modified surfaces by means of atomic force microscopy (AFM) in force mode calibration. This work presents a combination of AFM, self-assembled monolayers (SAMs), and crystallization techniques to study the forces of interaction between excipients and active ingredients used in pharmaceutical formulations. SAMs of 16-mercaptohexadecanoate, which represent magnesium stereate, were used to modify the probe tip, whereas CH3-, OH- and CONHCH3-functional SAMs were formed on a gold-coated mica substrate, and used as examples of the surfaces of lactose and theophylline. The crystals of lactose and theophylline were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The modification of gold surfaces with 16-mercaptohexadecanoate, 10-mercapto-1-decanol (OH-functional SAM), 1-decanethiol (CH3-functional) and N-methyl-11-mercaptoundecanamide (CONHCH3-functional SAM) was studied by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and Fourier transform-infrared spectroscopy (FT-IR) in specular reflectance mode. XPS and AES results of the modified surfaces showed the presence of sulfur binding, and kinetic energies that correspond to the presence of 10-mercapto-1-decanol, 1-decanethiol, N-methyl-11-mercaptoundecanamide and the salt of 16-mercaptohexadecanoic acid. The absorption bands in the IR spectra further confirm the modification of the gold-coated substrates with these compounds. Force versus distance measurements were performed between the modified tip and the modified gold-coated mica substrates. The mean adhesion forces between the COO-Ca2+ functionalized tip and the CH3-, OH-, and CONHCH3-modified substrates were determined to be 4.5, 8.9 and 6.3 nN, respectively. The magnitude of the adhesion force (ion-dipole) interaction between the modified tip and substrate decreases in the following order: COO-Ca2+/OH > COO-Ca2+/CONHCH3 > COO-Ca2+/CH3.

Direct patterning of a cyclotriveratrylene derivative for directed self-assembly of C60

NASA Astrophysics Data System (ADS)

Osner, Zachary R.; Nyamjav, Dorjderem; Holz, Richard C.; Becker, Daniel P.

2011-07-01

A novel apex-modified cyclotriveratrylene (CTV) derivative with an attached thiolane-containing lipoic acid linker was directly patterned onto gold substrates via dip-pen nanolithography (DPN). The addition of a dithiolane-containing linker to the apex of CTV provides a molecule that can adhere to a gold surface with its bowl-shaped cavity directed away from the surface, thereby providing a surface-bound CTV host that can be used for the directed assembly of guest molecules. Subsequent exposure of these CTV microarrays to C60 in toluene resulted in the directed assembly of predesigned, spatially controlled, high-density microarrays of C60. The molecular recognition capabilities of this CTV template toward C60 provides proof-of-concept that supramolecular CTV scaffolds can be directly patterned onto surfaces providing a foundation for the development of organic electronic and optoelectronic materials.

Characterization of a Self-Assembled Monolayer of 1-Thio-β-D-Glucose with Electrochemical Surface Enhanced Raman Spectroscopy Using a Nanoparticle Modified Gold Electrode.

PubMed

Smith, Scott R; Seenath, Ryan; Kulak, Monika R; Lipkowski, Jacek

2015-09-15

Preparation of a nanoparticle modified gold substrate designed for characterization of hydrophilic self-assembled monolayers (SAMs) of 1-thio-β-D-glucose (TG) with electrochemical surface-enhanced Raman spectroscopy (EC-SERS) is presented. Citrate stabilized gold nanoparticles were deposited on a polycrystalline gold electrode and subjected to an electrochemical desorption procedure to completely remove all traces of adsorbed citrate. Complete desorption of citrate was confirmed by recording cyclic voltammetry curves and SERS spectra. The citrate-free nanoparticle modified gold electrode was then incubated in a 1 mg mL(-1) aqueous solution of TG for 16 h prior to being characterized by EC-SERS. The SERS spectra confirmed that at potentials more negative than -0.10 V vs SCE thioglucose forms a monolayer in which the majority of the molecules preserve their lactol ring structure and only a small fraction of molecules appear to be oxidized. At potentials more positive than -0.10 V, the oxidation of TG molecules becomes prominent, and at potentials more positive than 0.20 V vs SCE, the monolayer of TG consists chiefly of oxidized product. The SERS spectra collected in the double layer region suggest the SAM of TG is well hydrated and hence can be used for hydrophilic modifications of a gold surface.

Induced Infiltration of Hole-Transporting Polymer into Photocatalyst for Staunch Polymer-Metal Oxide Hybrid Solar Cells.

PubMed

Park, Jong Hwan; Jung, Youngsuk; Yang, Yooseong; Shin, Hyun Suk; Kwon, Soonchul

2016-10-05

For efficient solar cells based on organic semiconductors, a good mixture of photoactive materials in the bulk heterojunction on the length scale of several tens of nanometers is an important requirement to prevent exciton recombination. Herein, we demonstrate that nanoporous titanium dioxide inverse opal structures fabricated using a self-assembled monolayer method and with enhanced infiltration of electron-donating polymers is an efficient electron-extracting layer, which enhances the photovoltaic performance. A calcination process generates an inverse opal structure of titanium dioxide (<70 nm of pore diameters) providing three-dimensional (3D) electron transport pathways. Hole-transporting polymers was successfully infiltrated into the pores of the surface-modified titanium dioxide under vacuum conditions at 200 °C. The resulting geometry expands the interfacial area between hole- and electron-transport materials, increasing the thickness of the active layer. The controlled polymer-coating process over titanium dioxide materials enhanced photocurrent of the solar cell device. Density functional theory calculations show improved interfacial adhesion between the self-assembled monolayer-modified surface and polymer molecules, supporting the experimental result of enhanced polymer infiltration into the voids. These results suggest that the 3D inverse opal structure of the surface-modified titanium dioxide can serve as a favorable electron-extracting layer in further enhancing optoelectronic performance based on organic or organic-inorganic hybrid solar cell.

Silane surface modification for improved bioadhesion of esophageal stents

NASA Astrophysics Data System (ADS)

Karakoy, Mert; Gultepe, Evin; Pandey, Shivendra; Khashab, Mouen A.; Gracias, David H.

2014-08-01

Stent migration occurs in 10-40% of patients who undergo placement of esophageal stents, with higher migration rates seen in those treated for benign esophageal disorders. This remains a major drawback of esophageal stent therapy. In this paper, we propose a new surface modification method to increase the adhesion between self-expandable metallic stents (SEMS) and tissue while preserving their removability. Taking advantage of the well-known affinity between epoxide and amine terminated silane coupling agents with amine and carboxyl groups that are abundant in proteins and related molecules in the human body; we modified the surfaces of silicone coated esophageal SEMS with these adhesive self-assembled monolayers (SAMs). We utilized vapor phase silanization to modify the surfaces of different substrates including PDMS strips and SEMS, and measured the force required to slide these substrates on a tissue piece. Our results suggest that surface modification of esophageal SEMS via covalent attachment of protein-binding coupling agents improves adhesion to tissue and could offer a solution to reduce SEMS migration while preserving their removability.

Ultrasmall Peptides Self-Assemble into Diverse Nanostructures: Morphological Evaluation and Potential Implications

PubMed Central

Lakshmanan, Anupama; Hauser, Charlotte A.E.

2011-01-01

In this study, we perform a morphological evaluation of the diverse nanostructures formed by varying concentration and amino acid sequence of a unique class of ultrasmall self-assembling peptides. We modified these peptides by replacing the aliphatic amino acid at the C-aliphatic terminus with different aromatic amino acids. We tracked the effect of introducing aromatic residues on self-assembly and morphology of resulting nanostructures. Whereas aliphatic peptides formed long, helical fibers that entangle into meshes and entrap >99.9% water, the modified peptides contrastingly formed short, straight fibers with a flat morphology. No helical fibers were observed for the modified peptides. For the aliphatic peptides at low concentrations, different supramolecular assemblies such as hollow nanospheres and membrane blebs were found. Since the ultrasmall peptides are made of simple, aliphatic amino acids, considered to have existed in the primordial soup, study of these supramolecular assemblies could be relevant to understanding chemical evolution leading to the origin of life on Earth. In particular, we propose a variety of potential applications in bioengineering and nanotechnology for the diverse self-assembled nanostructures. PMID:22016623

Methods of making functionalized nanorods

DOEpatents

Gur, Ilan [San Francisco, CA; Milliron, Delia [Berkeley, CA; Alivisatos, A Paul [Oakland, CA; Liu, Haitao [Berkeley, CA

2012-01-10

A process for forming functionalized nanorods. The process includes providing a substrate, modifying the substrate by depositing a self-assembled monolayer of a bi-functional molecule on the substrate, wherein the monolayer is chosen such that one side of the bi-functional molecule binds to the substrate surface and the other side shows an independent affinity for binding to a nanocrystal surface, so as to form a modified substrate. The process further includes contacting the modified substrate with a solution containing nanocrystal colloids, forming a bound monolayer of nanocrystals on the substrate surface, depositing a polymer layer over the monolayer of nanocrystals to partially cover the monolayer of nanocrystals, so as to leave a layer of exposed nanocrystals, functionalizing the exposed nanocrystals, to form functionalized nanocrystals, and then releasing the functionalized nanocrystals from the substrate.

Isolation and characterization of a new class of amphipathic biopolymers capable of self-assembly from aqueous media

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

Martin, G.G.; Cannon, G.C.; McCormick, C.L.

Extensive research is being done in many laboratories to investigate the role of synthetic hydrophobically-modified polymers and amphipathic proteins for their potential in phase-transfer, sequestration, and elimination of polluting hydrocarbons and surfactants. Our laboratory has begun a research program which is aimed at the development of a new class of environmentally benign biomaterials using the amphipathic proteins termed {open_quotes}hydrophobins{close_quotes} and an associated polysaccharide, schizophyllan. These biopolymers can stabilize oil dispersions, attach strongly to polyethylene and polytetrafluoroethylene surfaces rendering them hydrophilic, and can self-assemble into a stable, flexible membrane. Preliminary experiments in our laboratory and others have demonstrated the immense technologicalmore » potential of this class of biomaterials for surface modification of membranes and coatings, fouling resistance, controlled delivery, protective encapsulation, and drag reduction.« less

Annealing improves tribological property of poly(octadecene- alt -maleic anhydride) self-assembled film

NASA Astrophysics Data System (ADS)

Song, Shiyong; Liu, Lei; Zhang, Junyan

2011-09-01

A poly(octadecene-alt-maleic anhydride) (POMA) film was covalently immobilized on N-[3-(trimethoxylsilyl)propyl]ethylenediamine self-assembled monolayer modified silicon surface. Attenuated total reflectance Fourier transform infrared spectra were used to confirm the chemical bonding. Water contact angles and ellipsometric thicknesses were measured before and after annealing treatment. Atomic force microscopy was applied for top morphology, surface adhesion force and friction force. Anti-wear properties of the films were also evaluated on a ball-on-plate tribometer. It was found that annealing treatment which would evoke a conformation transform thermodynamically, was a critical step in the preparation of anti-wear films, especially for polymer ones. The correlation between structure and tribological property was revealed, which has profound meaning in designing excellent anti-wear nano-coatings used in microelectronic mechanical systems (MEMS).

High-Yield Excited Triplet States in Pentacene Self-Assembled Monolayers on Gold Nanoparticles through Singlet Exciton Fission.

PubMed

Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V; Hasobe, Taku

2016-04-18

One of the major drawbacks of organic-dye-modified self-assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13-bis(triisopropylsilylethynyl)pentacene-alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time-resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembled cyclodextrin-modified gold nanoparticles on silica beads as stationary phase for chiral liquid chromatography and hydrophilic interaction chromatography.

PubMed

Li, Yuanyuan; Wei, Manman; Chen, Tong; Zhu, Nan; Ma, Yulong

2016-11-01

A facile strategy based on self-assembly of Au nanoparticles (AuNPs) (60±10nm in size) on the surfaces of amino-functionalized porous silica spheres under mild conditions was proposed. The resulting material possessed a core-shell structure in which AuNPs were the shell and silica spheres were the core. Then, thiolated-β-cyclodextrin (SH-β-CD) was covalently attached onto the AuNPs as chiral selector for the enantioseparation. The resultant packing material was evaluated by high-performance liquid chromatography (HPLC). The separations of nine pairs of enantiomers were achieved by using the new chiral stationary phase (CSP) in the reversed-phase liquid chromatography (RPLC) mode, respectively. The results showed the new CSP have more sufficient interaction with the analytes due to the existence of AuNPs on silica surfaces, resulting in faster mass transfer rate, compared with β-CD modified silica column. The result shed light on potential usage of chemical modified NPs as chiral selector for enantioseparation based on HPLC. In addition, the new phase was also used in hydrophilic interaction liquid chromatography (HILIC) to separate polar compounds and highly hydrophilic compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

Morphology of self assembled monolayers using liquid phase reaction on silica and their effect on the morphology of adsorbed insulin

NASA Astrophysics Data System (ADS)

Sharma, Indu; Pattanayek, Sudip K.; Aggarwal, Varsha; Ghosh, Subhasis

2017-05-01

The effect of roughness of two different categories of self-assembled monolayers (SAMs) with propyl amine and propyl groups respectively on the morphology of adsorbed insulin is observed. SAMs are obtained by liquid phase reaction of silica with organo silane coupling agents (SCA). The influence of the morphology and physical characteristics of the SAMs on the reaction time and concentration of the modifiers are explored. We have tested three SCA containing propyl amine with varying groups linked to Si present on it. In addition, we have used a silane coupling agent to prepare SAM of methyl head group. The approach of these molecules towards the surface depends on the head group and the groups linked to Si of the SCA. The morphology of the surfaces is analysed using power spectral density distribution (PSD), skewness, ellipsometry thickness and surface energy. Both chemical nature and physical morphology of the adsorbent influence the morphology of the adsorbed insulin. In general, a low number of aggregates of big size are formed on the surfaces obtained from low concentration of SAMs, while a higher number but of smaller size of aggregates are formed over surfaces obtained from 1% concentration of SAMs modifiers. The peak to valley ratio of the aggregates of insulin is strongly influenced by the size of grains of SCA over the adsorbent.

Characterization of protein immobilization on nanoporous gold using atomic force microscopy and scanning electron microscopy†

PubMed Central

Tan, Yih Horng; Schallom, John R.; Ganesh, N. Vijaya; Fujikawa, Kohki; Demchenko, Alexei V.

2011-01-01

Nanoporous gold (NPG), made by dealloying low carat gold alloys, is a relatively new nanomaterial finding application in catalysis, sensing, and as a support for biomolecules. NPG has attracted considerable interest due to its open bicontinuous structure, high surface-to-volume ratio, tunable porosity, chemical stability and biocompatibility. NPG also has the attractive feature of being able to be modified by self-assembled monolayers. Here we use scanning electron microscopy (SEM) and atomic force microscopy (AFM) to characterize a highly efficient approach for protein immobilization on NPG using N-hydroxysuccinimide (NHS) ester functionalized self-assembled monolayers on NPG with pore sizes in the range of tens of nanometres. Comparison of coupling under static versus flow conditions suggests that BSA (Bovine Serum Albumin) and IgG (Immunoglobulin G) can only be immobilized onto the interior surfaces of free standing NPG monoliths with good coverage under flow conditions. AFM is used to examine protein coverage on both the exterior and interior of protein modified NPG. Access to the interior surface of NPG for AFM imaging is achieved using a special procedure for cleaving NPG. AFM is also used to examine BSA immobilized on rough gold surfaces as a comparative study. In principle, the general approach described should be applicable to many enzymes, proteins and protein complexes since both pore sizes and functional groups present on the NPG surfaces are controllable. PMID:21750834

Surface modification of GC and HOPG with diazonium, amine, azide, and olefin derivatives.

PubMed

Tanaka, Mutsuo; Sawaguchi, Takahiro; Sato, Yukari; Yoshioka, Kyoko; Niwa, Osamu

2011-01-04

Surface modification of glassy carbon (GC) and highly oriented pyrolytic graphite (HOPG) was carried out with diazonium, amine, azide, and olefin derivatives bearing ferrocene as an electroactive moiety. Features of the modified surfaces were evaluated by surface concentrations of immobilized molecule, blocking effect of the modified surface against redox reaction, and surface observation using cyclic voltammetry and electrochemical scanning tunneling microscope (EC-STM). The measurement of surface concentrations of immobilized molecule revealed the following three aspects: (i) Diazonium and olefin derivatives could modify substrates with the dense-monolayer concentration. (ii) The surface concentration of immobilized amine derivative did not reach to the dense-monolayer concentration reflecting their low reactivity. (iii) The surface modification with the dense-monolayer concentration was also possible with azide derivative, but the modified surface contained some oligomers produced by the photoreaction of azides. Besides, the blocking effect against redox reaction was observed for GC modified with diazonium derivative and for HOPG modified with diazonium and azide derivatives, suggesting fabrication of a densely modified surface. Finally, the surface observation for HOPG modified with diazonium derivative by EC-STM showed a typical monolayer structure, in which the ferrocene moieties were packed densely at random. On the basis of those results, it was demonstrated that surface modification of carbon substrates with diazonium could afford a dense monolayer similar to the self-assembled monolayer (SAM) formation.

Film Self-Assembly of Oppositely Charged Macromolecules Triggered by Electrochemistry through a Morphogenic Approach.

PubMed

Dochter, Alexandre; Garnier, Tony; Pardieu, Elodie; Chau, Nguyet Trang Thanh; Maerten, Clément; Senger, Bernard; Schaaf, Pierre; Jierry, Loïc; Boulmedais, Fouzia

2015-09-22

The development of new surface functionalization methods that are easy to use, versatile, and allow local deposition represents a real scientific challenge. Overcoming this challenge, we present here a one-pot process that consists in self-assembling, by electrochemistry on an electrode, films made of oppositely charged macromolecules. This method relies on a charge-shifting polyanion, dimethylmaleic-modified poly(allylamine) (PAHd), that undergoes hydrolysis at acidic pH, leading to an overall switching of its charge. When a mixture of the two polyanions, PAHd and poly(styrenesulfonate) (PSS), is placed in contact with an electrode, where the pH is decreased locally by electrochemistry, the transformation of PAHd into a polycation (PAH) leads to the continuous self-assembly of a nanometric PAH/PSS film by electrostatic interactions. The pH decrease is obtained by the electrochemical oxidation of hydroquinone, which produces protons locally over nanometric distances. Using a negatively charged enzyme, alkaline phosphatase (AP), instead of PSS, this one-pot process allows the creation of enzymatically active films. Under mild conditions, self-assembled PAH/AP films have an enzymatic activity which is adjustable simply by controlling the self-assembly time. The selective functionalization of microelectrode arrays by PAH/AP was achieved, opening the route toward miniaturized biosensors.

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

Regulating DNA Self-assembly by DNA-Surface Interactions.

PubMed

Liu, Longfei; Li, Yulin; Wang, Yong; Zheng, Jianwei; Mao, Chengde

2017-12-14

DNA self-assembly provides a powerful approach for preparation of nanostructures. It is often studied in bulk solution and involves only DNA-DNA interactions. When confined to surfaces, DNA-surface interactions become an additional, important factor to DNA self-assembly. However, the way in which DNA-surface interactions influence DNA self-assembly is not well studied. In this study, we showed that weak DNA-DNA interactions could be stabilized by DNA-surface interactions to allow large DNA nanostructures to form. In addition, the assembly can be conducted isothermally at room temperature in as little as 5 seconds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Chitosan-collagen polymer induced remineralization of tooth hard tissue through self-growing methods].

PubMed

Xun, Ren; Jing, Yao; Qin, Du; Chuhang, Liao; Kun, Tian

2014-10-01

To modify biomacromolecules, such as chitosan and collagen, to synthesize a mineralized template that will induce self-growing remineralization of tooth enamel. Natural polycation polysaccharide chitosan was modified through phosphorylation to synthesize the polyanion derivative ofphosphorylated chitosan. Parent hydrogels com- bined with chitosan and collagen I were built through peptide binding reaction using genipin as a crosslinker. The gels self- assembled on the tooth's inert surface, which was stimulated by ultraviolet radiation. The bionic saliva provided mineralized ion, and then the hydroxyapatite assembled and grew in situ on the tooth. The functional group P04(3-) (3,446 cm(-1)) was grafted on chitosan as confirmed by the Fourier transform infrared spectroscopy. The porous polyelectrolyte complex hydrogel formed by the interaction between the polycation chitosan and the polyanion phosphorylated chitosan could induce hydroxyapatite crystal nucleation and growth on the hydrogel fiber surfaces. The neonatal crystal was hydroxyapatite as confirmed by X-ray diffraction and was tightly connected to the tooth. A continuous structure of column crystals with sizes ranging from 30 nm to 60 nm was observed. The structure was in parallel direction similar to the direction of the enamel rod, and its hardness was close to dentin. The parent hydrogels that were easily obtained and controlled could mimic the template of the enamel mineralization and induce a self-growing hydroxyapatite, which is an important step in the structural bionics of enamel.

Freeform correction polishing for optics with semi-kinematic mounting

NASA Astrophysics Data System (ADS)

Huang, Chien-Yao; Kuo, Ching-Hsiang; Peng, Wei-Jei; Yu, Zong-Ru; Ho, Cheng-Fang; Hsu, Ming-Ying; Hsu, Wei-Yao

2015-10-01

Several mounting configurations could be applied to opto-mechanical design for achieving high precise optical system. The retaining ring mounting is simple and cost effective. However, it would deform the optics due to its unpredictable over-constraint forces. The retaining ring can be modified to three small contact areas becoming a semi-kinematic mounting. The semi-kinematic mounting can give a fully constrained in lens assembly and avoid the unpredictable surface deformation. However, there would be still a deformation due to self-weight in large optics especially in vertical setup applications. The self-weight deformation with a semi-kinematic mounting is a stable, repeatable and predictable combination of power and trefoil aberrations. This predictable deformation can be pre-compensated onto the design surface and be corrected by using CNC polisher. Thus it is a freeform surface before mounting to the lens cell. In this study, the freeform correction polishing is demonstrated in a Φ150 lens with semi-kinematic mounting. The clear aperture of the lens is Φ143 mm. We utilize ANSYS simulation software to analyze the lens deformation due to selfweight deformation with semi-kinematic mounting. The simulation results of the self-weight deformation are compared with the measurement results of the assembled lens cell using QED aspheric stitching interferometer (ASI). Then, a freeform surface of a lens with semi-kinematic mounting due to self-weight deformation is verified. This deformation would be corrected by using QED Magnetorheological Finishing (MRF® ) Q-flex 300 polishing machine. The final surface form error of the assembled lens cell after MRF figuring is 0.042 λ in peak to valley (PV).

Light-induced Self-Assembly and Diffusion of Nanoclusters

NASA Astrophysics Data System (ADS)

Lian, Wenxuan

Novel methods to build multiple types of three-dimensional structures from various nanoscale components are the most exciting and challenging questions in nano-science. The properties of the assembled structures can be potentially and designed, but the development of such approaches is challenging. In order to realize such rational assembly, a tunable interaction medium is often introduced into the system. Soft matter, such as polymers, surfactants and biomolecules are used to modify the surfaces of the nanoscale building blocks. Deoxyribonucleic acid (DNA) strands are known as polynucleotides since they are composed of simpler units called nucleotides. There are unique base pairing rules that are predictable and programmable, which can be used to regulate self-assembly process with high degree of control. Besides controlling static structure, it is important to develop methods for controlling systems in dynamic matter, with chemical stimuli or external fields. For example, here we study the use of azobezene-trimethylammonium bromide (AzoTAB) as a molecular agent that can control self-assembly via light excitation. In this thesis, DNA assisted self-assembly was conducted. The ability of AzoTAB as a light induced surfactant to control DNA assisted self-assembly was confirmed. The mechanism of AzoTAB as a light controlled self-assembly promoter was studied. In the second project, diffusion of nanoclusters was studied. The presence of polymers brings strong entanglement with nanoclusters. This entanglement is more obvious when the nanocluster is a framed structure like the octahedron in the study. The diffusion coefficient of the octahedron becomes larger during traveling. The following up studies are required to elucidate the origin of the observed effect.

IMPACT OF POLYCYCLIC AROMATIC HYDROCARBONS OF THE ELECTROCHEMICAL RESPONSES OF A FERRICYNIDE PROBE AT TEMPLATE-MODIFIED SELF ASSEMBLED MONOLAYERS ON GOLD ELECTRODES

EPA Science Inventory

The impact of pyrene on the electrochemical response of the ferricyanide probe using Self Assembled Monolayer (SAM)-modified gold electrodes was investigated using Cyclic Voltammetry (CV) and Square Wave Voltammetry (SWV). These results suggest the feasibility of using SAMs, par...

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.

Colloidal gold-modified optical fiber for chemical and biochemical sensing.

PubMed

Cheng, Shu-Fang; Chau, Lai-Kwan

2003-01-01

A novel class of fiber-optic evanescent-wave sensor was constructed on the basis of modification of the unclad portion of an optical fiber with self-assembled gold colloids. The optical properties and, hence, the attenuated total reflection spectrum of self-assembled gold colloids on the optical fiber changes with different refractive index of the environment near the colloidal gold surface. With sucrose solutions of increasing refractive index, the sensor response decreases linearly. The colloidal gold surface was also functionalized with glycine, succinic acid, or biotin to enhance the selectivity of the sensor. Results show that the sensor response decreases linearly with increasing concentration of each analyte. When the colloidal gold surface was functionalized with biotin, the detection limit of the sensor for streptavidin was 9.8 x 10(-11) M. Using this approach, we demonstrate proof-of-concept of a class of refractive index sensor that is sensitive to the refractive index of the environment near the colloidal gold surface and, hence, is suitable for label-free detection of molecular or biomolecular binding at the surface of gold colloids.

Surface analysis of gold nanoparticles functionalized with thiol-modified glucose SAMs for biosensor applications.

NASA Astrophysics Data System (ADS)

Spampinato, Valentina; Parracino, Mariaantonietta; La Spina, Rita; Rossi, Francois; Ceccone, Giacomo

2016-02-01

In this work, Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS), Principal Component Analysis (PCA) and X-ray Photoelectron Spectroscopy (XPS) have been used to characterize the surface chemistry of gold substrates before and after functionalization with thiol-modified glucose self-assembled monolayers and subsequent biochemical specific recognition of maltose binding protein (MBP). The results indicate that the surface functionalization is achieved both on flat and nanoparticles gold substrates thus showing the potential of the developed system as biodetection platform. Moreover, the method presented here has been found to be a sound and valid approach to characterize the surface chemistry of nanoparticles functionalized with large molecules. Both techniques were proved to be very useful tools for monitoring all the functionalization steps, including the investigation of the biological behaviour of the glucose-modified particles in presence of the maltose binding protein.

Surface Analysis of Gold Nanoparticles Functionalized with Thiol-Modified Glucose SAMs for Biosensor Applications

PubMed Central

Spampinato, Valentina; Parracino, Maria Antonietta; La Spina, Rita; Rossi, Francois; Ceccone, Giacomo

2016-01-01

In this work, Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS), Principal Component Analysis (PCA) and X-ray Photoelectron Spectroscopy (XPS) have been used to characterize the surface chemistry of gold substrates before and after functionalization with thiol-modified glucose self-assembled monolayers and subsequent biochemical specific recognition of maltose binding protein (MBP). The results indicate that the surface functionalization is achieved both on flat and nanoparticles gold substrates thus showing the potential of the developed system as biodetection platform. Moreover, the method presented here has been found to be a sound and valid approach to characterize the surface chemistry of nanoparticles functionalized with large molecules. Both techniques were proved to be very useful tools for monitoring all the functionalization steps, including the investigation of the biological behavior of the glucose-modified particles in the presence of the maltose binding protein. PMID:26973830

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.

Vapor-phase-processed fluorinated self-assembled monolayer for organic thin-film transistors

NASA Astrophysics Data System (ADS)

Roh, Jeongkyun; Lee, Changhee; Kwak, Jeonghun; Jung, Byung Jun; Kim, Hyeok

2015-09-01

A vapor-phase-processed fluorinated silazane self-assembled monolayer (SAM), 1,3-bis(trifluoropropyl)-1,1,3,3-tetramethyldisilazane (FPDS), was introduced as a surface modifier for pentacene-based organic thin-film transistors (OTFTs). A remarkable improvement in the field effect mobility from 0.25 cm2/Vs (without SAM-treatment) to 0.42 cm2/Vs (with FPDS-treatment) was observed, which was attributed to the better pentacene growth on a hydrophobic surface. A significant reduction in the contact resistance was also observed by FPDS treatment due to the improved bulk conductivity and diminished charge trapping at the gate dielectric surface by the SAM treatment. In addition, FPDS treatment efficiently improved the bias stability of the OTFTs; the drain-to-source current degradation by the bias stress was greatly reduced from 80% to 50% by FPDS treatment, and the characteristic time for charge trapping of the FPDS treated OTFTs was approximately one order of magnitude larger than that of the OTFTs without SAM treatment.

Self-assembly modified-mushroom nanocomposite for rapid removal of hexavalent chromium from aqueous solution with bubbling fluidized bed.

PubMed

Xu, Fei; Liu, Xu; Chen, Yijiao; Zhang, Ke; Xu, Heng

2016-05-18

A self-assembled modified Pleurotus Cornucopiae material (SMPM) combined with improved Intermittent Bubbling Fluidized Bed (IBFB) was investigated to remove the hexavalent chromium ions in aqueous solution. After the modification, the powder-like raw material gradually self-assembled together to SMPM, which had crinkly porous structure, improved the Cr-accommodation ability in a sound manner. Optimized by Taguchi method, Cr(VI) removal efficiency was up to 75.91% and 48.01% for 100 mg/L and 500 mg/L initial concentration of Cr(VI), respectively. Results indicated that the metal removal was dependent on dosage of adsorbent, particle diameter and treatment time. The experimental data obtained from the biosorption process was successfully correlated with Freundlich isotherm model. Thermodynamic study indicated the endothermic nature of the process. The results confirmed that self-assembly modified Pleurotus Cornucopiae material could be applied for the removal of heavy metal from wastewater in continuous fluidized bed process.

Self-assembly modified-mushroom nanocomposite for rapid removal of hexavalent chromium from aqueous solution with bubbling fluidized bed

PubMed Central

Xu, Fei; Liu, Xu; Chen, Yijiao; Zhang, Ke; Xu, Heng

2016-01-01

A self-assembled modified Pleurotus Cornucopiae material (SMPM) combined with improved Intermittent Bubbling Fluidized Bed (IBFB) was investigated to remove the hexavalent chromium ions in aqueous solution. After the modification, the powder-like raw material gradually self-assembled together to SMPM, which had crinkly porous structure, improved the Cr-accommodation ability in a sound manner. Optimized by Taguchi method, Cr(VI) removal efficiency was up to 75.91% and 48.01% for 100 mg/L and 500 mg/L initial concentration of Cr(VI), respectively. Results indicated that the metal removal was dependent on dosage of adsorbent, particle diameter and treatment time. The experimental data obtained from the biosorption process was successfully correlated with Freundlich isotherm model. Thermodynamic study indicated the endothermic nature of the process. The results confirmed that self-assembly modified Pleurotus Cornucopiae material could be applied for the removal of heavy metal from wastewater in continuous fluidized bed process. PMID:27188258

Self-assembly modified-mushroom nanocomposite for rapid removal of hexavalent chromium from aqueous solution with bubbling fluidized bed

NASA Astrophysics Data System (ADS)

Xu, Fei; Liu, Xu; Chen, Yijiao; Zhang, Ke; Xu, Heng

2016-05-01

A self-assembled modified Pleurotus Cornucopiae material (SMPM) combined with improved Intermittent Bubbling Fluidized Bed (IBFB) was investigated to remove the hexavalent chromium ions in aqueous solution. After the modification, the powder-like raw material gradually self-assembled together to SMPM, which had crinkly porous structure, improved the Cr-accommodation ability in a sound manner. Optimized by Taguchi method, Cr(VI) removal efficiency was up to 75.91% and 48.01% for 100 mg/L and 500 mg/L initial concentration of Cr(VI), respectively. Results indicated that the metal removal was dependent on dosage of adsorbent, particle diameter and treatment time. The experimental data obtained from the biosorption process was successfully correlated with Freundlich isotherm model. Thermodynamic study indicated the endothermic nature of the process. The results confirmed that self-assembly modified Pleurotus Cornucopiae material could be applied for the removal of heavy metal from wastewater in continuous fluidized bed process.

The mechanisms for nanoparticle surface diffusion and chain self-assembly determined from real-time nanoscale kinetics in liquid

DOE PAGES

Woehl, Taylor J.; Prozorov, Tanya

2015-08-20

The mechanisms for nanoparticle self-assembly are often inferred from the morphology of the final nanostructures in terms of attractive and repulsive interparticle interactions. Understanding how nanoparticle building blocks are pieced together during self-assembly is a key missing component needed to unlock new strategies and mechanistic understanding of this process. Here we use real-time nanoscale kinetics derived from liquid cell transmission electron microscopy investigation of nanoparticle self-assembly to show that nanoparticle mobility dictates the pathway for self-assembly and final nanostructure morphology. We describe a new method for modulating nanoparticle diffusion in a liquid cell, which we employ to systematically investigate themore » effect of mobility on self-assembly of nanoparticles. We interpret the observed diffusion in terms of electrostatically induced surface diffusion resulting from nanoparticle hopping on the liquid cell window surface. Slow-moving nanoparticles self-assemble predominantly into linear 1D chains by sequential attachment of nanoparticles to existing chains, while highly mobile nanoparticles self-assemble into chains and branched structures by chain–chain attachments. Self-assembly kinetics are consistent with a diffusion-driven mechanism; we attribute the change in self-assembly pathway to the increased self-assembly rate of highly mobile nanoparticles. Furthermore, these results indicate that nanoparticle mobility can dictate the self-assembly mechanism and final nanostructure morphology in a manner similar to interparticle interactions.« less

Self-organization of a self-assembled supramolecular rectangle, square, and three-dimensional cage on Au111 surfaces.

PubMed

Yuan, Qun-Hui; Wan, Li-Jun; Jude, Hershel; Stang, Peter J

2005-11-23

The structure and conformation of three self-assembled supramolecular species, a rectangle, a square, and a three-dimensional cage, on Au111 surfaces were investigated by scanning tunneling microscopy. These supramolecular assemblies adsorb on Au111 surfaces and self-organize to form highly ordered adlayers with distinct conformations that are consistent with their chemical structures. The faces of the supramolecular rectangle and square lie flat on the surface, preserving their rectangle and square conformations, respectively. The three-dimensional cage also forms well-ordered adlayers on the gold surface, forming regular molecular rows of assemblies. When the rectangle and cage were mixed together, the assemblies separated into individual domains, and no mixed adlayers were observed. These results provide direct evidence of the noncrystalline solid-state structures of these assemblies and information about how they self-organize on Au111 surfaces, which is of importance in the potential manufacturing of functional nanostructures and devices.

Fabrication and Characterization of a Stabilized Thin Film Ag/AgCl Reference Electrode Modified with Self-Assembled Monolayer of Alkane Thiol Chains for Rapid Biosensing Applications.

PubMed

Rahman, Tanzilur; Ichiki, Takanori

2017-10-13

The fabrication of miniaturized electrical biosensing devices can enable the rapid on-chip detection of biomarkers such as miRNA molecules, which is highly important in early-stage cancer detection. The challenge in realizing such devices remains in the miniaturization of the reference electrodes, which is an integral part of electrical detection. Here, we report on a novel thin film Ag/AgCl reference electrode (RE) that has been fabricated on top of a Au-sputtered glass surface, which was coated with a self-assembled monolayer (SAM) of 6-mercepto-1-hexanol (MCH). The electrode showed very little measurement deviation (-1.5 mv) from a commercial Ag/AgCl reference electrode and exhibited a potential drift of only ± 0.2 mV/h. In addition, the integration of this SAM-modified microfabricated thin film RE enabled the rapid detection (<30 min) of miRNA (let-7a). The electrode can be integrated seamlessly into a microfluidic device, allowing the highly stable and fast measurement of surface potential and is expected to be very useful for the development of miniature electrical biosensors.

Photocatalytic activity of self-assembled porous TiO2 nano-columns array fabricated by oblique angle sputter deposition

NASA Astrophysics Data System (ADS)

Shi, Pengjun; Li, Xibo; Zhang, Qiuju; Yi, Zao; Luo, Jiangshan

2018-04-01

A well-separated and oriented TiO2 nano-columns arrays with porous structure were fabricated by the oblique angle sputter deposition technique and subsequently annealing at 450 °C in Ar/O2 mixed atmosphere. The deposited substrate was firstly modified by a template of self-assembled close-packed arrays of 500 nm-diameter silica (SiO2) spheres. Scanning electronic microscopic (SEM) images show that the porous columnar nanostructure is formed as a result of the geometric shadowing effect and surface diffusion of the adatoms in oblique angle deposition (OAD). X-ray diffraction (XRD) measurements reveal that the physically OAD film with annealing treatment are generally mixed phase of rutile and anatase TiO2 polymorphic forms. The morphology induced absorbance and band gap tuning by different substrates was demonstrated by the UV–vis spectroscopy. The well-separated one-dimensional (1D) nano-columns array with specific large porous surface area is beneficial for charge separation in photocatalytic degradation. Compared with compact thin film, such self-assembled porous TiO2 nano-columns array fabricated by oblique angle sputter deposition performed an enhanced visible light induced photocatalytic activity by decomposing methyl orange (MO) solution. The well-designed periodic array-structured porous TiO2 films by using modified patterned substrates has been demonstrated significantly increased absorption edge in the UV-visible light region with a narrower optical band gap, which are expected to be favorable for application in photovoltaic, lithium-ion insertion and photocatalytic, etc.

Directed self-assembly of metal oxide quantum dots: Copper oxide on strontium titanium trioxide

NASA Astrophysics Data System (ADS)

Du, Yingge

2007-12-01

This dissertation explores the use of focused ion-beams (FIB) to direct the self-assembly of Cu2O quantum dots (QDs) on SrTiO3 (100) substrates via point implants of Ga+ at 30 keV After Ga+ implant and subsequent chemical and thermal surface preparation, oxygen plasma-assisted molecular beam-epitaxy (OPA-MBE) is used to grow Cu 2O QDs. The research of this dissertation finds that, for high FIB implant dose (5.6x1018 ions/cm2) and large interdot spacing (1000 nm), multiple QDs can be formed preferentially on the edges of FIB modified pits. For lower doses and/or smaller interdot spacings (8.8x1014 ions/cm2 and lower, 130 or 167 nm), individual QDs nucleate first within the pits. Under carefully controlled conditions, the separation and arrangement of the Cu2O QDs follows the FIB patterned template. This study finds that the FIB directed self-assembly technique works for different FIB doses, FIB interdot spacings and OPA-MBE deposition thicknesses, suggesting that this method is robust and flexible. Examination of QD growth on low-dose implant surfaces revealed a multi-step growth process. Initial deposition filled the pits just to the level of the original unmodified crystal growth surface. Following a pause in QD growth and the deposition of additional material, QD growth resumed on top of these perfectly filled pits. As growth continued, the dots reached a self-limiting size such that additional material deposition generated more QDs of similar size rather than continued growth of the large dots. This dissertation also seeks to increase understanding of the relative rolls played in the directed self-assembly process by local substrate chemistry, surface morphology, crystal-linity, and stress/strain. Experimental results revealed that although Ga concentration was noticeably higher on modified regions after FIB implant, no measurable Ga was found on the surface after high temperature annealing performed prior to QD growth. Thus Ga related chemistry/reactivity changes appear unlikely to be primary motivators of directed self-assembly. Low dose implant patterning created local depressions on the surface. This pit shape topography appears to be a strong contributor to the preferred nucleation within the pits, as the sidewalls of those surface pits could contain a high density of surface steps, which are known to decrease the adatom diffusion length and act as sinks to absorb the diffusing species. To further interpret the low dose implant results, calculations of total free-energy changes have been performed to study the differences between nucleation on a flat substrate surface and nucleation within a surface pit. This analysis shows that nucleation within a pit is almost always energetically favorable. In some special cases, assuming the pits have an inverted pyramidal shape, calculations show that island formation within the pits lowers the system total free-energy from the beginning of growth, i.e. there is no critical radius or energy barrier before a stable nucleus can be formed. The major geometric difference between high and low dose implantation area was revealed by AFM studies, which showed that pits generated by high implantation dose were still rounded after annealing and before growth, while pits from lower doses patterning had developed square edges oriented along the <100> directions of the substrate. These geometric differences suggest differences in crystalline or strain/stress states, either/both of which could have caused the subsequent different island growth characteristics. Continued study of directed self-assembly of metal oxide quantum dots should lead to better understanding of the creation of well ordered, precisely controlled, high density QD arrays, ultimately contributing to the development of next generation nanoelectronic, magnetic, and optical devices.

Attenuation of encrustation by self-assembled inorganic fullerene-like nanoparticles.

PubMed

Ron, Racheli; Zbaida, David; Kafka, Ilan Z; Rosentsveig, Rita; Leibovitch, Ilan; Tenne, Reshef

2014-05-21

Ureteral stents and urethral catheters are commonly used medical devices for maintaining urinary flow. However, long-term placement (>30 days) of these devices in the urinary tracts is limited by the development of encrustation, a phenomenon that holds a prevalence of 50% within this patient population, resulting in a great deal of morbidity to the patients. Here we report the influence of surface coating of an all-silicone catheter with rhenium-doped fullerene-like molybdenum disulfide (Re:IF-MoS2) nanoparticles on the growth and attachment of in vitro encrustation stones. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) analyses indicated a remarkable attenuation in encrustation occupation on the Re:IF-MoS2-coated catheter surfaces compared to neat catheters. The doped nanoparticles displayed a unique tendency to self-assemble into mosaic-like arrangements, modifying the surface to be encrustation-repellent. The mechanism of encrustation retardation on the surface coated catheters is discussed in some detail. The ramification of these results for the clogging of other body indwelling devices is briefly discussed.

Effect of surface chemical composition on the surface potential and iso-electric point of silicon substrates modified with self-assembled monolayers.

PubMed

Kuo, Che-Hung; Chang, Hsun-Yun; Liu, Chi-Ping; Lee, Szu-Hsian; You, Yun-Wen; Shyue, Jing-Jong

2011-03-07

Self-assembled monolayer (SAM)-modified nano-materials are a new technology to deliver drug molecules. While the majority of these depend on covalently immobilizing molecules on the surface, it is proposed that electrostatic interactions may be used to deliver drugs. By tuning the surface potential of solid substrates with SAMs, drug molecules could be either absorbed on or desorbed from substrates through the difference in electrostatic interactions around the selected iso-electric point (IEP). In this work, the surface of silicon substrates was tailored with various ratios of 3-aminopropyltrimethoxysilane (APTMS) and 3-mercaptopropyltrimethoxysilane (MPTMS), which form amine- and thiol-bearing SAMs, respectively. The ratio of the functional groups on the silicon surface was quantified by X-ray photoelectron spectrometry (XPS); in general, the deposition kinetics of APTMS were found to be faster than those of MPTMS. Furthermore, for solutions with high MPTMS concentrations, the relative deposition rate of APTMS increased dramatically due to the acid-base reaction in the solution and subsequent electrostatic interactions between the molecules and the substrate. The zeta potential in aqueous electrolytes was determined with an electro-kinetic analyzer. By depositing SAMs of binary functional groups in varied ratios, the surface potential and IEP of silicon substrates could be fine-tuned. For <50% amine concentration in SAMs, the IEP changed linearly with the chemical composition from <2 to 7.18. For higher amine concentrations, the IEP slowly increased with concentration to 7.94 because the formation of hydrogen-bonding suppressed the subsequent protonation of amines.

Crystalline TiO 2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

NASA Astrophysics Data System (ADS)

Zhao, Yuancong; Tu, Qiufen; Wang, Jin; Huang, Qiongjian; Huang, Nan

2010-12-01

Crystalline TiO 2 films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO 2 films by self-assembling, and the HUPA on TiO 2 films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO 2 films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

Silane surface modification for improved bioadhesion of esophageal stents

PubMed Central

Karakoy, Mert; Gultepe, Evin; Pandey, Shivendra; Khashab, Mouen A.; Gracias, David H.

2014-01-01

Stent migration occurs in 10-40% of patients who undergo placement of esophageal stents, with higher migration rates seen in those treated for benign esophageal disorders. This remains a major drawback of esophageal stent therapy. In this paper, we propose a new surface modification method to increase the adhesion between self-expandable metallic stents (SEMS) and tissue while preserving their removability. Taking advantage of the well-known affinity between epoxide and amine terminated silane coupling agents with amine and carboxyl groups that are abundant in proteins and related molecules in the human body; we modified the surfaces of silicone coated esophageal SEMS with these adhesive self-assembled monolayers (SAMs). We utilized vapor phase silanization to modify the surfaces of different substrates including PDMS strips and SEMS, and measured the force required to slide these substrates on a tissue piece. Our results suggest that surface modification of esophageal SEMS via covalent attachment of protein-binding coupling agents improves adhesion to tissue and could offer a solution to reduce SEMS migration while preserving their removability. PMID:25663731

Nano-Al{sub 2}O{sub 3} multilayer film deposition on cotton fabrics by layer-by-layer deposition method

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

Ugur, Sule S., E-mail: sule@mmf.sdu.edu.tr; Sariisik, Merih; Aktas, A. Hakan

Highlights: {yields} Cationic charges were created on the cotton fibre surfaces with 2,3-epoxypropyltrimethylammonium chloride. {yields} Al{sub 2}O{sub 3} nanoparticles were deposited on the cotton fabrics by layer-by-layer deposition. {yields} The fabrics deposited with the Al{sub 2}O{sub 3} nanoparticles exhibit better UV-protection and significant flame retardancy properties. {yields} The mechanical properties were improved after surface film deposition. -- Abstract: Al{sub 2}O{sub 3} nanoparticles were used for fabrication of multilayer nanocomposite film deposition on cationic cotton fabrics by electrostatic self-assembly to improve the mechanical, UV-protection and flame retardancy properties of cotton fabrics. Cotton fabric surface was modified with a chemical reaction tomore » build-up cationic charge known as cationization. Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy, X-ray Photoelectron Spectroscopy and Scanning Electron Microscopy were used to verify the presence of deposited nanolayers. Air permeability, whiteness value, tensile strength, UV-transmittance and Limited Oxygen Index properties of cotton fabrics were analyzed before and after the treatment of Al{sub 2}O{sub 3} nanoparticles by electrostatic self-assemblies. It was proved that the flame retardancy, tensile strength and UV-transmittance of cotton fabrics can be improved by Al{sub 2}O{sub 3} nanoparticle additive through electrostatic self-assembly process.« less

Electrochemically driven host-guest interactions on patterned donor/acceptor self-assembled monolayers.

PubMed

Maglione, Maria Serena; Casado-Montenegro, Javier; Fritz, Eva-Corinna; Crivillers, Núria; Ravoo, Bart Jan; Rovira, Concepció; Mas-Torrent, Marta

2018-03-25

Here, on ITO//Au patterned substrates SAMs of ferrocene (Fc) on the Au regions and of anthraquinone (AQ) on the ITO areas are prepared, exhibiting three stable redox states. Furthermore, by selectively oxidizing or reducing the Fc or AQ units, respectively, the surface properties are locally modified. As a proof-of-concept, such a confinement of the properties is exploited to locally form host-guest complexes with β-cyclodextrin on specific surface regions depending on the applied voltage.

Carbohydrate-protein interactions investigated on plastic chips statically coated with hydrophobically modified hydroxyethylcellulose.

PubMed

Dang, Fuquan; Maeda, Eiki; Osafune, Tomo; Nakajima, Kazuki; Kakehi, Kazuaki; Ishikawa, Mitsuru; Baba, Yoshinobu

2009-12-15

We developed a novel method for rapid screening of carbohydrate-protein interactions using poly(methyl methacrylate) (PMMA) channels statically coated with hydrophobically modified hydroxyethylcellulose (HM-HEC). We found that a self-assembled monolayer (SAM) of HM-HEC on a PMMA surface intact by water allows rapid and reproducible separations of glycan samples using a 20 mM phosphate without HM-HEC. The underlying mechanism for dynamic and static coatings on the PMMA surface is discussed. Simultaneous analysis of the molecular interaction between a complex mixture of carbohydrates from alpha1-acid glycoprotein and proteins has been successfully achieved in PMMA channels statically coated with a SAM of HM-HEC.

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.

The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol

NASA Astrophysics Data System (ADS)

Liriano, Melissa L.; Carrasco, Javier; Lewis, Emily A.; Murphy, Colin J.; Lawton, Timothy J.; Marcinkowski, Matthew D.; Therrien, Andrew J.; Michaelides, Angelos; Sykes, E. Charles H.

2016-03-01

The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopic understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule's intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface. Our data reveal that the chirality of a simple alcohol can be transferred to its surface binding geometry, drive the directionality of hydrogen-bonded networks and ultimately extended structure. Furthermore, this study provides the first microscopic insight into the surface properties of this important chiral modifier and provides a well-defined system for studying the network's enantioselective interaction with other molecules.

The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol

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

Liriano, Melissa L.; Lewis, Emily A.; Murphy, Colin J.

The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopicmore » understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule’s intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface. Our data reveal that the chirality of a simple alcohol can be transferred to its surface binding geometry, drive the directionality of hydrogen-bonded networks and ultimately extended structure. Furthermore, this study provides the first microscopic insight into the surface properties of this important chiral modifier and provides a well-defined system for studying the network’s enantioselective interaction with other molecules.« less

Self-assembled software and method of overriding software execution

DOEpatents

Bouchard, Ann M.; Osbourn, Gordon C.

2013-01-08

A computer-implemented software self-assembled system and method for providing an external override and monitoring capability to dynamically self-assembling software containing machines that self-assemble execution sequences and data structures. The method provides an external override machine that can be introduced into a system of self-assembling machines while the machines are executing such that the functionality of the executing software can be changed or paused without stopping the code execution and modifying the existing code. Additionally, a monitoring machine can be introduced without stopping code execution that can monitor specified code execution functions by designated machines and communicate the status to an output device.

Assembling new technologies at the interface of materials science and biology

NASA Astrophysics Data System (ADS)

Stendahl, John C.

Molecular self-assembly can be used to construct advanced materials by taking cues from nature and harnessing noncovalent interactions. This bottom-up approach affords molecular level precision that can cultivate pathways to improved materials function. The graduate research presented in this thesis integrates molecular self-assembly with traditional concepts in chemistry and materials science, with the ultimate goal of developing innovative solutions in technology and medicine. In the field of polymer engineering, self-assembly was used to create supramolecular nanoribbons that, when incorporated into polystyrene, modify its microstructure and significantly enhance its toughness and ductility. In medicine, self-assembly was used to create ordered, chemically functional materials to improve interactions with cells and other constituents of the biological environment. One system that was investigated is based on a triblock molecule in which cholesterol is connected to a lysine dendron by a flexible oligo-(L-lactic acid) spacer. These molecules self-assemble into polar surface coatings on fibrous poly(L-lactic acid) scaffolds that improve the scaffold's wettability and increase its retention of cells during seeding. Another self-assembling system that was investigated for biomedical applications is a family of molecules referred to as peptide amphiphiles (PA's). PA's consist of hydrophobic alkyl tails connected to short, hydrophilic peptides that incorporate biological signaling epitopes. These molecules spontaneously assemble into networks of well-defined nanofibers in aqueous environments, with the signaling epitopes presented in high density on the nanofiber exteriors. Nanofiber assembly is triggered by charge screening on the peptides and is able to produce self-supporting gels in concentrations of less than 1.0 wt.-%. The assembly process and mechanical properties of PA gels was investigated in detail with vibrational spectroscopy and oscillatory rheology. PA nanofibers were used in conjunction with fibrous poly(L-lactic acid] fabrics to create chemically functional scaffolds to facilitate islet cell transplantation. In transplant studies in diabetic mice, the use of scaffolds for islet delivery was shown to significantly improve transplant outcomes over free islet injections. Together, these studies illustrate that molecular self-assembly can be used to create functional materials for a variety of applications. These materials utilize noncovalent interactions to produce supramolecular structures that have important impacts on properties.

Molecular self-assembly in substituted alanine derivatives: XRD, Hirshfeld surfaces and DFT studies

NASA Astrophysics Data System (ADS)

Rajalakshmi, Periasamy; Srinivasan, Navaneethakrishnan; Sivaraman, Gandhi; Razak, Ibrahim Abdul; Rosli, Mohd Mustaqim; Krishnakumar, Rajaputi Venkatraman

2014-06-01

The molecular assemblage in the crystal structures of three modified chiral amino acids, two of which are isomeric D- and L-pairs boc-L-benzothienylalanine (BLA), boc-D-benzothienylalanine (BDA) and the other boc-D-naphthylalanine (NDA) differing from this pair very slightly in the chemical modification introduced, is accurately described. The aggregation of amino acid molecules is similar in all the crystals and may be described as a twisted double helical ladder in which two complementary long helical chains formed through O-H⋯O hydrogen bonds are interconnected through the characteristic head-to-tail N-H⋯O hydrogen bonds. Thus the molecular aggregation enabled through classical hydrogen bonds may be regarded as a mimic of the characteristic double helical structure of DNA. Also, precise structural information involving these amino acid molecules with lower symmetry exhibiting higher trigonal symmetry in their self-assembly is expected to throw light on the nature and strength of intermolecular interactions and their role in self-assembly of molecular aggregates, which are crucial in developing new or at least supplement existing crystal engineering strategies. Single crystal X-ray analysis and their electronic structures were calculated at the DFT level with a detailed analysis of Hirshfeld surfaces and fingerprint plots facilitating a comparison of intermolecular interactions in building different supramolecular architectures.

pH-Switchable Interaction of a Carboxybetaine Ester-Based SAM with DNA and Gold Nanoparticles.

PubMed

Filip, Jaroslav; Popelka, Anton; Bertok, Tomas; Holazova, Alena; Osicka, Josef; Kollar, Jozef; Ilcikova, Marketa; Tkac, Jan; Kasak, Peter

2017-07-11

We describe a self-assembled monolayer (SAM) on a gold surface with a carboxybetaine ester functionality to control the interaction between DNA and gold nanoparticles via pH. The negatively charged phosphate backbone of DNA interacts with and adsorbs to the positively charged carboxybetaine esters on the SAM. DNA release can be achieved by the hydrolysis of carboxybetaine ester (CBE) to a zwitterionic carboxybetaine state. Furthermore, the adsorption of negatively charged citrate-capped gold nanoparticles to a SAM-modified plain gold surface can be controlled by the pH. The SAM based on carboxybetaine ester allows for the homogeneous adsorption of particles, whereas the SAM after hydrolysis at high pH repels AuNP adsorption. The antifouling surface properties of the surface modified with carboxybetaine were investigated with protein samples.

Water transport mechanism through open capillaries analyzed by direct surface modifications on biological surfaces

NASA Astrophysics Data System (ADS)

Ishii, Daisuke; Horiguchi, Hiroko; Hirai, Yuji; Yabu, Hiroshi; Matsuo, Yasutaka; Ijiro, Kuniharu; Tsujii, Kaoru; Shimozawa, Tateo; Hariyama, Takahiko; Shimomura, Masatsugu

2013-10-01

Some small animals only use water transport mechanisms passively driven by surface energies. However, little is known about passive water transport mechanisms because it is difficult to measure the wettability of microstructures in small areas and determine the chemistry of biological surfaces. Herein, we developed to directly analyse the structural effects of wettability of chemically modified biological surfaces by using a nanoliter volume water droplet and a hi-speed video system. The wharf roach Ligia exotica transports water only by using open capillaries in its legs containing hair- and paddle-like microstructures. The structural effects of legs chemically modified with a self-assembled monolayer were analysed, so that the wharf roach has a smart water transport system passively driven by differences of wettability between the microstructures. We anticipate that this passive water transport mechanism may inspire novel biomimetic fluid manipulations with or without a gravitational field.

Electrochemical analysis of gold-coated magnetic nanoparticles for detecting immunological interaction

NASA Astrophysics Data System (ADS)

Pham, Thao Thi-Hien; Sim, Sang Jun

2010-01-01

An electrochemical impedance immunosensor was developed for detecting the immunological interaction between human immunoglobulin (IgG) and protein A from Staphylococcus aureus based on the immobilization of human IgG on the surface of modified gold-coated magnetic nanoparticles. The nanoparticles with an Au shell and Fe oxide cores were functionalized by a self-assembled monolayer of 11-mercaptoundecanoic acid. The electrochemical analysis was conducted on the modified magnetic carbon paste electrodes with the nanoparticles. The magnetic nanoparticles were attached to the surface of the magnetic carbon paste electrodes via magnetic force. The cyclic voltammetry technique and electrochemical impedance spectroscopy measurements of the magnetic carbon paste electrodes coated with magnetic nanoparticles-human IgG complex showed changes in its alternating current (AC) response both after the modification of the surface of the electrode and the addition of protein A. The immunological interaction between human IgG on the surface of the modified magnetic carbon paste electrodes and protein A in the solution could be successfully monitored.

Self-assembly of glucose oxidase on reduced graphene oxide-magnetic nanoparticles nanocomposite-based direct electrochemistry for reagentless glucose biosensor.

PubMed

Pakapongpan, Saithip; Poo-Arporn, Rungtiva P

2017-07-01

A novel approach of the immobilization of a highly selective and stable glucose biosensor based on direct electrochemistry was fabricated by a self-assembly of glucose oxidase (GOD) on reduced graphene oxide (RGO) covalently conjugated to magnetic nanoparticles (Fe 3 O 4 NPs) modified on a magnetic screen-printed electrode (MSPE). The RGO-Fe 3 O 4 nanocomposite has remarkable enhancement in large surface areas, is favorable environment for enzyme immobilization, facilitates electron transfer between enzymes and electrode surfaces and possesses superparamagnetism property. The morphology and electrochemical properties of RGO-Fe 3 O 4 /GOD were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, cyclic voltammetry (CV) and amperometry. The modified electrode was a fast, direct electron transfer with an apparent electron transfer rate constant (k s ) of 13.78s -1 . The proposed biosensor showed fast amperometric response (3s) to glucose with a wide linear range from 0.05 to 1mM, a low detection limit of 0.1μM at a signal to noise ratio of 3 (S/N=3) and good sensitivity (5.9μA/mM). The resulting biosensor has high stability, good reproducibility, excellent selectivity and successfully applied detection potential at -0.45V. This mediatorless glucose sensing used the advantages of covalent bonding and self-assembly as a new approach for immobilizing enzymes without any binder. It would be worth noting that it opens a new avenue for fabricating excellent electrochemical biosensors. This is a new approach that reporting the immobilization of glucose oxidase on reduced graphene oxide (RGO) covalently conjugated to magnetic nanoparticles (Fe 3 O 4 NPs) by electrostatic interaction and modified screen printed electrode. We propose the reagentless with fabrication method without binder and adhesive agents for immobilized enzyme. Fe 3 O 4 NPs increasing surface area to enhance the immobilization and prevent the leaching of enzymes at electrode surfaces by magnetic stickers which is improve the stability of the biosensor. Based on this synthesis technique, it is a good new strategy and simple used to fabrication of third-generation glucose biosensor and this nanocomposite could be used as a platform for disposable biosensor and biofuel cell applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Attenuation of encrustation by self-assembled inorganic fullerene-like nanoparticles

NASA Astrophysics Data System (ADS)

Ron, Racheli; Zbaida, David; Kafka, Ilan Z.; Rosentsveig, Rita; Leibovitch, Ilan; Tenne, Reshef

2014-04-01

Ureteral stents and urethral catheters are commonly used medical devices for maintaining urinary flow. However, long-term placement (>30 days) of these devices in the urinary tracts is limited by the development of encrustation, a phenomenon that holds a prevalence of 50% within this patient population, resulting in a great deal of morbidity to the patients. Here we report the influence of surface coating of an all-silicone catheter with rhenium-doped fullerene-like molybdenum disulfide (Re:IF-MoS2) nanoparticles on the growth and attachment of in vitro encrustation stones. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) analyses indicated a remarkable attenuation in encrustation occupation on the Re:IF-MoS2-coated catheter surfaces compared to neat catheters. The doped nanoparticles displayed a unique tendency to self-assemble into mosaic-like arrangements, modifying the surface to be encrustation-repellent. The mechanism of encrustation retardation on the surface coated catheters is discussed in some detail. The ramification of these results for the clogging of other body indwelling devices is briefly discussed.Ureteral stents and urethral catheters are commonly used medical devices for maintaining urinary flow. However, long-term placement (>30 days) of these devices in the urinary tracts is limited by the development of encrustation, a phenomenon that holds a prevalence of 50% within this patient population, resulting in a great deal of morbidity to the patients. Here we report the influence of surface coating of an all-silicone catheter with rhenium-doped fullerene-like molybdenum disulfide (Re:IF-MoS2) nanoparticles on the growth and attachment of in vitro encrustation stones. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) analyses indicated a remarkable attenuation in encrustation occupation on the Re:IF-MoS2-coated catheter surfaces compared to neat catheters. The doped nanoparticles displayed a unique tendency to self-assemble into mosaic-like arrangements, modifying the surface to be encrustation-repellent. The mechanism of encrustation retardation on the surface coated catheters is discussed in some detail. The ramification of these results for the clogging of other body indwelling devices is briefly discussed. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr06231g

Semiconductor nanocrystals covalently bound to solid inorganic surfaces using self-assembled monolayers

DOEpatents

Alivisatos, A. Paul; Colvin, Vicki L.

1998-01-01

Methods are described for attaching semiconductor nanocrystals to solid inorganic surfaces, using self-assembled bifunctional organic monolayers as bridge compounds. Two different techniques are presented. One relies on the formation of self-assembled monolayers on these surfaces. When exposed to solutions of nanocrystals, these bridge compounds bind the crystals and anchor them to the surface. The second technique attaches nanocrystals already coated with bridge compounds to the surfaces. Analyses indicate the presence of quantum confined clusters on the surfaces at the nanolayer level. These materials allow electron spectroscopies to be completed on condensed phase clusters, and represent a first step towards synthesis of an organized assembly of clusters. These new products are also disclosed.

Enhancement of pharmacokinetic and pharmacological behavior of ocular dorzolamide after factorial optimization of self-assembled nanostructures

PubMed Central

Afify, Enas A. M. R.; Elsayed, Ibrahim; Gad, Mary K.; Mohamed, Magdy I.

2018-01-01

Dorzolamide hydrochloride is frequently administered for the control of the intra-ocular pressure associated with glaucoma. The aim of this study is to develop and optimize self-assembled nanostructures of dorzolamide hydrochloride and L-α-Phosphatidylcholine to improve the pharmacokinetic parameters and extend the drug pharmacological action. Self-assembled nanostructures were prepared using a modified thin-film hydration technique. The formulae compositions were designed based on response surface statistical design. The prepared self-assembled nanostructures were characterized by testing their drug content, particle size, polydispersity index, zeta potential, partition coefficient, release half-life and extent. The optimized formulae having the highest drug content, zeta potential, partition coefficient, release half-life and extent with the lowest particle size and polydispersity index were subjected to further investigations including investigation of their physicochemical, morphological characteristics, in vivo pharmacokinetic and pharmacodynamic profiles. The optimized formulae were prepared at pH 8.7 (F5 and F6) and composed of L-α-Phosphatidylcholine and drug mixed in a ratio of 1:1 and 2:1 w/w, respectively. They showed significantly higher Cmax, AUC024 and AUC0∞ at the aqueous humor with extended control over the intra-ocular pressure, when compared to the marketed product; Trusopt®. The study introduced novel and promising self-assembled formulae able to permeate higher drug amount through the cornea and achieve sustained pharmacological effect at the site of action. PMID:29401498

Developing the Surface Chemistry of Transparent Butyl Rubber for Impermeable Stretchable Electronics.

PubMed

Vohra, Akhil; Carmichael, R Stephen; Carmichael, Tricia Breen

2016-10-11

Transparent butyl rubber is a new elastomer that has the potential to revolutionize stretchable electronics due to its intrinsically low gas permeability. Encapsulating organic electronic materials and devices with transparent butyl rubber protects them from problematic degradation due to oxygen and moisture, preventing premature device failure and enabling the fabrication of stretchable organic electronic devices with practical lifetimes. Here, we report a methodology to alter the surface chemistry of transparent butyl rubber to advance this material from acting as a simple device encapsulant to functioning as a substrate primed for direct device fabrication on its surface. We demonstrate a combination of plasma and chemical treatment to deposit a hydrophilic silicate layer on the transparent butyl rubber surface to create a new layered composite that combines Si-OH surface chemistry with the favorable gas-barrier properties of bulk transparent butyl rubber. We demonstrate that these surface Si-OH groups react with organosilanes to form self-assembled monolayers necessary for the deposition of electronic materials, and furthermore demonstrate the fabrication of stretchable gold wires using nanotransfer printing of gold films onto transparent butyl rubber modified with a thiol-terminated self-assembled monolayer. The surface modification of transparent butyl rubber establishes this material as an important new elastomer for stretchable electronics and opens the way to robust, stretchable devices.

Gold cleaning methods for preparation of cell culture surfaces for self-assembled monolayers of zwitterionic oligopeptides.

PubMed

Enomoto, Junko; Kageyama, Tatsuto; Myasnikova, Dina; Onishi, Kisaki; Kobayashi, Yuka; Taruno, Yoko; Kanai, Takahiro; Fukuda, Junji

2018-05-01

Self-assembled monolayers (SAMs) have been used to elucidate interactions between cells and material surface chemistry. Gold surfaces modified with oligopeptide SAMs exhibit several unique characteristics, such as cell-repulsive surfaces, micropatterns of cell adhesion and non-adhesion regions for control over cell microenvironments, and dynamic release of cells upon external stimuli under culture conditions. However, basic procedures for the preparation of oligopeptide SAMs, including appropriate cleaning methods of the gold surface before modification, have not been fully established. Because gold surfaces are readily contaminated with organic compounds in the air, cleaning methods may be critical for SAM formation. In this study, we examined the effects of four gold cleaning methods: dilute aqua regia, an ozone water, atmospheric plasma, and UV irradiation. Among the methods, UV irradiation most significantly improved the formation of oligopeptide SAMs in terms of repulsion of cells on the surfaces. We fabricated an apparatus with a UV light source, a rotation table, and HEPA filter, to treat a number of gold substrates simultaneously. Furthermore, UV-cleaned gold substrates were capable of detaching cell sheets without serious cell injury. This may potentially provide a stable and robust approach to oligopeptide SAM-based experiments for biomedical studies. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Dewetting of polymer thin films on modified curved surfaces: preparation of polymer nanoparticles with asymmetric shapes by anodic aluminum oxide templates.

PubMed

Liu, Chih-Ting; Tsai, Chia-Chan; Chu, Chien-Wei; Chi, Mu-Huan; Chung, Pei-Yun; Chen, Jiun-Tai

2018-04-18

We study the dewetting behaviors of poly(methyl methacrylate) (PMMA) thin films coated in the cylindrical nanopores of anodic aluminum oxide (AAO) templates by thermal annealing. Self-assembled monolayers (SAMs) of n-octadecyltrichlorosilane (ODTS) are introduced to modify the pore surfaces of the AAO templates to induce the dewetting process. By using scanning electron microscopy (SEM), the dewetting-induced morphology transformation from the PMMA thin films to PMMA nanoparticles with asymmetric shapes can be observed. The sizes of the PMMA nanoparticles can be controlled by the original PMMA solution concentrations. The dewetting phenomena on the modified nanopores are explained by taking into account the excess intermolecular interaction free energy (ΔG). This work opens a new possibility for creating polymer nanoparticles with asymmetric shapes in confined geometries.

PNA-PEG modified silicon platforms as functional bio-interfaces for applications in DNA microarrays and biosensors.

PubMed

Cattani-Scholz, Anna; Pedone, Daniel; Blobner, Florian; Abstreiter, Gerhard; Schwartz, Jeffrey; Tornow, Marc; Andruzzi, Luisa

2009-03-09

The synthesis and characterization of two types of silicon-based biofunctional interfaces are reported; each interface bonds a dense layer of poly(ethylene glycol) (PEG(n)) and peptide nucleic acid (PNA) probes. Phosphonate self-assembled monolayers were derivatized with PNA using a maleimido-terminated PEG(45). Similarly, siloxane monolayers were functionalized with PNA using a maleimido-terminated PEG(45) spacer and were subsequently modified with a shorter methoxy-terminated PEG(12) ("back-filling"). The long PEG(45) spacer was used to distance the PNA probe from the surface and to minimize undesirable nonspecific adsorption of DNA analyte. The short PEG(12) "back-filler" was used to provide additional passivation of the surface against nonspecific DNA adsorption. X-ray photoelectron spectroscopic (XPS) analysis near the C 1s and N 1s ionization edges was done to characterize chemical groups formed in the near-surface region, which confirmed binding of PEG and PNA to the phosphonate and silane films. XPS also indicated that additional PEG chains were tethered to the surface during the back-filling process. Fluorescence hybridization experiments were carried out with complementary and noncDNA strands; both phosphonate and siloxane biofunctional surfaces were effective for hybridization of cDNA strands and significantly reduced nonspecific adsorption of the analyte. Spatial patterns were prepared by polydimethylsiloxane (PDMS) micromolding on the PNA-functionalized surfaces; selective hybridization of fluorescently labeled DNA was shown at the PNA functionalized regions, and physisorption at the probe-less PEG-functionalized regions was dramatically reduced. These results show that PNA-PEG derivatized phosphonate monolayers hold promise for the smooth integration of device surface chemistry with semiconductor technology for the fabrication of DNA biosensors. In addition, our results confirm that PNA-PEG derivatized self-assembled carboxyalkylsiloxane films are promising substrates for DNA microarray applications.

A nanoscale bio-inspired light-harvesting system developed from self-assembled alkyl-functionalized metallochlorin nano-aggregates

NASA Astrophysics Data System (ADS)

Ocakoglu, Kasim; Joya, Khurram S.; Harputlu, Ersan; Tarnowska, Anna; Gryko, Daniel T.

2014-07-01

Self-assembled supramolecular organization of nano-structured biomimetic light-harvesting modules inside solid-state nano-templates can be exploited to develop excellent light-harvesting materials for artificial photosynthetic devices. We present here a hybrid light-harvesting system mimicking the chlorosomal structures of the natural photosynthetic system using synthetic zinc chlorin units (ZnChl-C6, ZnChl-C12 and ZnChl-C18) that are self-aggregated inside the anodic aluminum oxide (AAO) nano-channel membranes. AAO nano-templates were modified with a TiO2 matrix and functionalized with long hydrophobic chains to facilitate the formation of supramolecular Zn-chlorin aggregates. The transparent Zn-chlorin nano-aggregates inside the alkyl-TiO2 modified AAO nano-channels have a diameter of ~120 nm in a 60 μm length channel. UV-Vis studies and fluorescence emission spectra further confirm the formation of the supramolecular ZnChl aggregates from monomer molecules inside the alkyl-functionalized nano-channels. Our results prove that the novel and unique method can be used to produce efficient and stable light-harvesting assemblies for effective solar energy capture through transparent and stable nano-channel ceramic materials modified with bio-mimetic molecular self-assembled nano-aggregates.Self-assembled supramolecular organization of nano-structured biomimetic light-harvesting modules inside solid-state nano-templates can be exploited to develop excellent light-harvesting materials for artificial photosynthetic devices. We present here a hybrid light-harvesting system mimicking the chlorosomal structures of the natural photosynthetic system using synthetic zinc chlorin units (ZnChl-C6, ZnChl-C12 and ZnChl-C18) that are self-aggregated inside the anodic aluminum oxide (AAO) nano-channel membranes. AAO nano-templates were modified with a TiO2 matrix and functionalized with long hydrophobic chains to facilitate the formation of supramolecular Zn-chlorin aggregates. The transparent Zn-chlorin nano-aggregates inside the alkyl-TiO2 modified AAO nano-channels have a diameter of ~120 nm in a 60 μm length channel. UV-Vis studies and fluorescence emission spectra further confirm the formation of the supramolecular ZnChl aggregates from monomer molecules inside the alkyl-functionalized nano-channels. Our results prove that the novel and unique method can be used to produce efficient and stable light-harvesting assemblies for effective solar energy capture through transparent and stable nano-channel ceramic materials modified with bio-mimetic molecular self-assembled nano-aggregates. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01661k

Microcontact printing of self-assembled monolayers to pattern the light-emission of polymeric light-emitting diodes

NASA Astrophysics Data System (ADS)

Brondijk, J. J.; Li, X.; Akkerman, H. B.; Blom, P. W. M.; de Boer, B.

2009-04-01

By patterning a self-assembled monolayer (SAM) of thiolated molecules with opposing dipole moments on a gold anode of a polymer light-emitting diode (PLED), the charge injection and, therefore, the light-emission of the device can be controlled with a micrometer-scale resolution. Gold surfaces were modified with SAMs based on alkanethiols and perfluorinated alkanethiols, applied by microcontact printing, and their work functions have been measured. The molecules form a chemisorbed monolayer of only ˜1.5 nm on the gold surface, thereby locally changing the work function of the metal. Kelvin probe measurements show that the local work function can be tuned from 4.3 to 5.5 eV, which implies that this anode can be used as a hole blocking electrode or as a hole injecting electrode, respectively, in PLEDs based on poly( p-phenylene vinylene) (PPV) derivatives. By microcontact printing of SAMs with opposing dipole moments, the work function was locally modified and the charge injection in the PLED could be controlled down to the micrometer length scale. Consequently, the local light-emission exhibits a high contrast. Microcontact printing of SAMs is a simple and inexpensive method to pattern, with micrometer resolution, the light-emission for low-end applications like static displays.

Site-directed introduction of disulfide groups on antibodies for highly sensitive immunosensors.

PubMed

Acero Sánchez, Josep Ll; Fragoso, Alex; Joda, Hamdi; Suárez, Guillaume; McNeil, Calum J; O'Sullivan, Ciara K

2016-07-01

The interface between the sample and the transducer surface is critical to the performance of a biosensor. In this work, we compared different strategies for covalent self-assembly of antibodies onto bare gold substrates by introducing disulfide groups into the immunoglobulin structure, which acted as anchor molecules able to chemisorb spontaneously onto clean gold surfaces. The disulfide moieties were chemically introduced to the antibody via the primary amines, carboxylic acids, and carbohydrates present in its structure. The site-directed modification via the carbohydrate chains exhibited the best performance in terms of analyte response using a model system for the detection of the stroke marker neuron-specific enolase. SPR measurements clearly showed the potential for creating biologically active densely packed self-assembled monolayers (SAMs) in a one-step protocol compared to both mixed SAMs of alkanethiol compounds and commercial immobilization layers. The ability of the carbohydrate strategy to construct an electrochemical immunosensor was investigated using electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV) transduction. Graphical Abstract Left: Functionalization strategies of bare gold substrates via direct bio-SAM using disulfide-containing antibody chemically modified via their primary amines (A), carbohydrates (B) and carboxylic acids (C). Right: Dependence of the peak height with NSE concentration at NSE21-CHO modified electrochemical immunosensor. Inset: Logarithmic calibration plot.

Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries

PubMed Central

Zettsu, Nobuyuki; Kida, Satoru; Uchida, Shuhei; Teshima, Katsuya

2016-01-01

We demonstrate herein that an ultra-thin fluoroalkylsilane self-assembled monolayer coating can be used as a modifying agent at LiNi0.5Mn1.5O4−δcathode/electrolyte interfaces in 5V-class lithium-ion batteries. Bare LiNi0.5Mn1.5O4−δ cathode showed substantial capacity fading, with capacity dropping to 79% of the original capacity after 100 cycles at a rate of 1C, which was entirely due to dissolution of Mn3+ from the spinel lattice via oxidative decomposition of the organic electrolyte. Capacity retention was improved to 97% on coating ultra-thin FAS17-SAM onto the LiNi0.5Mn1.5O4 cathode surface. Such surface protection with highly ordered fluoroalkyl chains insulated the cathode from direct contact with the organic electrolyte and led to increased tolerance to HF. PMID:27553901

Surface-assisted DNA self-assembly: An enzyme-free strategy towards formation of branched DNA lattice

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

Bhanjadeo, Madhabi M.; Academy of Scientific and Innovative Research; Nayak, Ashok K.

DNA based self-assembled nanostructures and DNA origami has proven useful for organizing nanomaterials with firm precision. However, for advanced applications like nanoelectronics and photonics, large-scale organization of self-assembled branched DNA (bDNA) into periodic lattices is desired. In this communication for the first time we report a facile method of self-assembly of Y-shaped bDNA nanostructures on the cationic surface of Aluminum (Al) foil to prepare periodic two dimensional (2D) bDNA lattice. Particularly those Y-shaped bDNA structures having smaller overhangs and unable to self-assemble in solution, they are easily assembled on the surface of Al foil in the absence of ligase. Fieldmore » emission scanning electron microscopy (FESEM) analysis shows homogenous distribution of two-dimensional bDNA lattices across the Al foil. When the assembled bDNA structures were recovered from the Al foil and electrophoresed in nPAGE only higher order polymeric bDNA structures were observed without a trace of monomeric structures which confirms the stability and high yield of the bDNA lattices. Therefore, this enzyme-free economic and efficient strategy for developing bDNA lattices can be utilized in assembling various nanomaterials for functional molecular components towards development of DNA based self-assembled nanodevices. - Highlights: • Al foil surface-assisted self-assembly of monomeric structures into larger branched DNA lattice. • FESEM study confirms the uniform distribution of two-dimensional bDNA lattice structures across the surface of Al foil. • Enzyme-free and economic strategy to prepare higher order structures from simpler DNA nanostructures have been confirmed by recovery assay. • Use of well proven sequences for the preparation of pure Y-shaped monomeric DNA nanostructure with high yield.« less

Development of self-assembled molecular structures on polymeric surfaces and their applications as ultrasonically responsive barrier coatings for on-demand, pulsatile drug delivery

NASA Astrophysics Data System (ADS)

Kwok, Connie Sau-Kuen

Nature in the form of DNA, proteins, and cells has the remarkable ability to interact with its environment by processing biological information through specific molecular recognition at the interface. As such, materials that are capable of triggering an appropriate biological response need to be engineered at the biomaterial surface. Chemically and structurally well-defined self-assembled monolayers (SAMs), biomimetics of the lipid bilayer in cell membranes, have been created and studied mostly on rigid metallic surfaces. This dissertation is motivated by the lack of methods to generate a molecularly designed surface for biomedical polymers and thus provides an enabling technology to engineer a polymeric surface precisely at a molecular and cellular level. To take this innovation one step further, we demonstrated that such self-assembled molecular structure coated on drug-containing polymeric devices could act as a stimulus-responsive barrier for controlled drug delivery. A simple, one-step procedure for generating ordered, crystalline methylene chains on polymeric surfaces via urethane linkages was successfully developed. The self-assemblies and molecular structures of these crystalline methylene chains are comparable to the SAM model surfaces, as evidenced by various surface characterization techniques (XPS, TOF-SIMS, and FTIR-ATR). For the first time, these self-assembled molecular structures are shown to function collectively as an ultrasound-responsive barrier membrane for pulsatile drug delivery, including delivery of low-molecular-weight ciprofloxacin and high-molecular-weight insulin. Encouraging results, based on the insulin-activated deoxyglucose uptakes in adipocytes, indicate that the released insulin remained biologically active. Both chemical and acoustic analyses suggest that the ultrasound-assisted release mechanism is primarily induced by transient cavitation, which causes temporary disruption of the self-assembled overlayer, and thus allows temporal release of the encapsulated drugs. In addition to acoustic energy, self-assembled surfaces experience order-disorder transition and have a transition temperature higher than body temperature if longer alkyl chains (C18) are used. The C18-assembled surface barrier membrane exhibits a relatively superior impermeable coating than the shorter C12 chains. The versatility of derivatizing the terminal groups of the self-assembled molecular structures is illustrated by attaching poly (ethyleneoxide) oligomers to the alkyl chains to minimize nonspecific protein adsorption. This study lays an important foundation for future work in conjugating other biomolecules to develop surface-based diagnostics and biomaterials. With much success, this original research work of forming self-assembled crystalline structures on synthetic materials still allows for numerous opportunities for new applications and possibly even more new discoveries.

Glucose oxidase immobilization on different modified surfaces of platinum nanowire for application in glucose detection

NASA Astrophysics Data System (ADS)

Thanh Tuyen Le, Thi; Duy Tran, Phu; Pham, Xuan Tung; Hien Tong, Duy; Chien Dang, Mau

2010-09-01

In this work, the surface of platinum (Pt) nanowires was modified by using several chemicals, including a compound of gelatin gel with SiO2, polyvinyl alcohol (PVA) with Prussian blue (PB) mediator and cysteamine self-assembled monolayers (SAM). Then, glucose oxidase (GOD) enzyme was immobilized on the modified surfaces of Pt nanowire electrodes by using techniques of electrochemical adsorption and chemical binding. The GOD immobilized Pt nanowires were used for application in glucose detection by performing a cyclic voltammetry measurement. The detection results showed that GOD was immobilized on all of the tested surfaces and the highest glucose detection sensitivity of 60 μM was obtained when the Pt nanowires were modified by PVA with PB mediator. Moreover, the sensors showed very high current response when the Pt nanowires were modified with the cysteamine SAM. The stability and catalyst activity of GOD are also reported here. For instance, the catalyst activity of GOD retained about 60% of its initial value after it was stored at 4 °C in a 100 mM PBS buffer solution with a pH of 7.2 for a period of 30 days.

"Mixed-charge self-assembled monolayers" as a facile method to design pH-induced aggregation of large gold nanoparticles for near-infrared photothermal cancer therapy.

PubMed

Li, Huan; Liu, Xiangsheng; Huang, Nan; Ren, Kefeng; Jin, Qiao; Ji, Jian

2014-01-01

The acidic microenvironment of tumor tissues has proven to be one of the major differences from other normal tissues. The near-infrared (NIR) light irradiation of aggregated gold nanoparticles in a tumor acidic pH-induced manner could then provide an effect approach to treat solid tumors with the advantage of minimizing the undesired damage to normal tissues. Although it is well-known the aggregation of larger nanoparticles will result in a better NIR photothermal effect, the preparation of pH-sensitive gold nanoparticles in large sizes remains a big challenge because of their worse dispersive stability. In this paper, we introduce a facile way to endow large gold nanoparticles with tunable pH-aggregation behaviors by modifying the nanoparticle surface with mixed-charge self-assembly monolayers compromising positively and negatively charged thiol ligands. Four different size nanoparticles were used to study the general principle of tailoring the pH-induced aggregation behaviors of mixed-charge gold nanoparticles (MC-GNPs) by adjusting the surface ligand composition. With proper surface ligand composition, the MC-GNPs in four different sizes that all exhibited aggregation at tumor acidic pH were obtained. The biggest MC-GNPs showed the most encouraging aggregation-enhanced photothermal efficacy in vitro when they formed aggregates. The mixed-charge self-assembled monolayers were then proved as a facile method to design pH-induced aggregation of large gold nanoparticles for better NIR photothermal cancer therapy.

Thermodynamic assessment of adsorptive fouling with the membranes modified via layer-by-layer self-assembly technique.

PubMed

Shen, Liguo; Cui, Xia; Yu, Genying; Li, Fengquan; Li, Liang; Feng, Shushu; Lin, Hongjun; Chen, Jianrong

2017-05-15

In this study, polyvinylidene fluoride (PVDF) microfiltration membrane was coated by dipping the membrane alternatingly in solutions of the polyelectrolytes (poly-diallyldimethylammonium chloride (PDADMAC) and polystyrenesulfonate (PSS)) via layer-by-layer (LBL) self-assembly technique to improve the membrane antifouling ability. Filtration experiments showed that, sludge cake layer on the coated membrane could be more easily washed off, and moreover, the remained flux ratio (RFR) of the coated membrane was obviously improved as compared with the control membrane. Characterization of the membranes showed that a polyelectrolyte layer was successfully coated on the membrane surfaces, and the hydrophilicity, surface charge and surface morphology of the coated membrane were changed. Based on the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) approaches, quantification of interfacial interactions between foulants and membranes in three different scenarios was achieved. It was revealed that there existed a repulsive energy barrier when a particle foulant adhered to membrane surface, and the enhanced electrostatic double layer (EL) interaction and energy barrier should be responsible for the improved antifouling ability of the coated membrane. This study provided a combined solution to membrane modification and interaction energy evaluation related with membrane fouling simultaneously. Copyright © 2017 Elsevier Inc. All rights reserved.

Semiconductor nanocrystals covalently bound to solid inorganic surfaces using self-assembled monolayers

DOEpatents

Alivisatos, A.P.; Colvin, V.L.

1998-05-12

Methods are described for attaching semiconductor nanocrystals to solid inorganic surfaces, using self-assembled bifunctional organic monolayers as bridge compounds. Two different techniques are presented. One relies on the formation of self-assembled monolayers on these surfaces. When exposed to solutions of nanocrystals, these bridge compounds bind the crystals and anchor them to the surface. The second technique attaches nanocrystals already coated with bridge compounds to the surfaces. Analyses indicate the presence of quantum confined clusters on the surfaces at the nanolayer level. These materials allow electron spectroscopies to be completed on condensed phase clusters, and represent a first step towards synthesis of an organized assembly of clusters. These new products are also disclosed. 10 figs.

Self-assembly of proteins into a three-dimensional multilayer system: investigation of the surface of the human fungal pathogen Aspergillus fumigatus.

PubMed

Zykwinska, Agata; Pihet, Marc; Radji, Sadia; Bouchara, Jean-Philippe; Cuenot, Stéphane

2014-06-01

Hydrophobins are small surface active proteins that fulfil a wide spectrum of functions in fungal growth and development. The human fungal pathogen Aspergillus fumigatus expresses RodA hydrophobins that self-assemble on the outer conidial surface into tightly organized nanorods known as rodlets. AFM investigation of the conidial surface allows us to evidence that RodA hydrophobins self-assemble into rodlets through bilayers. Within bilayers, hydrophilic domains of hydrophobins point inward, thus making a hydrophilic core, while hydrophobic domains point outward. AFM measurements reveal that several rodlet bilayers are present on the conidial surface thus showing that proteins self-assemble into a complex three-dimensional multilayer system. The self-assembly of RodA hydrophobins into rodlets results from attractive interactions between stacked β-sheets, which conduct to a final linear cross-β spine structure. A Monte Carlo simulation shows that anisotropic interactions are the main driving forces leading the hydrophobins to self-assemble into parallel rodlets, which are further structured in nanodomains. Taken together, these findings allow us to propose a mechanism, which conducts RodA hydrophobins to a highly ordered rodlet structure. The mechanism of hydrophobin assembly into rodlets offers new prospects for the development of more efficient strategies leading to disruption of rodlet formation allowing a rapid detection of the fungus by the immune system. Copyright © 2014 Elsevier B.V. All rights reserved.

Binding of leachable components of polymethyl methacrylate (PMMA) and peptide on modified SPR chip

NASA Astrophysics Data System (ADS)

Szaloki, M.; Vitalyos, G.; Harfalvi, J.; Hegedus, Cs

2013-12-01

Many types of polymers are often used in dentistry, which may cause allergic reaction, mainly methyl methacrylate allergy due to the leachable, degradable components of polymerized dental products. The aim of this study was to investigate the interaction between the leachable components of PMMA and peptides by Fourier-transform Surface Plasmon Resonance (FT SPR). In our previous work binding of oligopeptides (Ph.D.-7 and Ph.D.-12 Peptide Library Kit) was investigated to PMMA surface by phage display technique. It was found that oligopeptides bounded specifically to PMMA surface. The most common amino acids were leucine and proline inside the amino acids sequences of DNA of phages. The binding of haptens, as formaldehyde and methacrylic acid, to frequent amino acids was to investigate on the modified gold SPR chip. Self assembled monolayer (SAM) modified the surface of gold chip and ensured the specific binding between the haptens and amino acids. It was found that amino acids bounded to modified SPR gold and the haptens bounded to amino acids by creating multilayer on the chip surface. By the application of phage display and SPR modern bioanalytical methods the interaction between allergens and peptides can be investigated.

A self-assembled 2D/2D-type protonated carbon nitride-modified graphene oxide nanocomposite with improved photocatalytic activity

NASA Astrophysics Data System (ADS)

Xie, Linfang; Ni, Jie; Tang, Bo; He, Guangyu; Chen, Haiqun

2018-03-01

A surface charge modified g-C3N4 was successfully prepared by protonation of nitric acid. Combination of the protonated g-C3N4 (pCN) and graphene oxide (GO) layers created a 2D/2D-type composite (pCN/GO) under the synergistic effect of sonication-exfoliation and self-assembly. The obtained 2D nanostructure of pCN/GO was explored by electron microscopy analysis. The photocatalytic degradation of rhodamine B (RhB) and ciprofloxacin (CIP) showed a distinctly high efficiency of pCN/GO-5% with excellent stability, which is superior not only to that of g-C3N4, pCN and g-C3N4/GO-5% nanocomposites we prepared, but also to what was reported previously. The optimized combination of GO and pCN afforded the pCN/GO composite intimate interfacial contact within the heterojunction, which promoted the separation of photogenerated electron-hole pairs as evidenced by zeta potential, photoluminescence and photocurrent measurements. A visible-light photocatalytic degradation mechanism associated with pCN/GO nanocomposites was also proposed.

Gold nanoparticles modified electrode via simple electrografting of in situ generated mercaptophenyl diazonium cations for development of DNA electrochemical biosensor.

PubMed

Li, Feng; Feng, Yan; Dong, Pingjun; Yang, Limin; Tang, Bo

2011-01-15

A novel protocol for development of DNA electrochemical biosensor based on gold nanoparticles (AuNPs) modified glassy carbon electrode (GCE) was proposed, which was carried out by the self-assembly of AuNPs on the mercaptophenyl film (MPF) via simple electrografting of in situ generated mercaptophenyl diazonium cations. The resulting MPF was covalently immobilized on GCE surface via C-C bond with high stability, which was desirable in fabrication of excellent performance biosensors. Probe DNA was self-assembled on AuNPs through the well-known Au-thiol binding. The recognition of fabricated DNA electrochemical biosensor toward complementary single-stranded DNA was determined by differential pulse voltammetry with the use of Co(phen)(3)(3+) as the electrochemical indicator. Taking advantage of amplification effects of AuNPs and stability of MPF, the developed biosensor could detect target DNA with the detection limit of 7.2×10(-11) M, which also exhibits good selectivity, stability and regeneration ability for DNA detection. Copyright © 2010 Elsevier B.V. All rights reserved.

Mineral Surface Chemistry and Nanoparticle-aggregation Control Membrane Self-Assembly

NASA Astrophysics Data System (ADS)

Sahai, Nita; Kaddour, Hussein; Dalai, Punam; Wang, Ziqiu; Bass, Garrett; Gao, Min

2017-03-01

The self-assembly of lipid bilayer membranes to enclose functional biomolecules, thus defining a “protocell,” was a seminal moment in the emergence of life on Earth and likely occurred at the micro-environment of the mineral-water interface. Mineral-lipid interactions are also relevant in biomedical, industrial and technological processes. Yet, no structure-activity relationships (SARs) have been identified to predict lipid self-assembly at mineral surfaces. Here we examined the influence of minerals on the self-assembly and survival of vesicles composed of single chain amphiphiles as model protocell membranes. The apparent critical vesicle concentration (CVC) increased in the presence of positively-charged nanoparticulate minerals at high loadings (mg/mL) suggesting unfavorable membrane self-assembly in such situations. Above the CVC, initial vesicle formation rates were faster in the presence of minerals. Rates were correlated with the mineral’s isoelectric point (IEP) and reactive surface area. The IEP depends on the crystal structure, chemical composition and surface hydration. Thus, membrane self-assembly showed rational dependence on fundamental mineral properties. Once formed, membrane permeability (integrity) was unaffected by minerals. Suggesting that, protocells could have survived on rock surfaces. These SARs may help predict the formation and survival of protocell membranes on early Earth and other rocky planets, and amphiphile-mineral interactions in diverse other phenomena.

Mineral Surface Chemistry and Nanoparticle-aggregation Control Membrane Self-Assembly

PubMed Central

Sahai, Nita; Kaddour, Hussein; Dalai, Punam; Wang, Ziqiu; Bass, Garrett; Gao, Min

2017-01-01

The self-assembly of lipid bilayer membranes to enclose functional biomolecules, thus defining a “protocell,” was a seminal moment in the emergence of life on Earth and likely occurred at the micro-environment of the mineral-water interface. Mineral-lipid interactions are also relevant in biomedical, industrial and technological processes. Yet, no structure-activity relationships (SARs) have been identified to predict lipid self-assembly at mineral surfaces. Here we examined the influence of minerals on the self-assembly and survival of vesicles composed of single chain amphiphiles as model protocell membranes. The apparent critical vesicle concentration (CVC) increased in the presence of positively-charged nanoparticulate minerals at high loadings (mg/mL) suggesting unfavorable membrane self-assembly in such situations. Above the CVC, initial vesicle formation rates were faster in the presence of minerals. Rates were correlated with the mineral’s isoelectric point (IEP) and reactive surface area. The IEP depends on the crystal structure, chemical composition and surface hydration. Thus, membrane self-assembly showed rational dependence on fundamental mineral properties. Once formed, membrane permeability (integrity) was unaffected by minerals. Suggesting that, protocells could have survived on rock surfaces. These SARs may help predict the formation and survival of protocell membranes on early Earth and other rocky planets, and amphiphile-mineral interactions in diverse other phenomena. PMID:28266537

Hydrophilic/hydrophobic surface modification impact on colloid lithography: Schottky-like defects, dislocation, and ideal distribution

NASA Astrophysics Data System (ADS)

Burtsev, Vasilii; Marchuk, Valentina; Kugaevskiy, Artem; Guselnikova, Olga; Elashnikov, Roman; Miliutina, Elena; Postnikov, Pavel; Svorcik, Vaclav; Lyutakov, Oleksiy

2018-03-01

Nano-spheres lithography is actually considered as a powerful tool to manufacture various periodic structures with a wide potential in the field of nano- and micro-fabrication. However, during self-assembling of colloid microspheres, various defects and mismatches can appear. In this work the size and quality of single-domains of closed-packed polystyrene (PS), grown up on thin Au layers modified by hydrophilic or hydrophobic functional groups via diazonium chemistry was studied. The effects of the surface modification on the quality and single-domain size of polystyrene (PS) microspheres array were investigated and discussed. Modified surfaces were characterized using the AFM and wettability tests. PS colloidal suspension was deposited using the drop evaporation method. Resulted PS microspheres array was characterized using the SEM, AFM and confocal microscopy technique.

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.

Easy approach to assembling a biomimetic color film with tunable structural colors.

PubMed

Wang, Wentao; Tang, Bingtao; Ma, Wei; Zhang, Jian; Ju, Benzhi; Zhang, Shufen

2015-06-01

The self-assembly of silica microspheres into a close-packed array is a simple method of fabricating three-dimensional photonic crystal structural color films. However, the color is very dull because of the interferences of scattering and background light. In this study, we added a small quantity of surface-modified carbon black (CB) to the system of colloidal silica in n-propanol. The use of n-propanol as a dispersant is beneficial to the rapid development of photonic crystal films during the process of dip-coating. The doping of CB into silica microspheres can absorb background and scattering light, resulting in vivid structural colors.

Nanoporous Gold as a Solid Support for Protein Immobilization for the Development of Immunoassays, and for Biomolecular Interaction Studies

NASA Astrophysics Data System (ADS)

Pandey, Binod Prasad

Nanoporous gold (NPG) is a versatile material of high surface area to volume ratio that can be readily modified with self-assembled monolayers of alkanethiols to which biomolecules can be linked. NPG presents new opportunities for the development of immunoassays, and for the development of carbohydrate based assays. This thesis explores the use of NPG as a support for self-assembled monolayers, their linkage to antibody-enzyme conjugates for immunoassay development, and for the study and application of carbohydrate-protein interactions. Direct kinetic electrochemical immunoassays were developed on NPG for prostate specific antigen (PSA) and carcinoembryonic antigen (CEA). The decrease in enzymatic conversion of p-aminophenylphosphate to p-aminophenol, by alkaline phosphatase conjugated to an antibody, due to steric hindrance caused by the presence of antigen on antibody, was observed as a drop in peak current in square-wave voltammetry. Detection limit of these assays was 0.075 ng mL -1 and 0.015 ng mL-1 for PSA and CEA, respectively. Similarly, the linear range of determination of these biomarkers extended up to 30 ng mL-1 and 10 ng mL-1 for PSA and CEA, respectively. Minimal interference was observed using newborn calf serum as a substitute for the human serum matrix. A rapid and sensitive enzyme linked lectinsorbant assay was also developed for the study of glycoprotein-lectin interactions on the NPG surface. Self-assembled monolayers of alkanethiols on NPG were characterized by cyclic voltammetry and electrochemical impedance spectroscopy. Similarly, the applicability of this surface for the formation of carbohydrate monolayers and its application for lectin carbohydrate interactions was also studied. Pure and mixed SAMs of 8-mercaptooctyl β-D-mannopyranoside (αMan-C8-SH) and α-D-Gal-(1→4)-β-D-Gal-(1α)-D-Glc-1-O-mercaptooctane (Gb3-C8-SH) with alkanethiols having varying tail groups were prepared. Binding affinity and binding kinetics of concanavalin A to mannoside and soybean agglutinin to galactose in these SAMs were found to be different on NPG than on flat polycrystalline gold, and was also sensitive to the chemical composition of the modified surfaces.

Biological Nanoplatforms for Self-Assembled Electronics

DTIC Science & Technology

2015-03-24

as M13 , a virus that infects Escherichia coli. Approximately one billion different amino acid sequences are displayed on different viruses in the...sequence when contained within a phage M13 coat protein sequence, not chemically linked to the surface of phage MS2 VLPs. Thus, binding properties may...gallium arsenide in a bacteriophage M13 phage display library, MS2 VLPs modified with the metal binding peptides do not display the same activity

Detection of biomolecular interaction between biotin and streptavidin on a self-assembled monolayer using magnetic nanoparticles.

PubMed

Arakaki, Atsushi; Hideshima, Sho; Nakagawa, Takahito; Niwa, Daisuke; Tanaka, Tsuyoshi; Matsunaga, Tadashi; Osaka, Tetsuya

2004-11-20

For developing a magnetic bioassay system, an investigation to determine the presence of a specific biomolecular interaction between biotin and streptavidin was done using magnetic nanoparticles and a silicon substrate with a self-assembled monolayer. Streptavidin was immobilized on the magnetic particles, and biotin was attached to the monolayer-modified substrate. The reaction of streptavidin-modified magnetic particles on the biotin-modified substrate was clearly observed under an optical microscope. The magnetic signals from the particles were detected using a magnetic force microscope. The results of this study demonstrate that the combination of a monolayer-modified substrate with biomolecule-modified magnetic particles is useful for detecting biomolecular interactions in medical and diagnostic analyses. (c) 2004 Wiley Periodicals, Inc

Surface-assisted DNA self-assembly: An enzyme-free strategy towards formation of branched DNA lattice.

PubMed

Bhanjadeo, Madhabi M; Nayak, Ashok K; Subudhi, Umakanta

2017-04-01

DNA based self-assembled nanostructures and DNA origami has proven useful for organizing nanomaterials with firm precision. However, for advanced applications like nanoelectronics and photonics, large-scale organization of self-assembled branched DNA (bDNA) into periodic lattices is desired. In this communication for the first time we report a facile method of self-assembly of Y-shaped bDNA nanostructures on the cationic surface of Aluminum (Al) foil to prepare periodic two dimensional (2D) bDNA lattice. Particularly those Y-shaped bDNA structures having smaller overhangs and unable to self-assemble in solution, they are easily assembled on the surface of Al foil in the absence of ligase. Field emission scanning electron microscopy (FESEM) analysis shows homogenous distribution of two-dimensional bDNA lattices across the Al foil. When the assembled bDNA structures were recovered from the Al foil and electrophoresed in nPAGE only higher order polymeric bDNA structures were observed without a trace of monomeric structures which confirms the stability and high yield of the bDNA lattices. Therefore, this enzyme-free economic and efficient strategy for developing bDNA lattices can be utilized in assembling various nanomaterials for functional molecular components towards development of DNA based self-assembled nanodevices. Copyright © 2017 Elsevier Inc. All rights reserved.

Drying induced upright sliding and reorganization of carbon nanotube arrays

NASA Astrophysics Data System (ADS)

Li, Qingwen; DePaula, Raymond; Zhang, Xiefei; Zheng, Lianxi; Arendt, Paul N.; Mueller, Fred M.; Zhu, Y. T.; Tu, Yi

2006-09-01

Driven by capillary force, wet carbon nanotube (CNT) arrays have been found to reorganize into cellular structures upon drying. During the reorganization process, individual CNTs are firmly attached to the substrate and have to lie down on the substrate at cell bottoms, forming closed cells. Here we demonstrate that by modifying catalyst structures, the adhesion of CNTs to the substrate can be weakened. Upon drying such CNT arrays, CNTs may slide away from their original sites on the surface and self-assemble into cellular patterns with bottoms open. It is also found that the sliding distance of CNTs increases with array height, and drying millimetre tall arrays leads to the sliding of CNTs over a few hundred micrometres and the eventual self-assembly into discrete islands. By introducing regular vacancies in CNT arrays, CNTs may be manipulated into different patterns.

Differences between tethered polyelectrolyte chains adsorbed onto bare mica and hydrophobically modified mica, comparison with theory.

NASA Astrophysics Data System (ADS)

Balastre, Marc; Tamashiro, Mario N.; Hernandez, Ernesto; Pincus, Philip; Tirrell, Matthew

2001-03-01

End-grafted polymers generated from the adsorption of asymmetric diblock copolymers on solid surface play an important role in many areas of science and technology. While the small insoluble block acts as an anchor, the charged soluble block confers useful properties to the surface. This study looks at tethered layers of poly(styrene sulfonate)/poly(t-butyl styrene) (PtBS-PSS) adsorbed on both mica (hydrophilic) and octadecyltriethoxysilane (OTE) modified mica (hydrophobic). Normal compressing forces at two different constant grafting densities (bare and modified mica) were measured with the surface force apparatus and compared with theoretical prediction. The effect of salt concentration (Cs) upon the thickness of the self-assembled layers (Lo) was measured in each case. For adsorption of diblock copolymers onto OTE the resulting scaling relationship is much closer to the brush theory, Lo Cs-1/3. This result suggests that the adsorbed amount on mica is not high enough to form a brush.

Conducting nanowires built by controlled self-assembly of amyloid fibers and selective metal deposition.

PubMed

Scheibel, Thomas; Parthasarathy, Raghuveer; Sawicki, George; Lin, Xiao-Min; Jaeger, Heinrich; Lindquist, Susan L

2003-04-15

Recent research in the field of nanometer-scale electronics has focused on the operating principles of small-scale devices and schemes to realize useful circuits. In contrast to established "top-down" fabrication techniques, molecular self-assembly is emerging as a "bottom-up" approach for fabricating nanostructured materials. Biological macromolecules, especially proteins, provide many valuable properties, but poor physical stability and poor electrical characteristics have prevented their direct use in electrical circuits. Here we describe the use of self-assembling amyloid protein fibers to construct nanowire elements. Self-assembly of a prion determinant from Saccharomyces cerevisiae, the N-terminal and middle region (NM) of Sup35p, produced 10-nm-wide protein fibers that were stable under a wide variety of harsh physical conditions. Their lengths could be roughly controlled by assembly conditions in the range of 60 nm to several hundred micrometers. A genetically modified NM variant that presents reactive, surface-accessible cysteine residues was used to covalently link NM fibers to colloidal gold particles. These fibers were placed across gold electrodes, and additional metal was deposited by highly specific chemical enhancement of the colloidal gold by reductive deposition of metallic silver and gold from salts. The resulting silver and gold wires were approximately 100 nm wide. These biotemplated metal wires demonstrated the conductive properties of a solid metal wire, such as low resistance and ohmic behavior. With such materials it should be possible to harness the extraordinary diversity and specificity of protein functions to nanoscale electrical circuitry.

Subtle charge balance controls surface-nucleated self-assembly of designed biopolymers.

PubMed

Charbonneau, Céline; Kleijn, J Mieke; Cohen Stuart, Martien A

2014-03-25

We report the surface-nucleated self-assembly into fibrils of a biosynthetic amino acid polymer synthesized by the yeast Pichia pastoris. This polymer has a block-like architecture, with a central silk-like block labeled SH, responsible for the self-assembly into fibrils, and two collagen-like random coil end blocks (C) that colloidally stabilize the fibers in aqueous solution. The silk-like block contains histidine residues (pKa≈6) that are positively charged in the low pH region, which hinders self-assembly. In aqueous solution, CSHC self-assembles into fibers above a pH-dependent critical nucleation concentration Ccb. Below Ccb, where no self-assembly occurs in solution, fibril formation can be induced by a negatively charged surface (silica) in the pH range of 3.5-7. The density of the fibers at the surface and their length are controlled by a subtle balance in charge between the protein polymer and the silica surface, which is evidenced from the dependence on pH. With increasing number density of the fibers at the surface, their average length decreases. The results can be explained on the basis of a nucleation-and-growth mechanism: the surface density of fibers depends on the rate of nucleation, while their growth rate is limited by transport of proteins from solution. Screening of the charges on the surface and histidine units by adding NaCl influences the nucleation-and-growth process in a complicated fashion: at low pH, the growth is improved, while at high pH, the nucleation is limited. Under conditions where nucleation in the bulk solution is not possible, growth of the surface-nucleated fibers into the solution--away from the surface--can still occur.

Fragmentation and reactivity in collisions of protonated diglycine with chemically modified perfluorinated alkylthiolate-self-assembled monolayer surfaces

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

Barnes, George L.; Yang Li; Hase, William L.

2011-03-07

Direct dynamics simulations are reported for quantum mechanical (QM)/molecular mechanical (MM) trajectories of N-protonated diglycine (gly{sub 2}-H{sup +}) colliding with chemically modified perfluorinated octanethiolate self-assembled monolayer (SAM) surfaces. The RM1 semiempirical theory is used for the QM component of the trajectories. RM1 activation and reaction energies were compared with those determined from higher-level ab initio theories. Two chemical modifications are considered in which a head group (-COCl or -CHO) is substituted on the terminal carbon of a single chain of the SAM. These surfaces are designated as the COCl-SAM and CHO-SAM, respectively. Fragmentation, peptide reaction with the SAM, and covalentmore » linkage of the peptide or its fragments with the SAM surface are observed. Peptide fragmentation via concerted CH{sub 2}-CO bond breakage is the dominant pathway for both surfaces. HCl formation is the dominant species produced by reaction with the COCl-SAM, while for the CHO-SAM a concerted H-atom transfer from the CHO-SAM to the peptide combined with either a H-atom or radical transfer from the peptide to the surface to form singlet reaction products is the dominant pathway. A strong collision energy dependence is found for the probability of peptide fragmentation, its reactivity, and linkage with the SAM. Surface deposition, i.e., covalent linkage between the surface and the peptide, is compared to recent experimental observations of such bonding by Laskin and co-workers [Phys. Chem. Chem. Phys. 10, 1512 (2008)]. Qualitative differences in reactivity are seen between the COCl-SAM and CHO-SAM showing that chemical identity is important for surface reactivity. The probability of reactive surface deposition, which is most closely analogous to experimental observables, peaks at a value of around 20% for a collision energy of 50 eV.« less

Spontaneous grafting: a novel approach to graft diazonium cations on gold nanoparticles in aqueous medium and their self-assembly on electrodes.

PubMed

Kesavan, Srinivasan; John, S Abraham

2014-08-15

The spontaneous grafting of aminophenyl groups on gold nanoparticles (AuNPs) by reaction with in situ generated 4-aminophenyl diazonium cations (APD) in an aqueous medium was described. The spontaneous grafting was likely to proceed by transfer of electrons from AuNPs to the APD cations to form an aminophenyl radical and subsequent attachment with AuNPs. The aminophenyl (AP) functionalized gold nanoparticles (AP-AuNPs) were characterized by UV-visible spectroscopy, high resolution-transmission electron microscopy (HR-TEM), X-ray diffraction, FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS) and surface-enhanced Raman spectroscopy (SERS). The absence of characteristic vibrational bands corresponding to diazonium group in the FT-IR spectrum confirmed the reduction of the aminophenyl diazonium cations at the surface of AuNPs. The spontaneous attachment of AP on AuNPs was confirmed by XPS from the observed binding energy values for -NH2 at 399.4 eV and -N=N- at 400.2 eV. The SERS spectrum reveals the presence Au-C (437 cm(-1)) bond on AP-AuNPs. Further, the AP-AuNPs were self-assembled on GC/ITO electrode (AP-AuNPs modified electrode) with the aid of free amine groups present on the surface of AP-AuNPs via Michael's nucleophilic addition reaction. The AP-AuNPs modified electrode was characterized by cyclic voltammetry, impedance spectroscopy, UV-visible spectroscopy and scanning electron microscopy. Impedance studies show that the electron transfer reaction of [Fe(CN)6](3-/4-) was higher at the AP-AuNPs modified electrode (1.81×10(-4) cm s(-1)) than at bare (3.77×10(-5) cm s(-1)) GC electrode. Finally, the electrocatalytic activity of the AP-AuNPs modified electrode was demonstrated by studying the oxidation of dopamine (DA). Copyright © 2014 Elsevier Inc. All rights reserved.

Dynamics of self-assembled cytosine nucleobases on graphene

NASA Astrophysics Data System (ADS)

Saikia, Nabanita; Johnson, Floyd; Waters, Kevin; Pandey, Ravindra

2018-05-01

Molecular self-assembly of cytosine (C n ) bases on graphene was investigated using molecular dynamics methods. For free-standing C n bases, simulation conditions (gas versus aqueous) determine the nature of self-assembly; the bases prefer to aggregate in the gas phase and are stabilized by intermolecular H-bonds, while in the aqueous phase, the water molecules disrupt base-base interactions, which facilitate the formation of π-stacked domains. The substrate-induced effects, on the other hand, find the polarity and donor-acceptor sites of the bases to govern the assembly process. For example, in the gas phase, the assembly of C n bases on graphene displays short-range ordered linear arrays stabilized by the intermolecular H-bonds. In the aqueous phase, however, there are two distinct configurations for the C n bases assembly on graphene. For the first case corresponding to low surface coverage, the bases are dispersed on graphene and are isolated. The second configuration archetype is disordered linear arrays assembled with medium and high surface coverage. The simulation results establish the role of H-bonding, vdW π-stacking, and the influence of graphene surface towards the self-assembly. The ability to regulate the assembly into well-defined patterns can aid in the design of self-assembled nanostructures for the next-generation DNA based biosensors and nanoelectronic devices.

Monolayer-directed Assembly and Magnetic Properties of FePt Nanoparticles on Patterned Aluminum Oxide

PubMed Central

Yildirim, Oktay; Gang, Tian; Kinge, Sachin; Reinhoudt, David N.; Blank, Dave H.A.; van der Wiel, Wilfred G.; Rijnders, Guus; Huskens, Jurriaan

2010-01-01

FePt nanoparticles (NPs) were assembled on aluminum oxide substrates, and their ferromagnetic properties were studied before and after thermal annealing. For the first time, phosph(on)ates were used as an adsorbate to form self-assembled monolayers (SAMs) on alumina to direct the assembly of NPs onto the surface. The Al2O3 substrates were functionalized with aminobutylphosphonic acid (ABP) or phosphonoundecanoic acid (PNDA) SAMs or with poly(ethyleneimine) (PEI) as a reference. FePt NPs assembled on all of these monolayers, but much less on unmodified Al2O3, which shows that ligand exchange at the NPs is the most likely mechanism of attachment. Proper modification of the Al2O3 surface and controlling the immersion time of the modified Al2O3 substrates into the FePt NP solution resulted in FePt NPs assembly with controlled NP density. Alumina substrates were patterned by microcontact printing using aminobutylphosphonic acid as the ink, allowing local NP assembly. Thermal annealing under reducing conditions (96%N2/4%H2) led to a phase change of the FePt NPs from the disordered FCC phase to the ordered FCT phase. This resulted in ferromagnetic behavior at room temperature. Such a process can potentially be applied in the fabrication of spintronic devices. PMID:20480007

Self-assembled biomimetic nanoreactors I: Polymeric template

NASA Astrophysics Data System (ADS)

McTaggart, Matt; Malardier-Jugroot, Cecile; Jugroot, Manish

2015-09-01

The variety of nanoarchitectures made feasible by the self-assembly of alternating copolymers opens new avenues for biomimicry. Indeed, self-assembled structures allow the development of nanoreactors which combine the efficiency of high surface area metal active centres to the effect of confinement due to the very small cavities generated by the self-assembly process. A novel self-assembly of high molecular weight alternating copolymers is characterized in the present study. The self-assembly is shown to organize into nanosheets, providing a 2 nm hydrophobic cavity with a 1D confinement.

Mechanical characteristics of beta sheet-forming peptide hydrogels are dependent on peptide sequence, concentration and buffer composition

PubMed Central

Müller, Michael; König, Finja; Meyer, Nina; Gattlen, Jasmin; Pieles, Uwe; Peters, Kirsten; Kreikemeyer, Bernd; Mathes, Stephanie; Saxer, Sina

2018-01-01

Self-assembling peptide hydrogels can be modified regarding their biodegradability, their chemical and mechanical properties and their nanofibrillar structure. Thus, self-assembling peptide hydrogels might be suitable scaffolds for regenerative therapies and tissue engineering. Owing to the use of various peptide concentrations and buffer compositions, the self-assembling peptide hydrogels might be influenced regarding their mechanical characteristics. Therefore, the mechanical properties and stability of a set of self-assembling peptide hydrogels, consisting of 11 amino acids, made from four beta sheet self-assembling peptides in various peptide concentrations and buffer compositions were studied. The formed self-assembling peptide hydrogels exhibited stiffnesses ranging from 0.6 to 205 kPa. The hydrogel stiffness was mostly affected by peptide sequence followed by peptide concentration and buffer composition. All self-assembling peptide hydrogels examined provided a nanofibrillar network formation. A maximum self-assembling peptide hydrogel dissolution of 20% was observed for different buffer solutions after 7 days. The stability regarding enzymatic and bacterial digestion showed less degradation in comparison to the self-assembling peptide hydrogel dissolution rate in buffer. The tested set of self-assembling peptide hydrogels were able to form stable scaffolds and provided a broad spectrum of tissue-specific stiffnesses that are suitable for a regenerative therapy. PMID:29657766

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.

Self-assembly and reactive molding techniques for controlling the interface and dispersion of the particulate phase in nanocomposites

NASA Astrophysics Data System (ADS)

Pranger, Lawrence A.

This research explored the processing and properties of PNCs using a polyfurfural alcohol (PFA) matrix. The precursor for PFA, furfuryl alcohol (FA) is sourced from feedstocks rich in hemicellulose, such as corn cobs, oat hulls and wood. To exploit FA as a polymerizable solvent, cellulose whiskers (CW) and montmorillonite clay (MMT) were used as the nanoparticle phase. Results from PNC processing show that CW and MMT can be dispersed in the PFA matrix by means of insitu polymerization, without the use of surfactants or dilution in solvents. Both CW and MMT nanoparticles catalyze the polymerization of furfuryl alcohol (FA). Moreover, the insitu intercalative polymerization of FA in the interlayer galleries of MMT leads to the complete exfoliation of the MMT in the PFA matrix. CW and MMT both function as effective matrix modifiers, increasing the thermal stability of PFA nanocomposites compared to pure PFA polymer. The increased thermal stability is seen as significant increases in the onset of degradation and in residual weight at high temperature. This research also explored the surface functionalization of Cu, Ni and Pt substrates by self-assembly of a range of difunctional linker molecules. Characterization by XPS and PM-IRRAS indicate that diisocyanides and dicarboxylic acids both form chemically "sticky" surfaces after self-assembly on Cu and Ni. Sticky surfaces may provide a means of increasing nanoparticle dispersion in metal nanocluster filled PNCs, by increasing their interaction with the matrix polymer. Another potential application for sticky surfaces on Cu is in the ongoing miniaturization of circuit boards. The functionalization of Cu bond pad substrates with linker molecules may provide an alternate means of bonding components to their bond pads, with higher placement accuracy compared to solder bumps.

Surface-enhanced Raman spectroscopic and surface plasmon resonance in situ study of self-assembly of 4-mercaptobenzoic acid on gold surface

NASA Astrophysics Data System (ADS)

Thi, Minh Do; Volka, Karel

2010-07-01

A feasibility study has been undertaken to assess the suitability of a commercially available SERS substrate for monitoring of self-assembling deposition process. Monolayer self-assembly of 4-mercaptobenzoic acid on SERS active substrate Klarite™ from absolute and acidified ethanol was studied and compared with deposition on SPR substrate from absolute ethanol. Changes in integral intensity of the phenyl bands at 1587 and 1076 cm -1 and ethanol band at 1451 cm -1 allow to follow structural changes in the monolayer. Stability of the monolayer assembled from acidified ethanol in contrast to the pure ethanol was demonstrated.

Self-assembly patterning of organic molecules on a surface

DOEpatents

Pan, Minghu; Fuentes-Cabrera, Miguel; Maksymovych, Petro; Sumpter, Bobby G.; Li, Qing

2017-04-04

The embodiments disclosed herein include all-electron control over a chemical attachment and the subsequent self-assembly of an organic molecule into a well-ordered three-dimensional monolayer on a metal surface. The ordering or assembly of the organic molecule may be through electron excitation. Hot-electron and hot-hole excitation enables tethering of the organic molecule to a metal substrate, such as an alkyne group to a gold surface. All-electron reactions may allow a direct control over the size and shape of the self-assembly, defect structures and the reverse process of molecular disassembly from single molecular level to mesoscopic scale.

Self-Assembled Polystyrene Beads for Templated Covalent Functionalization of Graphitic Substrates Using Diazonium Chemistry.

PubMed

Van Gorp, Hans; Walke, Peter; Bragança, Ana M; Greenwood, John; Ivasenko, Oleksandr; Hirsch, Brandon E; De Feyter, Steven

2018-04-11

A network of self-assembled polystyrene beads was employed as a lithographic mask during covalent functionalization reactions on graphitic surfaces to create nanocorrals for confined molecular self-assembly studies. The beads were initially assembled into hexagonal arrays at the air-liquid interface and then transferred to the substrate surface. Subsequent electrochemical grafting reactions involving aryl diazonium molecules created covalently bound molecular units that were localized in the void space between the nanospheres. Removal of the bead template exposed hexagonally arranged circular nanocorrals separated by regions of chemisorbed molecules. Small molecule self-assembly was then investigated inside the resultant nanocorrals using scanning tunneling microscopy to highlight localized confinement effects. Overall, this work illustrates the utility of self-assembly principles to transcend length scale gaps in the development of hierarchically patterned molecular materials.

Bulk- and surface-modified combinable PDMS capillary sensor array as an easy-to-use sensing device with enhanced sensitivity to elevated concentrations of multiple serum sample components.

PubMed

Fujii, Yuji; Henares, Terence G; Kawamura, Kunio; Endo, Tatsuro; Hisamoto, Hideaki

2012-04-21

To enhance sensitivity and facilitate easy sample introduction into a combinable poly(dimethylsiloxane) (PDMS) capillary (CPC) sensor array, PDMS was modified in bulk and on its surface to prepare "black" PDMS coated with a silver layer and self-assembled monolayer (SAM). India ink, a traditional Japanese black ink, was added to the PDMS pre-polymer for bulk modification. The surface was modified by a silver mirror reaction followed by SAM formation using cysteine. These modifications enhanced the fluorescence signals by reflecting them from the surface and reducing background interference. A decrease in the water contact angle led to enhanced sensitivity and easy sample introduction. Furthermore, a CPC sensor array for multiplex detection of serum sample components was prepared that could quantify the analytes glucose, potassium, and alkaline phosphatase (ALP). When serum samples were introduced by capillary action, the CPC sensor array showed fluorescence responses for each analyte and successfully identified the components with elevated concentrations in the serum samples.

Surface Analysis of 4-Aminothiophenol Adsorption at Polycrystalline Platinum Electrodes

NASA Technical Reports Server (NTRS)

Rosario-Castro, Belinda I.; Fachini, Estevao R.; Contes, Enid J.; Perez-Davis, Marla E.; Cabrera, Carlos R.

2008-01-01

Formation of self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been studied by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), Raman spectroscopy, reflection absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) experiments give an idea about the packing quality of the monolayer. RAIR and Raman spectra for 4-ATP modified platinum electrodes showed the characteristic adsorption bands for neat 4-ATP indicating the adsorption of 4-ATP molecules on platinum surface. The adsorption on platinum was also evidenced by the presence of sulfur and nitrogen peaks by XPS survey spectra of the modified platinum electrodes. High resolution XPS studies and RAIR spectrum for platinum electrodes modified with 4-ATP indicate that molecules are sulfur-bonded to the platinum surface. The formation of S-Pt bond suggests that ATP adsorption gives up an amino terminated SAM. Thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses. Derivatization of 4-ATP SAM was performed using 16-Br hexadecanoic acid.

Influence of ionic strength and surfactant concentration on electrostatic surfacial assembly of cetyltrimethylammonium bromide-capped gold nanorods on fully immersed glass.

PubMed

Ferhan, Abdul Rahim; Guo, Longhua; Kim, Dong-Hwan

2010-07-20

The effect of ionic strength as well as surfactant concentration on the surface assembly of cetyltrimethylammonium bromide (CTAB)-capped gold nanorods (GNRs) has been studied. Glass substrates were modified to yield a net negative charge through electrostatic coating of polystyrenesulfonate (PSS) over a self-assembled monolayer (SAM) of positively charged aminopropyltriethoxysilane (APTS). The substrates were then fully immersed in GNR solutions at different CTAB concentrations and ionic strengths. Under slightly excess CTAB concentrations, it was observed that the density of GNRs immobilized on a substrate was predictably tunable through the adjustment of NaCl concentration over a wide range. Motivated by the experimental observation, we hypothesize that electrostatic shielding of charges around the GNRs affects the density of GNR immobilization. This model ultimately explains that at moderate to high CTAB concentrations a second electrostatic shielding effect contributed by excess CTAB molecules occurs, resulting in a parabolic trend of nanorod surface density when ionic strength is continually increased. In contrast, at a low CTAB concentration, the effect of ionic strength becomes much less significant due to insufficient CTAB molecules to provide for the second electrostatic shielding effect. The tunability of electrostatic-based surface assembly of GNRs enables the attainment of a dense surface assembly of nanorods without significant removal of CTAB or any other substituted stabilizing agent, both of which could compromise the stability and morphology of GNRs in solution. An additional study performed to investigate the robustness of such electrostatic-based surface assembly also proved its reliability to be used as biosensing platforms.

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

Incorporating Bacteria as a Living Component in Supramolecular Self-Assembled Monolayers through Dynamic Nanoscale Interactions.

PubMed

Sankaran, Shrikrishnan; Kiren, Mustafa Can; Jonkheijm, Pascal

2015-01-01

Supramolecular assemblies, formed through noncovalent interactions, has become particularly attractive to develop dynamic and responsive architectures to address living systems at the nanoscale. Cucurbit[8]uril (CB[8]), a pumpkin shaped macrocylic host molecule, has been successfully used to construct various self-assembled architectures for biomedical applications since it can simultaneously bind two aromatic guest molecules within its cavity. Such architectures can also be designed to respond to external stimuli. Integrating living organisms as an active component into such supramolecular architectures would add a new dimension to the capabilities of such systems. To achieve this, we have incorporated supramolecular functionality at the bacterial surface by genetically modifying a transmembrane protein to display a CB[8]-binding motif as part of a cystine-stabilized miniprotein. We were able to confirm that this supramolecular motif on the bacterial surface specifically binds CB[8] and forms multiple intercellular ternary complexes leading to aggregation of the bacterial solution. We performed various aggregation experiments to understand how CB[8] interacts with this bacterial strain and also demonstrate that it can be chemically reversed using a competitor. To confirm that this strain can be incorporated with a CB[8] based architecture, we show that the bacterial cells were able to adhere to CB[8] self-assembled monolayers (SAMs) on gold and still retain considerable motility for several hours, indicating that the system can potentially be used to develop supramolecular bacterial biomotors. The bacterial strain also has the potential to be combined with other CB[8] based architectures like nanoparticles, vesicles and hydrogels.

A nanoscale bio-inspired light-harvesting system developed from self-assembled alkyl-functionalized metallochlorin nano-aggregates.

PubMed

Ocakoglu, Kasim; Joya, Khurram S; Harputlu, Ersan; Tarnowska, Anna; Gryko, Daniel T

2014-08-21

Self-assembled supramolecular organization of nano-structured biomimetic light-harvesting modules inside solid-state nano-templates can be exploited to develop excellent light-harvesting materials for artificial photosynthetic devices. We present here a hybrid light-harvesting system mimicking the chlorosomal structures of the natural photosynthetic system using synthetic zinc chlorin units (ZnChl-C6, ZnChl-C12 and ZnChl-C18) that are self-aggregated inside the anodic aluminum oxide (AAO) nano-channel membranes. AAO nano-templates were modified with a TiO2 matrix and functionalized with long hydrophobic chains to facilitate the formation of supramolecular Zn-chlorin aggregates. The transparent Zn-chlorin nano-aggregates inside the alkyl-TiO2 modified AAO nano-channels have a diameter of ∼120 nm in a 60 μm length channel. UV-Vis studies and fluorescence emission spectra further confirm the formation of the supramolecular ZnChl aggregates from monomer molecules inside the alkyl-functionalized nano-channels. Our results prove that the novel and unique method can be used to produce efficient and stable light-harvesting assemblies for effective solar energy capture through transparent and stable nano-channel ceramic materials modified with bio-mimetic molecular self-assembled nano-aggregates.

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.

A highly oriented hybrid microarray modified electrode fabricated by a template-free method for ultrasensitive electrochemical DNA recognition

NASA Astrophysics Data System (ADS)

Shi, Lei; Chu, Zhenyu; Dong, Xueliang; Jin, Wanqin; Dempsey, Eithne

2013-10-01

Highly oriented growth of a hybrid microarray was realized by a facile template-free method on gold substrates for the first time. The proposed formation mechanism involves an interfacial structure-directing force arising from self-assembled monolayers (SAMs) between gold substrates and hybrid crystals. Different SAMs and variable surface coverage of the assembled molecules play a critical role in the interfacial directing forces and influence the morphologies of hybrid films. A highly oriented hybrid microarray was formed on the highly aligned and vertical SAMs of 1,4-benzenedithiol molecules with rigid backbones, which afforded an intense structure-directing power for the oriented growth of hybrid crystals. Additionally, the density of the microarray could be adjusted by controlling the surface coverage of assembled molecules. Based on the hybrid microarray modified electrode with a large specific area (ca. 10 times its geometrical area), a label-free electrochemical DNA biosensor was constructed for the detection of an oligonucleotide fragment of the avian flu virus H5N1. The DNA biosensor displayed a significantly low detection limit of 5 pM (S/N = 3), a wide linear response from 10 pM to 10 nM, as well as excellent selectivity, good regeneration and high stability. We expect that the proposed template-free method can provide a new reference for the fabrication of a highly oriented hybrid array and the as-prepared microarray modified electrode will be a promising paradigm in constructing highly sensitive and selective biosensors.Highly oriented growth of a hybrid microarray was realized by a facile template-free method on gold substrates for the first time. The proposed formation mechanism involves an interfacial structure-directing force arising from self-assembled monolayers (SAMs) between gold substrates and hybrid crystals. Different SAMs and variable surface coverage of the assembled molecules play a critical role in the interfacial directing forces and influence the morphologies of hybrid films. A highly oriented hybrid microarray was formed on the highly aligned and vertical SAMs of 1,4-benzenedithiol molecules with rigid backbones, which afforded an intense structure-directing power for the oriented growth of hybrid crystals. Additionally, the density of the microarray could be adjusted by controlling the surface coverage of assembled molecules. Based on the hybrid microarray modified electrode with a large specific area (ca. 10 times its geometrical area), a label-free electrochemical DNA biosensor was constructed for the detection of an oligonucleotide fragment of the avian flu virus H5N1. The DNA biosensor displayed a significantly low detection limit of 5 pM (S/N = 3), a wide linear response from 10 pM to 10 nM, as well as excellent selectivity, good regeneration and high stability. We expect that the proposed template-free method can provide a new reference for the fabrication of a highly oriented hybrid array and the as-prepared microarray modified electrode will be a promising paradigm in constructing highly sensitive and selective biosensors. Electronic supplementary information (ESI) available: Four-probe method for determining the conductivity of the hybrid crystal (Fig. S1); stability comparisons of the hybrid films (Fig. S2); FESEM images of the hybrid microarray (Fig. S3); electrochemical characterizations of the hybrid films (Fig. S4); DFT simulations (Fig. S5); cross-sectional FESEM image of the hybrid microarray (Fig. S6); regeneration and stability tests of the DNA biosensor (Fig. S7). See DOI: 10.1039/c3nr03097k

Enzymatic glycosylation, inhibitor design, and synthesis and formation of glyco-self assembled monolayers for simulation of recognition.

PubMed

Scheppokat, Angela M; Gerber, Agnes; Schroven, Andreas; Meinke, Sebastian; Kopitzki, Sebastian; Beketow, Eugen; Thimm, Julian; Thiem, Joachim

2010-01-01

Glycosyltransferases from the albumen gland of Helix pomatia could be used in tandem mode for the chemoenzymatic synthesis of beta,1-3/beta,1-6-linked oligogalactans. By employing recombinant trans-sialidase of Trypanosoma cruzi (TcTS) the formation of a range of modified Galbeta,1-3GalNAc derivatives could be terminally alpha,2-3 sialylated. Biacore studies indicated the binding of these modified trisaccharides to myelin-associated glycoprotein (MAG). Using an eight-step synthetic route N-acyl-modified sialyl donor structures could be obtained. TcTS was used to transfer these structures to an isolactoside, and Michaelis constants of the donors indicated the kind and size of modifications allowed at the 5-nitrogen site. A number of sialic acid C-glycosides could be obtained via the C-allyl sialoside and subsequent metathesis. Biacore measurements showed derivatives substituted with aromatic residues to give K(D) values in the mM range. Benzaldehyde-functionalized glycosides of mono and disaccharides were synthesized by metathesis and could be used for the formation of novel glyco-self assembled monolayers (glyco-SAMs) employing various tether structures and attached to gold surfaces. Initial experiments were performed with concanavalin A and manno-SAMs. By atomic force microscopic measurements of tethered glycosides attached to gold-coated tips and surfaces weak forces in the nN range could be detected. Structure activity correlation of forces suggested rationales for complex interactions of various glycosides including minor stereochemical variations. Copyright (c) 2009 Elsevier GmbH. All rights reserved.

Simple and robust strategy for potentiometric detection of glucose using fluorinated phenylboronic acid self-assembled monolayer.

PubMed

Matsumoto, Akira; Matsumoto, Hiroko; Maeda, Yasuhiro; Miyahara, Yuji

2013-09-01

Field effect transistor (FET) based signal-transduction (Bio-FET) is an emerging technique for label-free and real-time basis biosensors for a wide range of targets. Glucose has constantly been of interest due to its clinical relevance. Use of glucose oxidase (GOD) and a lectin protein Concanavalin A are two common strategies to generate glucose-dependent electrochemical events. However, these protein-based materials are intolerant of long-term usage and storage due to their inevitable denaturing. A phenylboronic acid (PBA) modified self-assembled monolayer (SAM) on a gold electrode with an optimized disassociation constant of PBA, that is, 3-fluoro-4-carbamoyl-PBA possessing its pKa of 7.1, was prepared and utilized as an extended gate electrode for Bio-FET. The prepared electrode showed a glucose-dependent change in the surface potential under physiological conditions, thus providing a remarkably simple rationale for the glyco-sensitive Bio-FET. Importantly, the PBA modified electrode showed tolerance to relatively severe heat and drying treatments; conditions under which protein based materials would surely be denatured. A PBA modified SAM with optimized disassociation constant (pKa) can exhibit a glucose-dependent change in the surface potential under physiological conditions, providing a remarkably simple but robust method for the glyco-sensing. This protein-free, totally synthetic glyco-sensing strategy may offer cheap, robust and easily accessible platform that may be useful in developing countries. This article is part of a Special Issue entitled Organic Bioelectronics-Novel Applications in Biomedicine. Copyright © 2013 Elsevier B.V. All rights reserved.

Impact of hydrophilic and hydrophobic functionalization of flat TiO2/Ti surfaces on proteins adsorption

NASA Astrophysics Data System (ADS)

Fabre, Héloïse; Mercier, Dimitri; Galtayries, Anouk; Portet, David; Delorme, Nicolas; Bardeau, Jean-François

2018-02-01

Controlling adsorption of proteins onto medical devices is a key issue for implant-related infections. As self-assembled monolayers (SAMs) on titanium oxide represent a good model to study the surface-protein interactions, TiO2 surface properties were modified by grafting bisphosphonate molecules terminated with hydrophilic poly(ethylene glycol) groups and hydrophobic perfluoropolyether ones, respectively. Characterisation of the surface chemistry and surface topography of the modified surfaces was performed using XPS and atomic force microscopy (AFM). Quartz-crystal microbalance with dissipation (QCM-D) was used to determine the mass of adsorbed proteins as well as its kinetics. Poly(ethylene glycol)-terminated SAMs were the most effective surfaces to limit the adsorption of both BSA and fibrinogen in comparison to perfluorinated-terminated SAMs and non-modified TiO2 surfaces, as expected. The adsorption was not reversible in the case of BSA, while a partial reversibility was observed with Fg, most probably due to multilayers of proteins. The grafted surfaces adsorbed about the same quantity of proteins in terms of molecules per surface area, most probably in monolayer or island-like groups of adsorbed proteins. The adsorption on pristine TiO2 reveals a more important, non-specific adsorption of proteins.

Supramolecular domains in mixed peptide self-assembled monolayers on gold nanoparticles.

PubMed

Duchesne, Laurence; Wells, Geoff; Fernig, David G; Harris, Sarah A; Lévy, Raphaël

2008-09-01

Self-organization in mixed self-assembled monolayers of small molecules provides a route towards nanoparticles with complex molecular structures. Inspired by structural biology, a strategy based on chemical cross-linking is introduced to probe proximity between functional peptides embedded in a mixed self-assembled monolayer at the surface of a nanoparticle. The physical basis of the proximity measurement is a transition from intramolecular to intermolecular cross-linking as the functional peptides get closer. Experimental investigations of a binary peptide self-assembled monolayer show that this transition happens at an extremely low molar ratio of the functional versus matrix peptide. Molecular dynamics simulations of the peptide self-assembled monolayer are used to calculate the volume explored by the reactive groups. Comparison of the experimental results with a probabilistic model demonstrates that the peptides are not randomly distributed at the surface of the nanoparticle, but rather self-organize into supramolecular domains.

Directed self-assembly of proteins into discrete radial patterns

PubMed Central

Thakur, Garima; Prashanthi, Kovur; Thundat, Thomas

2013-01-01

Unlike physical patterning of materials at nanometer scale, manipulating soft matter such as biomolecules into patterns is still in its infancy. Self-assembled monolayer (SAM) with surface density gradient has the capability to drive biomolecules in specific directions to create hierarchical and discrete structures. Here, we report on a two-step process of self-assembly of the human serum albumin (HSA) protein into discrete ring structures based on density gradient of SAM. The methodology involves first creating a 2-dimensional (2D) polyethylene glycol (PEG) islands with responsive carboxyl functionalities. Incubation of proteins on such pre-patterned surfaces results in direct self-assembly of protein molecules around PEG islands. Immobilization and adsorption of protein on such structures over time evolve into the self-assembled patterns. PMID:23719678

Adhesion and Interphase Properties of Reinforced Polymeric Composites

NASA Astrophysics Data System (ADS)

Caldwell, Kyle Bernd

Reinforced polymeric composites are an increasingly utilized material with a wide range of applications. Fiber reinforced polymeric composites, in particular, possess impressive mechanical properties at a fraction of the weight of many other building materials. There will always, however, be a demand for producing lighter, stiffer, and stronger materials. Understanding the mechanism of adhesion and ways to engineer the reinforcement-matrix interphase can lead to the development of new materials with improved mechanical properties, and even impart additional functionality such as electrical conductivity. The performance of reinforced polymeric composites is critically dependent upon the adhesion between the reinforcement and the surrounding polymer. The relative adhesion between a filler and a thermoplastic matrix can be predicted using calculable thermodynamic quantities such as the Gibbs free energy of mixing. A recent model, COSMO-SAC, is capable of predicting the adhesion between organo-silane treated glass surfaces and several thermoplastic materials. COSMO-SAC uses information based on the charge distribution of a molecule's surface to calculate many thermodynamic properties. Density functional theory calculations, which are relative inexpensive computations, generate the information necessary to perform the COSMO-SAC analysis and can be performed on any given molecule. The flexibility of the COSMO-SAC model is one of the main advantages it possesses over other methods for calculating thermodynamic quantities. In many cases the adhesion between a reinforcing fiber and the surrounding matrix may be improved by incorporating interphase modifiers in the vicinity of the fiber surface. The modifiers can improve the fracture toughness and modulus of the interphase, which may improve the stress transfer from the matrix to the fiber. In addition, the interphase modifiers may improve the mechanical interlock between the fiber surface and the bulk polymer, leading to improved adhesion. In recent years, the use of so called "migrating agents" have been used to self-assemble nanoparticle reinforced fiber-matrix interphases in thermosetting resin systems. The inclusion of a modest amount of thermoplastic migrating agent can lead to the formation of a self-assembled interphase, without causing aggregation of nanoparticles in the bulk phase. Formulations containing excess migrating agent, however, can induce aggregation in the bulk of increasing severity with increasing migrating agent concentration. Several techniques were used to study the mechanism by which the migrating agents operate including, scanning electron microscopy, and in situ fluorescence microscopy. The self-assembly mechanism by which migrating agents operate is described well by depletion forces, which are depend on the geometry of the approaching objects, as well as the migrating agent molecular weight and concentration.

Fabrication of phosphonic acid films on nitinol nanoparticles by dynamic covalent assembly

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

Quinones, Rosalynn; Garretson, Samantha; Behnke, Grayce

Nitinol (NiTi) nanoparticles are a valuable metal alloy due to many unique properties that allow for medical applications. NiTi nanoparticles have the potential to form nanofluids, which can advance the thermal conductivity of fluids by controlling the surface functionalization through chemical attachment of organic acids to the surface to form self-assembled alkylphosphonate films. In this study, phosphonic functional head groups such as 16-phosphonohexadecanoic acid, octadecylphosphonic acid, and 12-aminododecylphosphonic acid were used to form an ordered and strongly chemically bounded film on the NiTi nanopowder. The surface of the NiTi nanoparticles was modified in order to tailor the chemical and physicalmore » properties to the desired application. The modified NiTi nanoparticles were characterized using infrared spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and 31P solid-state nuclear magnetic resonance. The interfacial bonding was identified by spectroscopic data suggesting the phosphonic head group adsorbs in a mixed bidentate/monodentate binding motif on the NiTi nanoparticles. Dynamic light scattering and scanning electron microscopy-energy dispersive X-ray spectroscopy revealed the particle sizes. Differential scanning calorimetry was used to examine the phase transitions. Zeta potential determination as a function of pH was examined to investigate the surface properties of charged nanoparticles. In conclusion, the influence of environmental stability of the surface modifications was also assessed.« less

Fabrication of phosphonic acid films on nitinol nanoparticles by dynamic covalent assembly

DOE PAGES

Quinones, Rosalynn; Garretson, Samantha; Behnke, Grayce; ...

2017-09-25

Nitinol (NiTi) nanoparticles are a valuable metal alloy due to many unique properties that allow for medical applications. NiTi nanoparticles have the potential to form nanofluids, which can advance the thermal conductivity of fluids by controlling the surface functionalization through chemical attachment of organic acids to the surface to form self-assembled alkylphosphonate films. In this study, phosphonic functional head groups such as 16-phosphonohexadecanoic acid, octadecylphosphonic acid, and 12-aminododecylphosphonic acid were used to form an ordered and strongly chemically bounded film on the NiTi nanopowder. The surface of the NiTi nanoparticles was modified in order to tailor the chemical and physicalmore » properties to the desired application. The modified NiTi nanoparticles were characterized using infrared spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and 31P solid-state nuclear magnetic resonance. The interfacial bonding was identified by spectroscopic data suggesting the phosphonic head group adsorbs in a mixed bidentate/monodentate binding motif on the NiTi nanoparticles. Dynamic light scattering and scanning electron microscopy-energy dispersive X-ray spectroscopy revealed the particle sizes. Differential scanning calorimetry was used to examine the phase transitions. Zeta potential determination as a function of pH was examined to investigate the surface properties of charged nanoparticles. In conclusion, the influence of environmental stability of the surface modifications was also assessed.« less

Poly(L-lysine) Interfaces via Dual Click Reactions on Surface-Bound Custom-Designed Dithiol Adsorbates.

PubMed

Shakiba, Amin; Jamison, Andrew C; Lee, T Randall

2015-06-09

Surfaces modified with poly(L-lysine) can be used to immobilize selected biomolecules electrostatically. This report describes the preparation of a set of self-assembled monolayers (SAMs) from three different azide-terminated adsorbates as platforms for performing controlled surface attachments and as a means of determining the parameters that afford stable poly(L-lysine)-modified SAM surfaces having controlled packing densities. A maleimide-terminated alkyne linker was "clicked" to the azide-terminated surfaces via a copper-catalyzed cycloaddition reaction to produce the attachment sites for the polypeptides. A thiol-Michael addition was then used to immobilize cysteine-terminated poly(L-lysine) moieties on the gold surface, avoiding adsorbate self-reactions with this two-step procedure. Each step in this process was analyzed by ellipsometry, X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, and contact angle goniometry to determine which adsorbate structure most effectively produced the targeted polypeptide interface. Additionally, a series of mixed SAMs using an azidoalkanethiol in combination with a normal alkanethiol having an equivalent alkyl chain were prepared to provide data to determine how dilution of the azide reactive site on the SAM surface influences the initial click reaction. Overall, the collected data demonstrate the advantages of an appropriately designed bidentate absorbate and its potential to form effective platforms for biomolecule surface attachment via click reactions.

Stepwise self-assembly of C60 mediated by atomic scale moiré magnifiers

NASA Astrophysics Data System (ADS)

Gruznev, D. V.; Matetskiy, A. V.; Bondarenko, L. V.; Utas, O. A.; Zotov, A. V.; Saranin, A. A.; Chou, J. P.; Wei, C. M.; Lai, M. Y.; Wang, Y. L.

2013-04-01

Self-assembly of atoms or molecules on a crystal surface is considered one of the most promising methods to create molecular devices. Here we report a stepwise self-assembly of C60 molecules into islands with unusual shapes and preferred sizes on a gold-indium-covered Si(111) surface. Specifically, 19-mer islands prefer a non-compact boomerang shape, whereas hexagonal 37-mer islands exhibit extraordinarily enhanced stability and abundance. The stepwise self-assembly is mediated by the moiré interference between an island with its underlying lattice, which essentially maps out the adsorption-energy landscape of a C60 on different positions of the surface with a lateral magnification factor and dictates the probability for the subsequent attachment of C60 to an island’s periphery. Our discovery suggests a new method for exploiting the moiré interference to dynamically assist the self-assembly of particles and provides an unexplored tactic of engineering atomic scale moiré magnifiers to facilitate the growth of monodispersed mesoscopic structures.

Controlling Self-Assembly of Engineered Peptides on Graphite by Rational Mutation

PubMed Central

So, Christopher R.; Hayamizu, Yuhei; Yazici, Hilal; Gresswell, Carolyn; Khatayevich, Dmitriy; Tamerler, Candan; Sarikaya, Mehmet

2012-01-01

Self-assembly of proteins on surfaces is utilized in many fields to integrate intricate biological structures and diverse functions with engineered materials. Controlling proteins at bio-solid interfaces relies on establishing key correlations between their primary sequences and resulting spatial organizations on substrates. Protein self-assembly, however, remains an engineering challenge. As a novel approach, we demonstrate here that short dodecapeptides selected by phage display are capable of self-assembly on graphite and form long-range ordered biomolecular nanostructures. Using atomic force microscopy and contact angle studies, we identify three amino-acid domains along the primary sequence that steer peptide ordering and lead to nanostructures with uniformly displayed residues. The peptides are further engineered via simple mutations to control fundamental interfacial processes, including initial binding, surface aggregation and growth kinetics, and intermolecular interactions. Tailoring short peptides via their primary sequence offers versatile control over molecular self-assembly, resulting in well-defined surface properties essential in building engineered, chemically rich, bio-solid interfaces. PMID:22233341

Formation of Polymer Particles by Direct Polymerization on the Surface of a Supramolecular Template.

PubMed

Schmuck, Carsten; Li, Mao; Zellermann, Elio

2018-04-06

Formation of polymeric materials on the surface of supramolecular assemblies is rather challenging due to the often weak non-covalent interactions between the self-assembled template and the monomers before polymerization. We herein describe that the introduction of a supramolecular anion recognition motif, the guanidiniocarbonyl pyrrole cation (GCP), into a short Fmoc-dipeptide 1 leads to self-assembled spherical nanoparticles in aqueous solution. Onto the surface of these nanoparticles negatively charged diacetylene monomers can be attached which after UV polymerization lead to the formation of a polymer shell around the self-assembled template. The hybrid supramolecular and polymeric nanoparticles demonstrated intriguing thermal hysteresis phenomenon. The template nanoparticle could be disassembled through the treatment with organic base which cleaved the Fmoc moiety on 1. This strategy thus showed that a supramolecular anion recognition motif allows the post-assembly formation of polymeric nanomaterials from anionic monomers around a cationic self-assembled template. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling the self-assembly of functionalized fullerenes on solid surfaces using Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Bubnis, Gregory J.

Since their discovery 25 years ago, carbon fullerenes have been widely studied for their unique physicochemical properties and for applications including organic electronics and photovoltaics. For these applications it is highly desirable for crystalline fullerene thin films to spontaneously self-assemble on surfaces. Accordingly, many studies have functionalized fullerenes with the aim of tailoring their intermolecular interactions and controlling interactions with the solid substrate. The success of these rational design approaches hinges on the subtle interplay of intermolecular forces and molecule-substrate interactions. Molecular modeling is well-suited to studying these interactions by directly simulating self-assembly. In this work, we consider three different fullerene functionalization approaches and for each approach we carry out Monte Carlo simulations of the self-assembly process. In all cases, we use a "coarse-grained" molecular representation that preserves the dominant physical interactions between molecules and maximizes computational efficiency. The first approach we consider is the traditional gold-thiolate SAM (self-assembled monolayer) strategy which tethers molecules to a gold substrate via covalent sulfur-gold bonds. For this we study an asymmetric fullerene thiolate bridged by a phenyl group. Clusters of 40 molecules are simulated on the Au(111) substrate at different temperatures and surface coverage densities. Fullerenes and S atoms are found to compete for Au(111) surface sites, and this competition prevents self-assembly of highly ordered monolayers. Next, we investigate self-assembled monolayers formed by fullerenes with hydrogen-bonding carboxylic acid substituents. We consider five molecules with different dimensions and symmetries. Monte Carlo cooling simulations are used to find the most stable solid structures of clusters adsorbed to Au(111). The results show cases where fullerene-Au(111) attraction, fullerene close-packing, and hydrogen-bonding interactions can cooperate to guide self-assembly or compete to hinder it. Finally, we consider three bis-fullerene molecules, each with a different "bridging group" covalently joining two fullerenes. To effectively study the competing "standing-up" and "lying-down" morphologies, we use Monte Carlo simulations in conjunction with replica exchange and force field biasing methods. For clusters adsorbed to smooth model surfaces, we determine free energy landscapes and demonstrate their utility for rationalizing and predicting self-assembly.

Understanding the role of thiol and disulfide self-assembled DNA receptor monolayers for biosensing applications.

PubMed

Carrascosa, Laura G; Martínez, Lidia; Huttel, Yves; Román, Elisa; Lechuga, Laura M

2010-09-01

A detailed study of the immobilization of three differently sulfur-modified DNA receptors for biosensing applications is presented. The three receptors are DNA-(CH)n-SH-, DNA-(CH)n-SS-(CH)n-DNA, and DNA-(CH)n-SS-DMTO. Nanomechanical and surface plasmon resonance biosensors and fluorescence and radiolabelling techniques were used for the experimental evaluation. The results highlight the critical role of sulfur linker type in DNA self-assembly, affecting the kinetic adsorption and spatial distribution of DNA chains within the monolayer and the extent of chemisorption and physisorption. A spacer (mercaptohexanol, MCH) is used to evaluate the relative efficiencies of chemisorption of the three receptors by analysing the extent to which MCH can remove physisorbed molecules from each type of monolayer. It is demonstrated that -SH derivatization is the most suitable for biosensing purposes as it results in densely packed monolayers with the lowest ratio of physisorbed probes.

On the design of composite protein-quantum dot biomaterials via self-assembly.

PubMed

Majithia, Ravish; Patterson, Jan; Bondos, Sarah E; Meissner, Kenith E

2011-10-10

Incorporation of nanoparticles during the hierarchical self-assembly of protein-based materials can impart function to the resulting composite materials. Herein we demonstrate that the structure and nanoparticle distribution of composite fibers are sensitive to the method of nanoparticle addition and the physicochemical properties of both the nanoparticle and the protein. Our model system consists of a recombinant enhanced green fluorescent protein-Ultrabithorax (EGFP-Ubx) fusion protein and luminescent CdSe-ZnS core-shell quantum dots (QDs), allowing us to optically assess the distribution of both the protein and nanoparticle components within the composite material. Although QDs favorably interact with EGFP-Ubx monomers, the relatively rough surface morphology of composite fibers suggests EGFP-Ubx-QD conjugates impact self-assembly. Indeed, QDs templated onto EGFP-Ubx film post-self-assembly can be subsequently drawn into smooth composite fibers. Additionally, the QD surface charge impacts QD distribution within the composite material, indicating that surface charge plays an important role in self-assembly. QDs with either positively or negatively charged coatings significantly enhance fiber extensibility. Conversely, QDs coated with hydrophobic moieties and suspended in toluene produce composite fibers with a heterogeneous distribution of QDs and severely altered fiber morphology, indicating that toluene severely disrupts Ubx self-assembly. Understanding factors that impact the protein-nanoparticle interaction enables manipulation of the structure and mechanical properties of composite materials. Since proteins interact with nanoparticle surface coatings, these results should be applicable to other types of nanoparticles with similar chemical groups on the surface.

Light-triggered self-assembly of triarylamine-based nanospheres

NASA Astrophysics Data System (ADS)

Moulin, Emilie; Niess, Frédéric; Fuks, Gad; Jouault, Nicolas; Buhler, Eric; Giuseppone, Nicolas

2012-10-01

Tailored triarylamine units modified with terpyridine ligands were coordinated to Zn2+ ions and characterized as discrete dimeric entities. Interestingly, when these complexes were subsequently irradiated with simple visible light in chloroform, they readily self-assembled into monodisperse spheres with a mean diameter of 160 nm.Tailored triarylamine units modified with terpyridine ligands were coordinated to Zn2+ ions and characterized as discrete dimeric entities. Interestingly, when these complexes were subsequently irradiated with simple visible light in chloroform, they readily self-assembled into monodisperse spheres with a mean diameter of 160 nm. Electronic supplementary information (ESI) available: Synthetic procedures and products' characterization (2-4 and 6-9). 1H NMR titration of compound 6 by Zn(OTf)2 to form complex 7. Kinetic measurements by UV-Vis-NIR spectroscopy. Transmission electron microscopy imaging for complexes 8 and 9. UV-Vis-NIR for an Fe2+ analogue of complex 7. Dynamic light scattering and time autocorrelation function for self-assembly of complexes 7-9. Copies of 1H and 13C NMR spectra for compounds 2-4 and 6. See DOI: 10.1039/c2nr32168h

Solvent-Tuned Self-Assembled Nanostructures of Chiral l/d-Phenylalanine Derivatives of Protoporphyrin IX

PubMed Central

Bobe, Mr Sharad R; Al Kobaisi, Mohammad; Bhosale, Sheshanath V; Bhosale, Sidhanath V

2015-01-01

Protoporphyrin IX is a naturally occurring amphiphilic porphyrin with a rigid hydrophobic nonpolar core and two polar propionic acid substitutions on the porphyrin ring. This molecule can be modified on the hydrophilic group, which can lead to strengthened π–π-stacking and spontaneous self-assembly into novel nanostructures. Herein, we use l- phenylalanine and d-phenylalanine to modify protoporphyrin IX, and use the two derivatives for solvophobic-controlled self-assembly. Both derivatives possess two important features: 1) the aromatic core of the porphyrin for dispersive interactions and 2) a chiral amino acid to maximize the influence of chirality on selfassembly. These derivatives lead to the formation of a variety of nanostructure morphologies, such as spheres, nanofibers, lamellar structures, and thread-like and spherical shells. Solution-based self-assembly was determined by UV/Vis, fluorescence, and circular dichroism spectroscopy, and the formed nanostructures were characterized by scanning electron microscopy (SEM). Such engineered porphyrin derivatives could have potential applications in energy transport and storage, supramolecular chemistry, materials science, and medicine. PMID:26478848

Solvent-Tuned Self-Assembled Nanostructures of Chiral l/d-Phenylalanine Derivatives of Protoporphyrin IX.

PubMed

Bobe, Mr Sharad R; Al Kobaisi, Mohammad; Bhosale, Sheshanath V; Bhosale, Sidhanath V

2015-08-01

Protoporphyrin IX is a naturally occurring amphiphilic porphyrin with a rigid hydrophobic nonpolar core and two polar propionic acid substitutions on the porphyrin ring. This molecule can be modified on the hydrophilic group, which can lead to strengthened π-π-stacking and spontaneous self-assembly into novel nanostructures. Herein, we use l- phenylalanine and d-phenylalanine to modify protoporphyrin IX, and use the two derivatives for solvophobic-controlled self-assembly. Both derivatives possess two important features: 1) the aromatic core of the porphyrin for dispersive interactions and 2) a chiral amino acid to maximize the influence of chirality on selfassembly. These derivatives lead to the formation of a variety of nanostructure morphologies, such as spheres, nanofibers, lamellar structures, and thread-like and spherical shells. Solution-based self-assembly was determined by UV/Vis, fluorescence, and circular dichroism spectroscopy, and the formed nanostructures were characterized by scanning electron microscopy (SEM). Such engineered porphyrin derivatives could have potential applications in energy transport and storage, supramolecular chemistry, materials science, and medicine.

Sum-frequency generation analyses of the structure of water at amphoteric SAM-liquid water interfaces.

PubMed

Nomura, Kouji; Nakaji-Hirabayashi, Tadashi; Gemmei-Ide, Makoto; Kitano, Hiromi; Noguchi, Hidenori; Uosaki, Kohei

2014-09-01

Surfaces of both a cover glass and the flat plane of a semi-cylindrical quartz prism were modified with a mixture of positively and negatively charged silane coupling reagents (3-aminopropyltriethoxysilane (APTES) and 3-(trihydroxysilyl)propylmethylphosphonate (THPMP), respectively). The glass surface modified with a self-assembled monolayer (SAM) prepared at a mixing ratio of APTES:THPMP=4:6 was electrically almost neutral and was resistant to non-specific adsorption of proteins, whereas fibroblasts gradually adhered to an amphoteric (mixed) SAM surface probably due to its stiffness, though the number of adhered cells was relatively small. Sum frequency generation (SFG) spectra indicated that total intensity of the OH stretching region (3000-3600cm(-1)) for the amphoteric SAM-modified quartz immersed in liquid water was smaller than those for the positively and negatively charged SAM-modified quartz prisms and a bare quartz prism in contact with liquid water. These results suggested that water molecules at the interface of water and an amphoteric SAM-modified quartz prism are not strongly oriented in comparison with those at the interface of a lopsidedly charged SAM-modified quartz prism and bare quartz. The importance of charge neutralization for the anti-biofouling properties of solid materials was strongly suggested. Copyright © 2014 Elsevier B.V. All rights reserved.

Surface Modification of Self-Assembled Graphene Oxide for Cell Culture Studies

NASA Astrophysics Data System (ADS)

Swain, John E., III

Thin films show great promise for biological applications, from in situ monitoring to pharmaceutical testing. In this study, a graphene oxide (GO) thin film is prepared with the aim to further functionalize the film for pharmaceutical toxicity screening applications. GO was selected due to its capability to be reduced into an optically transparent and electrically conductive thin film. In addition, GO is derived from carbon, a widely abundant element, in contrast to many other thin films that rely on resource-limited precious metals. Special care was taken to select GO and GO film synthesis methods that minimize the amount of organic-based solvents, maintain reactions at atmospheric pressure and moderate temperatures, and are scalable for manufacturing. Chemical oxidation of graphite flakes was carried out via a modified Hummer's Method with a pre-oxidation step. The resulting GO flakes were self-assembled using commercially available 4-sulfocalix[4]arene. Analytical characterizations (e.g., elemental analysis, XRD, FTIR, Raman, SEM, AFM) were performed to evaluate the success of graphite oxidation and formation of the self-assembled thin film. In order to gain a better understanding of the interactions between GO and sulfocalix (SCX), equilibrium conformations of the SCX molecule and truncated GO were calculated using Spartan'16 Parallels. This study demonstrates that the interaction between the GO and the SCX molecule to create a self-assembled thin film is the result of pi-pi stacking, as hypothesized by Sundramoorthy et al. (2015). The self-assembled GO film was successfully deposited on a polyethylene terephthalate (PET) substrate and functionalized with 3-aminopropyl triethoxysilane (APTES), which renders the film capable of further functionalization with proteins for yielding a three-dimensional cell culture or co-culture platform for different applications.

Mesoscopic self-organization of a self-assembled supramolecular rectangle on highly oriented pyrolytic graphite and Au(111) surfaces.

PubMed

Gong, Jian-Ru; Wan, Li-Jun; Yuan, Qun-Hui; Bai, Chun-Li; Jude, Hershel; Stang, Peter J

2005-01-25

A self-assembled supramolecular metallacyclic rectangle was investigated with scanning tunneling microscopy on highly oriented pyrolytic graphite and Au(111) surfaces. The rectangles spontaneously adsorb on both surfaces and self-organize into well ordered adlayers. On highly oriented pyrolytic graphite, the long edge of the rectangle stands on the surface, forming a 2D molecular network. In contrast, the face of the rectangle lays flat on the Au(111) surface, forming linear chains. The structures and intramolecular features obtained through high-resolution scanning tunneling microscopy imaging are discussed.

Comblike poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers as anti-infection surface modifying agents.

PubMed

Mai-ngam, Katanchalee

2006-05-01

A series of structurally well-defined poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers that undergo surface induced self assembly on hydrophobic biomaterial surfaces were synthesized and characterized. The surfactant polymers consist of low molecular weight (Mw) chitosan backbone with hydrophilic poly(ethylene oxide) (PEO) and hydrophobic hexyl pendant groups. Chitosan was depolymerized by nitrous acid deaminative cleavage. Hexanal and aldehyde-terminated PEO chains were simultaneously attached to low Mw chitosan hydrochloride via reductive amination. The surfactant polymers were prepared with various ratios of the two side chains. The molecular composition of the surfactant polymers was determined by FT-IR and 1H NMR. Surface active properties at the air-water interface were determined by Langmuir film balance measurements. The surfactant polymers with PEO/hexyl ratios of 1:3.0 and 1:14.4 were used as surface modifying agents to investigate their anti-infection properties. E. coli adhesion on Silastic surface was decreased significantly by the surfactant polymer with PEO/hexyl 1:3.0. Surface growth of adherent E. coli was effectively suppressed by both tested surfactant polymers.

DNA-Mediated Electrochemistry

PubMed Central

Gorodetsky, Alon A.; Buzzeo, Marisa C.

2009-01-01

The base pair stack of DNA has been demonstrated as a medium for long range charge transport chemistry both in solution and at DNA-modified surfaces. This chemistry is exquisitely sensitive to structural perturbations in the base pair stack as occur with lesions, single base mismatches, and protein binding. We have exploited this sensitivity for the development of reliable electrochemical assays based on DNA charge transport at self-assembled DNA monolayers. Here we discuss the characteristic features, applications, and advantages of DNA-mediated electrochemistry. PMID:18980370

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

Wang, Nana; Cheng, Lu; Wang, Jianpu, E-mail: iamjpwang@njtech.edu.cn

Amino acid self-assembled monolayers are used in the fabrication of light-emitting diodes based on organic-inorganic halide perovskites. The monolayers of amino acids provide modified interfaces by anchoring to the surfaces of ZnO charge-transporting layers using carboxyl groups, leaving the amino groups to facilitate the nucleation of MAPbBr{sub 3} perovskite films. This surface-modification strategy, together with chlorobenzene-assisted fast crystallization method, results in good surface coverage and reduced defect density of the perovskite films. These efforts lead to green perovskite light emitting diodes with a low turn-on voltage of 2 V and an external quantum efficiency of 0.43% at a brightness of ∼5000 cdmore » m{sup −2}.« less

Site-selective growth of surface-anchored metal-organic frameworks on self-assembled monolayer patterns prepared by AFM nanografting

PubMed Central

Ladnorg, Tatjana; Welle, Alexander; Heißler, Stefan; Wöll, Christof

2013-01-01

Summary Surface anchored metal-organic frameworks, SURMOFs, are highly porous materials, which can be grown on modified substrates as highly oriented, crystalline coatings by a quasi-epitaxial layer-by-layer method (liquid-phase epitaxy, or LPE). The chemical termination of the supporting substrate is crucial, because the most convenient method for substrate modification is the formation of a suitable self-assembled monolayer. The choice of a particular SAM also allows for control over the orientation of the SURMOF. Here, we demonstrate for the first time the site-selective growth of the SURMOF HKUST-1 on thiol-based self-assembled monolayers patterned by the nanografting technique, with an atomic force microscope as a structuring tool. Two different approaches were applied: The first one is based on 3-mercaptopropionic acid molecules which are grafted in a 1-decanethiolate SAM, which serves as a matrix for this nanolithography. The second approach uses 16-mercaptohexadecanoic acid, which is grafted in a matrix of an 1-octadecanethiolate SAM. In both cases a site-selective growth of the SURMOF is observed. In the latter case the roughness of the HKUST-1 is found to be significantly higher than for the 1-mercaptopropionic acid. The successful grafting process was verified by time-of-flight secondary ion mass spectrometry and atomic force microscopy. The SURMOF structures grown via LPE were investigated and characterized by atomic force microscopy and Fourier-transform infrared microscopy. PMID:24205458

Surfaces wettability and morphology modulation in a fluorene derivative self-assembly system

NASA Astrophysics Data System (ADS)

Cao, Xinhua; Gao, Aiping; Zhao, Na; Yuan, Fangyuan; Liu, Chenxi; Li, Ruru

2016-04-01

A new organogelator based on fluorene derivative (gelator 1) was designed and synthesized. Organogels could be obtained via the self-assembly of the derivative in acetone, toluene, ethyl acetate, hexane, DMSO and petroleum ether. The self-assembly process was thoroughly characterized using field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), UV-vis, FT-IR and the contact angle. Surfaces with different morphologies and wetting properties were formed via the self-assembly of gelator 1 in the six different solvents. Interestingly, a superhydrophobic surface with a contact angle of 150° was obtained from organogel 1 in DMSO and exhibited the lotus-effect. The sliding angle necessary for a water droplet to move on the glass was only 15°. Hydrogen bonding and van der Waals forces were attributed as the main driving forces for gel formation.

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

PubMed

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

2012-08-01

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

Hyper-Assembly of Self-Assembled Glycoclusters Mediated by Specific Carbohydrate-Carbohydrate Interactions.

PubMed

Yan, Gengwei; Yamaguchi, Takumi; Suzuki, Tatsuya; Yanaka, Saeko; Sato, Sota; Fujita, Makoto; Kato, Koichi

2017-05-04

Hybridization of a self-assembled, spherical complex with oligosaccharides containing Lewis X, a functional trisaccharide displayed on various cell surfaces, yielded well-defined glycoclusters. The self-assembled glycoclusters exhibited homophilic hyper-assembly in aqueous solution in a Ca 2+ -dependent manner through specific carbohydrate-carbohydrate interactions, offering a structural scaffold for functional biomimetic systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Control of Peptide Self-Organization on Atomically Flat Solid Surfaces: A Case Study with Graphite.

PubMed

Seki, Takakazu; So, Christopher R; Page, Tamon R; Starkebaum, David; Hayamizu, Yuhei; Sarikaya, Mehmet

2018-02-06

The nanoscale self-organization of biomolecules, such as proteins and peptides, on solid surfaces under controlled conditions is an important issue in establishing functional bio/solid soft interfaces for bioassays, biosensors, and biofuel cells. Electrostatic interaction between proteins and surfaces is one of the most essential parameters in the adsorption and self-assembly of proteins on solid surfaces. Although the adsorption of proteins has been studied with respect to the electrochemical surface potential, the self-assembly of proteins or peptides forming well-organized nanostructures templated by lattice structure of the solid surfaces has not been studied in the relation to the surface potential. In this work, we utilize graphite-binding peptides (GrBPs) selected by the phage display method to investigate the relationship between the electrochemical potential of the highly ordered pyrolytic graphite (HOPG) and peptide self-organization forming long-range-ordered structures. Under modulated electrical bias, graphite-binding peptides form various ordered structures, such as well-ordered nanowires, dendritic structures, wavy wires, amorphous (disordered) structures, and islands. A systematic investigation of the correlation between peptide sequence and self-organizational characteristics reveals that the presence of the bias-sensitive amino acid modules in the peptide sequence has a significant effect on not only surface coverage but also on the morphological features of self-assembled structures. Our results show a new method to control peptide self-assembly by means of applied electrochemical bias as well as peptide design-rules for the construction of functional soft bio/solid interfaces that could be integrated in a wide range of practical implementations.

Large surface-enhanced Raman scattering from self-assembled gold nanosphere monolayers

NASA Astrophysics Data System (ADS)

Fontana, Jake; Livenere, John; Bezares, Francisco J.; Caldwell, Joshua D.; Rendell, Ronald; Ratna, Banahalli R.

2013-05-01

We demonstrate an average surface-enhanced Raman scattering enhancement on the order of 108 from benzenethiol molecules using self-assembled, macroscopic, and tunable gold nanosphere monolayers on non-templated substrates. The self-assembly of the nanosphere monolayers uses a simple and efficient technique that allows for the creation of a high-density, chemically functionalized gold nanosphere monolayers with enhancement factors comparable to those produced using top-down fabrication techniques. These films may provide an approach for the future development of portable chemical/biological sensors.

Application of surface analytical methods in thin film analysis

NASA Astrophysics Data System (ADS)

Wen, Xingu

Self-assembly and the sol-gel process are two promising methods for the preparation of novel materials and thin films. In this research, these two methods were utilized to prepare two types of thin films: self-assembled monolayers of peptides on gold and SiO2 sol-gel thin films modified with Ru(II) complexes. The properties of the resulting thin films were investigated by several analytical techniques in order to explore their potential applications in biomaterials, chemical sensors, nonlinear optics and catalysis. Among the analytical techniques employed in the study, surface analytical techniques, such as X-ray photoelectron spectroscopy (XPS) and grazing angle reflection absorption Fourier transform infrared spectroscopy (RA-FTIR), are particularly useful in providing information regarding the compositions and structures of the thin films. In the preparation of peptide thin films, monodisperse peptides were self-assembled on gold substrate via the N-terminus-coupled lipoic acid. The film compositions were investigated by XPS and agreed well with the theoretical values. XPS results also revealed that the surface coverage of the self-assembled films was significantly larger than that of the physisorbed films and that the chemisorption between the peptides and gold surface was stable in solvent. Studies by angle dependent XPS (ADXPS) and grazing angle RA-FTIR indicated that the peptides were on average oriented at a small angle from the surface normal. By using a model of orientation distribution function, both the peptide tilt angle and film thickness can be well calculated. Ru(II) complex doped SiO2 sol-gel thin films were prepared by low temperature sol-gel process. The ability of XPS coupled with Ar + ion sputtering to provide both chemical and compositional depth profile information of these sol-gel films was evaluated. This technique, together with UV-VIS and electrochemical measurements, was used to investigate the stability of Ru complexes in the composite films. The stability of Ru complexes with respect to dopant leaching was dependent on the film microstructures. Three methods aiming to improve the dopant stability were also explored. In addition, the ion exchange properties of the composite films, upon exposure to various ions in aqueous solutions, were investigated by XPS, and the ion exchange mechanism was elucidated.

Hierarchical Self Assembly of Patterns from the Robinson Tilings: DNA Tile Design in an Enhanced Tile Assembly Model

PubMed Central

Padilla, Jennifer E.; Liu, Wenyan; Seeman, Nadrian C.

2012-01-01

We introduce a hierarchical self assembly algorithm that produces the quasiperiodic patterns found in the Robinson tilings and suggest a practical implementation of this algorithm using DNA origami tiles. We modify the abstract Tile Assembly Model, (aTAM), to include active signaling and glue activation in response to signals to coordinate the hierarchical assembly of Robinson patterns of arbitrary size from a small set of tiles according to the tile substitution algorithm that generates them. Enabling coordinated hierarchical assembly in the aTAM makes possible the efficient encoding of the recursive process of tile substitution. PMID:23226722

Hierarchical Self Assembly of Patterns from the Robinson Tilings: DNA Tile Design in an Enhanced Tile Assembly Model.

PubMed

Padilla, Jennifer E; Liu, Wenyan; Seeman, Nadrian C

2012-06-01

We introduce a hierarchical self assembly algorithm that produces the quasiperiodic patterns found in the Robinson tilings and suggest a practical implementation of this algorithm using DNA origami tiles. We modify the abstract Tile Assembly Model, (aTAM), to include active signaling and glue activation in response to signals to coordinate the hierarchical assembly of Robinson patterns of arbitrary size from a small set of tiles according to the tile substitution algorithm that generates them. Enabling coordinated hierarchical assembly in the aTAM makes possible the efficient encoding of the recursive process of tile substitution.

The study of VOPc thin film transistors on modified substrates

NASA Astrophysics Data System (ADS)

Song, De; Xu, Qi; Cheng, Hongcang; Li, Bao-zeng; Shang, Yubin

2018-02-01

The vanadyl phthalocyanine (VOPc) organic thin film transistors (OTFTs) were fabricated on the various organosilane self-assembled monolayer (SAM) modified substrates. And the effect of the surface properties on the performance of these transistors was studied. The atomic force morphologies and X-ray diffraction (XRD) spectrums of vanadyl phthalocyanine films on different SAM-modified surfaces were studied. They reveal that the terminal functional groups of organosilane affect the growth of VOPc film and device performance. The VOPc film on octadecyltrichlorosilane (OTS) modified substrate has larger crystal size and effective crystal thickness than those on phenyltrichlorosilane (PTS), 1H,1H,2H,2H-Perfluorodec-yltrichlorosilane (FDTS) as well as non-modified substrate, which contributes the mobility of corresponding device several and several dozen times relative to other ones. The effective crystal thickness and crystal grain size of VOPc film on PTS is between that on OTS treated and that on non-modified substrate due to the stronger attractive force between VOPc and SiO2. The VOPc films' performance and effective crystal thickness on FDTS treated are worse than that on PTS due to the existents of attractive force between -CF3 and VOPc.

Charge transport in fibre-based perylene-diimide transistors: effect of the alkyl substitution and processing technique.

PubMed

Savage, Rebecca C; Orgiu, Emanuele; Mativetsky, Jeffrey M; Pisula, Wojciech; Schnitzler, Tobias; Eversloh, Christian Lütke; Li, Chen; Müllen, Klaus; Samorì, Paolo

2012-04-07

We report a comparative study on the self-assembly from solution and electrical characterization of n-type semiconducting fibres obtained from five different perylenebis(dicarboximide) (PDI) derivatives. In particular we investigated the role of the nature of the alkyl chain covalently linked to the N,N' sites of the PDI in modulating the molecular solubility and aggregation capacity. We explored the morphologies of the self-assembled architectures physisorbed on dielectric surfaces and in particular how they can be modified by tuning the deposition and post-deposition procedures, i.e. by modulating the kinetics of the self-assembly process. To this end, alongside the conventional spin-coating, solvent vapour annealing (SVA) and solvent induced precipitation (SIP) have been employed. Both approaches led to fibres having widths of several hundred nanometres and lengths up to tens of micrometres. SVA formed isolated fibres which were tens of nanometres high, flat, and tapered at the ends. Conversely, SIP fibres exhibited nearly matching heights and widths, but organized into bundles. Despite these morphological differences, the same intermolecular packing is found by XRD in each type of structure, albeit with differing degrees of long-range order. The study of the electrical characteristics of the obtained low dimensional nano-assemblies has been accomplished by fabricating and characterizing organic field-effect transistors. This journal is © The Royal Society of Chemistry 2012

Cell Adhesion on RGD-Displaying Knottins with Varying Numbers of Tryptophan Amino Acids to Tune the Affinity for Assembly on Cucurbit[8]uril Surfaces.

PubMed

Sankaran, Shrikrishnan; Cavatorta, Emanuela; Huskens, Jurriaan; Jonkheijm, Pascal

2017-09-05

Cell adhesion is studied on multivalent knottins, displaying RGD ligands with a high affinity for integrin receptors, that are assembled on CB[8]-methylviologen-modified surfaces. The multivalency in the knottins stems from the number of tryptophan amino acid moieties, between 0 and 4, that can form a heteroternary complex with cucurbit[8]uril (CB[8]) and surface-tethered methylviologen (MV 2+ ). The binding affinity of the knottins with CB[8] and MV 2+ surfaces was evaluated using surface plasmon resonance spectroscopy. Specific binding occurred, and the affinity increased with the valency of tryptophans on the knottin. Additionally, increased multilayer formation was observed, attributed to homoternary complex formation between tryptophan residues of different knottins and CB[8]. Thus, we were able to control the surface coverage of the knottins by valency and concentration. Cell experiments with mouse myoblast (C2C12) cells on the self-assembled knottin surfaces showed specific integrin recognition by the RGD-displaying knottins. Moreover, cells were observed to elongate more on the supramolecular knottin surfaces with a higher valency, and in addition, more pronounced focal adhesion formation was observed on the higher-valency knottin surfaces. We attribute this effect to the enhanced coverage and the enhanced affinity of the knottins in their interaction with the CB[8] surface. Collectively, these results are promising for the development of biomaterials including knottins via CB[8] ternary complexes for tunable interactions with cells.

Biomolecular strategies for cell surface engineering

NASA Astrophysics Data System (ADS)

Wilson, John Tanner

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

Coarse-grained molecular simulation of self-assembly for nonionic surfactants on graphene nanostructures.

PubMed

Wu, Dan; Yang, Xiaoning

2012-10-04

Self-assembly of amphiphilic molecules on the surfaces of nanoscale materials has an important application in a variety of nanotechnology. Here, we report a coarse-grained molecular dynamics simulation on the structure and morphology of the nonionic surfactant, n-alkyl poly(ethylene oxide) (PEO), adsorbed on planar graphene nanostructures. The effects of concentration, surfactant structure, and size of graphene sheet are explored. Because of the finite dimension effect, various morphological hemimicelles can be formed on nanoscale graphene surfaces, which is somewhat different from the self-assembly structures on infinite carbon surfaces. The aggregate morphology is highly dependent on the concentration, the chain lengths, and the size of graphene nanosheets. For the nonionic surfactant, the PEO headgroups show strong dispersion interaction with the carbon surface, leading to a side edge adsorption behavior. This simulation provides insight into the supramolecular self-assembly nanostructures and the adsorption mechanism for the nonionic surfactants aggregated on graphene nanostructures, which could be exploited to guide fabrication of graphene-based nanocomposites.

Polymer adsorption-driven self-assembly of nanostructures.

PubMed

Chakraborty, A K; Golumbfskie, A J

2001-01-01

Driven by prospective applications, there is much interest in developing materials that can perform specific functions in response to external conditions. One way to design such materials is to create systems which, in response to external inputs, can self-assemble to form structures that are functionally useful. This review focuses on the principles that can be employed to design macromolecules that when presented with an appropriate two-dimensional surface, will self-assemble to form nanostructures that may be functionally useful. We discuss three specific examples: (a) biomimetic recognition between polymers and patterned surfaces. (b) control and manipulation of nanomechanical motion generated by biopolymer adsorption and binding, and (c) creation of patterned nanostructuctures by exposing molten diblock copolymers to patterned surfaces. The discussion serves to illustrate how polymer sequence can be manipulated to affect self-assembly characteristics near adsorbing surfaces. The focus of this review is on theoretical and computational work aimed toward elucidating the principles underlying the phenomena pertinent to the three topics noted above. However, synergistic experiments are also described in the appropriate context.

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

DNA-controlled assembly of a NaTl lattice structure from gold nanoparticles and protein nanoparticles

NASA Astrophysics Data System (ADS)

Cigler, Petr; Lytton-Jean, Abigail K. R.; Anderson, Daniel G.; Finn, M. G.; Park, Sung Yong

2010-11-01

The formation of diamond structures from tailorable building blocks is an important goal in colloidal crystallization because the non-compact diamond lattice is an essential component of photonic crystals for the visible-light range. However, designing nanoparticle systems that self-assemble into non-compact structures has proved difficult. Although several methods have been proposed, single-component nanoparticle assembly of a diamond structure has not been reported. Binary systems, in which at least one component is arranged in a diamond lattice, provide alternatives, but control of interparticle interactions is critical to this approach. DNA has been used for this purpose in a number of systems. Here we show the creation of a non-compact lattice by DNA-programmed crystallization using surface-modified Qβ phage capsid particles and gold nanoparticles, engineered to have similar effective radii. When combined with the proper connecting oligonucleotides, these components form NaTl-type colloidal crystalline structures containing interpenetrating organic and inorganic diamond lattices, as determined by small-angle X-ray scattering. DNA control of assembly is therefore shown to be compatible with particles possessing very different properties, as long as they are amenable to surface modification.

Integrated Nanosystems Templated by Self-assembled Virus Capsids

NASA Astrophysics Data System (ADS)

Stephanopoulos, Nicholas

This dissertation presents the synthesis and modeling of multicomponent nanosystems templated by self-assembled virus capsids. The design principles, synthesis, analysis, and future directions for these capsid-based materials are presented. Chapter 1 gives an overview of the literature on the application of virus capsids in constructing nanomaterials. The uses of capsids in three main areas are considered: (1) as templates for inorganic materials or nanoparticles; (2) as vehicles for biological applications like medical imaging and treatment; and (3) as scaffolds for catalytic materials. In light of this introduction, an overview of the material in this dissertation is described. Chapters 2-4 all describe integrated nanosystems templated by bacteriophage MS2, a spherical icosahedral virus capsid. MS2 possesses an interior and exterior surface that can be modified orthogonally using bioconjugation chemistry to create multivalent, multicomponent constructs with precise localization of components attached to the capsid proteins. Chapter 2 describes the use of MS2 to synthesize a photocatalytic construct by modifying the internal surface with sensitizing chromophores and the external surface with a photocatalytic porphyrin. The chromophores absorbed energy that the porphyrin could not, and transferred it to the porphyrin via FRET through the protein shell. The porphyrin was then able to utilize the energy to carry out photocatalysis at new wavelengths. In Chapter 3, porphyrins were installed on the interior surface of MS2 and DNA aptamers specific for Jurkat leukemia T cells on the exterior surface. The dual-modified capsids were able to bind to Jurkat cells, and upon illumination the porphyrins generated singlet oxygen to kill them selectively over non-targeted cells. Chapter 4 explores integrating MS2 with DNA origami in order to arrange the capsids at larger length scales. Capsids modified with fluorescent dyes inside and single-stranded DNA outside were able to bind to origami tiles bearing complementary DNA probes. The tiles could then be used to arrange the capsids in a one-dimensional array with dimensions far exceeding those of individual MS2 particles. In Chapter 5, the use of a different capsid, that of the tobacco mosaic virus (TMV) is described. The defect tolerance of light harvesting systems built using TMV as a scaffold was investigated using a kinetic Monte Carlo model to simulate the energy transfer processes. The results of the simulation were used to understand and explain experimental results obtained from the system.

Self-Assembled Magnetic Surface Swimmers: Theoretical Model

NASA Astrophysics Data System (ADS)

Aranson, Igor; Belkin, Maxim; Snezhko, Alexey

2009-03-01

The mechanisms of self-propulsion of living microorganisms are a fascinating phenomenon attracting enormous attention in the physics community. A new type of self-assembled micro-swimmers, magnetic snakes, is an excellent tool to model locomotion in a simple table-top experiment. The snakes self-assemble from a dispersion of magnetic microparticles suspended on the liquid-air interface and subjected to an alternating magnetic field. Formation and dynamics of these swimmers are captured in the framework of theoretical model coupling paradigm equation for the amplitude of surface waves, conservation law for the density of particles, and the Navier-Stokes equation for hydrodynamic flows. The results of continuum modeling are supported by hybrid molecular dynamics simulations of magnetic particles floating on the surface of fluid.

Synthesis and characterization of designed BMHP1-derived self-assembling peptides for tissue engineering applications

NASA Astrophysics Data System (ADS)

Silva, Diego; Natalello, Antonino; Sanii, Babak; Vasita, Rajesh; Saracino, Gloria; Zuckermann, Ronald N.; Doglia, Silvia Maria; Gelain, Fabrizio

2012-12-01

The importance of self-assembling peptides (SAPs) in regenerative medicine is becoming increasingly recognized. The propensity of SAPs to form nanostructured fibers is governed by multiple forces including hydrogen bonds, hydrophobic interactions and π-π aromatic interactions among side chains of the amino acids. Single residue modifications in SAP sequences can significantly affect these forces. BMHP1-derived SAPs is a class of biotinylated oligopeptides, which self-assemble in β-structured fibers to form a self-healing hydrogel. In the current study, selected modifications in previously described BMHP1-derived SAPs were designed in order to investigate the influence of modified residues on self-assembly kinetics and scaffold formation properties. The Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) analysis demonstrated the secondary structure (β-sheet) formation in all modified SAP sequences, whereas atomic force microscopy (AFM) analysis further confirmed the presence of nanofibers. Furthermore, the fiber shape and dimension analysis by AFM showed flattened and twisted fiber morphology ranging from ~8 nm to ~70 nm. The mechanical properties of the pre-assembled and post assembled solution were investigated by rheometry. The shear-thinning behavior and rapid re-healing properties of the pre-assembled solutions make them a preferable choice for injectable scaffolds. The wide range of stiffnesses (G') -from ~1000 to ~27 000 Pa - exhibited by the post-assembled scaffolds demonstrated their potential for a variety of tissue engineering applications. The extra cellular matrix (ECM) mimicking (physically and chemically) properties of SAP scaffolds enhanced cell adhesion and proliferation. The capability of the scaffold to facilitate murine neural stem cell (mNSC) proliferation was evaluated in vitro: the increased mNSCs adhesion and proliferation demonstrated the potential of newly synthesized SAPs for regenerative medicine approaches.The importance of self-assembling peptides (SAPs) in regenerative medicine is becoming increasingly recognized. The propensity of SAPs to form nanostructured fibers is governed by multiple forces including hydrogen bonds, hydrophobic interactions and π-π aromatic interactions among side chains of the amino acids. Single residue modifications in SAP sequences can significantly affect these forces. BMHP1-derived SAPs is a class of biotinylated oligopeptides, which self-assemble in β-structured fibers to form a self-healing hydrogel. In the current study, selected modifications in previously described BMHP1-derived SAPs were designed in order to investigate the influence of modified residues on self-assembly kinetics and scaffold formation properties. The Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) analysis demonstrated the secondary structure (β-sheet) formation in all modified SAP sequences, whereas atomic force microscopy (AFM) analysis further confirmed the presence of nanofibers. Furthermore, the fiber shape and dimension analysis by AFM showed flattened and twisted fiber morphology ranging from ~8 nm to ~70 nm. The mechanical properties of the pre-assembled and post assembled solution were investigated by rheometry. The shear-thinning behavior and rapid re-healing properties of the pre-assembled solutions make them a preferable choice for injectable scaffolds. The wide range of stiffnesses (G') -from ~1000 to ~27 000 Pa - exhibited by the post-assembled scaffolds demonstrated their potential for a variety of tissue engineering applications. The extra cellular matrix (ECM) mimicking (physically and chemically) properties of SAP scaffolds enhanced cell adhesion and proliferation. The capability of the scaffold to facilitate murine neural stem cell (mNSC) proliferation was evaluated in vitro: the increased mNSCs adhesion and proliferation demonstrated the potential of newly synthesized SAPs for regenerative medicine approaches. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr32656f

Plasma combined self-assembled monolayer pretreatment on electroplated-Cu surface for low temperature Cu-Sn bonding in 3D integration

NASA Astrophysics Data System (ADS)

Wang, Junqiang; Wang, Qian; Wu, Zijian; Tan, Lin; Cai, Jian; Wang, Dejun

2017-05-01

A novel pretreatment of plasma combined self-assembled monolayer (PcSAM) was proposed to improve surface properties of electroplated Cu for low temperature Cu-Sn bonding in 3D integration. Measurement results revealed that self-assemble monolayer (SAM) would be easier absorbed on plasma-activated Cu surface and protect the clean surface from re-oxidation when storage. The absorbed SAM layer could be removed by thermal desorption during bonding process. With optimal PcSAM pretreatment, oxygen content of the Cu surface was reduced to as low as 1.39%. The followed Cu-Sn bonding was realized at low temperature of 200 °C. Finally, bonding interface exhibited a defect-free interconnection, and bonding strength has reached as high as 68.7 MPa.

Building polyhedra by self-assembly: theory and experiment.

PubMed

Kaplan, Ryan; Klobušický, Joseph; Pandey, Shivendra; Gracias, David H; Menon, Govind

2014-01-01

We investigate the utility of a mathematical framework based on discrete geometry to model biological and synthetic self-assembly. Our primary biological example is the self-assembly of icosahedral viruses; our synthetic example is surface-tension-driven self-folding polyhedra. In both instances, the process of self-assembly is modeled by decomposing the polyhedron into a set of partially formed intermediate states. The set of all intermediates is called the configuration space, pathways of assembly are modeled as paths in the configuration space, and the kinetics and yield of assembly are modeled by rate equations, Markov chains, or cost functions on the configuration space. We review an interesting interplay between biological function and mathematical structure in viruses in light of this framework. We discuss in particular: (i) tiling theory as a coarse-grained description of all-atom models; (ii) the building game-a growth model for the formation of polyhedra; and (iii) the application of these models to the self-assembly of the bacteriophage MS2. We then use a similar framework to model self-folding polyhedra. We use a discrete folding algorithm to compute a configuration space that idealizes surface-tension-driven self-folding and analyze pathways of assembly and dominant intermediates. These computations are then compared with experimental observations of a self-folding dodecahedron with side 300 μm. In both models, despite a combinatorial explosion in the size of the configuration space, a few pathways and intermediates dominate self-assembly. For self-folding polyhedra, the dominant intermediates have fewer degrees of freedom than comparable intermediates, and are thus more rigid. The concentration of assembly pathways on a few intermediates with distinguished geometric properties is biologically and physically important, and suggests deeper mathematical structure.

Design of fluidic self-assembly bonds for precise component positioning

NASA Astrophysics Data System (ADS)

Ramadoss, Vivek; Crane, Nathan B.

2008-02-01

Self Assembly is a promising alternative to conventional pick and place robotic assembly of micro components. Its benefits include parallel integration of parts with low equipment costs. Various approaches to self assembly have been demonstrated, yet demanding applications like assembly of micro-optical devices require increased positioning accuracy. This paper proposes a new method for design of self assembly bonds that addresses this need. Current methods have zero force at the desired assembly position and low stiffness. This allows small disturbance forces to create significant positioning errors. The proposed method uses a substrate assembly feature to provide a high accuracy alignment guide to the part. The capillary bond region of the part and substrate are then modified to create a non-zero positioning force to maintain the part in the desired assembly position. Capillary force models show that this force aligns the part to the substrate assembly feature and reduces sensitivity of part position to process variation. Thus, the new configuration can substantially improve positioning accuracy of capillary self-assembly. This will result in a dramatic decrease in positioning errors in the micro parts. Various binding site designs are analyzed and guidelines are proposed for the design of an effective assembly bond using this new approach.

Complex collective dynamics of active torque-driven colloids at interfaces

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

Snezhko, Alexey

Modern self-assembly techniques aiming to produce complex structural order or functional diversity often rely on non-equilibrium conditions in the system. Light, electric, or magnetic fields are predominantly used to modify interaction profiles of colloidal particles during self-assembly or induce complex out-of-equilibrium dynamic ordering. The energy injection rate, properties of the environment are important control parameters that influence the outcome of active (dynamic) self-assembly. The current review is focused on a case of collective dynamics and self-assembly of particles with externally driven torques coupled to a liquid or solid interface. The complexity of interactions in such systems is further enriched bymore » strong hydrodynamic coupling between particles. Unconventionally ordered dynamic self-assembled patterns, spontaneous symmetry breaking phenomena, self-propulsion, and collective transport have been reported in torque-driven colloids. Some of the features of the complex collective behavior and dynamic pattern formation in those active systems have been successfully captured in simulations.« less

Photoswitching in azobenzene self-assembled monolayers capped on zinc oxide: nanodots vs nanorods.

PubMed

Shah, Syed Mujtaba; Martini, Cyril; Ackermann, Jörg; Fages, Frédéric

2012-02-01

We report the synthesis and spectroscopic characterization of nanohybrid structures consisting of an azobenzene compound grafted on the surface of zinc oxide nanoparticles. Characteristic bathochromic shifts indicate that the azobenzene photochromic molecules self-assemble onto the surface of the nanocrystals. The extent of packing is dependent on the shape of the nanoparticle. ZnO nanorods, with flat facets, enable a tighter organization of the molecules in the self-assembled monolayer than in the case of nanodots that display a more curvated shape. Consistently, the efficiency of photochromic switching of the self-assembled monolayer on ZnO nanoparticles is also shown to be strongly affected by nanoparticle shape. Copyright © 2011 Elsevier Inc. All rights reserved.

Biomimetic Superhydrophobic Hollowed-Out Pyramid Surface Based on Self-Assembly.

PubMed

Luo, Weipeng; Yu, Bin; Xiao, Dingbang; Zhang, Meng; Wu, Xuezhong; Li, Guoxi

2018-05-16

In this paper, we present a periodic hollowed-out pyramid microstructure with excellent superhydrophobicity. In our approach, T-topping pillars and capillary-induced self-assembly methods were combined with the photolithography process to fabricate a hollowed-out pyramid structure. First, a wideband ultraviolet source without a filter was used to fabricate the T-topping pillars during the exposure process; then, the evaporation-induced assembly collapsed the pillars and formed the hollowed-out pyramid structure. Scanning electron microscopy images showed the microstructures of the prepared surface. The contact angle of the surface was 154°. The surface showed excellent high temperature and ultraviolet irradiation tolerance, and the contact angle of the surface barely changed when the temperature dropped. This excellent environmental durability of our superhydrophobic surface has potential applications for self-cleaning and friction drag reduction under water.

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.

Ultrasensitive Detection of Cu2+ Using a Microcantilever Sensor Modified with L-Cysteine Self-Assembled Monolayer.

PubMed

Xu, Xiaohe; Zhang, Na; Brown, Gilbert M; Thundat, Thomas G; Ji, Hai-Feng

2017-10-01

A microcantilever was modified with a self-assembled monolayer (SAM) of L-cysteine for the sensitively and selectively response to Cu(II) ions in aqueous solution. The microcantilever undergoes bending due to sorption of Cu(II) ions. The interaction of Cu(II) ions with the L-cysteine on the cantilever is diffusion controlled and does not follow a simple Langmuir adsorption model. A concentration of 10 -10  M Cu(II) was detected in a fluid cell using this technology. Other cations, such as Ni 2+ , Zn 2+ , Pb 2+ , Cd 2+ , Ca 2+ , K + , and Na + , did not respond with a significant deflection, indicating that this L-cysteine-modified cantilever responded selectively and sensitively to Cu(II).

Bio-inspired metal ions regulate the structure evolution of self-assembled peptide-based nanoparticles

NASA Astrophysics Data System (ADS)

Xu, An-Ping; Yang, Pei-Pei; Yang, Chao; Gao, Yu-Juan; Zhao, Xiao-Xiao; Luo, Qiang; Li, Xiang-Dan; Li, Li-Zhong; Wang, Lei; Wang, Hao

2016-07-01

We report an assembly and transformation process of a supramolecular module, BP-KLVFF-RGD (BKR) in solution and on specific living cell surfaces for imaging and treatment. The BKR self-assembled into nanoparticles, which further transformed into nanofibers in situ induced by coordination with Ca2+ ions.We report an assembly and transformation process of a supramolecular module, BP-KLVFF-RGD (BKR) in solution and on specific living cell surfaces for imaging and treatment. The BKR self-assembled into nanoparticles, which further transformed into nanofibers in situ induced by coordination with Ca2+ ions. Electronic supplementary information (ESI) available: Experimental details; Fig. S1-S9. See DOI: 10.1039/c6nr03580a

DNA-Based Self-Assembly of Fluorescent Nanodiamonds.

PubMed

Zhang, Tao; Neumann, Andre; Lindlau, Jessica; Wu, Yuzhou; Pramanik, Goutam; Naydenov, Boris; Jelezko, Fedor; Schüder, Florian; Huber, Sebastian; Huber, Marinus; Stehr, Florian; Högele, Alexander; Weil, Tanja; Liedl, Tim

2015-08-12

As a step toward deterministic and scalable assembly of ordered spin arrays we here demonstrate a bottom-up approach to position fluorescent nanodiamonds (NDs) with nanometer precision on DNA origami structures. We have realized a reliable and broadly applicable surface modification strategy that results in DNA-functionalized and perfectly dispersed NDs that were then self-assembled in predefined geometries. With optical studies we show that the fluorescence properties of the nitrogen-vacancy color centers in NDs are preserved during surface modification and DNA assembly. As this method allows the nanoscale arrangement of fluorescent NDs together with other optically active components in complex geometries, applications based on self-assembled spin lattices or plasmon-enhanced spin sensors as well as improved fluorescent labeling for bioimaging could be envisioned.

Tuning the reactivity of Al/Fe{sub 2}O{sub 3} nanoenergetic materials via an approach combining soft template self-assembly with sol–gel process process

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

Zhang, Tianfu; Wang, Zhen; Li, Guoping

2015-10-15

A bottom-up approach combining soft template self-assembly with sol–gel process, was adopted to prepare the assembled Al/Fe{sub 2}O{sub 3} nanoenergetic materials, assembly-Al/Fe{sub 2}O{sub 3} sample. The other two unassembled Al/Fe{sub 2}O{sub 3}a nanoenergetic materials, sol–gel–Al/Fe{sub 2}O{sub 3} sample and mixing-Al/Fe{sub 2}O{sub 3} sample, were prepared by sol–gel method and physical mixing method respectively. The assembly process within the preparation of the assembly-Al/Fe{sub 2}O{sub 3} sample was analyzed through the changes in the average hydrodynamic diameters of the particles and the micelles in solution. SEM, EDS and TEM tests were performed to demonstrate a significant improvement regarding to dispersity and arrangementsmore » of the Al and Fe{sub 2}O{sub 3} particles in the assembled samples, compared to that of the unassembled Al/Fe{sub 2}O{sub 3} samples. DSC test was employed to characterize the reactivity of the samples. The heat release of the assembled Al/Fe{sub 2}O{sub 3} sample was 2088 J/g, about 400 and 990 J/g more than that of the sol–gel–Al/Fe{sub 2}O{sub 3} sample and mixing-Al/Fe{sub 2}O{sub 3} sample, respectively. - Graphical abstract: Modified aluminum (Al) nanoparticles with hydrophobic surface assembled into the Brij S10 micelle in Fe(III) sol, then the well dispersed system was transformed into Al/Fe{sub 2}O{sub 3} nanoenergetic materials with high reactivity. - Highlights: • An approach combining soft template self-assembly with sol–gel process was adopted. • The aggregation of Al nanoparticles in the final product was reduced significantly. • The reactivity of Al/Fe{sub 2}O{sub 3} nanoenergetic materials was improved to a large extent.« less

Ionic self-assembly of surface functionalized metal-organic polyhedra nanocages and their ordered honeycomb architecture at the air/water interface.

PubMed

Li, Yantao; Zhang, Daojun; Gai, Fangyuan; Zhu, Xingqi; Guo, Ya-nan; Ma, Tianliang; Liu, Yunling; Huo, Qisheng

2012-08-18

Metal-organic polyhedra (MOP) nanocages were successfully surface functionalized via ionic self-assembly and the ordered honeycomb architecture of the encapsulated MOP nanocages was also fabricated at the air/water surface. The results provide a novel synthetic method and membrane processing technique of amphiphilic MOP nanocages for various applications.

Simulations of molecular self-assembled monolayers on surfaces: packing structures, formation processes and functions tuned by intermolecular and interfacial interactions.

PubMed

Wen, Jin; Li, Wei; Chen, Shuang; Ma, Jing

2016-08-17

Surfaces modified with a functional molecular monolayer are essential for the fabrication of nano-scale electronics or machines with novel physical, chemical, and/or biological properties. Theoretical simulation based on advanced quantum chemical and classical models is at present a necessary tool in the development, design, and understanding of the interfacial nanostructure. The nanoscale surface morphology, growth processes, and functions are controlled by not only the electronic structures (molecular energy levels, dipole moments, polarizabilities, and optical properties) of building units but also the subtle balance between intermolecular and interfacial interactions. The switchable surfaces are also constructed by introducing stimuli-responsive units like azobenzene derivatives. To bridge the gap between experiments and theoretical models, opportunities and challenges for future development of modelling of ferroelectricity, entropy, and chemical reactions of surface-supported monolayers are also addressed. Theoretical simulations will allow us to obtain important and detailed information about the structure and dynamics of monolayer modified interfaces, which will guide the rational design and optimization of dynamic interfaces to meet challenges of controlling optical, electrical, and biological functions.

Host-Guest Chemistry in Integrated Porous Space Formed by Molecular Self-Assembly at Liquid-Solid Interfaces.

PubMed

Iritani, Kohei; Tahara, Kazukuni; De Feyter, Steven; Tobe, Yoshito

2017-05-16

Host-guest chemistry in two-dimensional (2D) space, that is, physisorbed monolayers of a single atom or a single molecular thickness on surfaces, has become a subject of intense current interest because of perspectives for various applications in molecular-scale electronics, selective sensors, and tailored catalysis. Scanning tunneling microscopy has been used as a powerful tool for the visualization of molecules in real space on a conducting substrate surface. For more than a decade, we have been investigating the self-assembly of a series of triangle-shaped phenylene-ethynylene macrocycles called dehydrobenzo[12]annulenes (DBAs). These molecules are substituted with six alkyl chains and are capable of forming hexagonal porous 2D molecular networks via van der Waals interactions between interdigitated alkyl chains at the interface of organic solvents and graphite. The dimension of the nanoporous space or nanowell formed by the self-assembly of DBAs can be controlled from 1.6 to 4.7 nm by simply changing the alkyl chain length from C 6 to C 20 . Single molecules as well as homoclusters and heteroclusters are capable of coadsorbing within the host matrix using shape- and size-complementarity principles. Moreover, on the basis of the versatility of the DBA molecules that allows chemical modification of the alkyl chain terminals, we were able to decorate the interior space of the nanoporous networks with functional groups such as azobenzenedicarboxylic acid for photoresponsive guest adsorption/desorption or fluoroalkanes and tetraethylene glycol groups for selective guest binding by electrostatic interactions and zinc-porphyrin units for complexation with a guest by charge-transfer interactions. In this Feature Article, we describe the general aspects of molecular self-assembly at liquid/solid interfaces, followed by the formation of programmed porous molecular networks using rationally designed molecular building blocks. We focus on our own work involving host-guest chemistry in integrated nanoporous space that is modified for specific purposes.

Controlled Supramolecular Self-Assembly of Super-charged β-Lactoglobulin A-PEG Conjugates into Nanocapsules.

PubMed

Khan, Amit Kumar; Gudlur, Sushanth; de Hoog, Hans-Peter M; Siti, Winna; Liedberg, Bo; Nallani, Madhavan

2017-09-18

The synthesis and characterization of a new protein-polymer conjugate composed of β lactoglobulin A (βLG A) and poly(ethylene glycol) PEG is described. βLG A was selectively modified to self-assemble by super-charging via amination or succinylation followed by conjugation with PEG. An equimolar mixture of the oppositely charged protein-polymer conjugates self-assemble into spherical capsules of 80-100 nm in diameter. The self-assembly proceeds by taking simultaneous advantage of the amphiphilicity and polyelectrolyte nature of the protein-polymer conjugate. These protein-polymer capsules or proteinosomes are reminiscent of protein capsids, and are capable of encapsulating solutes in their interior. We envisage this approach to be applicable to other globular proteins. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-Assembly of Optical Molecules with Supramolecular Concepts

PubMed Central

Okamoto, Ken; Chithra, Parayalil; Richards, Gary J.; Hill, Jonathan P.; Ariga, Katsuhiko

2009-01-01

Fabrication of nano-sized objects is one of the most important issues in nanoscience and nanotechnology. Soft nanomaterials with flexible properties have been given much attention and can be obtained through bottom-up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and techniques. Among the various functional molecules, dyes have become important materials in certain areas of nanotechnology and their self-assembling behaviors have been actively researched. In this short review, we briefly introduce recent progress in self-assembly of optical molecules and dyes, based mainly on supramolecular concepts. The introduced examples are classified into four categories: self-assembly of (i) low-molecular-weight dyes and (ii) polymeric dyes and dye self-assembly (iii) in nanoscale architectures and (iv) at surfaces. PMID:19564931

Photocatalysis and self-cleaning from g-C3N4 coated cotton fabrics under sunlight irradiation

NASA Astrophysics Data System (ADS)

Fan, Yunde; Zhou, Ji; Zhang, Jin; Lou, Yaqin; Huang, Zhenwu; Ye, Yong; Jia, Li; Tang, Bin

2018-05-01

Graphite-like carbon nitride (g-C3N4) nanosheets have been facilely assembled via electrostatic interaction onto cotton fabrics for achieving multi-functionalities. The surface morphologies, chemical composition and optical features of the g-C3N4-coated fabrics were characterized. The treated cotton fabrics exhibited remarkable photocatalytic degradation activity and superior self-cleaning performance. A complete degradation of Rhodamine B (RhB) and removal of stains were accomplished under simulated sunlight irradiation. More importantly, the modified fabrics can be reused in catalysis reactions with great durability. The practical treatment approach demonstrated from this work has great potential to be applied in textile industry for functional fabrics manufacture.

Mineral Surface-Templated Self-Assembling Systems: Case Studies from Nanoscience and Surface Science towards Origins of Life Research.

PubMed

Gillams, Richard J; Jia, Tony Z

2018-05-08

An increasing body of evidence relates the wide range of benefits mineral surfaces offer for the development of early living systems, including adsorption of small molecules from the aqueous phase, formation of monomeric subunits and their subsequent polymerization, and supramolecular assembly of biopolymers and other biomolecules. Each of these processes was likely a necessary stage in the emergence of life on Earth. Here, we compile evidence that templating and enhancement of prebiotically-relevant self-assembling systems by mineral surfaces offers a route to increased structural, functional, and/or chemical complexity. This increase in complexity could have been achieved by early living systems before the advent of evolvable systems and would not have required the generally energetically unfavorable formation of covalent bonds such as phosphodiester or peptide bonds. In this review we will focus on various case studies of prebiotically-relevant mineral-templated self-assembling systems, including supramolecular assemblies of peptides and nucleic acids, from nanoscience and surface science. These fields contain valuable information that is not yet fully being utilized by the origins of life and astrobiology research communities. Some of the self-assemblies that we present can promote the formation of new mineral surfaces, similar to biomineralization, which can then catalyze more essential prebiotic reactions; this could have resulted in a symbiotic feedback loop by which geology and primitive pre-living systems were closely linked to one another even before life’s origin. We hope that the ideas presented herein will seed some interesting discussions and new collaborations between nanoscience/surface science researchers and origins of life/astrobiology researchers.

Robust, self-assembled, biocompatible films

DOEpatents

Swanson, Basil I; Anderson, Aaron S.; Dattelbaum, Andrew M.; Schmidt, Jurgen G.

2014-06-24

The present invention provides a composite material including a substrate having an oxide surface, and, a continuous monolayer on the oxide surface, the monolayer including a silicon atom from a trifunctional alkyl/alkenyl/alkynyl silane group that attaches to the oxide surface, an alkyl/alkenyl/alkynyl portion of at least three carbon atoms, a polyalkylene glycol spacer group, and either a reactive site (e.g., a recognition ligand) or a site resistant to non-specific binding (e.g., a methoxy or the like) at the terminus of each modified SAM. The present invention further provides a sensor element, a sensor array and a method of sensing, each employing the composite material. Patterning is also provided together with backfilling to minimize non-specific binding.

Investigation of Supramolecular Coordination Self-Assembly and Polymerization Confined on Metal Surfaces Using Scanning Tunneling Microscopy

NASA Astrophysics Data System (ADS)

Lin, Tao

Organic molecules are envisioned as the building blocks for design and fabrication of functional devices in future, owing to their versatility, low cost and flexibility. Although some devices such as organic light-emitting diode (OLED) have been already applied in our daily lives, the field is still in its infancy and numerous challenges still remain. In particular, fundamental understanding of the process of organic material fabrication at a molecular level is highly desirable. This thesis focuses on the design and fabrication of supramolecular and macromolecular nanostructures on a Au(111) surface through self-assembly, polymerization and a combination of two. We used scanning tunneling microscopy (STM) as an experimental tool and Monte Carlo (MC) and kinetic Monte Carlo (KMC) simulations as theoretical tools to characterize the structures of these systems and to investigate the mechanisms of the self-assembly and polymerization processes at a single-molecular level. The results of this thesis consist of four parts as below: Part I addresses the mechanisms of two-dimensional multicomponent supramolecular self-assembly via pyridyl-Fe-terpyridyl coordination. Firstly, we studied four types of self-assembled metal-organic systems exhibiting different dimensionalities using specifically-designed molecular building blocks. We found that the two-dimensional system is under thermodynamic controls while the systems of lower dimension are under kinetic controls. Secondly, we studied the self-assembly of a series of cyclic supramolecular polygons. Our results indicate that the yield of on-surface cyclic polygon structures is very low independent of temperature and concentration and this phenomenon can be attributed to a subtle competition between kinetic and thermodynamic controls. These results shed light on thermodynamic and kinetic controls in on-surface coordination self-assembly. Part II addresses the two-dimensional supramolecular self-assembly of porphyrin derivatives. Firstly, we investigated the coordination self-assembly of a series of peripheral bromo-phenyl and pyridyl substituted porphyrins with Fe. The self-assembly of the porphyrin derivatives in which phenyl groups are substituted by bromo-phenyl results in coordination networks exhibiting identical structures to that of the parent compounds, but contained nanopores that are functionalized by bromine substitutes. Secondly, we studied a two-dimensional coordination networks formed by 5,10,15,20-tetra(4-pyridyl)porphyrin and Fe. We discovered a novel coordination motif in which a pair of vertically aligned Fe atoms is ligated by four equatorial pyridyl groups. Lateral manipulation, vertical manipulation and tunneling spectroscopy were employed to characterize the networks. These novel coordination networks decorated with Br or vertically aligned Fe atoms may provide potential functions as nano-receptor, molecular magnetism or catalyst. Part III addresses the mechanism of on-surface Ullmann coupling reaction. We studied Pd- and Cu-catalyzed Ullmann coupling reactions between phenyl bromide functionalized porphyrin derivatives. We discovered that the reactions catalyzed by Pd or Cu can be described as a two-phase process that involves an initial activation followed by C-C bond formation. Analysis of rate constants of the Pd-catalyzed reactions allowed us to determine its activation energy as (0.41 +/- 0.03) eV. These results provide a quantitative understanding of on-surface Ullmann coupling reaction. Part IV addresses the on-surface self-assembly driven by a combination of coordination bonds and covalent bonds. Firstly, we utilized metal-directed template to control the on-surface polymerization process. Taking advantage of efficient topochemical enhancement owing to the conformation flexibility of the Cu-pyridyl bonds, macromolecular porphyrin structures that exhibit a narrow size distribution were synthesized. The results reveal that the polymerization process profited from the rich chemistry of Cu which catalyzed the C-C bond formation, controlled the size of the macromolecular products, and organized the macromolecules in a highly ordered manner on the surface. Secondly, we demonstrated a two-step approach for assembling metal-organic coordination network exhibiting very large pores. The first step involves obtaining one kind of building blocks via on-surface Ullmann coupling and the second step is coordination self-assembly. Moreover, the modulation of the surface-state electrons in the network was studied. These results provide new approaches to design and fabricate on-surface nanostructures. In summary, we resolved the structures and studied the on-surface assembly and reaction mechanisms of supramolecular and macromolecular nanostructures at a sub-molecular level. These fundamental studies may shed lights on design and fabrication of low-dimensional organic materials.

Dynamic Self-Assembly of Gold/Polymer Nanocomposites: pH-Encoded Switching between 1D Nanowires and 3D Nanosponges.

PubMed

Zhang, Qi; Xu, Tian-Yi; Zhao, Cai-Xin; Jin, Wei-Hang; Wang, Qian; Qu, Da-Hui

2017-10-05

The design of tunable dynamic self-assembly of nanoparticles with switchable assembled dimensions and morphologies is a challenging goal whose realization is vital for the evolution of smart nanomaterials. Herein, we report on chitosan polymer as an effective supramolecular "glue" for aldehyde-modified Au nanoparticles to reversibly modulate the states of self-assembled nanocomposites. By simultaneous integration of dynamic covalent Schiff base interactions and noncovalent hydrogen bonds, the chitosan/Au nanocomposites could reversibly transform their assembled morphologies from one-dimensional nanowires to three-dimensional nanosponges in response to the variation of pH value. Moreover, the obtained nanosponges could be used as an efficient pH-controlled cargo release system. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Predicting supramolecular self-assembly on reconstructed metal surfaces

NASA Astrophysics Data System (ADS)

Roussel, Thomas J.; Barrena, Esther; Ocal, Carmen; Faraudo, Jordi

2014-06-01

The prediction of supramolecular self-assembly onto solid surfaces is still challenging in many situations of interest for nanoscience. In particular, no previous simulation approach has been capable to simulate large self-assembly patterns of organic molecules over reconstructed surfaces (which have periodicities over large distances) due to the large number of surface atoms and adsorbing molecules involved. Using a novel simulation technique, we report here large scale simulations of the self-assembly patterns of an organic molecule (DIP) over different reconstructions of the Au(111) surface. We show that on particular reconstructions, the molecule-molecule interactions are enhanced in a way that long-range order is promoted. Also, the presence of a distortion in a reconstructed surface pattern not only induces the presence of long-range order but also is able to drive the organization of DIP into two coexisting homochiral domains, in quantitative agreement with STM experiments. On the other hand, only short range order is obtained in other reconstructions of the Au(111) surface. The simulation strategy opens interesting perspectives to tune the supramolecular structure by simulation design and surface engineering if choosing the right molecular building blocks and stabilising the chosen reconstruction pattern.The prediction of supramolecular self-assembly onto solid surfaces is still challenging in many situations of interest for nanoscience. In particular, no previous simulation approach has been capable to simulate large self-assembly patterns of organic molecules over reconstructed surfaces (which have periodicities over large distances) due to the large number of surface atoms and adsorbing molecules involved. Using a novel simulation technique, we report here large scale simulations of the self-assembly patterns of an organic molecule (DIP) over different reconstructions of the Au(111) surface. We show that on particular reconstructions, the molecule-molecule interactions are enhanced in a way that long-range order is promoted. Also, the presence of a distortion in a reconstructed surface pattern not only induces the presence of long-range order but also is able to drive the organization of DIP into two coexisting homochiral domains, in quantitative agreement with STM experiments. On the other hand, only short range order is obtained in other reconstructions of the Au(111) surface. The simulation strategy opens interesting perspectives to tune the supramolecular structure by simulation design and surface engineering if choosing the right molecular building blocks and stabilising the chosen reconstruction pattern. GA image adapted from refs: (a) Phys. Chem. Chem. Phys., 2001, 3, 3399-3404, with permission from the PCCP Owner Societies, and (b) J. Phys. Chem. C, 2008, 112 (18), 7168-7172, reprinted with permission from the American Chemical Society, copyright © 2008.

Immobilization of cellulase on a silica gel substrate modified using a 3-APTES self-assembled monolayer

DOE PAGES

Zhang, Dezhi; Hegab, Hisham E.; Lvov, Yuri; ...

2016-01-20

Cellulase was immobilized onto silica gel surfaces pretreated with (3-aminopropyl) triethoxy-silane (3-APTES), and glutaraldehyde (GA) was used as a cross-linker. A carboxymethyl cellulose sodium salt (CMC) solution was used for activity experiments. Protein assay was performed to determine the mass immobilized and compare with free enzyme. Cellulase was successfully demonstrated to be immobilized on the modified silica gel surface, and no detectable amount of enzyme was stripped off during the hydrolysis of the CMC solution. The specific activity of the immobilized cellulase is 7 ± 2 % compared to the similar amount of free cellulase. Significant activity over multiple reusesmore » was observed. The seventh batch achieved 82 % activity of the initial batch, and the fifteenth batch retained 31 %. Lastly, it was observed that the immobilized cellulase retained 48 % of its initial activity after 4 days, and 22 % even after 14 days.« less

In situ Observation of Direct Electron Transfer Reaction of Cytochrome c Immobilized on ITO Electrode Modified with 11-{2-[2-(2-Methoxyethoxy)ethoxy]ethoxy}undecylphosphonic Acid Self-assembled Monolayer Film by Electrochemical Slab Optical Waveguide Spectroscopy.

PubMed

Matsuda, Naoki; Okabe, Hirotaka; Omura, Ayako; Nakano, Miki; Miyake, Koji

2017-01-01

To immobilize cytochrome c (cyt.c) on an ITO electrode while keeping its direct electron transfer (DET) functionality, the ITO electrode surface was modified with 11-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}undecylphosphonic acid (CH 3 O (CH 2 CH 2 O) 3 C 11 H 22 PO(OH) 2 , M-EG 3 -UPA) self-assembled monolayer (SAM) film. After a 100-times washing process to exchange a phosphate buffer saline solution surrounding cyt.c and ITO electrode to a fresh one, an in situ observation of visible absorption spectral change with slab optical waveguide (SOWG) spectroscopy showed that 87.7% of the cyt.c adsorbed on the M-EG 3 -UPA modified ITO electrode remained on the ITO electrode. The SOWG absorption spectra corresponding to oxidized and reduced cyt.c were observed with setting the ITO electrode potential at 0.3 and -0.3 V vs. Ag/AgCl, respectively, while probing the DET reaction between cyt.c and ITO electrode occurred. The amount of cyt.c was evaluated to be about 19.4% of a monolayer coverage based on the coulomb amount in oxidation and reduction peaks on cyclic voltammetry (CV) data. The CV peak current maintained to be 83.4% compared with the initial value for a M-EG 3 -UPA modified ITO electrode after 60 min continuous scan with 0.1 V/s between 0.3 and -0.3 V vs. Ag/AgCl.

Dithiocarbamate Self-Assembled Monolayers as Efficient Surface Modifiers for Low Work Function Noble Metals

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

Meyer, Dominik; Schäfer, Tobias; Schulz, Philip

2016-09-06

Tuning the work function of the electrode is one of the crucial steps to improve charge extraction in organic electronic devices. Here, we show that N,N-dialkyl dithiocarbamates (DTC) can be effectively employed to produce low work function noble metal electrodes. Work functions between 3.1 and 3.5 eV are observed for all metals investigated (Cu, Ag, and Au). Ultraviolet photoemission spectroscopy (UPS) reveals a maximum decrease in work function by 2.1 eV as compared to the bare metal surface. Electronic structure calculations elucidate how the complex interplay between intrinsic dipoles and dipoles induced by bond formation generates such large work functionmore » shifts. Subsequently, we quantify the improvement in contact resistance of organic thin film transistor devices with DTC coated source and drain electrodes. These findings demonstrate that DTC molecules can be employed as universal surface modifiers to produce stable electrodes for electron injection in high performance hybrid organic optoelectronics.« less

Chiral symmetry breaking during the self-assembly of monolayers from achiral purine molecules.

PubMed

Sowerby, S J; Heckl, W M; Petersen, G B

1996-11-01

Scanning tunneling microscopy was used to investigate the structure of the two-dimensional adsorbate formed by molecular self-assembly of the purine base, adenine, on the surfaces of the naturally occurring mineral molybdenite and the synthetic crystal highly oriented pyrolytic graphite. Although formed from adenine, which is achiral, the observed adsorbate surface structures were enantiomorphic on molybdenite. This phenomenon suggests a mechanism for the introduction of a localized chiral symmetry break by the spontaneous crystallization of these prebiotically available molecules on inorganic surfaces and may have some role in the origin of biomolecular optical asymmetry. The possibility that purine-pyrimidine arrays assembled on naturally occurring mineral surfaces might act as possible templates for biomolecular assembly is discussed.

A sturdy self-cleaning and anti-corrosion superhydrophobic coating assembled by amino silicon oil modifying potassium titanate whisker-silica particles

NASA Astrophysics Data System (ADS)

Lv, Chongjiang; Wang, Huaiyuan; Liu, Zhanjian; Zhang, Wenbo; Wang, Chijia; Tao, Ruifeng; Li, Meiling; Zhu, Yanji

2018-03-01

A sturdy self-cleaning and anticorrosion superhydrophobic coating based on poly(phenylene sulfide) (PPS) matrix has been successfully fabricated by combination of sol-gel and spraying technology without using any fluorine materials. The prepared coating possessed excellent superhydrophobicity with the water contact angle (WCA) (161 ± 1.2)° and slide angle (SA) (2 ± 1.5)°, which was ascribed to the synergistic effect of low-surface energy material amino silicon oil (ASO) and the binary potassium titanate whisker-silica (PTW-SiO2) composite particles formed by in-situ growth of SiO2 on modified PTW via sol-gel. Moreover, The PPS/ASO/PTW-SiO2 superhydrophobic coating exhibited decent self-cleaning property with clean surface even after 100 times immersion in muddy solution. The abrasion test demonstrated that the mechanical stability of prepared coating was about 2 times of the pure PPS coating. Simultaneously, the potentiodynamic polarization and electrochemical impedance spectroscopy testified the excellent corrosion resistance of prepared coating with the performance of lower corrosion current (1.289 × 10-10 A/cm2) and high protection efficiency (99.999%) even after immersion in 3.5 wt.% NaCl solution for 28 days. It is believed that this sturdy self-cleaning and anti-corrosion superhydrophobic coating might have a promising application prospect in industry.

Peptide-Mediated Platelet Capture at Gold Micropore Arrays.

PubMed

Adamson, Kellie; Spain, Elaine; Prendergast, Una; Moran, Niamh; Forster, Robert J; Keyes, Tia E

2016-11-30

Ordered spherical cap gold cavity arrays with 5.4, 1.6, and 0.98 μm diameter apertures were explored as capture surfaces for human blood platelets to investigate the impact of surface geometry and chemical modification on platelet capture efficiency and their potential as platforms for surface enhanced Raman spectroscopy of single platelets. The substrates were chemically modified with single-constituent self-assembled monolayers (SAM) or mixed SAMs comprised of thiol-functionalized arginine-glycine-aspartic acid (RGD, a platelet integrin target) with or without 1-octanethiol (adhesion inhibitor). As expected, platelet adhesion was promoted and inhibited at RGD and alkanethiol modified surfaces, respectively. Platelet adhesion was reversible, and binding efficiency at the peptide modified substrates correlated inversely with pore diameter. Captured platelets underwent morphological change on capture, the extent of which depended on the topology of the underlying substrate. Regioselective capture of the platelets enabled study for the first time of the surface enhanced Raman spectroscopy of single blood platelets, yielding high quality Raman spectroscopy of individual platelets at 1.6 μm diameter pore arrays. Given the medical importance of blood platelets across a range of diseases from cancer to psychiatric illness, such approaches to platelet capture may provide a useful route to Raman spectroscopy for platelet related diagnostics.

Nafion induced surface confinement of oxygen in carbon-supported oxygen reduction catalysts

DOE PAGES

Chlistunoff, Jerzy; Sansinena, Jose -Maria

2016-11-17

We studied the surface confinement of oxygen inside layers of Nafion self-assembled on carbon-supported oxygen reduction reaction (ORR) catalysts. It is demonstrated that oxygen accumulates in the hydrophobic component of the polymer remaining in contact with the carbon surface. Furthermore, the amount of surface confined oxygen increases with the degree of carbon surface graphitization, which promotes the self-assembly of the polymer. Planar macrocyclic ORR catalysts possessing a delocalized system of π electrons such as Co and Fe porphyrins and phthalocyanines have virtually no effect on the surface confinement of oxygen, in accordance with their structural similarity to graphitic carbon surfacesmore » where they adsorb. Platinum particles in carbon-supported ORR catalysts with high metal contents (20%) disrupt the self-assembly of Nafion and virtually eliminate the oxygen confinement, but the phenomenon is still observed for low Pt loading (4.8%) catalysts.« less

Nafion induced surface confinement of oxygen in carbon-supported oxygen reduction catalysts

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

Chlistunoff, Jerzy; Sansinena, Jose -Maria

We studied the surface confinement of oxygen inside layers of Nafion self-assembled on carbon-supported oxygen reduction reaction (ORR) catalysts. It is demonstrated that oxygen accumulates in the hydrophobic component of the polymer remaining in contact with the carbon surface. Furthermore, the amount of surface confined oxygen increases with the degree of carbon surface graphitization, which promotes the self-assembly of the polymer. Planar macrocyclic ORR catalysts possessing a delocalized system of π electrons such as Co and Fe porphyrins and phthalocyanines have virtually no effect on the surface confinement of oxygen, in accordance with their structural similarity to graphitic carbon surfacesmore » where they adsorb. Platinum particles in carbon-supported ORR catalysts with high metal contents (20%) disrupt the self-assembly of Nafion and virtually eliminate the oxygen confinement, but the phenomenon is still observed for low Pt loading (4.8%) catalysts.« less

Self-Assembled Modified Soy Protein/Dextran Nanogel Induced by Ultrasonication as a Delivery Vehicle for Riboflavin.

PubMed

Jin, Bei; Zhou, Xiaosong; Li, Xiangzhong; Lin, Weiqin; Chen, Guangbin; Qiu, Riji

2016-03-15

A simple and green approach was developed to produce a novel nanogel via self-assembly of modified soy protein and dextran, to efficiently deliver riboflavin. First, modified soy protein was prepared by heating denaturation at 60 °C for 30 min or Alcalase hydrolysis for 40 min. Second, modified soy protein was mixed with dextran and ultrasonicated for 70 min so as to assemble nanogels. The modified soy protein-dextran nanogels were characterized by Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) and ζ-potential studies to confirm the formation of NGs. Transmission electron microscopy (TEM) revealed the NGs to be spherical with core-shell structures, in the range of 32-40 nm size. The nanogels were stable against various environmental conditions. Furthermore, the particle size of the nanogels hardly changed with the incorporation of riboflavin. The encapsulation efficiency of nanogels was found to be up to 65.9% at a riboflavin concentration of 250 μg/mL. The nanogels exhibited a faster release in simulated intestine fluid (SIF) compared with simulated gastric fluid (SGF). From the results obtained it can be concluded that modified soy protein-dextran nanogels can be considered a promising carrier for drugs and other bioactive molecule delivery purposes.

Surface Patterning of Benzene Carboxylic Acids on Graphite: Influence of structure, solvent, and concentration on molecular self-assembly

NASA Astrophysics Data System (ADS)

Florio, Gina; Stiso, Kimberly; Campanelli, Joseph; Dessources, Kimberly; Folkes, Trudi

2012-02-01

Scanning tunneling microscopy (STM) was used to investigate the molecular self-assembly of four different benzene carboxylic acid derivatives at the liquid/graphite interface: pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid), trimellitic acid (1,2,4-benzenetricarboxylic acid), trimesic acid (1,3,5-benzenetricarboxylic acid), and 1,3,5-benzenetriacetic acid. A range of two dimensional networks are observed that depend sensitively on the number of carboxylic acids present, the nature of the solvent, and the solution concentration. We will describe our recent efforts to determine (a) the preferential two-dimensional structure(s) for each benzene carboxylic acid at the liquid/graphite interface, (b) the thermodynamic and kinetic factors influencing self-assembly (or lack thereof), (c) the role solvent plays in the assembly, (e) the effect of in situ versus ex situ dilution on surface packing density, and (f) the temporal evolution of the self-assembled monolayer. Results of computational analysis of analog molecules and model monolayer films will also be presented to aid assignment of network structures and to provide a qualitative picture of surface adsorption and network formation.

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.

Investigation of Self-Assembly Processes for Chitosan-Based Coagulant-Flocculant Systems: A Mini-Review

PubMed Central

Bhalkaran, Savi; Wilson, Lee D.

2016-01-01

The presence of contaminants in wastewater poses significant challenges to water treatment processes and environmental remediation. The use of coagulation-flocculation represents a facile and efficient way of removing charged particles from water. The formation of stable colloidal flocs is necessary for floc aggregation and, hence, their subsequent removal. Aggregation occurs when these flocs form extended networks through the self-assembly of polyelectrolytes, such as the amine-based polysaccharide (chitosan), which form polymer “bridges” in a floc network. The aim of this overview is to evaluate how the self-assembly process of chitosan and its derivatives is influenced by factors related to the morphology of chitosan (flocculant) and the role of the solution conditions in the flocculation properties of chitosan and its modified forms. Chitosan has been used alone or in conjunction with a salt, such as aluminum sulphate, as an aid for the removal of various waterborne contaminants. Modified chitosan relates to grafted anionic or cationic groups onto the C-6 hydroxyl group or the amine group at C-2 on the glucosamine monomer of chitosan. By varying the parameters, such as molecular weight and the degree of deacetylation of chitosan, pH, reaction and settling time, dosage and temperature, self-assembly can be further investigated. This mini-review places an emphasis on the molecular-level details of the flocculation and the self-assembly processes for the marine-based biopolymer, chitosan. PMID:27706052

Self-assembly of convex particles on spherocylindrical surfaces.

PubMed

Lázaro, Guillermo R; Dragnea, Bogdan; Hagan, Michael F

2018-05-25

The precise control of assembly and packing of proteins and colloids on curved surfaces has fundamental implications in nanotechnology. In this paper, we describe dynamical simulations of the self-assembly of conical subunits around a spherocylindrical template, and a continuum theory for the bending energy of a triangular lattice with spontaneous curvature on a surface with arbitrary curvature. We find that assembly depends sensitively on mismatches between subunit spontaneous curvature and the mean curvature of the template, as well as anisotropic curvature of the template (mismatch between the two principal curvatures). Our simulations predict assembly morphologies that closely resemble those observed in experiments in which virus capsid proteins self-assemble around metal nanorods. Below a threshold curvature mismatch, our simulations identify a regime of optimal assembly leading to complete, symmetrical particles. Outside of this regime we observe defective particles, whose morphologies depend on the degree of curvature mismatch. To learn how assembly is affected by the nonuniform curvature of a spherocylinder, we also study the simpler cases of assembly around spherical and cylindrical cores. Our results show that both the intrinsic (Gaussian) and extrinsic (mean) curvatures of a template play significant roles in guiding the assembly of anisotropic subunits, providing a rich design space for the formation of nanoscale materials.

Stability of Phosphonic Self Assembled Monolayers (SAMs) on Cobalt Chromium (Co-Cr) Alloy under Oxidative conditions

PubMed Central

Bhure, Rahul; Abdel-Fattah, Tarek M.; Bonner, Carl; Hall, Felicia; Mahapatro, Anil

2011-01-01

Cobalt Chromium (Co-Cr) alloys has been widely used in the biomedical arena for cardiovascular, orthopedic and dental applications. Surface modification of the alloy allows us to tailor the interfacial properties to address critical challenges of Co-Cr alloy in medical applications. Self assembled monolayers (SAMs) of Octadecylphosphonic acid (ODPA) have been used to form thin films on the oxide layer of the Co-Cr alloy surface by solution deposition technique. The SAMs formed were investigated for their stability to oxidative conditions of ambient laboratory environment over periods of 1, 3, 7 and 14 days. The samples were then characterized for their stability using X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and Contact Angle Measurements. Detailed high energy XPS elemental scans confirmed the presence of the phosphonic monolayer after oxidative exposure which suggested that the SAMs were firmly attached to the oxide layer of Co-Cr alloy. AFM images gave topographical data of the surface and showed islands of SAMs on Co-Cr alloy surface, before and after SAM formation and also over the duration of the oxidative exposure. Contact angle measurements confirmed the hydrophobicity of the surface over 14 days. Thus the SAMs were found to be stable for the duration of the study. These SAMs could be subsequently tailored by modifying the terminal functional groups and could be used for various potential biomedical applications such as drug delivery, biocompatibility and tissue integration PMID:21603056

Fabrication of artificial toroid nanostructures by modified β-sheet peptides.

PubMed

Li, Wen; Li, Jingfang; Lee, Myongsoo

2013-09-25

Facial peptide P1 carrying repeating hydrophobic and hydrophilic residues as well as lysine terminals self-assemble into uniform toroid structures. The sensitive balance between the hydrophobic interactions and electrostatic repulsion dominates the formation of highly curved assemblies.

Self-assembled monolayer and method of making

DOEpatents

Fryxell, Glen E [Kennewick, WA; Zemanian, Thomas S [Richland, WA; Liu, Jun [West Richland, WA; Shin, Yongsoon [Richland, WA

2003-03-11

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-assembled monolayer and method of making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2004-05-11

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-Assembled Monolayer And Method Of Making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2004-06-22

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-Assembled Monolayer And Method Of Making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2005-01-25

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Imaging energy landscapes with concentrated diffusing colloidal probes

NASA Astrophysics Data System (ADS)

Bahukudumbi, Pradipkumar; Bevan, Michael A.

2007-06-01

The ability to locally interrogate interactions between particles and energetically patterned surfaces provides essential information to design, control, and optimize template directed self-assembly processes. Although numerous techniques are capable of characterizing local physicochemical surface properties, no current method resolves interactions between colloids and patterned surfaces on the order of the thermal energy kT, which is the inherent energy scale of equilibrium self-assembly processes. Here, the authors describe video microscopy measurements and an inverse Monte Carlo analysis of diffusing colloidal probes as a means to image three dimensional free energy and potential energy landscapes due to physically patterned surfaces. In addition, they also develop a consistent analysis of self-diffusion in inhomogeneous fluids of concentrated diffusing probes on energy landscapes, which is important to the temporal imaging process and to self-assembly kinetics. Extension of the concepts developed in this work suggests a general strategy to image multidimensional and multiscale physical, chemical, and biological surfaces using a variety of diffusing probes (i.e., molecules, macromolecules, nanoparticles, and colloids).

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.

Self-assembly of peptide-amphiphile nanofibers: the roles of hydrogen bonding and amphiphilic packing.

PubMed

Paramonov, Sergey E; Jun, Ho-Wook; Hartgerink, Jeffrey D

2006-06-07

The role of hydrogen bonding and amphiphilic packing in the self-assembly of peptide-amphiphiles (PAs) was investigated using a series of 26 PA derivatives, including 19 N-methylated variants and 7 alanine mutants. These were studied by circular dichroism spectroscopy, a variety of Fourier transform infrared spectroscopies, rheology, and vitreous ice cryo-transmission electron microscopy. From these studies, we have been able to determine which amino acids are critical for the self-assembly of PAs into nanofibers, why the nanofiber is favored over other possible nanostructures, the orientation of hydrogen bonding with respect to the nanofiber axis, and the constraints placed upon the portion of the peptide most intimately associated with the biological environment. Furthermore, by selectively eliminating key hydrogen bonds, we are able to completely change the nanostructure resulting from self-assembly in addition to modifying the macroscopic mechanical properties associated with the assembled gel. This study helps to clarify the mechanism of self-assembly for peptide amphiphiles and will thereby help in the design of future generations of PAs.

Covalent Functionalization of NiTi Surfaces with Bioactive Peptide Amphiphile Nanofibers

PubMed Central

Sargeant, Timothy D.; Rao, Mukti S.; Koh, Chung-Yan

2009-01-01

Surface modification enables the creation of bioactive implants using traditional material substrates without altering the mechanical properties of the bulk material. For applications such as bone plates and stents, it is desirable to modify the surface of metal alloy substrates to facilitate cellular attachment, proliferation, and possibly differentiation. In this work we present a general strategy for altering the surface chemistry of nickel-titanium shape memory alloy (NiTi) in order to covalently attach self-assembled peptide amphiphile (PA) nanofibers with bioactive functions. Bioactivity in the systems studied here includes biological adhesion and proliferation of osteoblast and endothelial cell types. The optimized surface treatment creates a uniform TiO2 layer with low levels of Ni on the NiTi surface, which is subsequently covered with an aminopropylsilane coating using a novel, lower temperature vapor deposition method. This method produces an aminated surface suitable for covalent attachment of PA molecules containing terminal carboxylic acid groups. The functionalized NiTi surfaces have been characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), and atomic force microscopy (AFM). These techniques offer evidence that the treated metal surfaces consist primarily of TiO2 with very little Ni, and also confirm the presence of the aminopropylsilane overlayer. Self-assembled PA nanofibers presenting the biological peptide adhesion sequence Arg-Gly-Asp-Ser are capable of covalently anchoring to the treated substrate, as demonstrated by spectrofluorimetry and AFM. Cell culture and scanning electron microscopy (SEM) demonstrate cellular adhesion, spreading, and proliferation on these functionalized metal surfaces. Furthermore, these experiments demonstrate that covalent attachment is crucial for creating robust PA nanofiber coatings, leading to confluent cell monolayers. PMID:18083225

Biomimetics in thin film design: Niche-like wrinkles designed for i-cell progenitor cell differentiation.

PubMed

Major, Roman; Lackner, Juergen M; Sanak, Marek; Major, Boguslaw

2017-11-01

The future and development of science are in interdisciplinary areas, such as biomedical engineering. Self-assembled structures, similar to stem cell niches, inhibit rapid cellular division processes and enable the capture of stem cells from blood flow. By modifying the surface topography and stiffness properties, progenitor cells were differentiated towards the formation of endothelial cell monolayers to effectively inhibit the coagulation cascade. Wrinkled material layers in the form of thin polymeric coatings were prepared. An optimized surface topography led to proper cell differentiation and influenced the appropriate formation of endothelial cell monolayers. Blood activation was decelerated by the formed endothelium. Copyright © 2017 Elsevier B.V. All rights reserved.

Characterization and kinetics of surface functionalization and binding of biologically and chemically significant molecules

NASA Astrophysics Data System (ADS)

Steiner, Rachel

The purpose of this project is to investigate intermolecular interactions of organic molecular assemblies. By understanding the structure and physical interactions in these assemblies, we gain insights into practical applications for nanoscale systems built upon these surface structures. It is possible for organic chemists to create many forms of modified organic molecules, functionalizing them with specific reactive end groups. Through surface functionalization, enabling covalent or highly associative binding, it is possible to create ordered molecular assemblies of these molecules. Scientists can study the nature of this structure and the intermolecular interactions through spectroscopic, optical, and scattering experiments. To understand the self-assembly process in molecular systems, we preliminarily created monolayer films on silica substrates with a variety of organic molecules. In particular, we functionalized silica substrates with hydroxyl groups and covalently bound acid chloride functionalized aromatic compounds, with and without an underlying adhesion layer of 3-aminopropyltriethoxysilane. We characterized the monolayer assemblies with ellipsometry, UV-vis absorption spectroscopy, FTIR spectroscopy, and fluorescence/photoemission spectroscopy, obtaining a quantitative measure of the molecular surface coverage. In order to understand the nature of these molecular assemblies, we also pursued an in-depth kinetic study to control and optimize the monolayer formation process. Through use of UV-vis spectroscopy, we determined that the monolayer formation can best be modeled with diffusion-limited Langmuir kinetics. Specifically, we concluded that for anthracene acid chloride in dichloromethane the average diffusion coefficient was 1.6x10-7 cm2/sec. Additionally, we find we are able to achieve surface coverages of approximately 2x1014 molecules/cm2. Having established the ability to create ordered molecular assemblies, through surface functionalization, enabling covalent or highly associative binding, we continued to explore the field of molecular assemblies by studying the binding and structure of molecules to carbon nanostructures. Previous studies have shown that alkyl side chains and aromatic compounds, such as pyrene, will bind non-covalently to the sidewalls of carbon nanotubes through pi-pi interactions. We explored functionalization of carbon nanotubes and graphene by using microscopy to examine the adsorption of biomolecules onto nanotube sidewalls and graphene.

Gibbs–Thomson Effect in Planar Nanowires: Orientation and Doping Modulated Growth

DOE PAGES

Shen, Youde; Chen, Renjie; Yu, Xuechao; ...

2016-06-02

Epitaxy-enabled bottom-up synthesis of self-assembled planar nanowires via the vapor–liquid–solid mechanism is an emerging and promising approach toward large-scale direct integration of nanowire-based devices without postgrowth alignment. In this paper, by examining large assemblies of indium tin oxide nanowires on yttria-stabilized zirconia substrate, we demonstrate for the first time that the growth dynamics of planar nanowires follows a modified version of the Gibbs–Thomson mechanism, which has been known for the past decades to govern the correlations between thermodynamic supersaturation, growth speed, and nanowire morphology. Furthermore, the substrate orientation strongly influences the growth characteristics of epitaxial planar nanowires as opposed tomore » impact at only the initial nucleation stage in the growth of vertical nanowires. The rich nanowire morphology can be described by a surface-energy-dependent growth model within the Gibbs–Thomson framework, which is further modulated by the tin doping concentration. Our experiments also reveal that the cutoff nanowire diameter depends on the substrate orientation and decreases with increasing tin doping concentration. Finally, these results enable a deeper understanding and control over the growth of planar nanowires, and the insights will help advance the fabrication of self-assembled nanowire devices.« less

Gibbs-Thomson Effect in Planar Nanowires: Orientation and Doping Modulated Growth.

PubMed

Shen, Youde; Chen, Renjie; Yu, Xuechao; Wang, Qijie; Jungjohann, Katherine L; Dayeh, Shadi A; Wu, Tom

2016-07-13

Epitaxy-enabled bottom-up synthesis of self-assembled planar nanowires via the vapor-liquid-solid mechanism is an emerging and promising approach toward large-scale direct integration of nanowire-based devices without postgrowth alignment. Here, by examining large assemblies of indium tin oxide nanowires on yttria-stabilized zirconia substrate, we demonstrate for the first time that the growth dynamics of planar nanowires follows a modified version of the Gibbs-Thomson mechanism, which has been known for the past decades to govern the correlations between thermodynamic supersaturation, growth speed, and nanowire morphology. Furthermore, the substrate orientation strongly influences the growth characteristics of epitaxial planar nanowires as opposed to impact at only the initial nucleation stage in the growth of vertical nanowires. The rich nanowire morphology can be described by a surface-energy-dependent growth model within the Gibbs-Thomson framework, which is further modulated by the tin doping concentration. Our experiments also reveal that the cutoff nanowire diameter depends on the substrate orientation and decreases with increasing tin doping concentration. These results enable a deeper understanding and control over the growth of planar nanowires, and the insights will help advance the fabrication of self-assembled nanowire devices.

Yeast cytochrome c integrated with electronic elements: a nanoscopic and spectroscopic study down to single-molecule level

NASA Astrophysics Data System (ADS)

Delfino, I.; Bonanni, B.; Andolfi, L.; Baldacchini, C.; Bizzarri, A. R.; Cannistraro, S.

2007-06-01

Various aspects of redox protein integration with nano-electronic elements are addressed by a multi-technique investigation of different yeast cytochrome c (YCC)-based hybrid systems. Three different immobilization strategies on gold via organic linkers are explored, involving either covalent bonding or electrostatic interaction. Specifically, Au surfaces are chemically modified by self-assembled monolayers (SAMs) exposing thiol-reactive groups, or by acid-oxidized single-wall carbon nanotubes (SWNTs). Atomic force microscopy and scanning tunnelling microscopy are employed to characterize the morphology and the electronic properties of single YCC molecules adsorbed on the modified gold surfaces. In each hybrid system, the protein molecules are stably assembled, in a native configuration. A standing-up arrangement of YCC on SAMs is suggested, together with an enhancement of the molecular conduction, as compared to YCC directly assembled on gold. The electrostatic interaction with functionalized SWNTs allows several YCC adsorption geometries, with a preferential high-spin haem configuration, as outlined by Raman spectroscopy. Moreover, the conduction properties of YCC, explored in different YCC nanojunctions by conductive atomic force microscopy, indicate the effectiveness of electrical conduction through the molecule and its dependence on the electrode material. The joint employment of several techniques confirms the key role of a well-designed immobilization strategy, for optimizing biorecognition capabilities and electrical coupling with conductive substrates at the single-molecule level, as a starting point for advanced applications in nano-biotechnology.

Self-Assembly of Rod-Coil Block Copolymers on Carbon Nanotubes: A Route toward Diverse Surface Nanostructures.

PubMed

Han, Yang; Cai, Chunhua; Lin, Jiaping; Gong, Shuting; Xu, Wenheng; Hu, Rui

2018-04-14

In this work, it is reported that poly(γ-benzyl-l-glutamate)-block-poly(ethylene glycol) (PBLG-b-PEG) rod-coil block copolymers (BCPs) can disperse carbon nanotubes (CNTs) in solution and form various surface nanostructures on the CNTs via solution self-assembly. In an organic solvent that dissolves the BCPs, the PBLG rod blocks adsorb on CNT surfaces, and the BCPs form conformal coatings. Then, by the introduction of water, a selective solvent for PEG blocks, the BCPs in the coatings further self-assemble into diverse surface nanostructures, such as helices (left-handed or right-handed), gyros, spheres, and rings. The morphology of the surface nanostructure can be tailored by initial organic solvent composition, preparation temperature, feeding ratio of BCPs to CNTs, degree of polymerization of PBLG blocks, and diameter of the CNTs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conformal dip-coating of patterned surfaces for capillary die-to-substrate self-assembly

NASA Astrophysics Data System (ADS)

Mastrangeli, M.; Ruythooren, W.; Van Hoof, C.; Celis, J.-P.

2009-04-01

Capillarity-driven self-assembly of small chips onto planar target substrates is a promising alternative to robotic pick-and-place assembly. It critically relies on the selective deposition of thin fluid films on patterned binding sites, which is anyway normally non-conformal. We found that the addition of a thin wetting sidewall, surrounding the entire site perimeter, enables the conformal fluid coverage of arbitrarily shaped sites through dip-coating, significantly improves the reproducibility of the coating process and strongly reduces its sensitivity to surface defects. In this paper we support the feasibility and potential of this method by demonstrating the conformal dip-coating of square and triangular sites conditioned with combinations of different hydrophobic and hydrophilic surface chemistries. We present both experimental and simulative evidence of the advantages brought by the introduction of the wetting boundary on film coverage accuracy. Application of our surface preparation method to capillary self-assembly could result in higher precision in die-to-substrate registration and larger freedom in site shape design.

Molecular Origin of the Self-Assembly of Lanreotide into Nanotubes: A Mutational Approach☆

PubMed Central

Valéry, Céline; Pouget, Emilie; Pandit, Anjali; Verbavatz, Jean-Marc; Bordes, Luc; Boisdé, Isabelle; Cherif-Cheikh, Roland; Artzner, Franck; Paternostre, Maité

2008-01-01

Lanreotide, a synthetic, therapeutic octapeptide analog of somatostatin, self-assembles in water into perfectly hollow and monodisperse (24-nm wide) nanotubes. Lanreotide is a cyclic octapeptide that contains three aromatic residues. The molecular packing of the peptide in the walls of a nanotube has recently been characterized, indicating four hierarchical levels of organization. This is a fascinating example of spontaneous self-organization, very similar to the formation of the gas vesicle walls of Halobacterium halobium. However, this unique peptide self-assembly raises important questions about its molecular origin. We adopted a directed mutation approach to determine the molecular parameters driving the formation of such a remarkable peptide architecture. We have modified the conformation by opening the cycle and by changing the conformation of a Lys residue, and we have also mutated the aromatic side chains of the peptide. We show that three parameters are essential for the formation of lanreotide nanotubes: i), the specificity of two of the three aromatic side chains, ii), the spatial arrangement of the hydrophilic and hydrophobic residues, and iii), the aromatic side chain in the β-turn of the molecule. When these molecular characteristics are modified, either the peptides lose their self-assembling capability or they form less-ordered architectures, such as amyloid fibers and curved lamellae. Thus we have determined key elements of the molecular origins of lanreotide nanotube formation. PMID:17993497

Self-Assembly at the Colloidal Scale

NASA Astrophysics Data System (ADS)

Zhong, Xiao

The existence of self-assembly, the phenomenon of spontaneous structural formation from building blocks, transcends many orders of magnitude, ranging from molecular to cosmic. It is arguably the most common, important, and complex question in science. This thesis aims for understanding a spectrum of self-assembly-self assembly at the colloidal scale. Of the whole spectrum of self-assembly, the colloidal scale is of particular interest and importance to researchers, for not only comprehensive tools for colloidal scale studies have been well established, but also the various promising applications colloidal self-assembly can facilitate. In this thesis, a high throughput technique-Polymer Pen Lithography (PPL) is modified and its potential for creating corrals for colloidal assembly is evaluated. Then two different approaches of assembling colloids are explored in depth. One of them is by using a phenomenon called dielectrophoresis (DEP) as driving force to manipulate colloidal nucleation and crystal growth. And the other takes advantage of the Pt-catalyzed H2O 2 redox reaction to drive micrometer-scaled, rod-shaped colloids to swim and assemble. Lastly, an optical method called Holographic Video Microscopy (HVM) is used to monitor and characterize "bad" self-assembly of proteins, that is their aggregations. The four studies discussed in this thesis represent advancements in the colloidal scale from different aspects. The PPL technique enriched the toolbox for colloidal self-assembly. The DEP driven colloidal nucleation and crystal growth shed light on deeper understanding the mechanism of crystallization. And the swimming and assembly of micro-scale rods leads to kinetics reminiscent of bacterial run-and-tumble motion. Finally, the HVM technique for monitoring and understanding protein aggregation could potentially lead to better quality assurance for therapeutic proteins and could be a powerful tool for assessing their shelf lives.

Fractal assembly of micrometre-scale DNA origami arrays with arbitrary patterns.

PubMed

Tikhomirov, Grigory; Petersen, Philip; Qian, Lulu

2017-12-06

Self-assembled DNA nanostructures enable nanometre-precise patterning that can be used to create programmable molecular machines and arrays of functional materials. DNA origami is particularly versatile in this context because each DNA strand in the origami nanostructure occupies a unique position and can serve as a uniquely addressable pixel. However, the scale of such structures has been limited to about 0.05 square micrometres, hindering applications that demand a larger layout and integration with more conventional patterning methods. Hierarchical multistage assembly of simple sets of tiles can in principle overcome this limitation, but so far has not been sufficiently robust to enable successful implementation of larger structures using DNA origami tiles. Here we show that by using simple local assembly rules that are modified and applied recursively throughout a hierarchical, multistage assembly process, a small and constant set of unique DNA strands can be used to create DNA origami arrays of increasing size and with arbitrary patterns. We illustrate this method, which we term 'fractal assembly', by producing DNA origami arrays with sizes of up to 0.5 square micrometres and with up to 8,704 pixels, allowing us to render images such as the Mona Lisa and a rooster. We find that self-assembly of the tiles into arrays is unaffected by changes in surface patterns on the tiles, and that the yield of the fractal assembly process corresponds to about 0.95 m - 1 for arrays containing m tiles. When used in conjunction with a software tool that we developed that converts an arbitrary pattern into DNA sequences and experimental protocols, our assembly method is readily accessible and will facilitate the construction of sophisticated materials and devices with sizes similar to that of a bacterium using DNA nanostructures.

MURI Center for Materials Chemistry in the Space Environment

DTIC Science & Technology

2006-11-30

ionic species in relevant reaction environments, surface photochemistry expertise, synchrotron-based measurement and irradiation, synthesis of structural...and Ne+ ions with dodecanethiolate and semifluorinated dodecanethiolate self-assembled monolayers (SAM), polyhedral oligomeric silsesquioxane (POSS...POSS/Kapton models as gas phase species, and with alkane thiol self assembled monolayers on gold surfaces, and with liquid squalane. We have also

Altered Calcium Dynamics in Cardiac Cells Grown on Silane-Modified Surfaces

PubMed Central

Ravenscroft-Chang, Melissa S.; Stohlman, Jayna; Molnar, Peter; Natarajan, Anupama; Canavan, Heather E.; Teliska, Maggie; Stancescu, Maria; Krauthamer, Victor; Hickman, J.J.

2013-01-01

Chemically defined surfaces were created using self-assembled monolayers (SAMs) of hydrophobic and hydrophilic silanes as models for implant coatings, and the morphology and physiology of cardiac myocytes plated on these surfaces were studied in vitro. We focused on changes in intracellular Ca2+ because of its essential role in regulating heart cell function. The SAM-modified coverslips were analyzed using X-ray Photoelectron Spectroscopy to verify composition. The morphology and physiology of the cardiac cells were examined using fluorescence microscopy and intracellular Ca2+ imaging. The imaging experiments used the fluorescent ratiometric dye fura-2, AM to establish both the resting Ca2+ concentration and the dynamic responses to electrical stimulation. A significant difference in excitation-induced Ca2+ changes on the different silanated surfaces was observed. However, no significant change was noted based on the morphological analysis. This result implies a difference in internal Ca2+ dynamics, and thus cardiac function, occurs when the composition of the surface is different, and this effect is independent of cellular morphology. This finding has implications for histological examination of tissues surrounding implants, the choice of materials that could be beneficial as implant coatings and understanding of cell-surface interactions in cardiac systems. PMID:19828193

Guided molecular self-assembly: a review of recent efforts

NASA Astrophysics Data System (ADS)

Huie, Jiyun C.

2003-04-01

This paper serves as an introductory review of significant and novel successes achieved in the fields of nanotechnology, particularly in the formation of nanostructures using guided molecular self-assembly methods. Self-assembly is a spontaneous process by which molecules and nanophase entities may materialize into organized aggregates or networks. Through various interactive mechanisms of self-assembly, such as electrostatics, chemistry, surface properties, and via other mediating agents, the technique proves indispensable to recent functional materials and device realizations. The discussion will extend to spontaneous and Langmuir-Blodgett formation of self-assembled monolayers on various substrates, and a number of different categories of self-assembly techniques based on the type of interaction exploited. Combinatorial techniques, known as soft lithography, of micro-contact printing and dip-pen nanolithography, which can be effectively used to up-size nanostructured molecular assemblies to submicrometer and micrometer scale patterns, will also be mentioned.

Molecular Mechanism of Thioflavin-T Binding to the Surface of [beta]-Rich Peptide Self-Assemblies

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

Biancalana, Matthew; Makabe, Koki; Koide, Akiko

A number of small organic molecules have been developed that bind to amyloid fibrils, a subset of which also inhibit fibrillization. Among these, the benzothiol dye Thioflavin-T (ThT) has been used for decades in the diagnosis of protein-misfolding diseases and in kinetic studies of self-assembly (fibrillization). Despite its importance, efforts to characterize the ThT-binding mechanism at the atomic level have been hampered by the inherent insolubility and heterogeneity of peptide self-assemblies. To overcome these challenges, we have developed a minimalist approach to designing a ThT-binding site in a 'peptide self-assembly mimic' (PSAM) scaffold. PSAMs are engineered water-soluble proteins that mimicmore » a segment of beta-rich peptide self-assembly, and they are amenable to standard biophysical techniques and systematic mutagenesis. The PSAM beta-sheet contains rows of repetitive amino acid patterns running perpendicular to the strands (cross-strand ladders) that represent a ubiquitous structural feature of fibril-like surfaces. We successfully designed a ThT-binding site that recapitulates the hallmarks of ThT-fibril interactions by constructing a cross-strand ladder consisting of contiguous tyrosines. The X-ray crystal structures suggest that ThT interacts with the beta-sheet by docking onto surfaces formed by a single tyrosine ladder, rather than in the space between adjacent ladders. Systematic mutagenesis further demonstrated that tyrosine surfaces across four or more beta-strands formed the minimal binding site for ThT. Our work thus provides structural insights into how this widely used dye recognizes a prominent subset of peptide self-assemblies, and proposes a strategy to elucidate the mechanisms of fibril-ligand interactions.« less

Design of Nanostructured Biological Materials Through Self-Assembly of Peptides and Proteins

DTIC Science & Technology

2002-01-01

of applications, including scaffolding for tissue repair in regenerative medicine, drug delivery and biological surface engineering. Tirrell and...colleagues [2] designed artificial proteins that undergo self-assembly to form hydrogels responsive to pH and other environmental changes. Ghadiri and...showed that other β-sheet peptide systems can also undergo self-assembly into regular nanofiber structures. Although they share no sequence

Templated electrokinetic directed chemical assembly for the fabrication of close-packed plasmonic metamolecules

NASA Astrophysics Data System (ADS)

Thrift, W. J.; Darvishzadeh-Varcheie, M.; Capolino, F.; Ragan, R.

2017-08-01

Colloidal self-assembly combined with templated surfaces holds the promise of fabricating large area devices in a low cost facile manner. This directed assembly approach improves the complexity of assemblies that can be achieved with self-assembly while maintaining advantages of molecular scale control. In this work, electrokinetic driving forces, i.e., electrohydrodynamic flow, are paired with chemical crosslinking between colloidal particles to form close-packed plasmonic metamolecules. This method addresses challenges of obtaining uniformity in nanostructure geometry and nanometer scale gap spacings in structures. Electrohydrodynamic flows yield robust driving forces between the template and nanoparticles as well as between nanoparticles on the surface promoting the assembly of close-packed metamolecules. Here, electron beam lithography defined Au pillars are used as seed structures that generate electrohydrodynamic flows. Chemical crosslinking between Au surfaces enables molecular control over gap spacings between nanoparticles and Au pillars. An as-fabricated structure is analyzed via full wave electromagnetic simulations and shown to produce large magnetic field enhancements on the order of 3.5 at optical frequencies. This novel method for directed self-assembly demonstrates the synergy between colloidal driving forces and chemical crosslinking for the fabrication of plasmonic metamolecules with unique electromagnetic properties.

Thiol-ene immobilisation of carbohydrates onto glass slides as a simple alternative to gold-thiol monolayers, amines or lipid binding.

PubMed

Biggs, Caroline I; Edmondson, Steve; Gibson, Matthew I

2015-01-01

Carbohydrate arrays are a vital tool in studying infection, probing the mechanisms of bacterial, viral and toxin adhesion and the development of new treatments, by mimicking the structure of the glycocalyx. Current methods rely on the formation of monolayers of carbohydrates that have been chemically modified with a linker to enable interaction with a functionalised surface. This includes amines, biotin, lipids or thiols. Thiol-addition to gold to form self-assembled monolayers is perhaps the simplest method for immobilisation as thiolated glycans are readily accessible from reducing carbohydrates in a single step, but are limited to gold surfaces. Here we have developed a quick and versatile methodology which enables the use of thiolated carbohydrates to be immobilised as monolayers directly onto acrylate-functional glass slides via a 'thiol-ene'/Michael-type reaction. By combining the ease of thiol chemistry with glass slides, which are compatible with microarray scanners this offers a cost effective, but also useful method to assemble arrays.

Self-assembled microstructures of confined rod-coil diblock copolymers by self-consistent field theory.

PubMed

Yang, Guang; Tang, Ping; Yang, Yuliang; Wang, Qiang

2010-11-25

We employ the self-consistent field theory (SCFT) incorporating Maier-Saupe orientational interactions between rods to investigate the self-assembly of rod-coil diblock copolymers (RC DBC) in bulk and especially confined into two flat surfaces in 2D space. A unit vector defined on a spherical surface for describing the orientation of rigid blocks in 3D Euclidean space is discretized with an icosahedron triangular mesh to numerically integrate over rod orientation, which is confirmed to have numerical accuracy and stability higher than that of the normal Gaussian quadrature. For the hockey puck-shaped phases in bulk, geometrical confinement, i.e., the film thickness, plays an important role in the self-assembled structures' transitions for the neutral walls. However, for the lamellar phase (monolayer smectic-C) in bulk, the perpendicular lamellae are always stable, less dependent on the film thicknesses because they can relax to the bulk spacing with less-paid coil-stretching in thin films. In particular, a very thin rod layer near the surfaces is formed even in a very thin film. When the walls prefer rods, parallel lamellae are obtained, strongly dependent on the competition between the degree of the surface fields and film geometrical confinement, and the effect of surface field on lamellar structure as a function of film thickness is investigated. Our simulation results provide a guide to understanding the self-assembly of the rod-coil films with desirable application prospects in the fabrication of organic light emitting devices.

Thiolated polyethylene oxide as a non-fouling element for nano-patterned bio-devices

NASA Astrophysics Data System (ADS)

Lisboa, Patrícia; Valsesia, Andrea; Colpo, Pascal; Gilliland, Douglas; Ceccone, Giacomo; Papadopoulou-Bouraoui, Andri; Rauscher, Hubert; Reniero, Fabiano; Guillou, Claude; Rossi, François

2007-03-01

This work describes the synthesis of a thiolated polyethylene oxide that self-assembles on gold to create a non-fouling surface. Thiolated polyethylene oxide was synthesised by reacting 16-mercaptohexadecanoic acid with polyethylene glycol mono methyl ether. The coverage of the thiolated polyethylene oxide on gold was studied by cyclic voltammetry, and the modified surfaces were characterised by X-ray photoelectron spectroscopy and ellipsometry. Protein resistance was assessed using quartz crystal microbalance. Results showed a non-fouling character produced by the thiolated polyethylene oxide. The synthesised product was used as the passivation layer on nano-patterned surfaces consisting of arrayed nano-spots, fabricated by plasma based colloidal lithography. The specific adsorption of anti-bovine serum albumin in the mercaptohexadecanoic acid spots was verified by atomic force microscopy.

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.

Vacuum ultraviolet trimming of oxygenated functional groups from oxidized self-assembled hexadecyl monolayers in an evacuated environment

NASA Astrophysics Data System (ADS)

Soliman, Ahmed I. A.; Utsunomiya, Toru; Ichii, Takashi; Sugimura, Hiroyuki

2017-09-01

Vacuum ultraviolet light irradiation in dry air generates active oxygen species, which have powerful oxidation abilities. These active oxygen species (O) can oxidize the alkyl moieties of polymers, and generate new oxygenated groups such as OH, CHO and COOH groups. Reducing the oxygen content in the exposure environment decreases the rate of oxidation processes. In this study, we examined the influences of the 172 nm VUV irradiation in a high vacuum (HV, < 10-3 Pa) environment on the chemical constituents, surface properties and morphological structure of well-defined VUV/(O)-modified hexadecyl (HD-) self-assembled monolayer (SAM) prepared on hydrogen-terminated silicon (H-Si) substrate. After VUV light irradiation in a HV environment (HV-VUV), the chemical constituents and surface properties were changed in two distinct stages. At short irradiation time (the first stage), the Csbnd O and COO groups decreased rapidly, while the Cdbnd O groups slightly changed. The dissociation of nonderivatizable groups (such as ether (Csbnd Osbnd C) and ester (Csbnd COOsbnd C) groups) compensated the dissociated OH, CHO, Csbnd COsbnd C and COOH groups. With further irradiation (the second stage), the quantities of the oxygenated groups slightly decreased. The carbon skeleton (Csbnd C) of SAM was scarcely dissociated during the HV-VUV treatment. These chemical changes affected the surface properties, such as wettability and morphology.

Two-dimensional honeycomb network through sequence-controlled self-assembly of oligopeptides.

PubMed

Abb, Sabine; Harnau, Ludger; Gutzler, Rico; Rauschenbach, Stephan; Kern, Klaus

2016-01-12

The sequence of a peptide programs its self-assembly and hence the expression of specific properties through non-covalent interactions. A large variety of peptide nanostructures has been designed employing different aspects of these non-covalent interactions, such as dispersive interactions, hydrogen bonding or ionic interactions. Here we demonstrate the sequence-controlled fabrication of molecular nanostructures using peptides as bio-organic building blocks for two-dimensional (2D) self-assembly. Scanning tunnelling microscopy reveals changes from compact or linear assemblies (angiotensin I) to long-range ordered, chiral honeycomb networks (angiotensin II) as a result of removal of steric hindrance by sequence modification. Guided by our observations, molecular dynamic simulations yield atomistic models for the elucidation of interpeptide-binding motifs. This new approach to 2D self-assembly on surfaces grants insight at the atomic level that will enable the use of oligo- and polypeptides as large, multi-functional bio-organic building blocks, and opens a new route towards rationally designed, bio-inspired surfaces.

Charge transfer through amino groups-small molecules interface improving the performance of electroluminescent devices

NASA Astrophysics Data System (ADS)

Havare, Ali Kemal; Can, Mustafa; Tozlu, Cem; Kus, Mahmut; Okur, Salih; Demic, Şerafettin; Demirak, Kadir; Kurt, Mustafa; Icli, Sıddık

2016-05-01

A carboxylic group functioned charge transporting was synthesized and self-assembled on an indium tin oxide (ITO) anode. A typical electroluminescent device [modified ITO/TPD (50 nm)/Alq3 (60 nm)/LiF (2 nm)/(120 nm)] was fabricated to investigate the effect of the amino groups-small molecules interface on the characteristics of the device. The increase in the surface work function of ITO is expected to facilitate the hole injection from the ITO anode to the Hole Transport Layer (HTL) in electroluminescence. The modified electroluminescent device could endure a higher current and showed a much higher luminance than the nonmodified one. For the produced electroluminescent devices, the I-V characteristics, optical characterization and quantum yields were performed. The external quantum efficiency of the modified electroluminescent device is improved as the result of the presence of the amino groups-small molecules interface.

Self-assembled monolayer and multilayer films of the nanocluster [HxPMo12O40 subsetH4Mo72Fe30(O2CMe)15O254(H2O)68] on gold.

PubMed

Colorado, Ramon; Crouse, Christopher A; Zeigler, Christopher N; Barron, Andrew R

2008-08-19

Films of the molybdenum-iron nanocluster [H x PMo 12O 40 subsetH 4Mo 72Fe 30(O 2CMe) 15O 254(H2O) 68] (FeMoC) were generated on gold via the self-assembly technique using two divergent routes. The first route entails the self-assembly of unfunctionalized FeMoC onto a preprepared carboxyl-terminated SAM on gold. The second route involves the preparation of thiol-terminated functionalized FeMoC clusters, which are then allowed to self-assemble onto bare gold surfaces. Monolayer films of FeMoC clusters are attained via both routes, with the second route requiring shorter immersion times (2 days) than the first route (6 days). Multilayer films of FeMoC are formed via the second route for immersion times longer than 2 days. Characterization of these films using optical ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy confirm the self-assembly of the clusters on the surfaces.

Electroactive oligoaniline-containing self-assembled monolayers for tissue engineering applications.

PubMed

Guo, Yi; Li, Mengyan; Mylonakis, Andreas; Han, Jingjia; MacDiarmid, Alan G; Chen, Xuesi; Lelkes, Peter I; Wei, Yen

2007-10-01

A novel electroactive silsesquioxane precursor, N-(4-aminophenyl)-N'-(4'-(3-triethoxysilyl-propyl-ureido) phenyl-1,4-quinonenediimine) (ATQD), was successfully synthesized from the emeraldine form of amino-capped aniline trimers via a one-step coupling reaction and subsequent purification by column chromatography. The physicochemical properties of ATQD were characterized using mass spectrometry as well as by nuclear magnetic resonance and UV-vis spectroscopy. Analysis by cyclic voltammetry confirmed that the intrinsic electroactivity of ATQD was maintained upon protonic acid doping, exhibiting two distinct reversible oxidative states, similar to polyaniline. The aromatic amine terminals of self-assembled monolayers (SAMs) of ATQD on glass substrates were covalently modified with an adhesive oligopeptide, cyclic Arg-Gly-Asp (RGD) (ATQD-RGD). The mean height of the monolayer coating on the surfaces was approximately 3 nm, as measured by atomic force microscopy. The biocompatibility of the novel electroactive substrates was evaluated using PC12 pheochromocytoma cells, an established cell line of neural origin. The bioactive, derivatized electroactive scaffold material, ATQD-RGD, supported PC12 cell adhesion and proliferation, similar to control tissue-culture-treated polystyrene surfaces. Importantly, electroactive surfaces stimulated spontaneous neuritogenesis in PC12 cells, in the absence of neurotrophic growth factors, such as nerve growth factor (NGF). As expected, NGF significantly enhanced neurite extension on both control and electroactive surfaces. Taken together, our results suggest that the newly electroactive SAMs grafted with bioactive peptides, such as RGD, could be promising biomaterials for tissue engineering.

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.

A new organofunctional ethoxysilane self-assembly monolayer for promoting adhesion of rubber to aluminum.

PubMed

Wang, Fang; Xu, Juan; Luo, Heyi; Wang, Jinggang; Wang, Qian

2009-10-12

Practical adhesion of rubber to aluminum is measured for various aluminum silanization treatments. In this study, 6-(3-triethoxysilylpropylamino)-1,3,5-triazine-2,4-dithiol (TES) was used as the coupling agent for preparing self-assembly monolayers (SAMs) on an aluminum surface. The structure and chemical composition of the SAMs were analyzed using Fourier transform infra-red spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The changes in the surface features of the aluminum surface due to TES treatment were investigated by atomic force microscopy (AFM). The adhesive properties of the silanized aluminum surface and EPDM rubber have been evaluated by a T-peel strength test. The results suggested that the Si-O-Al bonding at aluminum TES interface existed and a TES self-assembly monolayer was formed on the aluminum surface. More than 6.0 KN/m adhesion strength is obtained when the aluminum is silanized with 2.5 mmol/dm(3) TES, cured at 160 degrees C and vulcanized with EPDM rubber at 160 degrees C for 30 min. It is suggested that the TES self-assembly monolayer is bound to aluminum through its ethoxysilyl functional group, and the thiol function group is strongly crosslinked to EPDM rubber, respectively.

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).

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

A Robust and Engineerable Self-Assembling Protein Template for the Synthesis and Patterning of Ordered Nanoparticle Arrays

NASA Technical Reports Server (NTRS)

McMillan, R. Andrew; Howard, Jeanie; Zaluzec, Nestor J.; Kagawa, Hiromi K.; Li, Yi-Fen; Paavola, Chad D.; Trent, Jonathan D.

2004-01-01

Self-assembling biomolecules that form highly ordered structures have attracted interest as potential alternatives to conventional lithographic processes for patterning materials. Here we introduce a general technique for patterning materials on the nanoscale using genetically modified protein cage structures called chaperonins that self-assemble into crystalline templates. Constrained chemical synthesis of transition metal nanoparticles is specific to templates genetically functionalized with poly-Histidine sequences. These arrays of materials are ordered by the nanoscale structure of the crystallized protein. This system may be easily adapted to pattern a variety of materials given the rapidly growing list of peptide sequences selected by screening for specificity for inorganic materials.

Role of Surface Charge Density in Nanoparticle-templated Assembly of Bromovirus Protein Cages

PubMed Central

Daniel, Marie-Christine; Tsvetkova, Irina B.; Quinkert, Zachary T.; Murali, Ayaluru; De, Mrinmoy; Rotello, Vincent M.; Kao, C. Cheng; Dragnea, Bogdan

2010-01-01

Self-assembling icosahedral protein cages have potencially useful physical and chemical characteristics for a variety of nanotechnology applications, ranging from therapeutic or diagnostic vectors to building blocks for hierarchical materials. For application-specific functional control of protein cage assemblies, a deeper understanding of the interaction between the protein cage and its payload is necessary. Protein-cage encapsulated nanoparticles, with their well-defined surface chemistry, allow for systematic control over key parameters of encapsulation such as the surface charge, hydrophobicity, and size. Independent control over these variables allows experimental testing of different assembly mechanism models. Previous studies done with Brome mosaic virus capsids and negatively-charged gold nanoparticles indicated that the result of the self-assembly process depends on the diameter of the particle. However, in these experiments, the surface-ligand density was maintained at saturation levels, while the total charge and the radius of curvature remained coupled variables, making the interpretation of the observed dependence on the core size difficult. The current work furnishes evidence of a critical surface charge density for assembly through an analysis aimed at decoupling the surface charge the core size. PMID:20575505

Fractal assembly of micrometre-scale DNA origami arrays with arbitrary patterns

NASA Astrophysics Data System (ADS)

Tikhomirov, Grigory; Petersen, Philip; Qian, Lulu

2017-12-01

Self-assembled DNA nanostructures enable nanometre-precise patterning that can be used to create programmable molecular machines and arrays of functional materials. DNA origami is particularly versatile in this context because each DNA strand in the origami nanostructure occupies a unique position and can serve as a uniquely addressable pixel. However, the scale of such structures has been limited to about 0.05 square micrometres, hindering applications that demand a larger layout and integration with more conventional patterning methods. Hierarchical multistage assembly of simple sets of tiles can in principle overcome this limitation, but so far has not been sufficiently robust to enable successful implementation of larger structures using DNA origami tiles. Here we show that by using simple local assembly rules that are modified and applied recursively throughout a hierarchical, multistage assembly process, a small and constant set of unique DNA strands can be used to create DNA origami arrays of increasing size and with arbitrary patterns. We illustrate this method, which we term ‘fractal assembly’, by producing DNA origami arrays with sizes of up to 0.5 square micrometres and with up to 8,704 pixels, allowing us to render images such as the Mona Lisa and a rooster. We find that self-assembly of the tiles into arrays is unaffected by changes in surface patterns on the tiles, and that the yield of the fractal assembly process corresponds to about 0.95m - 1 for arrays containing m tiles. When used in conjunction with a software tool that we developed that converts an arbitrary pattern into DNA sequences and experimental protocols, our assembly method is readily accessible and will facilitate the construction of sophisticated materials and devices with sizes similar to that of a bacterium using DNA nanostructures.

Strain-driven growth of GaAs(111) quantum dots with low fine structure splitting

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

Yerino, Christopher D.; Jung, Daehwan; Lee, Minjoo Larry, E-mail: minjoo.lee@yale.edu

2014-12-22

Symmetric quantum dots (QDs) on (111)-oriented surfaces are promising candidates for generating polarization-entangled photons due to their low excitonic fine structure splitting (FSS). However, (111) QDs are difficult to grow. The conventional use of compressive strain to drive QD self-assembly fails to form 3D nanostructures on (111) surfaces. Instead, we demonstrate that (111) QDs self-assemble under tensile strain by growing GaAs QDs on an InP(111)A substrate. Tensile GaAs self-assembly produces a low density of QDs with a symmetric triangular morphology. Coherent, tensile QDs are observed without dislocations, and the QDs luminescence at room temperature. Single QD measurements reveal low FSSmore » with a median value of 7.6 μeV, due to the high symmetry of the (111) QDs. Tensile self-assembly thus offers a simple route to symmetric (111) QDs for entangled photon emitters.« less

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

Structural and optical properties of self-assembled chains of plasmonic nanocubes

DOE PAGES

Klinkova, Anna; Gang, Oleg; Therien-Aubin, Heloise; ...

2014-10-10

Solution-based linear self-assembly of metal nanoparticles offers a powerful strategy for creating plasmonic polymers, which, so far, have been formed from spherical nanoparticles and nanorods. Here, we report linear solution-based self-assembly of metal nanocubes (NCs), examine the structural characteristics of the NC chains and demonstrate their advanced optical characteristics. Predominant face-to-face assembly of large NCs coated with short polymer ligands led to a larger volume of hot spots in the chains, a nearly uniform E-field enhancement in the gaps between co-linear NCs and a new coupling mode for NC chains, in comparison with chains of nanospheres with similar dimensions, compositionmore » and surface chemistry. The NC chains exhibited a stronger surface enhanced Raman scattering (SERS) signal, in comparison with linear assemblies of nanospheres. The experimental results were in agreement with finite difference time domain (FDTD) simulations.« less

Coevolutionary constraints in the sequence-space of macromolecular complexes reflect their self-assembly pathways.

PubMed

Mallik, Saurav; Kundu, Sudip

2017-07-01

Is the order in which biomolecular subunits self-assemble into functional macromolecular complexes imprinted in their sequence-space? Here, we demonstrate that the temporal order of macromolecular complex self-assembly can be efficiently captured using the landscape of residue-level coevolutionary constraints. This predictive power of coevolutionary constraints is irrespective of the structural, functional, and phylogenetic classification of the complex and of the stoichiometry and quaternary arrangement of the constituent monomers. Combining this result with a number of structural attributes estimated from the crystal structure data, we find indications that stronger coevolutionary constraints at interfaces formed early in the assembly hierarchy probably promotes coordinated fixation of mutations that leads to high-affinity binding with higher surface area, increased surface complementarity and elevated number of molecular contacts, compared to those that form late in the assembly. Proteins 2017; 85:1183-1189. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Tuning of peptide assembly through force balance adjustment.

PubMed

Cao, Meiwen; Cao, Changhai; Zhang, Lijuan; Xia, Daohong; Xu, Hai

2013-10-01

Controlled self-assembly of amphiphilic tripeptides into distinct nanostructures is achieved via a controlled design of the molecular architecture. The tripeptide Ac-Phe-Phe-Lys-CONH2 (FFK), hardly soluble in water, forms long amyloid-like tubular structures with the aid of β-sheet hydrogen bonding and aromatic π-π stacking. Substitution of phenylalanine (F) with tyrosine (Y), that is, only a subtle structural variation in adding a hydroxyl group to the phenyl ring, results in great change in molecular self-assembly behavior. When one F is substituted with Y, the resulting molecules of FYK and YFK self-assemble into long thinner fibrils with high propensity for lateral association. When both Fs are substituted with Y, the resulting YYK molecule forms spherical aggregates. Introduction of hydroxyl groups into the molecule modifies aromatic interactions and introduces hydrogen bonding. Moreover, since the driving forces for peptide self-assembly including hydrogen bonding, electrostatic repulsion, and π-π stacking have high interdependence with each other, changes in aromatic interaction induce a Domino effect and cause a shift of force balance to a new state. This leads to significant variations in self-assembly behavior. Copyright © 2013 Elsevier Inc. All rights reserved.

A new building block for DNA network formation by self-assembly and polymerase chain reaction.

PubMed

Bußkamp, Holger; Keller, Sascha; Robotta, Marta; Drescher, Malte; Marx, Andreas

2014-01-01

The predictability of DNA self-assembly is exploited in many nanotechnological approaches. Inspired by naturally existing self-assembled DNA architectures, branched DNA has been developed that allows self-assembly to predesigned architectures with dimensions on the nanometer scale. DNA is an attractive material for generation of nanostructures due to a plethora of enzymes which modify DNA with high accuracy, providing a toolbox for many different manipulations to construct nanometer scaled objects. We present a straightforward synthesis of a rigid DNA branching building block successfully used for the generation of DNA networks by self-assembly and network formation by enzymatic DNA synthesis. The Y-shaped 3-armed DNA construct, bearing 3 primer strands is accepted by Taq DNA polymerase. The enzyme uses each arm as primer strand and incorporates the branched construct into large assemblies during PCR. The networks were investigated by agarose gel electrophoresis, atomic force microscopy, dynamic light scattering, and electron paramagnetic resonance spectroscopy. The findings indicate that rather rigid DNA networks were formed. This presents a new bottom-up approach for DNA material formation and might find applications like in the generation of functional hydrogels.

DNA biosensor for detection of Salmonella typhi from blood sample of typhoid fever patient using gold electrode modified by self-assembled monolayers of thiols

NASA Astrophysics Data System (ADS)

Suryapratiwi, Windha Novita; Paat, Vlagia Indira; Gaffar, Shabarni; Hartati, Yeni Wahyuni

2017-05-01

Electrochemical biosensors are currently being developed in order to handle various clinical problems in diagnosing infectious diseases caused by pathogenic bacteria, or viruses. On this research, voltammetric DNA biosensor using gold electrode modified by thiols with self-assembled monolayers had been developed to detect a certain sequence of Salmonella typhi DNA from blood sample of typhoid fever patient. Thiol groups of cysteamines (Cys) and aldehyde groups from glutaraldehydes (Glu) were used as a link to increase the performance of gold electrode in detecting guanine oxidation signal of hybridized S. typhi DNA and ssDNA probe. Standard calibration method was used to determine analytical parameters from the measurements. The result shown that, the detection of S. typhi DNA from blood sample of typhoid fever patient can be carried out by voltammetry using gold electrode modified by self-assembled monolayers of thiols. A characteristic oxidation potential of guanine using Au/Cys/Gluwas obtained at +0.17 until +0.20 V. Limit of detection and limit of quantification from this measurements were 1.91μg mL-1 and 6.35 μg mL-1. The concentration of complement DNA from sample was 6.96 μg mL-1.

Tailoring peptide amphiphiles and their assemblies for biomedical applications

NASA Astrophysics Data System (ADS)

Lin, Brian

Peptide amphiphiles (PAs) are molecules composed of a peptide conjugated to a hydrophobic moiety, commonly a fatty acid. They closely resemble the structure of naturally occurring lipopeptides, produced by microbes as signaling and antimicrobial agents. The amphiphilic nature of PAs in concert with the large number of discovered functional peptides inspired scientists to exploit this molecular architecture for producing synthetic self-assembled bioactive materials. PA assemblies are sought after for a wide breadth of applications including disease therapy, regenerative medicine, and catalysis. However, with PAs, the peptide chemistry is a double-edged sword. The peptide component contributes significantly to both the activity and self-assembly. The physiochemical properties of different PAs lead to unique aggregation stability and morphological characteristics which are unpredictable, a priori. Therefore it is challenging to design bioactive PAs and control their self-assembly, simultaneously. This limitation slows the development of PAs for medical use. In this dissertation, methods to control the self-assembly of PAs and the effects of acylating a functional peptide will be discussed. In one part, efforts to direct the self-assembly of PAs into small spherical aggregates, a morphology infrequently observed, will be described. In another section, a strategy to control the stability of PA assemblies will be discussed. In the last section, a pH-responsive membrane perturbing peptide was modified with fatty acid tails and the properties of the resulting PAs will be presented. This dissertation provides some fundamental insight for the use and design of PA self-assemblies.

Self-assembly of heterogeneous supramolecular structures with uniaxial anisotropy.

PubMed

Ruiz-Osés, M; Gonzalez-Lakunza, N; Silanes, I; Gourdon, A; Arnau, A; Ortega, J E

2006-12-28

Uniaxial anisotropy in two-dimensional self-assembled supramolecular structures is achieved by the coadsorption of two different linear molecules with complementary amine and imide functionalization. The two-dimensional monolayer is defined by a one-dimensional stack of binary chains, which can be forced to line up along steps in vicinal surfaces. The competing driving forces in the self-organization process are discussed in light of the structures observed during single molecule adsorption and coadsorption on flat and vicinal surfaces and the corresponding theoretical calculations.

A new pyruvate oxidase biosensor based on 3-mercaptopropionic acid/6-aminocaproic acid modified gold electrode.

PubMed

Bayram, Ezgi; Akyilmaz, Erol

2014-12-01

In the biosensor construction, 3-mercaptopropionic acid (3-MPA) and 6-aminocaproic acid (6-ACA) were used for forming self-assembled monolayer (SAM) on a gold disc electrode and pyruvate oxidase was immobilized on the modified electrode surface by using glutaraldehyde. Biosensor response is linearly related to pyruvate concentration at 2.5-50 μM, detection limit is 1.87 μM and response time of the biosensor is 6 s for differential pulse voltammograms. From the repeatability studies (n = 6) for 30.0 μM pyruvate revealed that the average value ([Formula: see text]), standard deviation (S.D) and coefficient of variation (CV %) were calculated to be 31.02 μM, ± 0.1914 μM and 0.62%, respectively.

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

A self-assembling nanomedicine of conjugated linoleic acid-paclitaxel conjugate (CLA-PTX) with higher drug loading and carrier-free characteristic

NASA Astrophysics Data System (ADS)

Zhong, Ting; Yao, Xin; Zhang, Shuang; Guo, Yang; Duan, Xiao-Chuan; Ren, Wei; Dan Huang; Yin, Yi-Fan; Zhang, Xuan

2016-11-01

The main objective of this study was to demonstrate the proof-of-principle for the hypothesis that conjugated linoleic acid-paclitaxel conjugate (CLA-PTX), a novel fatty acid modified anti-cancer drug conjugate, could self-assemble forming nanoparticles. The results indicated that a novel self-assembling nanomedicine, CLA-PTX@PEG NPs (about 105 nm), with Cremophor EL (CrEL)-free and organic solvent-free characteristics, was prepared by a simple precipitation method. Being the ratio of CLA-PTX:DSPE-PEG was only 1:0.1 (w/w), the higher drug loading CLA-PTX@PEG NPs (about 90%) possessed carrier-free characteristic. The stability results indicated that CLA-PTX@PEG NPs could be stored for at least 9 months. The safety of CLA-PTX@PEG NPs was demonstrated by the MTD results. The anti-tumor activity and cellular uptake were also confirmed in the in vitro experiments. The lower crystallinity, polarity and solubility of CLA-PTX compared with that of paclitaxel (PTX) might be the possible reason for CLA-PTX self-assembling forming nanoparticles, indicating a relationship between PTX modification and nanoparticles self-assembly. Overall, the data presented here confirm that this drug self-delivery strategy based on self-assembly of a CLA-PTX conjugate may offer a new way to prepare nanomedicine products for cancer therapy involving the relationship between anticancer drug modification and self-assembly into nanoparticles.

Surface Chemical Conversion of Organosilane Self-Assembled Monolayers with Active Oxygen Species Generated by Vacuum Ultraviolet Irradiation of Atmospheric Oxygen Molecules

NASA Astrophysics Data System (ADS)

Kim, Young-Jong; Lee, Kyung-Hwang; Sano, Hikaru; Han, Jiwon; Ichii, Takashi; Murase, Kuniaki; Sugimura, Hiroyuki

2008-01-01

The chemical conversion of the top surface of n-octadecyltrimethoxy silane self-assembled monolayers (ODS-SAMs) on oxide-covered Si substrates using active oxygen species generated from atmospheric oxygen molecules irradiated with vacuum ultraviolet (VUV) light at 172 nm in wavelength has been studied on the basis of water contact angle measurements, ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy. An ODS-SAM whose water contact angle was 104° on average was prepared using chemical vapor deposition with substrate and vapor temperatures of 150 °C. The VUV treatment of an ODS-SAM sample was carried out by placing the sample in air and then irradiating the sample surface with a Xe-excimer lamp. The distance between the lamp and the sample was regulated so that the VUV light emitted from the lamp was almost entirely absorbed by atmospheric oxygen molecules to generate active oxygen species, such as ozone and atomic oxygen before reaching the sample surface. Hence, the surface chemical conversion of the ODS-SAM was primarily promoted through chemical reactions with the active oxygen species. Photochemical changes in the ODS-SAM were found to be the generation of polar functional groups, such as -COOH, -CHO, and -OH, on the surface and the subsequent etching of the monolayer. Irradiation parameters, such as irradiation time, were optimized to achieve a better functionalization of the SAM top surface while minimizing the etching depth of the ODS-SAM. The ability to graft another SAM onto the modified ODS-SAM bearing polar functional groups was demonstrated by the formation of alkylsilane bilayers.

Influences of surface charge, size, and concentration of colloidal nanoparticles on fabrication of self-organized porous silica in film and particle forms.

PubMed

Nandiyanto, Asep Bayu Dani; Suhendi, Asep; Arutanti, Osi; Ogi, Takashi; Okuyama, Kikuo

2013-05-28

Studies on preparation of porous material have attracted tremendous attention because existence of pores can provide material with excellent performances. However, current preparation reports described successful production of porous material with only partial information on charges, interactions, sizes, and compositions of the template and host materials. In this report, influences of self-assembly parameters (i.e., surface charge, size, and concentration of colloidal nanoparticles) on self-organized porous material fabrication were investigated. Silica nanoparticles (as a host material) and polystyrene (PS) spheres (as a template) were combined to produce self-assembly porous materials in film and particle forms. The experimental results showed that the porous structure and pore size were controllable and strongly depended on the self-assembly parameters. Materials containing highly ordered pores were effectively created only when process parameters fall within appropriate conditions (i.e., PS surface charge ≤ -30 mV; silica-to-PS size ratio ≤0.078; and silica-to-PS mass ratio of about 0.50). The investigation of the self-assembly parameter landscape was also completed using geometric considerations. Because optimization of these parameters provides significant information in regard to practical uses, results of this report could be relevant to other functional properties.

Self-assembled diatom substrates with plasmonic functionality

NASA Astrophysics Data System (ADS)

Kwon, Sun Yong; Park, Sehyun; Nichols, William T.

2014-04-01

Marine diatoms have an exquisitely complex exoskeleton that is promising for engineered surfaces such as sensors and catalysts. For such applications, creating uniform arrays of diatom frustules across centimeter scales will be necessary. Here, we present a simple, low-cost floating interface technique to self-assemble the diatom frustules. We show that well-prepared diatoms form floating hexagonal close-packed arrays at the air-water interface that can be transferred directly to a substrate. We functionalize the assembled diatom surfaces with gold and characterize the plasmonic functionality by using surface enhanced Raman scattering (SERS). Thin gold films conform to the complex, hierarchical diatom structure and produce a SERS enhancement factor of 2 × 104. Small gold nanoparticles attached to the diatom's surface produce a higher enhancement of 7 × 104 due to stronger localization of the surface plasmons. Taken together, the large-scale assembly and plasmonic functionalization represent a promising platform to control the energy and the material flows at a complex surface for applications such as sensors and plasmonic enhanced catalysts.

Lock and Key Colloids through Polymerization-Induced Buckling of Monodispersed Silicon Oil Droplets

NASA Astrophysics Data System (ADS)

Sacanna, Stefano; Irvine, William T. M.; Chaikin, Paul M.; Pine, David J.

2010-03-01

Colloidal particles can spontaneously associate into larger structured aggregates when driven by selective and directional interactions. Colloidal organization can be programmed by engineering shapes and interactions of basic building blocks in a manner similar to molecular self-assembly. Examples of successful strategies that allow non-trivial assembly of particles include template-directed patterning, capillary forces and, most commonly, the functionalization of the particle surfaces with ``sticky patches'' of biological or synthetic molecules. The level of complexity of the realizable assemblies, increases when particles with well defined shape anisotropies are used. In particular depletion forces and specific surface treatments in combination with non spherical particles have proven to be powerful tools to self-assembly complex microstructures. We describe a simple, high yield, synthetic pathway to fabricate monodisperse hybrid silica spheres with well defined cavities. Because the particle morphologies are reproducible and tunable with precision, the resulting particles can be used as basic building blocks in the assembly of larger monodisperse clusters. This is demonstrated using depletion to drive the self-assembly.

Bimodal self-assembly of an amphiphilic gelator into a hydrogel-nanocatalyst and an organogel with different morphologies and photophysical properties.

PubMed

Sutar, Papri; Maji, Tapas Kumar

2016-11-18

We design a flexible, amphiphilic LMWG consisting of donor and acceptor π-chromophores which self-assembles into a hydrogel and an organogel with different nano-morphologies. Different mechanisms of self-assembly evolve charge transfer (CT) emission in the hydrogel and LMWG-based emission in the organogel. Moreover, the hydrogel-nanostructure with surface exposed amide groups is explored for catalyzing Knoevenagel condensation reaction.

Super-Hydrophobic/Icephobic Coatings Based on Silica Nanoparticles Modified by Self-Assembled Monolayers.

PubMed

Liu, Junpeng; Janjua, Zaid A; Roe, Martin; Xu, Fang; Turnbull, Barbara; Choi, Kwing-So; Hou, Xianghui

2016-12-02

A super-hydrophobic surface has been obtained from nanocomposite materials based on silica nanoparticles and self-assembled monolayers of 1 H ,1 H ,2 H ,2 H -perfluorooctyltriethoxysilane (POTS) using spin coating and chemical vapor deposition methods. Scanning electron microscope images reveal the porous structure of the silica nanoparticles, which can trap small-scale air pockets. An average water contact angle of 163° and bouncing off of incoming water droplets suggest that a super-hydrophobic surface has been obtained based on the silica nanoparticles and POTS coating. The monitored water droplet icing test results show that icing is significantly delayed by silica-based nano-coatings compared with bare substrates and commercial icephobic products. Ice adhesion test results show that the ice adhesion strength is reduced remarkably by silica-based nano-coatings. The bouncing phenomenon of water droplets, the icing delay performance and the lower ice adhesion strength suggest that the super-hydrophobic coatings based on a combination of silica and POTS also show icephobicity. An erosion test rig based on pressurized pneumatic water impinging impact was used to evaluate the durability of the super-hydrophobic/icephobic coatings. The results show that durable coatings have been obtained, although improvement will be needed in future work aiming for applications in aerospace.

Polarity Control of Heteroepitaxial GaN Nanowires on Diamond.

PubMed

Hetzl, Martin; Kraut, Max; Hoffmann, Theresa; Stutzmann, Martin

2017-06-14

Group III-nitride materials such as GaN nanowires are characterized by a spontaneous polarization within the crystal. The sign of the resulting sheet charge at the top and bottom facet of a GaN nanowire is determined by the orientation of the wurtzite bilayer of the different atomic species, called N and Ga polarity. We investigate the polarity distribution of heteroepitaxial GaN nanowires on different substrates and demonstrate polarity control of GaN nanowires on diamond. Kelvin Probe Force Microscopy is used to determine the polarity of individual selective area-grown and self-assembled nanowires over a large scale. At standard growth conditions, mixed polarity occurs for selective GaN nanowires on various substrates, namely on silicon, on sapphire and on diamond. To obtain control over the growth orientation on diamond, the substrate surface is modified by nitrogen and oxygen plasma exposure prior to growth, and the growth parameters are adjusted simultaneously. We find that the surface chemistry and the substrate temperature are the decisive factors for obtaining control of up to 93% for both polarity types, whereas the growth mode, namely selective area or self-assembled growth, does not influence the polarity distribution significantly. The experimental results are discussed by a model based on the interfacial bonds between the GaN nanowires, the termination layer, and the substrate.

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.

Electron Transfer Mechanism in Gold Surface Modified with Self-Assembly Monolayers from First Principles

NASA Astrophysics Data System (ADS)

Lima, Filipe C. D. A.; Iost, Rodrigo M.; Crespilho, Frank N.; Caldas, Marília J.; Calzolari, Arrigo; Petrilli, Helena M.

2013-03-01

We report the investigation of electron tunneling mechanism of peptide ferrocenyl-glycylcystamine self-assembled monolayers (SAMs) onto Au (111) electrode surfaces. Recent experimental investigations showed that electron transfer in peptides can occur across long distances by separating the donor from the acceptor. This mechanism can be further fostered by the presence of electron donor terminations of Fc terminal units on SAMs but the charge transfer mechanism is still not clear. We study the interaction of the peptide ferrocenyl-glycylcystamine on the Au (111) from first principles calculations to evaluate the electron transfer mechanism. For this purpose, we used the Kohn Sham (KS) scheme for the Density Functional Theory (DFT) as implemented in the Quantum-ESPRESSO suit of codes, using Vandebilt ultrasoft pseudopotentials and GGA-PBE exchange correlation functional to evaluate the ground-state atomic and electronic structure of the system. The analysis of KS orbital at the Fermi Energy showed high electronic density localized in Fc molecules and the observation of a minor contribution from the solvent and counter ion. Based on the results, we infer evidences of electron tunneling mechanism from the molecule to the Au(111). We acknowledge FAPESP for grant support. Also, LCCA/USP, RICE and CENAPAD for computational resources.

Multifunctional Nanoparticles Self-Assembled from Small Organic Building Blocks for Biomedicine.

PubMed

Xing, Pengyao; Zhao, Yanli

2016-09-01

Supramolecular self-assembly shows significant potential to construct responsive materials. By tailoring the structural parameters of organic building blocks, nanosystems can be fabricated, whose performance in catalysis, energy storage and conversion, and biomedicine has been explored. Since small organic building blocks are structurally simple, easily modified, and reproducible, they are frequently employed in supramolecular self-assembly and materials science. The dynamic and adaptive nature of self-assembled nanoarchitectures affords an enhanced sensitivity to the changes in environmental conditions, favoring their applications in controllable drug release and bioimaging. Here, recent significant research advancements of small-organic-molecule self-assembled nanoarchitectures toward biomedical applications are highlighted. Functionalized assemblies, mainly including vesicles, nanoparticles, and micelles are categorized according to their topological morphologies and functions. These nanoarchitectures with different topologies possess distinguishing advantages in biological applications, well incarnating the structure-property relationship. By presenting some important discoveries, three domains of these nanoarchitectures in biomedical research are covered, including biosensors, bioimaging, and controlled release/therapy. The strategies regarding how to design and characterize organic assemblies to exhibit biomedical applications are also discussed. Up-to-date research developments in the field are provided and research challenges to be overcome in future studies are revealed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ordered Self-Assembled Monolayers of Peptide Nucleic Acids with DNA Recognition Capability

NASA Astrophysics Data System (ADS)

Briones, C.; Mateo-Marti, E.; Gómez-Navarro, C.; Parro, V.; Román, E.; Martín-Gago, J. A.

2004-11-01

We report on the formation of ordered self-assembled monolayers (SAMs) of single-stranded peptide nucleic acids (ssPNA). In spite of their remarkable length (7nm) thiolated PNAs assemble standing up on gold surfaces similarly to the SAMs of short alkanethiols. SAMs of ssPNA recognize complementary nucleic acids, acting as specific biosensors that discriminate even a point mutation in target ssDNA. These results are obtained by surface characterization techniques that avoid labeling of the target molecule: x-ray photoemission, x-ray absorption and atomic force microscopy.

Controlling the Surface Chemistry of Graphite by Engineered Self-Assembled Peptides

PubMed Central

Khatayevich, Dmitriy; So, Christopher R.; Hayamizu, Yuhei; Gresswell, Carolyn; Sarikaya, Mehmet

2012-01-01

The systematic control over surface chemistry is a long-standing challenge in biomedical and nanotechnological applications for graphitic materials. As a novel approach, we utilize graphite-binding dodecapeptides that self-assemble into dense domains to form monolayer thick long-range ordered films on graphite. Specifically, the peptides are rationally designed through their amino acid sequences to predictably display hydrophilic and hydrophobic characteristics while maintaining their self-assembly capabilities on the solid substrate. The peptides are observed to maintain a high tolerance for sequence modification, allowing the control over surface chemistry via their amino acid sequence. Furthermore, through a single step co-assembly of two different designed peptides, we predictably and precisely tune the wettability of the resulting functionalized graphite surfaces from 44 to 83 degrees. The modular molecular structures and predictable behavior of short peptides demonstrated here give rise to a novel platform for functionalizing graphitic materials that offers numerous advantages, including non-invasive modification of the substrate, bio-compatible processing in an aqueous environment, and simple fusion with other functional biological molecules. PMID:22428620

Structure and electrochemical behaviour of 4,7-diazaheptyl-trimethoxy-silane and vinyl-trialkoxy-silane adsorbed at silver surface

NASA Astrophysics Data System (ADS)

Łuczak, Teresa; Pankiewicz, Radosław; Łęska, Bogusława; Schroeder, Grzegorz; Bełtowska-Brzezinska, Maria; Brzezinski, Bogumil

2006-12-01

Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li + cations were calculated and visualised by the AM1d and PM5 semi-empirical methods.

Injection-modulated polarity conversion by charge carrier density control via a self-assembled monolayer for all-solution-processed organic field-effect transistors

NASA Astrophysics Data System (ADS)

Roh, Jeongkyun; Lee, Taesoo; Kang, Chan-Mo; Kwak, Jeonghun; Lang, Philippe; Horowitz, Gilles; Kim, Hyeok; Lee, Changhee

2017-04-01

We demonstrated modulation of charge carrier densities in all-solution-processed organic field-effect transistors (OFETs) by modifying the injection properties with self-assembled monolayers (SAMs). The all-solution-processed OFETs based on an n-type polymer with inkjet-printed Ag electrodes were fabricated as a test platform, and the injection properties were modified by the SAMs. Two types of SAMs with different dipole direction, thiophenol (TP) and pentafluorobenzene thiol (PFBT) were employed, modifying the work function of the inkjet-printed Ag (4.9 eV) to 4.66 eV and 5.24 eV with TP and PFBT treatments, respectively. The charge carrier densities were controlled by the SAM treatment in both dominant and non-dominant carrier-channel regimes. This work demonstrates that control of the charge carrier densities can be efficiently achieved by modifying the injection property with SAM treatment; thus, this approach can achieve polarity conversion of the OFETs.

Boundaries Control Collective Dynamics of Inertial Self-Propelled Robots.

PubMed

Deblais, A; Barois, T; Guerin, T; Delville, P H; Vaudaine, R; Lintuvuori, J S; Boudet, J F; Baret, J C; Kellay, H

2018-05-04

Simple ingredients, such as well-defined interactions and couplings for the velocity and orientation of self-propelled objects, are sufficient to produce complex collective behavior in assemblies of such entities. Here, we use assemblies of rodlike robots made motile through self-vibration. When confined in circular arenas, dilute assemblies of these rods act as a gas. Increasing the surface fraction leads to a collective behavior near the boundaries: polar clusters emerge while, in the bulk, gaslike behavior is retained. The coexistence between a gas and surface clusters is a direct consequence of inertial effects as shown by our simulations. A theoretical model, based on surface mediated transport accounts for this coexistence and illustrates the exact role of the boundaries. Our study paves the way towards the control of collective behavior: By using deformable but free to move arenas, we demonstrate that the surface induced clusters can lead to directed motion, while the topology of the surface states can be controlled by biasing the motility of the particles.

A review of molecular phase separation in binary self-assembled monolayers of thiols on gold surfaces

NASA Astrophysics Data System (ADS)

Ong, Quy; Nianias, Nikolaos; Stellacci, Francesco

2017-09-01

Binary self-assembled monolayers (SAMs) on gold surfaces have been known to undergo molecular phase separation to various degrees and have been subject to both experimental and theoretical studies. On gold nanoparticles in particular, binary SAMs ligand shells display intriguing morphologies. Consequently, unexpected behaviors of the nanoparticles with respect to their biological, chemical, and interfacial properties have been observed. It is critical that the phase separation of binary SAMs be understood at both molecular and macroscopic level to create, and then manipulate, the useful properties of the functionalized surfaces. We look into the current understanding of molecular phase separation of binary SAMs on gold surfaces, represented by Au(111) flat surfaces and Au nanoparticles, from both theoretical and experimental aspects. We point out shortcomings and describe several research strategies that will address them in the future. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Pule Pileni.

Boundaries Control Collective Dynamics of Inertial Self-Propelled Robots

NASA Astrophysics Data System (ADS)

Deblais, A.; Barois, T.; Guerin, T.; Delville, P. H.; Vaudaine, R.; Lintuvuori, J. S.; Boudet, J. F.; Baret, J. C.; Kellay, H.

2018-05-01

Simple ingredients, such as well-defined interactions and couplings for the velocity and orientation of self-propelled objects, are sufficient to produce complex collective behavior in assemblies of such entities. Here, we use assemblies of rodlike robots made motile through self-vibration. When confined in circular arenas, dilute assemblies of these rods act as a gas. Increasing the surface fraction leads to a collective behavior near the boundaries: polar clusters emerge while, in the bulk, gaslike behavior is retained. The coexistence between a gas and surface clusters is a direct consequence of inertial effects as shown by our simulations. A theoretical model, based on surface mediated transport accounts for this coexistence and illustrates the exact role of the boundaries. Our study paves the way towards the control of collective behavior: By using deformable but free to move arenas, we demonstrate that the surface induced clusters can lead to directed motion, while the topology of the surface states can be controlled by biasing the motility of the particles.

Multistep hierarchical self-assembly of chiral nanopore arrays

PubMed Central

Kim, Hanim; Lee, Sunhee; Shin, Tae Joo; Korblova, Eva; Walba, David M.; Clark, Noel A.; Lee, Sang Bok; Yoon, Dong Ki

2014-01-01

A series of simple hierarchical self-assembly steps achieve self-organization from the centimeter to the subnanometer-length scales in the form of square-centimeter arrays of linear nanopores, each one having a single chiral helical nanofilament of large internal surface area and interfacial interactions based on chiral crystalline molecular arrangements. PMID:25246585

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.

Branched poly(ethyleneimine): a versatile scaffold for patterning polymer brushes by means of remote photocatalytic lithography

NASA Astrophysics Data System (ADS)

Panzarasa, Guido; Dübner, Matthias; Soliveri, Guido; Edler, Matthias; Griesser, Thomas

2017-09-01

Patterning of functional surfaces is one of the cornerstones of nanotechnology as it allows the fabrication of sensors and lab-on-a-chip devices. Here, the patterning of self-assembled monolayers of branched poly(ethyleneimine) (bPEI) on silica was achieved by means of remote photocatalytic lithography. Moreover, when 2-bromoisobutyryl-modified bPEI was used, the resulting pattern could be amplified by grafting polymer brushes by means of surface-initiated atom transfer radical polymerization. In contrast to previous reports for the patterning of bPEI, the present approach can be conducted in minutes instead of hours, reducing the exposure time to UV radiation and enhancing the overall efficiency. Furthermore, our approach is much more user-friendly, allowing a facile fabrication of patterned initiator-modified surfaces and the use of inexpensive instrumentation such as a low-power UV source and a simple photomask. Considering the versatility of bPEI as a scaffold for the development of biosensors, patterning by means of remote photocatalytic lithography will open new opportunities in a broad field of applications.

Controlled Synthesis of Pd/Pt Core Shell Nanoparticles Using Area-selective Atomic Layer Deposition

PubMed Central

Cao, Kun; Zhu, Qianqian; Shan, Bin; Chen, Rong

2015-01-01

We report an atomic scale controllable synthesis of Pd/Pt core shell nanoparticles (NPs) via area-selective atomic layer deposition (ALD) on a modified surface. The method involves utilizing octadecyltrichlorosilane (ODTS) self-assembled monolayers (SAMs) to modify the surface. Take the usage of pinholes on SAMs as active sites for the initial core nucleation, and subsequent selective deposition of the second metal as the shell layer. Since new nucleation sites can be effectively blocked by surface ODTS SAMs in the second deposition stage, we demonstrate the successful growth of Pd/Pt and Pt/Pd NPs with uniform core shell structures and narrow size distribution. The size, shell thickness and composition of the NPs can be controlled precisely by varying the ALD cycles. Such core shell structures can be realized by using regular ALD recipes without special adjustment. This SAMs assisted area-selective ALD method of core shell structure fabrication greatly expands the applicability of ALD in fabricating novel structures and can be readily applied to the growth of NPs with other compositions. PMID:25683469

Self-assembly and graft polymerization route to Monodispersed Fe3O4@SiO2--polyaniline core-shell composite nanoparticles: physical properties.

PubMed

Reddy, Kakarla Raghava; Lee, Kwang-Pill; Kim, Ju Young; Lee, Youngil

2008-11-01

This study describes the synthesis of monodispersed core-shell composites of silica-modified magnetic nanoparticles and conducting polyaniline by self-assembly and graft polymerization. Magnetic ferrite nanoparticles (Fe3O4) were prepared by coprecipitation of Fe+2 and Fe+3 ions in alkaline solution, and then silananized. The silanation of magnetic particles (Fe3O4@SiO2) was carried out using 3-bromopropyltrichlorosilane (BPTS) as the coupling agent. FT-IR spectra indicated the presence of Fe--O--Si chemical bonds in Fe3O4@SiO2. Core-shell type nanocomposites (Fe3O4@SiO2/PANI) were prepared by grafting polyaniline (PANI) on the surface of silanized magnetic particles through surface initiated in-situ chemical oxidative graft polymerization. The nanocomposites were characterized by high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), Fourier transform infrared (FTIR) spectra, UV-visible spectroscopy, photoluminescence (PL) spectra, electrical conductivity and magnetic characteristics. HRTEM images of the nanocomposites revealed that the silica-modified magnetic particles made up the core while PANI made up the shell. The XPS spectrum revealed the presence of silica in the composites, and the XRD results showed that the composites were more crystalline than pure PANI. PL spectra show that composites exhibit photoluminescent property. Conductivity of the composites (6.2 to 9.4 x 10(-2) S/cm) was higher than that of pristine PANI (3.7 x 10(-3) S/cm). The nanocomposites exhibited superparamagnetism. Formation mechanism of the core-shell structured nanocomposites and the effect of modified magnetic nanoparticles on the electro-magnetic properties of the Fe3O4@SiO2/PANI nanocomposites are also investigated. This method provides a new strategy for the generation of multi-functional nanocomposites that composed of other conducting polymers and metal nanoparticles.

Self-assembly of short amyloidogenic peptides at the air-water interface.

PubMed

Chaudhary, Nitin; Nagaraj, Ramakrishnan

2011-08-01

Short peptide stretches in amyloidogenic proteins can form amyloid fibrils in vitro and have served as good models for studying amyloid fibril formation. Recently, these amyloidogenic peptides have gained considerable attention, as non-amyloid ordered structures can be obtained from these peptides by carefully tuning the conditions of self-assembly, especially pH, temperature and presence of organic solvents. We have examined the effect of surface pressure on the self-assembled structures of two amyloidogenic peptides, Pβ(2)m (Ac-DWSFYLLYYTEFT-am) and AcPHF6 (Ac-VQIVYK-am) at the air-water interface when deposited from different solvents. Both the peptides are surface-active and form Thioflavin T (ThT) positive structures at the air-water interface. There is considerable hysteresis in the compression and expansion isotherms, suggesting the occurrence of structural rearrangements during compression. Preformed Pβ(2)m fibrillar structures at the air-water interface are disrupted as peptide is compressed to lower molecular areas but restored if the film is expanded, suggesting that the process is reversible. AcPHF6, on the other hand, shows largely sheet-like structures at lower molecular areas. The solvents used for dissolution of the peptides appear to influence the nature of the aggregates formed. Our results show that like hydrostatic pressure, surface pressure can also be utilized for modulating the self-assembly of the amyloidogenic and self-assembling peptides. Copyright © 2011 Elsevier Inc. All rights reserved.

Self-assembly concepts in the formation of nanostructured particles using a liquid-phase synthesis method

NASA Astrophysics Data System (ADS)

Nandiyanto, Asep Bayu Dani

2016-02-01

When synthesizing particles using a liquid-phase synthesis method, reactant components show interaction with the reaction system itself. However, current reports described successful synthesis of material with only partial information on the component-component interaction and possible self-assembly mechanism occurring during the material synthesis process. Here, self-assembly concepts in the formation of nanostructured particles are presented. Influences of self-assembly parameters (i.e., surface charge, size, and concentration of components involving the reaction) on self-organized material fabrication are described. Because understanding the interaction of the component provides significant information in regard to practical uses, this report can be relevant to further material development and fabrication.

Bioengineered-inorganic nanosystems for nanophotonics and bio-nanotechnology

NASA Astrophysics Data System (ADS)

Leong, Kirsty; Zin, Melvin T.; Ma, Hong; Huang, Fei; Sarikaya, Mehmet; Jen, Alex K.

2008-08-01

Here we nanoengineered tunable quantum dot and cationic conjugated polymer nanoarrays based on surface plasmon enhanced fluorescence where we achieved a 15-fold and 25-fold increase in their emission intensities, respectively. These peptide mediated hybrid systems were fabricated by horizontally tuning the localized surface plasmon resonance of gold nanoarrays and laterally tuning the distance of the fluorophore from the metal surface. This approach permits a comprehensive control both laterally (i.e., lithographically defined gold nanoarrays) and vertically (i.e., QD/CCP-metal distance) of the collectively behaving QD-NP and CP-NP assemblies by way of biomolecular recognition. The highest photoluminescence was achieved when the quantum dots and cationic conjugated polymers were self-assembled at a distance of 16.00 nm and 18.50 nm from the metal surface, respectively. Specifically, we demonstrated the spectral tuning of plasmon resonant metal nanoarrays and the self-assembly of protein-functionalized QDs/CCPs in a step-wise fashion with a concomitant incremental increase in separation from the metal surface through biotin-streptavidin spacer units. These well-controlled self-assembled patterned arrays provide highly organized architectures for improving optoelectronic devices and/or increasing the sensitivity of bio-chemical sensors.

Dilution effects on combined magnetic and electric dipole interactions: A study of ferromagnetic cobalt nanoparticles with tuneable interactions

NASA Astrophysics Data System (ADS)

Hod, M.; Dobroserdova, A.; Samin, S.; Dobbrow, C.; Schmidt, A. M.; Gottlieb, M.; Kantorovich, S.

2017-08-01

Improved understanding of complex interactions between nanoparticles will facilitate the control over the ensuing self-assembled structures. In this work, we consider the dynamic changes occurring upon dilution in the self-assembly of a system of ferromagnetic cobalt nanoparticles that combine magnetic, electric, and steric interactions. The systems examined here vary in the strength of the magnetic dipole interactions and the amount of point charges per particle. Scattering techniques are employed for the characterization of the self-assembly aggregates, and zeta-potential measurements are employed for the estimation of surface charges. Our experiments show that for particles with relatively small initial number of surface electric dipoles, an increase in particle concentration results in an increase in diffusion coefficients; whereas for particles with relatively high number of surface dipoles, no effect is observed upon concentration changes. We attribute these changes to a shift in the adsorption/desorption equilibrium of the tri-n-octylphosphine oxide (TOPO) molecules on the particle surface. We put forward an explanation, based on the combination of two theoretical models. One predicts that the growing concentration of electric dipoles, stemming from the addition of tri-n-octylphosphine oxide (TOPO) as co-surfactant during particle synthesis, on the surface of the particles results in the overall repulsive interaction. Secondly, using density functional theory, we explain that the observed behaviour of the diffusion coefficient can be treated as a result of the concentration dependent nanoparticle self-assembly: additional repulsion leads to the reduction in self-assembled aggregate size despite the shorter average interparticle distances, and as such provides the growth of the diffusion coefficient.

Dilution effects on combined magnetic and electric dipole interactions: A study of ferromagnetic cobalt nanoparticles with tuneable interactions.

PubMed

Hod, M; Dobroserdova, A; Samin, S; Dobbrow, C; Schmidt, A M; Gottlieb, M; Kantorovich, S

2017-08-28

Improved understanding of complex interactions between nanoparticles will facilitate the control over the ensuing self-assembled structures. In this work, we consider the dynamic changes occurring upon dilution in the self-assembly of a system of ferromagnetic cobalt nanoparticles that combine magnetic, electric, and steric interactions. The systems examined here vary in the strength of the magnetic dipole interactions and the amount of point charges per particle. Scattering techniques are employed for the characterization of the self-assembly aggregates, and zeta-potential measurements are employed for the estimation of surface charges. Our experiments show that for particles with relatively small initial number of surface electric dipoles, an increase in particle concentration results in an increase in diffusion coefficients; whereas for particles with relatively high number of surface dipoles, no effect is observed upon concentration changes. We attribute these changes to a shift in the adsorption/desorption equilibrium of the tri-n-octylphosphine oxide (TOPO) molecules on the particle surface. We put forward an explanation, based on the combination of two theoretical models. One predicts that the growing concentration of electric dipoles, stemming from the addition of tri-n-octylphosphine oxide (TOPO) as co-surfactant during particle synthesis, on the surface of the particles results in the overall repulsive interaction. Secondly, using density functional theory, we explain that the observed behaviour of the diffusion coefficient can be treated as a result of the concentration dependent nanoparticle self-assembly: additional repulsion leads to the reduction in self-assembled aggregate size despite the shorter average interparticle distances, and as such provides the growth of the diffusion coefficient.

Template mediated protein self-assembly as a valuable tool in regenerative therapy.

PubMed

Kundu, B; Eltohamy, M; Yadavalli, V K; Reis, R L; Kim, H W

2018-04-11

The assembly of natural proteinaceous biopolymers into macro-scale architectures is of great importance in synthetic biology, soft-material science and regenerative therapy. The self-assembly of protein tends to be limited due to anisotropic interactions among protein molecules, poor solubility and stability. Here, we introduce a unique platform to self-immobilize diverse proteins (fibrous and globular, positively and negatively charged, low and high molecular weight) using silicon surfaces with pendant -NH 2 groups via a facile one step diffusion limited aggregation (DLA) method. All the experimental proteins (type I collagen, bovine serum albumin and cytochrome C) self-assemble into seaweed-like branched dendritic architectures via classical DLA in the absence of any electrolytes. The notable differences in branching architectures are due to dissimilarities in protein colloidal sub-units, which is typical for each protein type, along with the heterogeneous distribution of surface -NH 2 groups. Fractal analysis of assembled structures is used to explain the underlying route of fractal deposition; which concludes how proteins with different functionality can yield similar assembly. Further, the nano-micro-structured surfaces can be used to provide functional topographical cues to study cellular responses, as demonstrated using rat bone marrow stem cells. The results indicate that the immobilization of proteins via DLA does not affect functionality, instead serving as topographical cues to guide cell morphology. This indicates a promising design strategy at the tissue-material interface and is anticipated to guide future surface modifications. A cost-effective standard templating strategy is therefore proposed for fundamental and applied particle aggregation studies, which can be used at multiple length scales for biomaterial design and surface reformation.

Self-assembly behavior of tail-to-tail superstructure formed by mono-6-O-(4-carbamoylmethoxy-benzoyl)-β-cyclodextrin in solution and the solid state.

PubMed

Xu, Zhe; Chen, Xin; Liu, Jing; Yan, Dong-Qing; Diao, Chun-Hua; Guo, Min-Jie; Fan, Zhi

2014-07-01

A novel mono-modified β-cyclodextrin (β-CD) consisting of 4-carbamoylmethoxy-benzoyl unit at the primary side was synthesized and its self-assembly behavior was determined by X-ray crystallography and NMR spectroscopy. The crystal structure shows a 'Yin-Yang'-like packing mode, in which the modified β-CD exhibits a channel superstructure formed by a tail-to-tail dimer as the repeating motif with the substituted group embedded within the hydrophobic cavity of the facing β-CD. The geometry of the substituted group is determined by the inclusion of the cavity and is further stabilized by two intermolecular hydrogen bonds between the carbonyl O atom and phenyl group. Furthermore, NMR ROESY investigation indicates that the self-assembly behavior of the substituted group within the β-CD cavity is retained in aqueous solution, and the effective binding constant Ka was calculated to be 1330 M(-1) by means of (1)H NMR titration according to iterative determination. Copyright © 2014 Elsevier Ltd. All rights reserved.

Dual-Targeting Lactoferrin-Conjugated Polymerized Magnetic Polydiacetylene-Assembled Nanocarriers with Self-Responsive Fluorescence/Magnetic Resonance Imaging for In Vivo Brain Tumor Therapy.

PubMed

Fang, Jen-Hung; Chiu, Tsung-Lang; Huang, Wei-Chen; Lai, Yen-Ho; Hu, Shang-Hsiu; Chen, You-Yin; Chen, San-Yuan

2016-03-01

Maintaining a high concentration of therapeutic agents in the brain is difficult due to the restrictions of the blood-brain barrier (BBB) and rapid removal from blood circulation. To enable controlled drug release and enhance the blood-brain barrier (BBB)-crossing efficiency for brain tumor therapy, a new dual-targeting magnetic polydiacetylene nanocarriers (PDNCs) delivery system modified with lactoferrin (Lf) is developed. The PDNCs are synthesized using the ultraviolet (UV) cross-linkable 10,12-pentacosadiynoic acid (PCDA) monomers through spontaneous assembling onto the surface of superparamagnetic iron oxide (SPIO) nanoparticles to form micelles-polymerized structures. The results demonstrate that PDNCs will reduce the drug leakage and further control the drug release, and display self-responsive fluorescence upon intracellular uptake for cell trafficking and imaging-guided tumor treatment. The magnetic Lf-modified PDNCs with magnetic resonance imaging (MRI) and dual-targeting ability can enhance the transportation of the PDNCs across the BBB for tracking and targeting gliomas. An enhanced therapeutic efficiency can be obtained using Lf-Cur (Curcumin)-PDNCs by improving the retention time of the encapsulated Cur and producing fourfold higher Cur amounts in the brain compared to free Cur. Animal studies also confirm that Lf targeting and controlled release act synergistically to significantly suppress tumors in orthotopic brain-bearing rats. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development and application of 3-chloro-1,2-propandiol electrochemical sensor based on a polyaminothiophenol modified molecularly imprinted film.

PubMed

Sun, Xiulan; Zhang, Lijuan; Zhang, Hongxia; Qian, He; Zhang, Yinzhi; Tang, Lili; Li, Zaijun

2014-05-21

In this work, a novel electrochemical sensor for 3-chloro-1,2-propandiol (3-MCPD) detection based on a gold nanoparticle-modified glassy carbon electrode (AuNP/GCE) coated with a molecular imprinted polymer (MIP) film was constructed. p-Aminothiophenol (p-ATP) and 3-MCPD were self-assembled on a AuNP/GCE surface, and then a MIP film was formed by electropolymerization. The 3-MCPD template combined with p-ATP during self-assembly and electropolymerization, and the cavities matching 3-MCPD remained after the removal of the template. The MIP sensor was characterized by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and scanning electron microscopy (SEM). Many factors that affected the performance of the MIP membrane were discussed and optimized. Under optimal conditions, the DPV current was linear with the log of the 3-MCPD concentration in the range from 1.0 × 10(-17) to 1.0 × 10(-13) mol L(-1) (R(2) = 0.9939), and the detection limit was 3.8 × 10(-18) mol L(-1) (S/N = 3). The average recovery rate of 3-MCPD from spiked soy sauce samples ranged from 95.0% to 106.4% (RSD < 3.49%). Practically, the sensor showed high sensitivity, good selectivity, excellent reproducibility, and stability during the quantitative determination of 3-MCPD.

Integrated electrochemical gluconic acid biosensor based on self-assembled monolayer-modified gold electrodes. Application to the analysis of gluconic acid in musts and wines.

PubMed

Campuzano, S; Gamella, M; Serra, B; Reviejo, A J; Pingarrón, J M

2007-03-21

An integrated amperometric gluconic acid biosensor constructed using a gold electrode (AuE) modified with a self-assembled monolayer (SAM) of 3-mercaptopropionic acid (MPA) on which gluconate dehydrogenase (GADH, 0.84 U) and the mediator tetrathiafulvalene (TTF, 1.5 micromol) were coimmobilized by covering the electrode surface with a dialysis membrane is reported. The working conditions selected were Eapp=+0.15 V and 25+/-1 degrees C. The useful lifetime of one single TTF-GADH-MPA-AuE was surprisingly long. After 53 days of continuous use, the biosensor exhibited 86% of the original sensitivity. A linear calibration plot was obtained for gluconic acid over the 6.0x10(-7) to 2.0x10(-5) M concentration range, with a limit of detection of 1.9x10(-7) M. The effect of potential interferents (glucose, fructose, galactose, arabinose, and tartaric, citric, malic, ascorbic, gallic, and caffeic acids) on the biosensor response was evaluated. The behavior of the biosensor in a flow-injection system in connection with amperometric detection was tested. The analytical usefulness of the biosensor was evaluated by determining gluconic acid in wine and must samples, and the results obtained were validated by comparison with those provided by using a commercial enzyme test kit.

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.

Self-assembly of coiled coil peptides into nanoparticles vs 2-d plates: effects of assembly pathway

NASA Astrophysics Data System (ADS)

Kim, Kyunghee; Pochan, Darrin

Molecular solution assembly, or self-assembly, is a process by which ordered nanostructures or patterns are formed by non-covalent interactions during assembly. Biomimicry, the use of bioinspired molecules or biologically relevant materials, is an important area of self-assembly research with peptides serving a critical role as molecular tools. The morphology of peptide assemblies can be controlled by adjusting solution conditions such as the concentration of peptides, the temperature, and pH. Herein, spherical nanostructures, which have potential for creating an encapsulation system, are formed by self-assembly when coiled coil peptides are combined in solution. These peptides are homotrimeric and heterodimeric coiled-coil bundles and the homotrimer is connected with each of heterodimer through their external surfaces via disulfide bonds. The resultant covalent constructs could co-assemble into complementary trimeric hubs, respectively. The two peptide constructs are directly mixed and assembled in solution in order to produce either spherical particles or 2-d plates depending on the solution conditions and kinetic pathway of assembly. In particular, structural changes of the self-assembled peptides are explored by control of the thermal history of the assembly solution.

Self-Assembly Behavior of Pullulan Abietate

NASA Astrophysics Data System (ADS)

Gradwell, Sheila; Esker, Alan; Glasser, Wolgang; Heinze, Thomas

2003-03-01

Wood is one of nature's most fascinating biological composites due to its toughness and resistance to fracture properties. These properties stem from the self-assembly of cellulose microfibrils in an amorphous matrix of hemicellulose and lignin. In recent years, science has looked to nature for guidance in preparing synthetic materials with desirable physical properties. In order to study the self-assembly process in wood, a model system composed of a polysaccharide, pullulan abietate, and a biomimetic cellulose substrate prepared by the Langmuir-Blodgett technique has been developed. Interfacial tension and surface plasmon resonance measurements used to study the self-assembly process will be discussed for different pullulan derivatives.

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

Efficient inverted bulk-heterojunction polymer solar cells with self-assembled monolayer modified zinc oxide.

PubMed

Kim, Wook Hyun; Lyu, Hong-Kun; Han, Yoon Soo; Woo, Sungho

2013-10-01

The performance of poly(3-hexylthiophen) (P3HT) and [6, 6]phenyl C61 butyric acid methyl ester ([60]PCBM)-based inverted bulk-heterojunction (BHJ) polymer solar cells (PSCs) is enhanced by the modification of zinc oxide (ZnO)/BHJ interface with carboxylic-acid-functionalized self-assembled monolayers (SAMs). Under simulated solar illumination of AM 1.5 (100 mW/cm2), the inverted devices fabricated with SAM-modified ZnO achieved an enhanced power conversion efficiency (PCE) of 3.34% due to the increased fill factor and photocurrent density as compared to unmodified cells with PCE of 2.60%. This result provides an efficient method for interface engineering in inverted BHJ PSCs.

Self-assembled tunable networks of sticky colloidal particles

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

Demortiere, Arnaud; Snezhko, Oleksiy Alexey; Sapozhnikov, Maksim

Self-assembled tunable networks of microscopic polymer fibers ranging from wavy colloidal "fur" to highly interconnected networks are created from polymer systems and an applied electric field. The networks emerge via dynamic self-assembly in an alternating (ac) electric field from a non-aqueous suspension of "sticky" polymeric colloidal particles with a controlled degree of polymerization. The resulting architectures are tuned by the frequency and amplitude of the electric field and surface properties of the particles.

Theoretical Study of the Initial Stages of Self-Assembly of a Carboxysome’s Facet

DOE PAGES

Mahalik, J. P.; Brown, Kirsten A.; Cheng, Xiaolin; ...

2016-02-24

Bacterial microcompartments, BMCs, are organelles that exist within wide variety of bacteria and act as nanofactories. Among the different types of known BMCs, the carboxysome has been studied the most. The carboxysome plays an important role in the light-independent part of the photosynthesis process, where its icosahedral-like proteinaceous shell acts as a membrane that controls the transport of metabolites. Although a structural model exists for the carboxysome shell, it remains largely unknown how the shell proteins self-assemble. Understanding the self-assembly process can provide insights into how the shell affects the carboxysome s function and how it can be modified tomore » create new functionalities, such as artificial nanoreactors and artificial protein membranes. Here, we explain a theoretical framework that employs Monte Carlo simulations with a coarse-grain potential that reproduces well the atomistic potential of mean force; employing this framework, we are able to capture the initial stages of the 2D self-assembly of CcmK2 hexamers, a major protein-shell component of the carboxysome's facet. The simulations reveal that CcmK2 hexamers self-assemble into clusters that resemble what was seen experimentally in 2D layers. Further analysis of the simulation results suggests that the 2D self-assembly of carboxysome s facets is driven by a nucleation growth process, which in turn could play an important role in the hierarchical self- assembly of BMC shells in general.« less

Self-assembly of gold nanorods into symmetric superlattices directed by OH-terminated hexa(ethylene glycol) alkanethiol.

PubMed

Xie, Yong; Guo, Shengming; Ji, Yinglu; Guo, Chuanfei; Liu, Xinfeng; Chen, Ziyu; Wu, Xiaochun; Liu, Qian

2011-09-20

The self-assembly of anisotropic gold nanorods (GNRs) into ordered phases remains a challenge. Herein, we demonstrated the fabrication of symmetric circular- or semicircular-like self-assembled superlattices composed of multilayers of standing GNRs by fine-tuning the repulsive interactions among GNRs. The repulsive force is tailored from electrostatic interaction to steric force by replacing the surface coating of cetyltrimethylammonium bromide (CTAB) (ζ potential of 20-50 mV) with an OH-terminated hexa(ethylene glycol) alkanethiol (here termed as EG(6)OH, ζ potential of -10 mV). The assembly mechanism is discussed via theoretical analyses of the major interactions, and an effective balance between the repulsive steric and attractive depletion interactions is the main driving force for the self-assembly. The real-time observations of solution assembly (UV-vis-NIR absorption spectroscopy) supports the mechanism that we suggested. The superlattices obtained here not only enrich the categories of the self-assembled structures but more importantly deepen the insight of the self-assembly process and pave the way for various potential applications. © 2011 American Chemical Society

Self-assembling of calcium salt of the new DNA base 5-carboxylcytosine

NASA Astrophysics Data System (ADS)

Irrera, Simona; Ruiz-Hernandez, Sergio E.; Reggente, Melania; Passeri, Daniele; Natali, Marco; Gala, Fabrizio; Zollo, Giuseppe; Rossi, Marco; Portalone, Gustavo

2017-06-01

Supramolecular architectures involving DNA bases can have a strong impact in several fields such as nanomedicine and nanodevice manufacturing. To date, in addition to the four canonical nucleobases (adenine, thymine, guanine and cytosine), four other forms of cytosine modified at the 5 position have been identified in DNA. Among these four new cytosine derivatives, 5-carboxylcytosine has been recently discovered in mammalian stem cell DNA, and proposed as the final product of the oxidative epigenetic demethylation pathway on the 5 position of cytosine. In this work, a calcium salt of 5-carboxylcytosine has been synthesized and deposited on graphite surface, where it forms self-assembled features as long range monolayers and up to one micron long filaments. These structures have been analyzed in details combining different theoretical and experimental approaches: X-ray single-crystal diffraction data were used to simulate the molecule-graphite interaction, first using molecular dynamics and then refining the results using density functional theory (DFT); finally, data obtained with DFT were used to rationalize atomic force microscopy (AFM) results.

Ultra-tough and strong, hybrid thin films based on ionically crosslinked polymers and 2D inorganic platelets

NASA Astrophysics Data System (ADS)

Ji, Dong Hwan; Choi, Suji; Kim, Jaeyun; nanobiomaterials lab Team

Integration of high strength and toughness tend to be mutually exclusive and synthesized hybrid films with superior mechanical properties have been difficult to fabricate controllable shapes and various scales. Although diverse synthesized hybrid films consisting of organic matrix and inorganic materials with brick-and-mortar structure, show improved mechanical properties, these films are still limited in toughness and fabrication methods. Herein, we report ultra-tough and strong hybrid thin films with self-assembled uniform microstructures with controllable shapes and various scale based on hydrogel-mediated process. Ca2+-crosslinking in alginate chains and well-aligned alumina platelets in alginate matrix lead to a synergistic enhancement of strength and toughness in the resulting film. Consequentially, Ca2+-crosslinked Alg/Alu films showed outstanding toughness of 29 MJ m-3 and tensile strength of 160 MPa. Furthermore, modifying Alu surface with polyvinylpyrrolidone (PVP), tensile strength was further improved up to 200 MPa. Our results suggest an alternative approach to design and processing of self-assembled hydrogel-mediated hybrid films with outstanding mechanical properties.

Self-Assembly of Antisite Defectless nano-LiFePO4 @C/Reduced Graphene Oxide Microspheres for High-Performance Lithium-Ion Batteries.

PubMed

Wang, Hongbin; Liu, Lijia; Wang, Runwei; Yan, Xiao; Wang, Ziqi; Hu, Jiangtao; Chen, Haibiao; Jiang, Shang; Ni, Ling; Qiu, Hailong; Tang, Haitong; Wei, Yingjin; Zhang, Zongtao; Qiu, Shilun; Pan, Feng

2018-05-18

LiFePO 4 @C/reduced graphene oxide (rGO) hierarchical microspheres with superior electrochemical activity and a high tap density were first synthesized by using a Fe 3+ -based single inorganic precursor (LiFePO 4 OH@RF/GO; RF=resorcinol-formaldehyde, GO=graphene oxide) obtained from a template-free self-assembly synthesis followed by direct calcination. The synthetic process requires no physical mixing step. The phase transformation pathway from tavorite LiFePO 4 OH to olivine LiFePO 4 upon calcination was determined by means of the in situ high-temperature XRD technique. Benefitting from the unique structure of the material, these microspheres can be densely packed together, giving a high tap density of 1.3 g cm -3 , and simultaneously, defectless LiFePO 4 primary nanocrystals modified with a highly conductive surface carbon layer and ultrathin rGO provide good electronic and ionic kinetics for fast electron/Li + ion transport. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-Assembled Nanocarriers Based on Amphiphilic Natural Polymers for Anti- Cancer Drug Delivery Applications.

PubMed

Sabra, Sally; Abdelmoneem, Mona; Abdelwakil, Mahmoud; Mabrouk, Moustafa Taha; Anwar, Doaa; Mohamed, Rania; Khattab, Sherine; Bekhit, Adnan; Elkhodairy, Kadria; Freag, May; Elzoghby, Ahmed

2017-01-01

Micellization provides numerous merits for the delivery of water insoluble anti-cancer therapeutic agents including a nanosized 'core-shell' drug delivery system. Recently, hydrophobically-modified polysaccharides and proteins are attracting much attention as micelle forming polymers to entrap poorly soluble anti-cancer drugs. By virtue of their small size, the self-assembled micelles can passively target tumor tissues via enhanced permeation and retention effect (EPR). Moreover, the amphiphilic micelles can be exploited for active-targeted drug delivery by attaching specific targeting ligands to the outer micellar hydrophilic surface. Here, we review the conjugation techniques, drug loading methods, physicochemical characteristics of the most important amphiphilic polysaccharides and proteins used as anti-cancer drug delivery systems. Attention focuses on the mechanisms of tumor-targeting and enhanced anti-tumor efficacy of the encapsulated drugs. This review will highlight the remarkable advances of hydrophobized polysaccharide and protein micelles and their potential applications as anti-cancer drug delivery nanosystems. Micellar nanocarriers fabricated from amphiphilic natural polymers hold great promise as vehicles for anti-cancer drugs. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Self-Assembly of Octopus Nanoparticles into Pre-Programmed Finite Clusters

NASA Astrophysics Data System (ADS)

Halverson, Jonathan; Tkachenko, Alexei

2012-02-01

The precise control of the spatial arrangement of nanoparticles (NP) is often required to take full advantage of their novel optical and electronic properties. NPs have been shown to self-assemble into crystalline structures using either patchy surface regions or complementary DNA strands to direct the assembly. Due to a lack of specificity of the interactions these methods lead to only a limited number of structures. An emerging approach is to bind ssDNA at specific sites on the particle surface making so-called octopus NPs. Using octopus NPs we investigate the inverse problem of the self-assembly of finite clusters. That is, for a given target cluster (e.g., arranging the NPs on the vertices of a dodecahedron) what are the minimum number of complementary DNA strands needed for the robust self-assembly of the cluster from an initially homogeneous NP solution? Based on the results of Brownian dynamics simulations we have compiled a set of design rules for various target clusters including cubes, pyramids, dodecahedrons and truncated icosahedrons. Our approach leads to control over the kinetic pathway and has demonstrated nearly perfect yield of the target.

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.

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.

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

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.

Peristalticity-driven banded chemical garden

NASA Astrophysics Data System (ADS)

Pópity-Tóth, É.; Schuszter, G.; Horváth, D.; Tóth, Á.

2018-05-01

Complex structures in nature are often formed by self-assembly. In order to mimic the formation, to enhance the production, or to modify the structures, easy-to-use methods are sought to couple engineering and self-assembly. Chemical-garden-like precipitation reactions are frequently used to study such couplings because of the intrinsic chemical and hydrodynamic interplays. In this work, we present a simple method of applying periodic pressure fluctuations given by a peristaltic pump which can be used to achieve regularly banded precipitate membranes in the copper-phosphate system.

Study of strain boundary conditions and GaAs buffer sizes in InGaAs quantum dots

NASA Technical Reports Server (NTRS)

Oyafuso, F.; Klimeck, G.; Boykin, T. B.; Bowen, R. C.; Allmen, P. von

2003-01-01

NEMO 3-D has been developed for the simulation of electronic structure in self-assembled InGaAs quantum dots on GaAs substrates. Typical self-assembled quantum dots in that material system contain about 0.5 to 1 million atoms. Effects of strain by the surrounding GaAs buffer modify the electronic structure inside the quantum dot significantly and a large GaAs buffer must be included in the strain and electronic structure.

Osseointegration properties of titanium dental implants modified with a nanostructured coating based on ordered porous silica and bioactive glass nanoparticles

NASA Astrophysics Data System (ADS)

Covarrubias, Cristian; Mattmann, Matías; Von Marttens, Alfredo; Caviedes, Pablo; Arriagada, Cristián; Valenzuela, Francisco; Rodríguez, Juan Pablo; Corral, Camila

2016-02-01

The fabrication of a nanoporous silica coating loaded with bioactive glass nanoparticles (nBG/NSC) on titanium dental implant surface and its in vitro and in vivo evaluation is presented. The coating was produced by a combined sol-gel and evaporation induced self-assembly process. In vitro bioactivity was assessed in simulated body fluid (SBF) and investigating the osteogenic differentiation of human bone marrow mesenchymal stem cells (hBMSCs). A rat tibial model was employed to analyze the bone response to nBG/NSC-modified titanium implant surface in vivo. The nBG/NSC coating was confirmed at nano level to be constituted by a highly ordered nanoporous silica structure. The coating nanotopography in conjunction with the bioactivity of the BG particles accelerate the in vitro apatite formation and promote the osteogenic differentiation of hBMSCs in absence of osteogenic supplements. These properties accelerate the formation of bone tissue in the periphery of the implant after 3 weeks of implantation. Backscattered scanning electron microscopy images revealed the presence of gaps and soft tissue in the unmodified implant after 6 weeks, whereas the nBG/NSC-modified implant showed mature bone in intimate contact with the implant surface. The nBG/NSC coating appears promising for accelerating the osseointegration of dental implants.

The effects of motif net charge and amphiphilicity on the self-assembly of functionally designer RADA16-I peptides.

PubMed

Wu, Dongni; Zhang, Shuangying; Zhao, Yuyuan; Ao, Ningjian; Ramakrishna, Seeram; He, Liumin

2018-03-16

RADA16-I (Ac-(RADA) 4 -CONH 2 ) is a widely investigated self-assembling peptide (SAP) in the biomedical field. It can undergo ordered self-assembly to form stable secondary structures, thereby further forming a nanofiber hydrogel. The modification of RADA16-I with functional peptide motifs has become a popular research topic. Researchers aim to exhibit particular biomedical signaling, and subsequently, further expand its applications. However, only a few fundamental reports are available on the influences of the peptide motifs on self-assembly mechanisms of designer functional RADA16-I SAPs. In this study, we designed RGD-modified RADA16-I SAPs with a series of net charges and amphiphilicities. The assembly/reassembly of these functionally designer SAPs was thoroughly studied using Raman spectroscopy, CD spectroscopy, and AFM. The nanofiber morphology and the secondary structure largely depended on the balance between the hydrophobic effects versus like-charge repulsions of the motifs, which should be to the focus in order to achieve a tailored nanostructure. Our study would contribute insight into considerations for sophisticated design of SAPs for biomedical applications.

Modified silicas with different structure of grafted methylphenylsiloxane layer

NASA Astrophysics Data System (ADS)

Bolbukh, Yuliia; Terpiłowski, Konrad; Kozakevych, Roman; Sternik, Dariusz; Deryło-Marczewska, Anna; Tertykh, Valentin

2016-06-01

The method of a chemical assembly of the surface polymeric layer with high contents of the modifying agent was developed. Powders of nanodispersed silica with chemisorbed polymethylphenylsiloxane (PMPS) were synthesized by solvent-free chemical assembly technique with a dimethyl carbonate (DMC) as scission agent. Samples were characterized using FTIR spectroscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM), and elemental analysis (CHN analysis). Coating microstructure, morphology, and hydrophilic-hydrophobic properties of nanoparticles were estimated. The results indicate a significant effect of the PMPS/DMC ratio at each modification stage on hydrophobic properties of modified silicas. Modification with a similar composition of the PMPS/DMC mixture, even with different polymer amount at each stage, provides the worst hydrophobicity. Results suggest that the highest hydrophobicity (contact angle θ = 135°-140°) is achieved in the case when silica modified with the PMPS/DMC mixture using multistage approach that providing a formation of the monomolecular layer of polysiloxane at the first modification step. The characteristics of surface structure were interpreted in terms of density of polymer-silica bonds at the interfaces that, usually, are reduced for modified surfaces, in a coupling with conformation model that accented the shape of chains (arch- and console-like) adsorbed on solid surfaces.

Self-assembly of (perfluoroalkyl)alkanes on a substrate surface from solutions in supercritical carbon dioxide.

PubMed

Gallyamov, Marat O; Mourran, Ahmed; Tartsch, Bernd; Vinokur, Rostislav A; Nikitin, Lev N; Khokhlov, Alexei R; Schaumburg, Kjeld; Möller, Martin

2006-06-14

Toroidal self-assembled structures of perfluorododecylnonadecane and perfluorotetradecyloctadecane have been deposited on mica and highly oriented pyrolytic graphite surfaces by exposure of the substrates to solutions of the (pefluoroalkyl)alkanes in supercritical carbon dioxide. Scanning force microscopy (SFM) images have displayed a high degree of regularity of these self-assembled nanoobjects regarding size, shape, and packing in a monolayer. Analysis of SFM images allowed us to estimate that each toroidal domain has an outer diameter of about 50 nm and consists of several thousands of molecules. We propose a simple model explaining the clustering of the molecules to objects with a finite size. The model based on the close-packing principles predicts formation of toroids, whose size is determined by the molecular geometry. Here, we consider the amphiphilic nature of the (perfluoroalkyl)alkane molecules in combination with incommensurable packing parameters of the alkyl- and the perfluoralkyl-segments to be a key factor for such a self-assembly.

Liquid Crystalline Assembly of Coil-Rod-Coil Molecules with Lateral Methyl Groups into 3-D Hexagonal and Tetragonal Assemblies

PubMed Central

Wang, Zhuoshi; Lan, Yu; Zhong, Keli; Liang, Yongri; Chen, Tie; Jin, Long Yi

2014-01-01

In this paper, we report the synthesis and self-assembly behavior of coil-rod-coil molecules, consisting of three biphenyls linked through a vinylene unit as a conjugated rod segment and poly(ethylene oxide) (PEO) with a degree of polymerization (DP) of 7, 12 and 17, incorporating lateral methyl groups between the rod and coil segments as the coil segment. Self-organized investigation of these molecules by means of differential scanning calorimetry (DSC), thermal polarized optical microscopy (POM) and X-ray diffraction (XRD) reveals that the lateral methyl groups attached to the surface of rod and coil segments, dramatically influence the self-assembling behavior in the liquid-crystalline mesophase. Molecule 1 with a relatively short PEO coil length (DP = 7) self-assembles into rectangular and oblique 2-dimensional columnar assemblies, whereas molecules 2 and 3 with DP of 12 and 17 respectively, spontaneously self-organize into unusual 3-dimensional hexagonal close-packed or body-centered tetragonal assemblies. PMID:24699045

Electric field induced self-assembly of monolayers of gold nanoparticles for surface enhanced Raman scattering applications

NASA Astrophysics Data System (ADS)

Das, Suchandra; Musunuri, Naga; Kucheryavy, Pavel; Lockard, Jenny; Fischer, Ian; Singh, Pushpendra; New Jersey Institute of Technology Collaboration; Rutgers University Newark Collaboration

2017-11-01

We present a technique that uses an electric field in the direction normal to the interface for self-assembling monolayers of gold nanoparticles on fluid-liquid interfaces and freezing these monolayers onto the surface of a flexible thin film. The electric field gives rise to dipole-dipole and capillary forces which cause the particles to arrange in a triangular pattern. The technique involves assembling the monolayer on the interface between a UV-curable resin and another fluid by applying an electric field, and then curing the resin by applying UV light. The monolayer becomes embedded on the surface of the solidified resin film. We are using these films for surface enhanced Raman scattering (SERS) applications. Initial measurements indicate improved performance over commercially available SERS substrates.

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

PubMed

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

2017-02-01

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

Targeted partial surface modification with nano-SiO2@Li2CoPO4F as high-voltage cathode material for LIBs

NASA Astrophysics Data System (ADS)

Chang, Caiyun; Huang, Zhipeng; Tian, Runsai; Jiang, Xinyu; Li, Chunsheng; Feng, Jijun

2017-10-01

Tuning whole/partial surface modification on cathode material with oxide material is a sought-after method to enhance the electrochemical performance in power storage field. Herein, nano-SiO2 targeted partial surface modified high voltage cathode material Li2CoPO4F has been successfully fabricated via a facile self-assembly process in silica dispersion at ambient temperature. With the aid of polar -OH groups attracted on the surface of SiO2 micelles, the nano-SiO2 preferentially nestle up along the borders and boundaries of Li2CoPO4F particles, where protection should be deployed with emphasis against the undesirable interactions between materials and electrolytes. Compared with pristine Li2CoPO4F, the SiO2 selectively modified Li2CoPO4F cathode materials, especially LCPF-3S, exhibit desirable electrochemical performances with higher discharge capacity, more outstanding cycle stability and favorable rate capability without any additional carbon involved. The greatly enhanced electrochemical properties can be attributed to the improved lithium-ion diffusion kinetics and structure tolerance during repeated lithiation/delithiation process. Such findings reveal a great potential of nano-SiO2 modified Li2CoPO4F as high energy cathode material for lithium ion batteries.

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

Novel High-Activity Organic Piezoelectric Materials - From Single-Molecule Response to Energy Harvesting Films

DTIC Science & Technology

2015-08-24

microcontact printing techniques to deposit and pattern intrinsically polar self - assembled monolayers (SAMs) on smooth template-stripped gold films...and large piezoresponse. Stamp Stamp Gold Gold 10 μm 10 μ m 1.5 1.0 0.5 0.0 -0.5 -1.0 -1.5 nm Fig. 7. Patterned self - assembled monolayers of...SAM. Importantly, deposition and patterning of thiol self - assembled monolayers on gold surfaces is facile, creating in intrinsically polar film for

M13 Bacteriophage-Based Self-Assembly Structures and Their Functional Capabilities.

PubMed

Moon, Jong-Sik; Kim, Won-Geun; Kim, Chuntae; Park, Geun-Tae; Heo, Jeong; Yoo, So Y; Oh, Jin-Woo

2015-06-01

Controlling the assembly of basic structural building blocks in a systematic and orderly fashion is an emerging issue in various areas of science and engineering such as physics, chemistry, material science, biological engineering, and electrical engineering. The self-assembly technique, among many other kinds of ordering techniques, has several unique advantages and the M13 bacteriophage can be utilized as part of this technique. The M13 bacteriophage (Phage) can easily be modified genetically and chemically to demonstrate specific functions. This allows for its use as a template to determine the homogeneous distribution and percolated network structures of inorganic nanostructures under ambient conditions. Inexpensive and environmentally friendly synthesis can be achieved by using the M13 bacteriophage as a novel functional building block. Here, we discuss recent advances in the application of M13 bacteriophage self-assembly structures and the future of this technology.

M13 Bacteriophage-Based Self-Assembly Structures and Their Functional Capabilities

PubMed Central

Moon, Jong-Sik; Kim, Won-Geun; Kim, Chuntae; Park, Geun-Tae; Heo, Jeong; Yoo, So Y; Oh, Jin-Woo

2015-01-01

Controlling the assembly of basic structural building blocks in a systematic and orderly fashion is an emerging issue in various areas of science and engineering such as physics, chemistry, material science, biological engineering, and electrical engineering. The self-assembly technique, among many other kinds of ordering techniques, has several unique advantages and the M13 bacteriophage can be utilized as part of this technique. The M13 bacteriophage (Phage) can easily be modified genetically and chemically to demonstrate specific functions. This allows for its use as a template to determine the homogeneous distribution and percolated network structures of inorganic nanostructures under ambient conditions. Inexpensive and environmentally friendly synthesis can be achieved by using the M13 bacteriophage as a novel functional building block. Here, we discuss recent advances in the application of M13 bacteriophage self-assembly structures and the future of this technology. PMID:26146494

Micro Galvanic Cell To Generate PtO and Extend the Triple-Phase Boundary during Self-Assembly of Pt/C and Nafion for Catalyst Layers of PEMFC.

PubMed

Long, Zhi; Gao, Liqin; Li, Yankai; Kang, Baotao; Lee, Jin Yong; Ge, Junjie; Liu, Changpeng; Ma, Shuhua; Jin, Zhao; Ai, Hongqi

2017-11-08

The self-assembly powder (SAP) with varying Nafion content was synthesized and characterized by XRD, XPS, HRTEM, and mapping. It is observed that the oxygen from oxygen functional groups transfers to the surface of Pt and generate PtO during the process of self-assembly with the mechanism of micro galvanic cell, where Pt, carbon black, and Nafion act as the anode, cathode and electrolyte, respectively. The appearance of PtO on the surface of Pt leads to a turnover of Nafion structure, and therefore more hydrophilic sulfonic groups directly contact with Pt, and thus the triple-phase boundary (TPB) has been expanded.

Controllable Nanoparticle Assembly and Actuation with Modified Dipole Potentials in Simulation

NASA Astrophysics Data System (ADS)

Dempster, Joshua

Science at the nanoscale poses several recurring difficulties. How can we control the assembly of objects too small for direct manipulation to be practical? How can we extend that control to in vivo systems so we can make use of nanotechnology in medicine? And how can we recreate the extraordinary capacities of Nature: healing, replication, growth, adaptation, self-regulation? One of the most powerful tools for addressing these challenges is the simple, familiar dipole moment. Since their debut as fuel control devices at NASA in the early sixties, possible applications for dipole suspensions have grown to areas far beyond what their creators envisioned. A multitude of ambitious new medical and mechanical applications make use of dipolar colloids. Dipoles are attractive from a practical standpoint because one can use fields to control not just their orientation and location, but also their mutual interactions. From a physical standpoint, dipoles are compelling as an exceptionally simple form of symmetry-breaking that leads to a variety of complex phenomena. This thesis studies the assembly and control of spherical colloids with a dipolar interaction modified by additional conditions using simulations. Three cases are examined in detail. The first is the case of an electrical dipole moment created by regions of opposite charge density on the surface of a colloid. Here the dipole potential is modified by strong screening. Such a system is interesting as a model for certain proteins in a high-salt solution and suggests possible uses for inverse Janus colloids. The resulting phases have little resemblance to the usual dipole phases and can be controlled with small quantities of homogeneously charged particles. In the second case, superparamagnetic dipoles are linked into chains. Such chains have been realized in a wide variety of experimental schemes. A general theory is developed for the equilibrium shapes of the chains in a precessing field when their endpoints are fixed. This theory reveals that the chains are good candidates for contracting muscles in microscopic devices with a conveniently harmonic form for their potentials. Ensembles of free chains can be put to more elaborate uses. To illustrate, a regime is designed that spins the chains into a self-healing cross-linked gel. Finally, we will turn to self-replication. Decorating a permanent dipole with a single permanent binding site is enough to enable self-replication using dimers as the template. A periodic magnetic drive provides the energy to drive replication. Several theoretical principles regarding the statistics of linear self-replicators are deduced and used to optimize the dipole replicating system.

Electrostatic Self-Assembly of Diamond Nanoparticles onto Al- and N-Polar Sputtered Aluminum Nitride Surfaces.

PubMed

Yoshikawa, Taro; Reusch, Markus; Zuerbig, Verena; Cimalla, Volker; Lee, Kee-Han; Kurzyp, Magdalena; Arnault, Jean-Charles; Nebel, Christoph E; Ambacher, Oliver; Lebedev, Vadim

2016-11-17

Electrostatic self-assembly of diamond nanoparticles (DNPs) onto substrate surfaces (so-called nanodiamond seeding) is a notable technique, enabling chemical vapor deposition (CVD) of nanocrystalline diamond thin films on non-diamond substrates. In this study, we examine this technique onto differently polarized (either Al- or N-polar) c -axis oriented sputtered aluminum nitride (AlN) film surfaces. This investigation shows that Al-polar films, as compared to N-polar ones, obtain DNPs with higher density and more homogeneously on their surfaces. The origin of these differences in density and homogeneity is discussed based on the hydrolysis behavior of AlN surfaces in aqueous suspensions.

Formation and Characterization of Self-Assembled Phenylboronic Acid Derivative Monolayers toward Developing Monosaccharide Sensing-Interface

PubMed Central

Chen, Hongxia; Lee, Minsu; Lee, Jaebeom; Kim, Jae-Ho; Gal, Yeong-Soon; Hwang, Yoon-Hwae; An, Won Gun; Koh, Kwangnak

2007-01-01

We designed and synthesized phenylboronic acid as a molecular recognition model system for saccharide detection. The phenylboronic acid derivatives that have boronic acid moiety are well known to interact with saccharides in aqueous solution; thus, they can be applied to a functional interface of saccharide sensing through the formation of self-assembled monolayer (SAM). In this study, self-assembled phenylboronic acid derivative monolayers were formed on Au surface and carefully characterized by atomic force microscopy (AFM), Fourier transform infrared reflection absorption spectroscopy (FTIR-RAS), surface enhanced Raman spectroscopy (SERS), and surface electrochemical measurements. The saccharide sensing application was investigated using surface plasmon resonance (SPR) spectroscopy. The phenylboronic acid monolayers showed good sensitivity of monosaccharide sensing even at the low concentration range (1.0 × 10−12 M). The SPR angle shift derived from interaction between phenylboronic acid and monosaccharide was increased with increasing the alkyl spacer length of synthesized phenylboronic acid derivatives.

Self-assembled molecular magnets on patterned silicon substrates: bridging bio-molecules with nanoelectronics.

PubMed

Chang, Chia-Ching; Sun, Kien Wen; Lee, Shang-Fan; Kan, Lou-Sing

2007-04-01

The paper reports the methods of preparing molecular magnets and patterning of the molecules on a semiconductor surface. A highly magnetically aligned metallothionein containing Mn and Cd (Mn,Cd-MT-2) is first synthesized, and the molecules are then placed into nanopores prepared on silicon (001) surfaces using electron beam lithography and reactive ion-etching techniques. We have observed the self-assemble growth of the MT molecules on the patterned Si surface such that the MT molecules have grown into rod or ring type three-dimensional nanostructures, depending on the patterned nanostructures on the surface. We also provide scanning electron microscopy, atomic force microscopy, and magnetic force microscope studies of the molecular nanostructures. This engineered molecule shows molecular magnetization and is biocompatible with conventional semiconductors. These features make Mn,Cd-MT-2 a good candidate for biological applications and sensing sources of new nanodevices. Using molecular self-assembly and topographical patterning of the semiconductor substrate, we can close the gap between bio-molecules and nanoelectronics built into the semiconductor chip.

Fabrication and characteristics of MOSFET protein chip for detection of ribosomal protein.

PubMed

Park, Keun-Yong; Kim, Min-Suk; Choi, Sie-Young

2005-04-15

A metal oxide silicon field effect transistor (MOSFET) protein chip for the easy detection of protein was fabricated and its characteristics were investigated. Generally, the drain current of the MOSFET is varied by the gate potential. It is expected that the formation of an antibody-antigen complex on the gate of MOSFET would lead to a detectable change in the charge distribution and thus, directly modulate the drain current of MOSFET. As such, the drain current of the MOSFET protein chip can be varied by ribosomal proteins absorbed by the self-assembled monolayer (SAM) immobilized on the gate (Au) surface, as ribosomal protein has positive charge, and these current variations then used as the response of the protein chip. The gate of MOSFET protein chip is not directly biased by an external voltage source, so called open gate or floating gate MOSFET, but rather chemically modified by immobilized molecular receptors called self-assembled monolayer (SAM). In our experiments, the current variation in the proposed protein chip was about 8% with a protein concentration of 0.7 mM. As the protein concentration increased, the drain current also gradually increased. In addition, there were some drift of the drain current in the device. It is considered that these drift might be caused by the drift from the MOSFET itself or protein absorption procedures that are relied on the facile attachment of thiol (-S) ligands to the gate (Au) surface. We verified the formation of SAM on the gold surface and the absorption of protein through the surface plasmon resonance (SPR) measurement.

Collagen peptide-based biomaterials for protein delivery and peptide-promoted self-assembly of gold nanoparticles

NASA Astrophysics Data System (ADS)

Ernenwein, Dawn M.

2011-12-01

Bottom-up self-assembly of peptides has driven the research progress for the following two projects: protein delivery vehicles of collagen microflorettes and the assembly of gold nanoparticles with coiled-coil peptides. Collagen is the most abundant protein in the mammals yet due to immunogenic responses, batch-to-batch variability and lack of sequence modifications, synthetic collagen has been designed to self-assemble into native collagen-like structures. In particular with this research, metal binding ligands were incorporated on the termini of collagen-like peptides to generate micron-sized particles, microflorettes. The over-arching goal of the first research project is to engineer MRI-active microflorettes, loaded with His-tagged growth factors with differential release rates while bound to stem cells that can be implemented toward regenerative cell-based therapies. His-tagged proteins, such as green fluorescent protein, have successfully been incorporated on the surface and throughout the microflorettes. Protein release was monitored under physiological conditions and was related to particle degradation. In human plasma full release was obtained within six days. Stability of the microflorettes under physiological conditions was also examined for the development of a therapeutically relevant delivery agent. Additionally, MRI active microflorettes have been generated through the incorporation of a gadolinium binding ligand, DOTA within the collagen-based peptide sequence. To probe peptide-promoted self-assemblies of gold nanoparticles (GNPs) by non-covalent, charge complementary interactions, a highly anionic coiled-coil peptide was designed and synthesized. Upon formation of peptide-GNP interactions, the hydrophobic domain of the coiled-coil were shown to promote the self-assembly of peptide-GNPs clustering. Hydrophobic forces were found to play an important role in the assembly process, as a peptide with an equally overall negative charge, but lacking an ordered hydrophobic face had no effect on GNP assembly. The self-assembly system herein is advantageous due to its reversible nature upon addition of high salt concentrations which masks the surface charge. There is great potential for using this uniquely designed self-assembled peptide-gold nanoparticle system for exploring the interplay between peptide ligation and GNP self-assembly.

Nanofibers of Human Tropoelastin-inspired peptides: Structural characterization and biological properties.

PubMed

Secchi, Valeria; Franchi, Stefano; Fioramonti, Marco; Polzonetti, Giovanni; Iucci, Giovanna; Bochicchio, Brigida; Battocchio, Chiara

2017-08-01

Regenerative medicine is taking great advantage from the use of biomaterials in the treatments of a wide range of diseases and injuries. Among other biomaterials, self-assembling peptides are appealing systems due to their ability to spontaneously form nanostructured hydrogels that can be directly injected into lesions. Indeed, self-assembling peptide scaffolds are expected to behave as biomimetic matrices able to surround cells, to promote specific interactions, and to control and modify cell behavior by mimicking the native environment as well. We selected three pentadecapeptides inspired by Human Tropoelastin, a natural protein of the extracellular matrix, expected to show high biocompatibility. Moreover, the here proposed self-assembling peptides (SAPs) are able to spontaneously aggregate in nanofibers in biological environment, as revealed by AFM (Atomic Force Microscopy). Peptides were characterized by XPS (X-ray Photoelectron Spectroscopy) and IRRAS (Infrared Reflection Absorption Spectroscopy) both as lyophilized (not aggregated) and as aggregated (nanofibers) samples in order to investigate some potential differences in their chemical composition and intermolecular interactions, and to analyze the surface and interface of nanofibers. Finally, an accurate investigation of the biological properties of the SAPs and of their interaction with cells was performed by culturing for the first time human Mesenchymal Stem Cells (hMSCs) in presence of SAPs. The final aim of this work was to assess if Human Tropoelastin-inspired nanostructured fibers could exert a cytotoxic effect and to evaluate their biocompatibility, cellular adhesion and proliferation. Copyright © 2017 Elsevier B.V. All rights reserved.

Far-from-equilibrium magnetic granular layers: dynamic patterns, magnetic order and self-assembled swimmers

NASA Astrophysics Data System (ADS)

Snezhko, Alexey

2010-03-01

Ensembles of interacting particles subject to an external periodic forcing often develop nontrivial collective behavior and self-assembled dynamic patterns. We study emergent phenomena in magnetic granular ensembles suspended at a liquid-air and liquid-liquid interfaces and subjected to a transversal alternating magnetic field. Experiments reveal a new type of nontrivially ordered dynamic self-assembled structures (in particular, ``magnetic snakes'', ``asters'', ``clams'') emerging in such systems in a certain range of excitation parameters. These non-equilibrium dynamic structures emerge as a result of the competition between magnetic and hydrodynamic forces and have complex magnetic ordering. Transition between different self-assembled phases with parameters of external driving magnetic field is observed. I will show that above some frequency threshold magnetic snakes spontaneously break the symmetry of the self-induced surface flows (symmetry breaking instability) and turn into swimmers. Self-induced surface flows symmetry can be also broken in a controlled fashion by introduction of a large bead to a magnetic snake (bead-snake hybrid), that transforms it into a robust self-locomoting entity. Some features of the self-localized structures can be understood in the framework of an amplitude equation for parametric waves coupled to the conservation law equation describing the evolution of the magnetic particle density and the Navier-Stokes equation for hydrodynamic flows.

Preface: special topic on supramolecular self-assembly at surfaces.

PubMed

Bartels, Ludwig; Ernst, Karl-Heinz; Gao, Hong-Jun; Thiel, Patricia A

2015-03-14

Supramolecular self-assembly at surfaces is one of the most exciting and active fields in Surface Science today. Applications can take advantage of two key properties: (i) versatile pattern formation over a broad length scale and (ii) tunability of electronic structure and transport properties, as well as frontier orbital alignment. It provides a new frontier for Chemical Physics as it uniquely combines the versatility of Organic Synthesis and the Physics of Interfaces. The Journal of Chemical Physics is pleased to publish this Special Topic Issue, showcasing recent advances and new directions.

Giant Enhancement of Small Photoluminescent Signals on Glass Surfaces Covered by Self-Assembled Silver Nanorings.

PubMed

Sousanis, A; Poulopoulos, P; Karoutsos, V; Trachylis, D; Politis, C

2017-02-01

Self-assembled nanostructures with the shape of nanospheres or nanorings were formed after annealing of ultrathin Ag films grown on glass, in a furnace with air at 460 °C. Intense localized surface plasmon resonances were recorded for these nanostructures with maxima at the green-blue light. The surface became functional in terms of enhancing the weak photoluminescence of glass between 2–400 times. This system provides an easy way of enhancing the photoluminescence emission of initially low performance materials.

High-Resolution Structure of a Self-Assembly-Competent Form of a Hydrophobic Peptide Captured in a Soluble [beta]-Sheet Scaffold

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

Makabe, Koki; Biancalana, Matthew; Yan, Shude

2010-02-08

{beta}-Rich self-assembly is a major structural class of polypeptides, but still little is known about its atomic structures and biophysical properties. Major impediments for structural and biophysical studies of peptide self-assemblies include their insolubility and heterogeneous composition. We have developed a model system, termed peptide self-assembly mimic (PSAM), based on the single-layer {beta}-sheet of Borrelia outer surface protein A. PSAM allows for the capture of a defined number of self-assembly-like peptide repeats within a water-soluble protein, making structural and energetic studies possible. In this work, we extend our PSAM approach to a highly hydrophobic peptide sequence. We show that amore » penta-Ile peptide (Ile{sub 5}), which is insoluble and forms {beta}-rich self-assemblies in aqueous solution, can be captured within the PSAM scaffold in a form capable of self-assembly. The 1.1-{angstrom} crystal structure revealed that the Ile{sub 5} stretch forms a highly regular {beta}-strand within this flat {beta}-sheet. Self-assembly models built with multiple copies of the crystal structure of the Ile5 peptide segment showed no steric conflict, indicating that this conformation represents an assembly-competent form. The PSAM retained high conformational stability, suggesting that the flat {beta}-strand of the Ile{sub 5} stretch primed for self-assembly is a low-energy conformation of the Ile{sub 5} stretch and rationalizing its high propensity for self-assembly. The ability of the PSAM to 'solubilize' an otherwise insoluble peptide stretch suggests the potential of the PSAM approach to the characterization of self-assembling peptides.« less

Overcoming the Instability of Nanoparticle-Based Catalyst Films in Alkaline Electrolyzers by using Self-Assembling and Self-Healing Films.

PubMed

Barwe, Stefan; Masa, Justus; Andronescu, Corina; Mei, Bastian; Schuhmann, Wolfgang; Ventosa, Edgar

2017-07-10

Engineering stable electrodes using highly active catalyst nanopowders for electrochemical water splitting remains a challenge. We report an innovative and general approach for attaining highly stable catalyst films with self-healing capability based on the in situ self-assembly of catalyst particles during electrolysis. The catalyst particles are added to the electrolyte forming a suspension that is pumped through the electrolyzer. Particles with negatively charged surfaces stick onto the anode, while particles with positively charged surfaces stick to the cathode. The self-assembled catalyst films have self-healing properties as long as sufficient catalyst particles are present in the electrolyte. The proof-of-concept was demonstrated in a non-zero gap alkaline electrolyzer using NiFe-LDH and Ni x B catalyst nanopowders for anode and cathode, respectively. Steady cell voltages were maintained for at least three weeks during continuous electrolysis at 50-100 mA cm -2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioinspired synthesis and self-assembly of hybrid organic–inorganic nanomaterials

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

Zhang, Honghu

Nature is replete with complex organic–inorganic hierarchical materials of diverse yet specific functions. These materials are intricately designed under physiological conditions through biomineralization and biological self-assembly processes. Tremendous efforts have been devoted to investigating mechanisms of such biomineralization and biological self-assembly processes as well as gaining inspiration to develop biomimetic methods for synthesis and self-assembly of functional nanomaterials. In this work, we focus on the bioinspired synthesis and self-assembly of functional inorganic nanomaterials templated by specialized macromolecules including proteins, DNA and polymers. The in vitro biomineralization process of the magnetite biomineralizing protein Mms6 has been investigated using small-angle X-ray scattering.more » Templated by Mms6, complex magnetic nanomaterials can be synthesized on surfaces and in the bulk. DNA and synthetic polymers have been exploited to construct macroscopic two- and three-dimensional (2D and 3D) superlattices of gold nanocrystals. Employing X-ray scattering and spectroscopy techniques, the self-assembled structures and the self-assembly mechanisms have been studied, and theoretical models have been developed. Our results show that specialized macromolecules including proteins, DNA and polymers act as effective templates for synthesis and self-assembly of nanomaterials. These bottom-up approaches provide promising routes to fabricate hybrid organic–inorganic nanomaterials with rationally designed hierarchical structures, targeting specific functions.« less

Toward three-dimensional microelectronic systems: directed self-assembly of silicon microcubes via DNA surface functionalization.

PubMed

Lämmerhardt, Nico; Merzsch, Stephan; Ledig, Johannes; Bora, Achyut; Waag, Andreas; Tornow, Marc; Mischnick, Petra

2013-07-02

The huge and intelligent processing power of three-dimensional (3D) biological "processors" like the human brain with clock speeds of only 0.1 kHz is an extremely fascinating property, which is based on a massively parallel interconnect strategy. Artificial silicon microprocessors are 7 orders of magnitude faster. Nevertheless, they do not show any indication of intelligent processing power, mostly due to their very limited interconnectivity. Massively parallel interconnectivity can only be realized in three dimensions. Three-dimensional artificial processors would therefore be at the root of fabricating artificially intelligent systems. A first step in this direction would be the self-assembly of silicon based building blocks into 3D structures. We report on the self-assembly of such building blocks by molecular recognition, and on the electrical characterization of the formed assemblies. First, planar silicon substrates were functionalized with self-assembling monolayers of 3-aminopropyltrimethoxysilane for coupling of oligonucleotides (single stranded DNA) with glutaric aldehyde. The oligonucleotide immobilization was confirmed and quantified by hybridization with fluorescence-labeled complementary oligonucleotides. After the individual processing steps, the samples were analyzed by contact angle measurements, ellipsometry, atomic force microscopy, and fluorescence microscopy. Patterned DNA-functionalized layers were fabricated by microcontact printing (μCP) and photolithography. Silicon microcubes of 3 μm edge length as model objects for first 3D self-assembly experiments were fabricated out of silicon-on-insulator (SOI) wafers by a combination of reactive ion etching (RIE) and selective wet etching. The microcubes were then surface-functionalized using the same protocol as on planar substrates, and their self-assembly was demonstrated both on patterned silicon surfaces (88% correctly placed cubes), and to cube aggregates by complementary DNA functionalization and hybridization. The yield of formed aggregates was found to be about 44%, with a relative fraction of dimers of some 30%. Finally, the electrical properties of the formed dimers were characterized using probe tips inside a scanning electron microscope.

Effect of amino acid sequence and pH on nanofiber formation of self-assembling peptides EAK16-II and EAK16-IV.

PubMed

Hong, Yooseong; Legge, Raymond L; Zhang, S; Chen, P

2003-01-01

Atomic force microscopy (AFM) and axisymmetric drop shape analysis-profile (ASDA-P) were used to investigate the mechanism of self-assembly of peptides. The peptides chosen consisted of 16 alternating hydrophobic and hydrophilic amino acids, where the hydrophilic residues possess alternating negative and positive charges. Two types of peptides, AEAEAKAKAEAEAKAK (EAK16-II) and AEAEAEAEAKAKAKAK (EAK16-IV), were investigated in terms of nanostructure formation through self-assembly. The experimental results, which focused on the effects of the amino acid sequence and pH, show that the nanostructures formed by the peptides are dependent on the amino acid sequence and the pH of the solution. For pH conditions around neutrality, one of the peptides used in this study, EAK16-IV, forms globular assemblies and has lower surface tension at air-water interfaces than another peptide, EAK16-II, which forms fibrillar assemblies at the same pH. When the pH is lowered below 6.5 or raised above 7.5, there is a transition from globular to fibrillar structures for EAK16-IV, but EAK16-II does not show any structural transition. Surface tension measurements using ADSA-P showed different surface activities of peptides at air-water interfaces. EAK16-II does not show a significant difference in surface tension for the pH range between 4 and 9. However, EAK16-IV shows a noticeable decrease in surface tension at pH around neutrality, indicating that the formation of globular assemblies is related to the molecular hydrophobicity.

Bidisperse silica nanoparticles close-packed monolayer on silicon substrate by three step spin method

NASA Astrophysics Data System (ADS)

Khanna, Sakshum; Marathey, Priyanka; Utsav, Chaliawala, Harsh; Mukhopadhyay, Indrajit

2018-05-01

We present the studies on the structural properties of monolayer Bidisperse silica (SiO2) nanoparticles (BDS) on Silicon (Si-100) substrate using spin coating technique. The Bidisperse silica nanoparticle was synthesised by the modified sol-gel process. Nanoparticles on the substrate are generally assembled in non-close/close-packed monolayer (CPM) form. The CPM form is obtained by depositing the colloidal suspension onto the silicon substrate using complex techniques. Here we report an effective method for forming a monolayer of bidisperse silica nanoparticle by three step spin coating technique. The samples were prepared by mixing the monodisperse solutions of different particles size 40 and 100 nm diameters. The bidisperse silica nanoparticles were self-assembled on the silicon substrate forming a close-packed monolayer film. The scanning electron microscope images of bidisperse films provided in-depth film structure of the film. The maximum surface coverage obtained was around 70-80%.

Supramolecular assembly/reassembly processes: molecular motors and dynamers operating at surfaces.

PubMed

Ciesielski, Artur; Samorì, Paolo

2011-04-01

Among the many significant advances within the field of supramolecular chemistry over the past decades, the development of the so-called "dynamers" features a direct relevance to materials science. Defined as "combinatorial dynamic polymers", dynamers are constitutional dynamic systems and materials resulting from the application of the principles of supramolecular chemistry to polymer science. Like supramolecular materials in general, dynamers are reversible dynamic multifunctional architectures, capable of modifying their constitution by exchanging, recombining, incorporating components. They may exhibit a variety of novel properties and behave as adaptive materials. In this review we focus on the design of responsive switchable monolayers, i.e. monolayers capable to undergo significant changes in their physical or chemical properties as a result of external stimuli. Scanning tunneling microscopy studies provide direct evidence with a sub-nanometre resolution, on the formation and dynamic response of these self-assembled systems featuring controlled geometries and properties.

Spontaneous adsorption on a hydrophobic surface governed by hydrogen bonding.

PubMed

Dang, Fuquan; Hasegawa, Takeshi; Biju, Vasudevanpillai; Ishikawa, Mitsuru; Kaji, Noritada; Yasui, Takao; Baba, Yoshinobu

2009-08-18

Spontaneous adsorption from solution onto solid surface is a common phenomenon in nature, but the force that governs adsorption is still a matter of considerable debate. (1, 2) We found that surfactants and cellulose adsorb from solution onto a poly(methyl methacrylate) (PMMA) surface in an ordered and cooperative way governed by hydrogen bonding. The glucose rings of n-dodecyl-beta-D-maltoside (DDM) and hydroxyethylcellulose (HEC) stand perpendicular to the surface, H-bond to the surface COOMe groups with their C=O and Me-O bonds parallel to the surface, and form a tight monolayer. The non-H-bonded COOMe groups orient their C=O bonds perpendicular to the surface. In contrast, the glucose rings of hydrophobically modified hydroxyethylcellulose (HMHEC) lie flat with the side chains perpendicular to the surface and H-bond to the perpendicular-oriented C=O groups. The non-H-bonded COOMe groups orient their C=O bonds parallel but Me-O bonds near-perpendicular to the surface for stabilizing HMHEC. The current work provides a detailed picture of how surface-active molecules interact with a solid surface and self-assemble into greatly different architectures.

Formation of hydroxyl-functionalized stilbenoid molecular sieves at the liquid/solid interface on top of a 1-decanol monolayer.

PubMed

Bellec, Amandine; Arrigoni, Claire; Douillard, Ludovic; Fiorini-Debuisschert, Céline; Mathevet, Fabrice; Kreher, David; Attias, André-Jean; Charra, Fabrice

2014-10-31

Specific molecular tectons can be designed to form molecular sieves through self-assembly at the solid-liquid interface. After demonstrating a model tecton bearing apolar alkyl chains, we then focus on a modified structure involving asymmetric functionalization of some alkyl chains with polar hydroxyl groups in order to get chemical selectivity in the sieving. As the formation of supramolecular self-assembled networks strongly depends on molecule-molecule, molecule-substrate and molecule-solvent interactions, we compared the tectons' self-assembly on graphite for two types of solvent. We demonstrate the possibility to create hydroxylated stilbenoid molecular sieves by using 1-decanol as a solvent. Interestingly, with this solvent, the porous network is developed on top of a 1-decanol monolayer.

Nanostructures as promising tools for delivery of antimicrobial peptides.

PubMed

Brandelli, A

2012-07-01

Antimicrobial peptides have been extensively investigated for their potential applications as therapeutics and food biopreservatives. The antimicrobial activity may be impaired by the susceptibility for proteolytic degradation and undesirable interactions of the antimicrobial peptide in the biological environment. Development of nanostructures for entrapment and delivery of antimicrobial peptides may represent an alternative to the direct application of these substances. Lipid nanovesicles have been developed for encapsulation of antimicrobial peptides. Phosphatidylcholine is often employed in liposome manufacture, which is mostly achieved by the thin-film hydration method. Nanofibers may allow different physical modes of drug loading, including direct adsorption on the nanofiber surface or the assembly of drug-loaded nanoparticles. Self-assembled peptides reveal attractive features as nanostructures for applications in drug delivery and promising as antimicrobial agent for treatment of brain infections. Magnetic nanoparticles and nanotubules are also potential structures for entrapment of antimicrobial peptides. Nanoparticles can be also chemically modified with specific cell surface ligands to enhance cell adhesion and site specific delivery. This article reviews the most important nanostructures as promising tools for peptide delivery systems.

Probing the Self-Assembly and the Accompanying Structural Changes of Hydrophobin SC3 on a Hydrophobic Surface by Mass Spectrometry

PubMed Central

Wang, X.; Permentier, H. P.; Rink, R.; Kruijtzer, J. A. W.; Liskamp, R. M. J.; Wösten, H. A. B.; Poolman, B.; Robillard, G. T.

2004-01-01

The fungal class I hydrophobin SC3 self-assembles into an amphipathic membrane at hydrophilic-hydrophobic interfaces such as the water-air and water-Teflon interface. During self-assembly, the water-soluble state of SC3 proceeds via the intermediate α-helical state to the stable end form called the β-sheet state. Self-assembly of the hydrophobin at the Teflon surface is arrested in the α-helical state. The β-sheet state can be induced at elevated temperature in the presence of detergent. The structural changes of SC3 were monitored by various mass spectrometry techniques. We show that the so-called second loop of SC3 (C39–S72) has a high affinity for Teflon. Binding of this part of SC3 to Teflon was accompanied by the formation of α-helical structure and resulted in low solvent accessibility. The solvent-protected region of the second loop extended upon conversion to the β-sheet state. In contrast, the C-terminal part of SC3 became more exposed to the solvent. The results indicate that the second loop of class I hydrophobins plays a pivotal role in self-assembly at the hydrophilic-hydrophobic interface. Of interest, this loop is much smaller in case of class II hydrophobins, which may explain the differences in their assembly. PMID:15345568

Use of side-chain incompatibility for tailoring long-range p/n heterojunctions: photoconductive nanofibers formed by self-assembly of an amphiphilic donor-acceptor dyad consisting of oligothiophene and perylenediimide.

PubMed

Li, Wei-Shi; Saeki, Akinori; Yamamoto, Yohei; Fukushima, Takanori; Seki, Shu; Ishii, Noriyuki; Kato, Kenichi; Takata, Masaki; Aida, Takuzo

2010-07-05

To tailor organic p/n heterojunctions with molecular-level precision, a rational design strategy using side-chain incompatibility of a covalently connected donor-acceptor (D-A) dyad has been successfully carried out. An oligothiophene-perylenediimide dyad, when modified with triethylene glycol side chains at one terminus and dodecyl side chains at the other (2(Amphi)), self-assembles into nanofibers with a long-range D/A heterojunction. In contrast, when the dyad is modified with dodecyl side chains at both termini (2(Lipo)), ill-defined microfibers result. In steady-state measurements using microgap electrodes, a cast film of the nanofiber of 2(Amphi) displays far better photoconducting properties than that of the microfiber of 2(Lipo). Flash-photolysis time-resolved microwave conductivity measurements, in conjunction with transient absorption spectroscopy, clearly indicate that the nanofiber of 2(Amphi) intrinsically allows for better carrier generation and transport properties than the microfibrous assembly of 2(Lipo).

Graphene Oxide-Polymer Composite Langmuir Films Constructed by Interfacial Thiol-Ene Photopolymerization

NASA Astrophysics Data System (ADS)

Luo, Xiaona; Ma, Kai; Jiao, Tifeng; Xing, Ruirui; Zhang, Lexin; Zhou, Jingxin; Li, Bingbing

2017-02-01

The effective synthesis and self-assembly of graphene oxide (GO) nanocomposites are of key importance for a broad range of nanomaterial applications. In this work, a one-step chemical strategy is presented to synthesize stable GO-polymer Langmuir composite films by interfacial thiol-ene photopolymerization at room temperature, without use of any crosslinking agents and stabilizing agents. It is discovered that photopolymerization reaction between thiol groups modified GO sheets and ene in polymer molecules is critically responsible for the formation of the composite Langmuir films. The film formed by Langmuir assembly of such GO-polymer composite films shows potential to improve the mechanical and chemical properties and promotes the design of various GO-based nanocomposites. Thus, the GO-polymer composite Langmuir films synthesized by interfacial thiol-ene photopolymerization with such a straightforward and clean manner, provide new alternatives for developing chemically modified GO-based hybrid self-assembled films and nanomaterials towards a range of soft matter and graphene applications.

Materials Design for Block Copolymer Lithography

NASA Astrophysics Data System (ADS)

Sweat, Daniel Patrick

Block copolymers (BCPs) have attracted a great deal of scientific and technological interest due to their ability to spontaneously self-assemble into dense periodic nanostructures with a typical length scale of 5 to 50 nm. The use of self-assembled BCP thin-films as templates to form nanopatterns over large-area is referred to as BCP lithography. Directed self-assembly of BCPs is now viewed as a viable candidate for sub-20 nm lithography by the semiconductor industry. However, there are multiple aspects of assembly and materials design that need to be addressed in order for BCP lithography to be successful. These include substrate modification with polymer brushes or mats, tailoring of the block copolymer chemistry, understanding thin-film assembly and developing epitaxial like methods to control long range alignment. The rational design, synthesis and self-assembly of block copolymers with large interaction parameters (chi) is described in the first part of this dissertation. Two main blocks were chosen for introducing polarity into the BCP system, namely poly(4-hydroxystyrene) and poly(2-vinylpyridine). Each of these blocks are capable of ligating Lewis acids which can increase the etch contrast between the blocks allowing for facile pattern transfer to the underlying substrate. These BCPs were synthesized by living anionic polymerization and showed excellent control over molecular weight and dispersity, providing access to sub 5-nm domain sizes. Polymer brushes consist of a polymer chain with one end tethered to the surface and have wide applicability in tuning surface energy, forming responsive surfaces and increasing biocompatibility. In the second part of the dissertation, we present a universal method to grow dense polymer brushes on a wide range of substrates and combine this chemistry with BCP assembly to fabricate nanopatterned polymer brushes. This is the first demonstration of introducing additional functionality into a BCP directing layer and opens up a wide slew of applications from directed self-assembly to biomaterial engineering.

Ultrasensitive colorimetric detection of heparin based on self-assembly of gold nanoparticles on graphene oxide.

PubMed

Fu, Xiuli; Chen, Lingxin; Li, Jinhua

2012-08-21

A novel colorimetric method was developed for ultrasensitive detection of heparin based on self-assembly of gold nanoparticles (AuNPs) onto the surface of graphene oxide (GO). Polycationic protamine was used as a medium for inducing the self-assembly of citrate-capped AuNPs on GO through electrostatic interaction, resulting in a shift in the surface plasmon resonance (SPR) absorption of AuNPs and exhibiting a blue color. Addition of polyanionic heparin disturbed the self-assemble of AuNPs due to its strong affinity to protamine. With the increase of heparin concentration, the amounts of self-assembly AuNPs decreased and the color changed from blue to red in solution. Therefore, a "blue-to-red" colorimetric sensing strategy based on self-assembly of AuNPs could be established for heparin detection. Compared with the commonly reported aggregation-based methods ("red-to-blue"), the color change from blue to red was more eye-sensitive, especially in low concentration of target. Moreover, stronger interaction between protamine and heparin led to distinguish heparin from its analogues as well as various potentially coexistent physiological species. The strategy was simply achieved by the self-assembly nature of AuNPs and the application of two types of polyionic media, showing it to be label-free, simple, rapid and visual. This method could selectively detect heparin with a detection limit of 3.0 ng mL(-1) in standard aqueous solution and good linearity was obtained over the range 0.06-0.36 μg mL(-1) (R = 0.9936). It was successfully applied to determination of heparin in fetal bovine serum samples as low as 1.7 ng mL(-1) with a linear range of 0-0.8 μg mL(-1).

A Library of the Nanoscale Self-Assembly of Amino Acids on Metal Surfaces

NASA Astrophysics Data System (ADS)

Iski, Erin; Yitamben, Esmeralda; Guisinger, Nathan

2012-02-01

The investigation of the hierarchical self-assembly of amino acids on surfaces represents a unique test-bed for the origin of enantio-favoritism in biology and the transmission of chirality from single molecules to complete surface layers. These chiral systems, in particular the assembly of isoleucine and alanine on Cu(111), represent a direct link to the understanding of certain biological processes, specifically the preference for some amino acids to form alpha helices vs. beta-pleated sheets in the secondary structure of proteins. Low temperature, ultra-high vacuum, scanning tunneling microscopy (LT UHV-STM) is used to study the hierarchical self-assembly of different amino acids on a Cu(111) single crystal in an effort to build a library of their two-dimensional structure with molecular-scale resolution for enhanced protein and peptide studies. Both enantiopure and racemic structures are studied in order to elucidate how chirality can affect the self-assembly of the amino acids. In some cases, density functional theory (DFT) models can be used to confirm the experimental structure. The advent of such a library with fully resolved, two-dimensional structures at different molecular coverages would address some of the complex questions surrounding the preferential formation of alpha helices vs. beta-pleated sheets in proteins and lead to a better understanding of the key role played by these amino acids in protein sequencing.

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.

Tribology and hydrophobicity of a biocompatible GPTMS/PFPE coating on Ti6Al4V surfaces.

PubMed

Panjwani, Bharat; Sinha, Sujeet K

2012-11-01

Tribological properties of perfluoropolyether (PFPE) coated 3-glycidoxypropyltrimethoxy silane (GPTMS) SAMs (self-assembled monolayers) onto Ti6Al4V alloy substrate were studied using ball-on-disk experiments. GPTMS SAMs deposition onto a Ti6Al4V alloy surface was carried out using solution phase method. Ultra-thin layer of PFPE was dip-coated onto SAMs modified specimens. Tribological tests were carried out at 0.2 N normal load and rotational speed of 200 rpm using track radius of 2 mm. Wear track and counterface surface conditions were investigated using optical microscopy. PFPE modified specimens were baked at 150 °C for 1h to investigate the effect of thermal treatment on tribological properties. Surface characterization tests such as contact angle measurement, AFM morphology and X-ray photoelectron spectroscopy were carried out for differently modified specimens. PFPE overcoat meets the requirements of cytotoxicity test using the ISO 10993-5 elution method. PFPE top layer lowered the coefficient of friction and increased wear durability for different specimens (with and without GPTMS intermediate layer). PFPE overcoat onto GPTMS showed significant increase in the wear resistance compared with overcoat onto bare Ti6Al4V specimens. The observed improvement in the tribological properties can be attributed to the change in the interaction of PFPE molecules with the substrate surface due to the GPTMS intermediate layer. Copyright © 2012 Elsevier Ltd. All rights reserved.

Enhancing the Properties of Carbon and Gold Substrates by Surface Modification

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

Harnisch, Jennifer Anne

2001-01-01

The properties of both carbon and gold substrates are easily affected by the judicious choice of a surface modification protocol. Several such processes for altering surface composition have been published in literature. The research presented in this thesis primarily focuses on the development of on-column methods to modify carbon stationary phases used in electrochemically modulated liquid chromatography (EMLC). To this end, both porous graphitic carbon (PGC) and glassy carbon (GC) particles have been modified on-column by the electroreduction of arenediazonium salts and the oxidation of arylacetate anions (the Kolbe reaction). Once modified, the carbon stationary phases show enhanced chromatographic performancemore » both in conventional liquid chromatographic columns and EMLC columns. Additionally, one may also exploit the creation of aryl films to by electroreduction of arenediazonium salts in the creation of nanostructured materials. The formation of mercaptobenzene film on the surface of a GC electrode provides a linking platform for the chemisorption of gold nanoparticles. After deposition of nanoparticles, the surface chemistry of the gold can be further altered by self-assembled monolayer (SAM) formation via the chemisorption of a second thiol species. Finally, the properties of gold films can be altered such that they display carbon-like behavior through the formation of benzenehexathiol (BHT) SAMs. BHT chemisorbs to the gold surface in a previously unprecedented planar fashion. Carbon and gold substrates can be chemically altered by several methodologies resulting in new surface properties. The development of modification protocols and their application in the analytical arena is considered herein.« less

The self-assembled behavior of DNA bases on the interface.

PubMed

Liu, Lei; Xia, Dan; Klausen, Lasse H; Dong, Mingdong

2014-01-27

A successful example of self-assembly in a biological system is that DNA can be an excellent agent to self-assemble into desirable two and three-dimensional nanostructures in a well-ordered manner by specific hydrogen bonding interactions between the DNA bases. The self-assembly of DNA bases have played a significant role in constructing the hierarchical nanostructures. In this review article we will introduce the study of nucleic acid base self-assembly by scanning tunneling microscopy (STM) at vacuum and ambient condition (the liquid/solid interface), respectively. From the ideal condition to a more realistic environment, the self-assembled behaviors of DNA bases are introduced. In a vacuum system, the energetic advantages will dominate the assembly formation of DNA bases, while at ambient condition, more factors such as conformational freedom and the biochemical environment will be considered. Therefore, the assemblies of DNA bases at ambient condition are different from the ones obtained under vacuum. We present the ordered nanostructures formed by DNA bases at both vacuum and ambient condition. To construct and tailor the nanostructure through the interaction between DNA bases, it is important to understand the assembly behavior and features of DNA bases and their derivatives at ambient condition. The utilization of STM offers the advantage of investigating DNA base self-assembly with sub-molecular level resolution at the surface.

The Self-Assembled Behavior of DNA Bases on the Interface

PubMed Central

Liu, Lei; Xia, Dan; Klausen, Lasse H.; Dong, Mingdong

2014-01-01

A successful example of self-assembly in a biological system is that DNA can be an excellent agent to self-assemble into desirable two and three-dimensional nanostructures in a well-ordered manner by specific hydrogen bonding interactions between the DNA bases. The self-assembly of DNA bases have played a significant role in constructing the hierarchical nanostructures. In this review article we will introduce the study of nucleic acid base self-assembly by scanning tunneling microscopy (STM) at vacuum and ambient condition (the liquid/solid interface), respectively. From the ideal condition to a more realistic environment, the self-assembled behaviors of DNA bases are introduced. In a vacuum system, the energetic advantages will dominate the assembly formation of DNA bases, while at ambient condition, more factors such as conformational freedom and the biochemical environment will be considered. Therefore, the assemblies of DNA bases at ambient condition are different from the ones obtained under vacuum. We present the ordered nanostructures formed by DNA bases at both vacuum and ambient condition. To construct and tailor the nanostructure through the interaction between DNA bases, it is important to understand the assembly behavior and features of DNA bases and their derivatives at ambient condition. The utilization of STM offers the advantage of investigating DNA base self-assembly with sub-molecular level resolution at the surface. PMID:24473140

Toughening of Epoxies: Novel Self-Assembling Block Copolymers Versus Traditional Telechelic Oligomers

NASA Astrophysics Data System (ADS)

Bacigalupo, Lauren N.

Epoxy resins are commonly utilized because of their adhesive capacity and high strength. However, epoxies are inherently brittle; so much research has been dedicated to improving their fracture toughness. This study will focus on a comparing a traditional telechelic oligomer, CTBN, and a novel self-assembling block copolymer, SBM, as it relates to improving the fracture toughness of a lightly crosslinked epoxy system. After characterizing the modified systems for fracture toughness, mechanical and thermal properties, namely yield stress and the glass transition, will be determined in order to discern the impact these modifiers have on the overall properties of the blend. TEM, SEM and TOM techniques will be utilized for characterizing morphology, fractography and subsurface damage, respectively. Once this was accomplished, it was deduced that the toughening mechanisms of CTBN and SBM-modified epoxies are very similar. The main difference between the two is that the inherent structure of SBM allows the SBM-modified epoxy to retain its compressive yield strength. This, consequently, makes SBM ideal for thin bondline applications in the industrial adhesive and/or electronics industry.

Simultaneous monitoring of humidity and chemical changes using quartz crystal microbalance sensors modified with nano-thin films.

PubMed

Selyanchyn, Roman; Korposh, Serhiy; Wakamatsu, Shunichi; Lee, Seung-Woo

2011-01-01

Quartz crystal microbalance (QCM) electrodes modified with nano-thin films were used to develop a system for measuring significant environment changes (smoke, humidity, hazardous material release). A layer-by-layer approach was used for the deposition of sensitive coatings with a nanometer thickness on the electrode surface. The QCM electrode was modified with self-assembled alternate layers of tetrakis-(4-sulfophenyl) porphine (TSPP) (or its manganese derivative, MnTSPP) and poly(diallyldimethylammonium chloride) (PDDA). The QCM sensors, which had been reported previously for humidity sensing purposes, revealing a high possibility to recognize significant environmental changes. Identifying of the origin of environmental change is possible via differential signal analysis of the obtained data. The sensors showed different responses to humidity changes, hazardous gas (ammonia) or cigarette smoke exposure. Even qualitative analysis is not yet available; it has been shown that ventilation triggers or alarms for monitoring smoke or hazardous material release can be built using the obtained result.

Demonstration of near infrared gas sensing using gold nanodisks on functionalized silicon.

PubMed

Rodríguez-Cantó, P J; Martínez-Marco, M; Rodríguez-Fortuño, F J; Tomás-Navarro, B; Ortuño, R; Peransí-Llopis, S; Martínez, A

2011-04-11

In this work, we demonstrate experimentally the use of an array of gold nanodisks on functionalized silicon for chemosensing purposes. The metallic nanostructures are designed to display a very strong plasmonic resonance in the infrared regime, which results in highly sensitive sensing. Unlike usual experiments which are based on the functionalization of the metal surface, we functionalized here the silicon substrate. This silicon surface was modified chemically by buildup of an organosilane self-assembled monolayer (SAM) containing isocyanate as functional group. These groups allow for an easy surface regeneration by simple heating, thanks to the thermally reversible interaction isocyanate-analyte, which allows the cyclic use of the sensor. The technique showed a high sensitivity to surface binding events in gas and allowed the surface regeneration by heating of the sensor at 150 °C. A relative wavelength shift ∆λ(max)λ(0)=0.027 was obtained when the saturation level was reached. © 2011 Optical Society of America

Comparative Study of Protein Immobilization Properties on Calixarene Monolayers

PubMed Central

Chen, Hongxia; Lee, Minsu; Choi, Sungwook; Kim, Jae-Ho; Choi, Heung-Jin; Kim, Sung-Hoon; Lee, Jeabeom; Koh, Kwangnak

2007-01-01

Three calix[4]arene (Cal-4) derivatives of which contain ethylester (1), carboxylic acid (2), and crownether (3) at the lower rim with a common reactive thiol at the upper rim were synthesized and constructed to self-assembled monolayers (SAMs) on Au films. After spectroscopic characterization of monolayers, the interaction between Cal-4 and surface confined bovine serum albumin (BSA) in the SAMs was analyzed by surface plasmon resonance (SPR). The estimated surface concentration of BSA on the Cal-4 SAM with crownether group was the highest among the three Cal-4 derivatives. Anti-hIgG and hIgG pair was employed for the investigation of protein-protein interaction. Molecular interaction between anti-hIgG and hIgG can be detected in a concentration range of 10 pg/mL to 200 pg/mL on the Cal-4 derivative 3 SAM modified SPR chip.

Structure and Modification of Electrode Materials for Protein Electrochemistry.

PubMed

Jeuken, Lars J C

The interactions between proteins and electrode surfaces are of fundamental importance in bioelectrochemistry, including photobioelectrochemistry. In order to optimise the interaction between electrode and redox protein, either the electrode or the protein can be engineered, with the former being the most adopted approach. This tutorial review provides a basic description of the most commonly used electrode materials in bioelectrochemistry and discusses approaches to modify these surfaces. Carbon, gold and transparent electrodes (e.g. indium tin oxide) are covered, while approaches to form meso- and macroporous structured electrodes are also described. Electrode modifications include the chemical modification with (self-assembled) monolayers and the use of conducting polymers in which the protein is imbedded. The proteins themselves can either be in solution, electrostatically adsorbed on the surface or covalently bound to the electrode. Drawbacks and benefits of each material and its modifications are discussed. Where examples exist of applications in photobioelectrochemistry, these are highlighted.

Method for selective immobilization of macromolecules on self assembled monolayer surfaces

DOEpatents

Laskin, Julia [Richland, WA; Wang, Peng [Billerica, MA

2011-11-29

Disclosed is a method for selective chemical binding and immobilization of macromolecules on solid supports in conjunction with self-assembled monolayer (SAM) surfaces. Immobilization involves selective binding of peptides and other macromolecules to SAM surfaces using reactive landing (RL) of mass-selected, gas phase ions. SAM surfaces provide a simple and convenient platform for tailoring chemical properties of a variety of substrates. The invention finds applications in biochemistry ranging from characterization of molecular recognition events at the amino acid level and identification of biologically active motifs in proteins, to development of novel biosensors and substrates for stimulated protein and cell adhesion.

Surface Assisted Transient Displacement Charge Technique. II. Effect of Gases on Photoinduced Charge Transfer in Self-Assembled Monolayers

PubMed Central

Krasnoslobodtsev, Alexey V.; Smirnov, Sergei N.

2008-01-01

Surface assisted photoinduced transient displacement charge (SPTDC) technique was used to study charge transfer in self-assembled monolayers of 7-diethylaminocoumarin covalently linked to oxide surface in atmosphere of different gases. The dipole signal was found to be opposite to that in solution and dependent on the nature of gas and its pressure. The results were explained by collision-induced relaxation that impedes uninhibited tilting of molecules onto the surface. Collisions with paramagnetic oxygen induce intersystem crossing to long-lived triplet dipolar states of coumarin with the rate close to the half of that for the collision rate. PMID:16956285

Electrochemical and surface plasmon resonance characterization of β-cyclodextrin-based self-assembled monolayers and evaluation of their inclusion complexes with glucocorticoids

NASA Astrophysics Data System (ADS)

Frasconi, Marco; Mazzei, Franco

2009-07-01

This paper describes the characterization of a self-assembled β-cyclodextrin (β-CD)-derivative monolayer (β-CD-SAM) on a gold surface and the study of their inclusion complexes with glucocorticoids. To this aim the arrangement of a self-assembled β-cyclodextrin-derivative monolayer on a gold surface was monitored in situ by means of surface plasmon resonance (SPR) spectroscopy and double-layer capacitance measurements. Film thickness and dielectric constant were evaluated for a monolayer of β-CD using one-color-approach SPR. The selectivity of the β-CD host surface was verified by using electroactive species permeable and impermeable in the β-CD cavity. The redox probe was selected according to its capacity to permeate the β-CD monolayer and its electrochemical behavior. In order to evaluate the feasibility of an inclusion complex between β-CD-SAM with some steroids such as cortisol and cortisone, voltammetric experiments in the presence of the redox probes as molecules competitive with the steroids have been performed. The formation constant of the surface host-guest by β-CD-SAM and the steroids under study was calculated.

Self-assembly of silver nanoparticles as high active surface-enhanced Raman scattering substrate for rapid and trace analysis of uranyl(VI) ions

NASA Astrophysics Data System (ADS)

Wang, Shaofei; Jiang, Jiaolai; Wu, Haoxi; Jia, Jianping; Shao, Lang; Tang, Hao; Ren, Yiming; Chu, Mingfu; Wang, Xiaolin

2017-06-01

A facile surface-enhanced Raman scattering (SERS) substrate based on the self-assembly of silver nanoparticles on the modified silicon wafer was obtained, and for the first time, an advanced SERS analysis method basing on this as-prepared substrate was established for high sensitive and rapid detection of uranyl ions. Due to the weakened bond strength of Odbnd Udbnd O resulting from two kinds of adsorption of uranyl species (;strong; and ;weak; adsorption) on the substrate, the ν1 symmetric stretch vibration frequency of Odbnd Udbnd O shifted from 871 cm- 1 (normal Raman) to 720 cm- 1 and 826 cm- 1 (SERS) along with significant Raman enhancement. Effects of the hydrolysis of uranyl ions on SERS were also investigated, and the SERS band at 826 cm- 1 was first used to approximately define the constitution of uranyl species at trace quantity level. Besides, the SERS intensity was proportional to the variable concentrations of uranyl nitrate ranging from 10- 7 to 10- 3 mol L- 1 with an excellent linear relation (R2 = 0.998), and the detection limit was 10- 7 mol L- 1. Furthermore, the related SERS approach involves low-cost substrate fabrication, rapid and trace analysis simultaneously, and shows great potential applications for the field assays of uranyl ions in the nuclear fuel cycle and environmental monitoring.

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.

Surface functionalization of copper via oxidative graft polymerization of 2,2'-bithiophene and immobilization of silver nanoparticles for combating biocorrosion.

PubMed

Wan, Dong; Yuan, Shaojun; Neoh, K G; Kang, E T

2010-06-01

An environmentally benign approach to surface modification was developed to impart copper surface with enhanced resistance to corrosion, bacterial adhesion and biocorrosion. Oxidative graft polymerization of 2,2'-bithiophene from the copper surface with self-assembled 2,2'-bithiophene monolayer, and subsequent reduction of silver ions to silver nanoparticles (Ag NPs) on the surface, give rise to a homogeneous bithiophene polymer (PBT) film with densely coupled Ag NPs on the copper surface (Cu-g-PBT-Ag NP surface). The immobilized Ag NPs were found to significantly inhibit bacterial adhesion and enhance the antibacterial properties of the PBT modified copper surface. The corrosion inhibition performance of the functionalized copper substrates was evaluated by Tafel polarization curves and electrochemical impedance spectroscopy. Arising from the chemical affinity of thiols for the noble and coinage metals, the copper surface functionalized with both PBT brushes and Ag NPs also exhibits long-term stability, and is thus potentially useful for combating the combined problems of corrosion and biocorrosion in harsh marine and aquatic environments.

Electrostatic Self-Assembly of Diamond Nanoparticles onto Al- and N-Polar Sputtered Aluminum Nitride Surfaces

PubMed Central

Yoshikawa, Taro; Reusch, Markus; Zuerbig, Verena; Cimalla, Volker; Lee, Kee-Han; Kurzyp, Magdalena; Arnault, Jean-Charles; Nebel, Christoph E.; Ambacher, Oliver; Lebedev, Vadim

2016-01-01

Electrostatic self-assembly of diamond nanoparticles (DNPs) onto substrate surfaces (so-called nanodiamond seeding) is a notable technique, enabling chemical vapor deposition (CVD) of nanocrystalline diamond thin films on non-diamond substrates. In this study, we examine this technique onto differently polarized (either Al- or N-polar) c-axis oriented sputtered aluminum nitride (AlN) film surfaces. This investigation shows that Al-polar films, as compared to N-polar ones, obtain DNPs with higher density and more homogeneously on their surfaces. The origin of these differences in density and homogeneity is discussed based on the hydrolysis behavior of AlN surfaces in aqueous suspensions. PMID:28335345

Directed Self-Assembly of Gradient Concentric Carbon Nanotube Rings

NASA Astrophysics Data System (ADS)

Hong, Suck Won; Jeong, Wonje; Ko, Hyunhyub; Tsukruk, Vladimir; Kessler, Michael; Lin, Zhiqun

2008-03-01

Hundreds of gradient concentric rings of linear conjugated polymer, (poly[2-methoxy-5-(2-ethylhexyloxy)-1,4- phenylenevinylene], i.e., MEH-PPV) with remarkable regularity over large areas were produced by controlled, repetitive ``stick- slip'' motions of the contact line in a confined geometry consisting of a sphere on a flat substrate (i.e., sphere-on-flat geometry). Subsequently, MEH-PPV rings exploited as template to direct the formation of gradient concentric rings of multiwalled carbon nanotubes (MWNTs) with controlled density. This method is simple, cost effective, and robust, combining two consecutive self-assembly processes, namely, evaporation-induced self- assembly of polymers in a sphere-on-flat geometry, followed by subsequent directed self-assembly of MWNTs on the polymer- templated surfaces.

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.

Biocatalytic Self-Assembly on Magnetic Nanoparticles.

PubMed

Conte, Maria P; Sahoo, Jugal Kishore; Abul-Haija, Yousef M; Lau, K H Aaron; Ulijn, Rein V

2018-01-24

Combining (bio)catalysis and molecular self-assembly provides an effective approach for the production and processing of self-assembled materials by exploiting catalysis to direct the assembly kinetics and hence controlling the formation of ordered nanostructures. Applications of (bio)catalytic self-assembly in biologically interfacing systems and in nanofabrication have recently been reported. Inspired by self-assembly in biological cells, efforts to confine catalysts on flat or patterned surfaces to exert spatial control over molecular gelator generation and nanostructure self-assembly have also emerged. Building on our previous work in the area, we demonstrate in this report the use of enzymes immobilized onto magnetic nanoparticles (NPs) to spatially localize the initiation of peptide self-assembly into nanofibers around NPs. The concept is generalized for both an equilibrium biocatalytic system that forms stable hydrogels and a nonequilibrium system that normally has a preset lifetime. Characterization of the hydrogels shows that self-assembly occurs at the site of enzyme immobilization on the NPs to give rise to gels with a "hub-and-spoke" morphology, where the nanofibers are linked through the enzyme-NP conjugates. This NP-controlled arrangement of self-assembled nanofibers enables both remarkable enhancements in the shear strength of hydrogel systems and a dramatic extension of the hydrogel stability in the nonequilibrium system. We are also able to show that the use of magnetic NPs enables the external control of both the formation of the hydrogel and its overall structure by application of an external magnetic field. We anticipate that the enhanced properties and stimuli-responsiveness of our NP-enzyme system will have applications ranging from nanomaterial fabrication to biomaterials and biosensing.

Selective Surface Acoustic Wave-Based Organophosphorus Sensor Employing a Host-Guest Self-Assembly Monolayer of β-Cyclodextrin Derivative

PubMed Central

Pan, Yong; Mu, Ning; Shao, Shengyu; Yang, Liu; Wang, Wen; Xie, Xiao; He, Shitang

2015-01-01

Self-assembly and molecular imprinting technologies are very attractive technologies for the development of artificial recognition systems and provide chemical recognition based on need and not happenstance. In this paper, we employed a β-cyclodextrin derivative surface acoustic wave (SAW) chemical sensor for detecting the chemical warfare agents (CWAs) sarin (O-Isoprophyl methylphosphonofluoridate, GB). Using sarin acid (isoprophyl hydrogen methylphosphonate) as an imprinting template, mono[6-deoxy-6-[(mercaptodecamethylene)thio

Self-assembly of nanosize coordination cages on si(100) surfaces.

PubMed

Busi, Marco; Laurenti, Marco; Condorelli, Guglielmo G; Motta, Alessandro; Favazza, Maria; Fragalà, Ignazio L; Montalti, Marco; Prodi, Luca; Dalcanale, Enrico

2007-01-01

Bottom-up fabrication of 3D organic nanostructures on Si(100) surfaces has been achieved by a two-step procedure. Tetradentate cavitand 1 was grafted on the Si surface together with 1-octene (Oct) as a spatial spectator by photochemical hydrosilylation. Ligand exchange between grafted cavitand 1 and self-assembled homocage 2, derived from cavitand 5 bearing a fluorescence marker, led to the formation of coordination cages on Si(100). Formation, quantification, and distribution of the nanoscale molecular containers on a silicon surface was assessed by using three complementary analytical techniques (AFM, XPS, and fluorescence) and validated by control experiments on cavitand-free silicon surfaces. Interestingly, the fluorescence of pyrene at approximately 4 nm above the Si(100) surface can be clearly observed.

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.

On a chaotic potential at the surface of a compensated semiconductor under conditions of the self-assembly of electrically active defects

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

Bondarenko, V. B., E-mail: enter@spbstu.ru; Filimonov, A. V.

2015-09-15

Natural irregularities of the electric potential on the surface of a semiconductor under conditions of the partial self-assembly of electrically active defects, i.e., on the formation of donor–acceptor pairs in depletion layers, are studied. The amplitude and character of the spatial distribution of the chaotic potential on the surface of a semiconductor in the cases of localized and delocalized states are determined. The dependence of the amplitude of the chaotic potential on the degree of compensation of the semiconductor is obtained.

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.

Highly sensitive electrochemical detection of cocaine on graphene/AuNP modified electrode via catalytic redox-recycling amplification.

PubMed

Jiang, Bingying; Wang, Min; Chen, Ying; Xie, Jiaqing; Xiang, Yun

2012-02-15

We demonstrated a new strategy for highly sensitive electrochemical detection of cocaine by using two engineered aptamers in connection to redox-recycling signal amplification. The graphene/AuNP nanocomposites were electrochemically deposited on a screen printed carbon electrode to enhance the electron transfers. The cocaine primary binding aptamers were self-assembled on the electrode surface through sulfur-Au interactions. The presence of the target cocaine and the biotin-modified secondary binding aptamers leads to the formation of sandwich complexes on the electrode surface. The streptavidin-conjugated alkaline phosphatases (ALPs) were used as labels to generate quantitative signals. The addition of the ALP substrate and the co-reactant NADH results in the formation of a redox cycle between the enzymatic product and the electrochemically oxidized species and the signal is thus significantly amplified. Because of the effective modification of the sensing surface and signal amplification, low nanomolar (1 nM) detection limit for cocaine is achieved. The proposed aptamer-based sandwich sensing approach for amplified detection of cocaine thus opens new opportunities for highly sensitive determination of other small molecules. Copyright © 2011 Elsevier B.V. All rights reserved.

Directed self-assembly of virus particles at nanoscale chemical templates

NASA Astrophysics Data System (ADS)

Chung, Sung-Wook; Cheung, Chin Li; Chatterji, Anju; Lin, Tianwei; Johnson, Jack; de Yoreo, Jim

2006-03-01

Because viruses can be site-specifically engineered to present catalytic, electronic, and optical moieties, they are attractive as building blocks for hierarchical nanostructures. We report results using scanned probe nanolithography to direct virus organization into 1D and 2D patterns and in situ AFM investigations of organization dynamics as pattern geometry, inter-viral potential, virus flux, and virus-pattern interaction are varied. Cowpea Mosaic Virus was modified to present surface sites with histidine (His) or cysteine (Cys) groups. Flat gold substrates were patterned with 10-100nm features of alkyl thiols terminated by Ni-NTA or meleimide groups to reversibly and irreversibly bind to the Hys and Cys groups, respectively. We show how assembly kinetics, degree of ordering and cluster-size distribution at these templates depend on the control parameters and present a physical picture of virus assembly at templates that incorporates growth dynamics of small-molecule epitaxial systems and condensation dynamics of colloidal systems. This work was performed under the auspices of the U. S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under Contract No. W-7405-Eng-48.

Controlled surface-induced flows from the motion of self-assembled colloidal walkers.

PubMed

Sing, Charles E; Schmid, Lothar; Schneider, Matthias F; Franke, Thomas; Alexander-Katz, Alfredo

2010-01-12

Biological flows at the microscopic scale are important for the transport of nutrients, locomotion, and differentiation. Here, we present a unique approach for creating controlled, surface-induced flows inspired by a ubiquitous biological system, cilia. Our design is based on a collection of self-assembled colloidal rotors that "walk" along surfaces in the presence of a rotating magnetic field. These rotors are held together solely by magnetic forces that allow for reversible assembly and disassembly of the chains. Furthermore, rotation of the magnetic field allows for straightforward manipulation of the shape and motion of these chains. This system offers a simple and versatile approach for designing microfluidic devices as well as for studying fundamental questions in cooperative-driven motion and transport at the microscopic level.

Structure formation in binary mixtures of lipids and detergents: self-assembly and vesicle division.

PubMed

Noguchi, Hiroshi

2013-01-14

Self-assembly dynamics in binary surfactant mixtures and structure changes of lipid vesicles induced by detergent solution are studied using coarse-grained molecular simulations. Disk-shaped micelles, the bicelles, are stabilized by detergents surrounding the rim of a bilayer disk of lipids. The self-assembled bicelles are considerably smaller than bicelles formed from vesicle rupture, and their size is determined by the concentrations of lipids and detergents and the interactions between the two species. The detergent-adsorption induces spontaneous curvature of the vesicle bilayer and results in vesicle division into two vesicles or vesicle rupture into worm-like micelles. The division occurs mainly via the inverse pathway of the modified stalk model. For large spontaneous curvature of the monolayers of the detergents, a pore is often opened, thereby leading to vesicle division or worm-like micelle formation.

Mixed carboranethiol self-assembled monolayers on gold surfaces

NASA Astrophysics Data System (ADS)

Yavuz, Adem; Sohrabnia, Nima; Yilmaz, Ayşen; Danışman, M. Fatih

2017-08-01

Carboranethiol self-assembled monolayers on metal surfaces have been shown to be very convenient systems for surface engineering. Here we have studied pure and mixed self-assembled monolayers (SAMs) of three different carboranethiol (CT) isomers on gold surfaces. The isomers were chosen with dipole moments pointing parallel to (m-1-carboranethiol, M1), out of (m-9-carboranethiol, M9) and into (o-1-carboranethiol, O1) the surface plane, in order to investigate the effect of dipole moment orientation on the film properties. In addition, influence of the substrate surface morphology on the film properties was also studied by using flame annealed (FA) and template stripped (TS) gold surfaces. Contact angle measurements indicate that in M1/M9 and M1/O1 mixed SAMs, M1 is the dominant species on the surface even for low M1 ratio in the growth solution. Whereas for O1/M9 mixed SAMs no clear evidence could be observed indicating dominance of one of the species over the other one. Though contact angle values were lower and hysteresis values were higher for SAMs grown on TS gold surfaces, the trends in the behavior of the contact angles with changing mixing ratio were identical for SAMs grown on both substrates. Atomic force microscopy images of the SAMs on TS gold surfaces indicate that the films have similar morphological properties regardless of mixing ratio.

Chiral permselectivity in surface-modified nanoporous opal films.

PubMed

Cichelli, Julie; Zharov, Ilya

2006-06-28

Nanoporous 7 mum thin opal films comprising 35 layers of 200 nm diameter SiO2 spheres were assembled on Pt electrodes and modified with chiral selector moieties on the silica surface. Diffusion of chiral redox species through the opals was studied by cyclic voltammetry. The chiral opal films demonstrate high selectivity for transport of one enantiomer over the other. This chiral permselectivity is attributed to the surface-facilitated transport utilizing noncovalent interactions between the chiral permeant molecules and surface-bound chiral selectors.

Natural Deposition Strategy for Interfacial, Self-Assembled, Large-Scale, Densely Packed, Monolayer Film with Ligand-Exchanged Gold Nanorods for In Situ Surface-Enhanced Raman Scattering Drug Detection.

PubMed

Mao, Mei; Zhou, Binbin; Tang, Xianghu; Chen, Cheng; Ge, Meihong; Li, Pan; Huang, Xingjiu; Yang, Liangbao; Liu, Jinhuai

2018-03-15

Liquid interfacial self-assembly of metal nanoparticles holds great promise for its various applications, such as in tunable optical devices, plasmonics, sensors, and catalysis. However, the construction of large-area, ordered, anisotropic, nanoparticle monolayers and the acquisition of self-assembled interface films are still significant challenges. Herein, a rapid, validated method to fabricate large-scale, close-packed nanomaterials at the cyclohexane/water interface, in which hydrophilic cetyltrimethylammonium bromide coated nanoparticles and gold nanorods (AuNRs) self-assemble into densely packed 2D arrays by regulating the surface ligand and suitable inducer, is reported. Decorating AuNRs with polyvinylpyrrolidone not only extensively decreases the charge of AuNRs, but also diminishes repulsive forces. More importantly, a general, facile, novel technique to transfer an interfacial monolayer through a designed in situ reaction cell linked to a microfluidic chip is revealed. The self-assembled nanofilm can then automatically settle on the substrate and be directly detected in the reaction cell in situ by means of a portable Raman spectrometer. Moreover, a close-packed monolayer of self-assembled AuNRs provides massive, efficient hotspots to create great surface-enhanced Raman scattering (SERS) enhancement, which provides high sensitivity and reproducibility as the SERS-active substrate. Furthermore, this strategy was exploited to detect drug molecules in human urine for cyclohexane-extracted targets acting as the oil phase to form an oil/water interface. A portable Raman spectrometer was employed to detect methamphetamine down to 100 ppb levels in human urine, exhibiting excellent practicability. As a universal platform, handy tool, and fast pretreatment method with a good capability for drug detection in biological systems, this technique shows great promise for rapid, credible, and on-spot drug detection. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal adatoms generated by the co-play of melamine assembly and subsequent CO adsorption.

PubMed

Wang, Li; Chen, Qiwei; Shi, Hong; Liu, Huihui; Ren, Xinguo; Wang, Bing; Wu, Kai; Shao, Xiang

2016-01-28

Molecular self-assembly films are expected to tailor the surface process by the periodic nanostructures and add-on functional groups. In this work, a molecular network of melamine with featured pores of subnanometer size is prepared on the Au(111) surface, and is found to be able to trap the gold adatoms and concomitant single vacancies generated under the impingement of CO molecules at room temperature. DFT calculations suggest that the strong CO-Au adatom interaction as well as the high adhesion of the Au adatom inside the melamine pore could well be the driving force behind such process. This study not only sheds light onto the interactions between gasses and the metal surface that is covered by molecular self-assembly films, but also provides a novel route to manipulate the monoatomic surface species which is of catalytic interest.

Biofriendly bonding processes for nanoporous implantable SU-8 microcapsules for encapsulated cell therapy.

PubMed

Nemani, Krishnamurthy; Kwon, Joonbum; Trivedi, Krutarth; Hu, Walter; Lee, Jeong-Bong; Gimi, Barjor

2011-01-01

Mechanically robust, cell encapsulating microdevices fabricated using photolithographic methods can lead to more efficient immunoisolation in comparison to cell encapsulating hydrogels. There is a need to develop adhesive bonding methods which can seal such microdevices under physiologically friendly conditions. We report the bonding of SU-8 based substrates through (i) magnetic self assembly, (ii) using medical grade photocured adhesive and (iii) moisture and photochemical cured polymerization. Magnetic self-assembly, carried out in biofriendly aqueous buffers, provides weak bonding not suitable for long term applications. Moisture cured bonding of covalently modified SU-8 substrates, based on silanol condensation, resulted in weak and inconsistent bonding. Photocured bonding using a medical grade adhesive and of acrylate modified substrates provided stable bonding. Of the methods evaluated, photocured adhesion provided the strongest and most stable adhesion.

Numerical simulation of colloidal self-assembly of super-hydrophobic arachnid cerotegument structures.

PubMed

Filippov, Alexander É; Wolff, Jonas O; Seiter, Michael; Gorb, Stanislav N

2017-10-07

Certain arachnids exhibit complex coatings of their exoskeleton, consisting of globular structures with complex surface features. This, so-called, cerotegument is formed by a multi-component colloidal secretion that self-assembles and cures on the body surface, and leads to high water repellency. Previous ultrastructural studies revealed the involvement of different glandular cells that contribute different components to the secretion mixture, but the overall process of self-assembly into the complex regular structures observed remained highly unclear. Here we study this process from a theoretical point of view, starting from the so-called Tammes-problem. We show that slight changes of simple parameters lead to a variety of morphologies that are highly similar to the ones observed in the species specific cerotegument structures of whip-spiders. These results are not only important for our understanding of the formation of globular hierarchical structures in nature, but also for the fabrication of novel surface coatings by colloidal lithography. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Kinetics of the as Grown and Annealed Self-Assembled Monolayer Studied by Force Spectroscopy

NASA Astrophysics Data System (ADS)

Habib, Huma; Yasar, M.; Mehmood, S.; Rafique, Saima; Bhatti, A. S.; Naeem, Aisha

The growth of biological systems like DNA, peptides and proteins are accredited to the self-assembly processes from the molecular level to the nanoscale. The flawless immobilization of DNA on any surface is quite an important step to the development of DNA-based biosensors. The present paper reports the use of atomic force microscopy to determine the mechanical properties of the as grown and annealed self-assembled monolayer (SAM) as well as the mutated DNA immobilized on the SAM. The SAM of alkane thiol (16-mercapto-1-hexadecanol) was developed on Au surface, which was then annealed and analyzed for its structural and mechanical properties. The surface coverage, height and monolayer’s order was studied as a function of incubation time and annealing time. Excessive annealing led to the defragmentation and desorption of SAM structures due to breaking of hydrocarbon bonds. AFM was employed to determine the detach separation, pull-off and work of adhesion of the as grown and annealed SAM.

Interface electronic structures of reversible double-docking self-assembled monolayers on an Au(111) surface

PubMed Central

Zhang, Tian; Ma, Zhongyun; Wang, Linjun; Xi, Jinyang; Shuai, Zhigang

2014-01-01

Double-docking self-assembled monolayers (DDSAMs), namely self-assembled monolayers (SAMs) formed by molecules possessing two docking groups, provide great flexibility to tune the work function of metal electrodes and the tunnelling barrier between metal electrodes and the SAMs, and thus offer promising applications in both organic and molecular electronics. Based on the dispersion-corrected density functional theory (DFT) in comparison with conventional DFT, we carry out a systematic investigation on the dual configurations of a series of DDSAMs on an Au(111) surface. Through analysing the interface electronic structures, we obtain the relationship between single molecular properties and the SAM-induced work-function modification as well as the level alignment between the metal Fermi level and molecular frontier states. The two possible conformations of one type of DDSAM on a metal surface reveal a strong difference in the work-function modification and the electron/hole tunnelling barriers. Fermi-level pinning is found to be a key factor to understand the interface electronic properties. PMID:24615153

The effect of self-assembled monolayers on graphene conductivity and morphology

NASA Astrophysics Data System (ADS)

Moore, T. L.; Chen, J. H.; Riddick, B.; Williams, E. D.

2009-03-01

Graphene transport properties are limited by charge defects in SiO2, and by large charge density due to strong interaction with SiC. To modify these effects we have treated 300 nm SiO2 with tricholosilanes with different termination groups including pure and fluoro and amino-terminated hydrocarbons for use as substrates for mechanical exfoliation of graphene. XPS measurements verify the presence of the expected termination groups. AFM measurements reveal modified monolayer roughness and correlation lengths; for a fluorinated carbon chain the RMS roughness is 0.266 ± 0.017 nm and the correlation length is 10.2 ± 0.7 nm compared to 0.187 ± 0.011 nm and 19.8 ± 2.5 nm for SiO2. Surface free energies of the monolayers and the SiO2 blank have been computed from static contact angle measurements and all decrease the SiO2 surface free energy; for the fluorinated carbon chain monolayer a decrease of 20 mJ/m^2 from SiO2. We will discuss the ease of exfoliation, and the morphology and conductivity of graphene on these monolayers.

On-line observation of cell growth in a three-dimensional matrix on surface-modified microelectrode arrays.

PubMed

Lin, Shu-Ping; Kyriakides, Themis R; Chen, Jia-Jin J

2009-06-01

Despite many successful applications of microelectrode arrays (MEAs), typical two-dimensional in-vitro cultures do not project the full scale of the cell growth environment in the three-dimensional (3D) in-vivo setting. This study aims to on-line monitor in-vitro cell growth in a 3D matrix on the surface-modified MEAs with a dynamic perfusion culture system. A 3D matrix consisting of poly(ethylene glycol) hydrogel supplemented with poly-D-lysine was subsequently synthesized in situ on the self-assembled monolayer modified MEAs. FTIR spectrum analysis revealed a peak at 2100 cm(-1) due to the degradation of the structure of the 3D matrix. After 2 wks, microscopic examination revealed that the non-degraded area was around 1500 microm(2) and provided enough space for cell growth. Fluorescence microscopy revealed that the degraded 3D matrix was non-cytotoxic allowing the growth of NIH3T3 fibroblasts and cortical neurons in vitro. Time-course changes of total impedance including resistance and reactance were recorded for 8 days to evaluate the cell growth in the 3D matrix on the MEA. A consistent trend reflecting changes of reactance and total impedance was observed. These in-vitro assays demonstrate that our 3D matrix can construct a biomimetic system for cell growth and analysis of cell surface interactions.

Sensing specific adhesion of liposomal and micellar systems with attached carbohydrate recognition structures at lectin surfaces.

PubMed

Hildebrand, Annegret; Schaedlich, Anita; Rothe, Ulrich; Neubert, Reinhard H H

2002-05-15

A quartz crystal microbalance was used to investigate the adsorption behavior of liposomes and mixed micelles with attached carbohydrate recognition structures at lectin-coated quartz plates. With a self-assembly technique, the quartz was coated with the lectin Concanavalin A. In a first attempt, liposomes of natural soybean PC as well as synthetic POPC, containing 10% reactive N-Glut-PE each, were decorated with a mannopyranoside recognition structure to investigate the specific adsorption at the lectin-coated quartz surface in dependence on the concentration. In a second model, the bile salt sodium cholate was introduced to solubilize the mannopyranoside-modified liposomes and to transform them into mannopyranoside-modified binary mixed micelles. The adsorption of these micelles was further investigated. In a third approach, the adsorption behavior of mannopyranoside-modified ternary mixed bile salt-phosphatidylcholine-fatty acid micelles was characterized with sodium laurate, palmitate, and oleate as fatty acids. The micelles with oleate showed only a small frequency decrease, whereas the micelles with laurate and palmitate induced higher frequency changes. A dependence on the alkyl chain length could be detected. While the adsorption of liposomes containing recognition structures at QCM surfaces is nowadays well-established, the QCM detection of the adsorption of mixed bile salt micelles, transformed from these liposomes by solubilization, is a novel and very promising field for the development of innovative colloidal drug delivery systems.

Cooling of weapons with graphite foam

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

Klett, James W.; Trammell, Michael P.

Disclosed are examples of an apparatus for cooling a barrel 12 of a firearm 10 and examples of a cooled barrel assembly 32 for installation into an existing firearm 10. When assembled with the barrel 12, a contact surface 16 of a shell 14 is proximate to, and in thermal communication with, the outer surface of the barrel 18. The shell 14 is formed of commercially available or modified graphite foam.

Applications of Graphene-Modified Electrodes in Microbial Fuel Cells

PubMed Central

Yu, Fei; Wang, Chengxian; Ma, Jie

2016-01-01

Graphene-modified materials have captured increasing attention for energy applications due to their superior physical and chemical properties, which can significantly enhance the electricity generation performance of microbial fuel cells (MFC). In this review, several typical synthesis methods of graphene-modified electrodes, such as graphite oxide reduction methods, self-assembly methods, and chemical vapor deposition, are summarized. According to the different functions of the graphene-modified materials in the MFC anode and cathode chambers, a series of design concepts for MFC electrodes are assembled, e.g., enhancing the biocompatibility and improving the extracellular electron transfer efficiency for anode electrodes and increasing the active sites and strengthening the reduction pathway for cathode electrodes. In spite of the challenges of MFC electrodes, graphene-modified electrodes are promising for MFC development to address the reduction in efficiency brought about by organic waste by converting it into electrical energy. PMID:28773929

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.

Pressure effect on micellization of non-ionic surfactant Triton X-100

NASA Astrophysics Data System (ADS)

Espinosa, Yanis R.; Caffarena, Ernesto R.; Martínez, Yanina Berrueta; Grigera, J. Raúl

2018-02-01

Micellar aggregates can be arranged in new types of conformational assemblies when they are isotropically compressed. Thus, the pressure effects in the underlying fundamental interactions leading to self-assembly of micellar aggregates can be represented by changes in the phase boundaries with increasing pressure. In this paper, we have employed molecular dynamics simulations to study the self-assembly of micelles composed of the non-ionic surfactant Triton X-100 at the atomic scale, monitoring the changes in the solvation dynamics when the micelles are subjected to a wide range of hydrostatic pressures. The computational molecular model was capable of self-assembling and forming a non-ionic micelle, which subsequently was coupled to a high-pressure barostat producing a geometric transition of the micelle due to changes in the solvation dynamics. Accordingly, under a high pressure regime, the hydrogen bonds are redistributed, the water density is modified, and water acts as an unstructured liquid, capable of penetrating into the micelle.

Self-locking telescoping manipulator arm

NASA Technical Reports Server (NTRS)

Nesmith, M. F. (Inventor)

1985-01-01

A telescoping manipulator arm and pivotable finger assembly are disclosed. The telescoping arm assembly includes a generally T-shaped arm having three outwardly extending fingers guided on grooved roller guides to compensate for environmental variations. The pivotable finger assembly includes four pivoting fingers. Arcuate teeth are formed on the ends of the fingers. A rack having teeth on four sides meshes with each one of the fingers. One surface of the rack includes teeth along its entire surface which mesh with teeth of one of the fingers. The teeth at the remote end of the rack engage teeth of a gear wheel. The wheel includes a worm which meshes with a worn drive shaft of the drive motor providing a ninety degree self-locking drive for locking the fingers in a desired position. A similar drive provides a self-locking drive for positioning the telescoping arm.

The polymeric nanofilm of triazinedithiolsilane fabricated by self-assembled technique on copper surface. Part 2: Characterization of composition and morphology

NASA Astrophysics Data System (ADS)

Wang, Yabin; Liu, Zhong; Huang, Yudong; Qi, Yutai

2015-11-01

In the first part, a novel design route for metal protection against corrosion was proposed, and a class of triazinedithiolsilane compounds was conceived as protector for copper. The protective capability of the polymeric nanofilm, fabricated by self-assembling one representative (abbreviated as TESPA) of triazinedithiolsilane compounds onto copper surface, has been investigated and evaluated by electrochemical tests. The results show that the polymeric nanofilm significantly inhibits copper corrosion. This study, on the one hand, concentrates on the chemical composition of the TESPA polymeric nanofilm by means of X-ray photoelectron spectroscopy (XPS). The XPS results reveal that the chemical bonds between copper and TESPA monomers, three dimensional disulfide units and siloxane networks are responsible for the satisfactory protection of TESPA polymeric nanofilm against copper corrosion. On the other hand, scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS) are utilized to reveal the morphology and the uniformity of the TESPA polymeric nanofilm. The SEM-EDS results demonstrate that the copper surfaces are uniformly covered with TESPA self-assembled monolayer and the polymeric nanofilm. The TESPA-covered copper surfaces turn out to be smoother than that of the bare copper surface.

Selective in situ potential-assisted SAM formation on multi electrode arrays

NASA Astrophysics Data System (ADS)

Haag, Ann-Lauriene; Toader, Violeta; Lennox, R. Bruce; Grutter, Peter

2016-11-01

The selective modification of individual components in a biosensor array is challenging. To address this challenge, we present a generalizable approach to selectively modify and characterize individual gold surfaces in an array, in an in situ manner. This is achieved by taking advantage of the potential dependent adsorption/desorption of surface-modified organic molecules. Control of the applied potential of the individual sensors in an array where each acts as a working electrode provides differential derivatization of the sensor surfaces. To demonstrate this concept, two different self-assembled monolayer (SAM)-forming electrochemically addressable ω-ferrocenyl alkanethiols (C11) are chemisorbed onto independent but spatially adjacent gold electrodes. The ferrocene alkanethiol does not chemisorb onto the surface when the applied potential is cathodic relative to the adsorption potential and the electrode remains underivatized. However, applying potentials that are modestly positive relative to the adsorption potential leads to extensive coverage within 10 min. The resulting SAM remains in a stable state while held at potentials <200 mV above the adsorption potential. In this state, the chemisorbed SAM does not significantly desorb nor do new ferrocenylalkythiols adsorb. Using three set applied potentials provides for controlled submonolayer alkylthiol marker coverage of each independent gold electrode. These three applied potentials are dependent upon the specifics of the respective adsorbate. Characterization of the ferrocene-modified electrodes via cyclic voltammetry demonstrates that each specific ferrocene marker is exclusively adsorbed to the desired target electrode.

UV/vis and NIR light-responsive spiropyran self-assembled monolayers.

PubMed

Ivashenko, Oleksii; van Herpt, Jochem T; Feringa, Ben L; Rudolf, Petra; Browne, Wesley R

2013-04-02

Self-assembled monolayers of a 6-nitro BIPS spiropyran (SP) modified with a disulfide-terminated aliphatic chain were prepared on polycrystalline gold surfaces and characterized by UV/vis absorption, surface-enhanced Raman scattering (SERS), and X-ray photoelectron spectroscopies (XPS). The SAMs obtained are composed of the ring-closed form (i.e., spiropyran) only. Irradiation with UV light results in conversion of the monolayer to the merocyanine form (MC), manifested in the appearance of an N(+) contribution in the N 1s region of the XPS spectrum of the SAMs, the characteristic absorption band of the MC form in the visible region at 555 nm, and the C-O stretching band in the SERS spectrum. Recovery of the initial state of the monolayer was observed both thermally and after irradiation with visible light. Several switching cycles were performed and monitored by SERS spectroscopy, demonstrating the stability of the SAMs during repeated switching between SP and MC states. A key finding in the present study is that ring-opening of the surface-immobilized spiropyrans can be induced by irradiation with continuous wave NIR (785 nm) light as well as by irradiation with UV light. We demonstrate that ring-opening by irradiation at 785 nm proceeds by a two-photon absorption pathway both in the SAMs and in the solid state. Hence, spiropyran SAMs on gold can undergo reversible photochemical switching from the SP to the MC form with both UV and NIR and the reverse reaction induced by irradiation with visible light or heating. Furthermore, the observation of NIR-induced switching with a continuous wave source holds important consequences in the study of photochromic switches on surfaces using SERS and emphasizes the importance of the use of multiple complementary techniques in characterizing photoresponsive SAMs.

Optimisation and Characterisation of Anti-Fouling Ternary SAM Layers for Impedance-Based Aptasensors

PubMed Central

Miodek, Anna; Regan, Edward M.; Bhalla, Nikhil; Hopkins, Neal A.E.; Goodchild, Sarah A.; Estrela, Pedro

2015-01-01

An aptasensor with enhanced anti-fouling properties has been developed. As a case study, the aptasensor was designed with specificity for human thrombin. The sensing platform was developed on screen printed electrodes and is composed of a self-assembled monolayer made from a ternary mixture of 15-base thiolated DNA aptamers specific for human thrombin co-immobilised with 1,6-hexanedithiol (HDT) and further passivated with 1-mercapto-6-hexanol (MCH). HDT binds to the surface by two of its thiol groups forming alkyl chain bridges and this architecture protects from non-specific attachment of molecules to the electrode surface. Using Electrochemical Impedance Spectroscopy (EIS), the aptasensor is able to detect human thrombin as variations in charge transfer resistance (Rct) upon protein binding. After exposure to a high concentration of non-specific Bovine Serum Albumin (BSA) solution, no changes in the Rct value were observed, highlighting the bio-fouling resistance of the surface generated. In this paper, we present the optimisation and characterisation of the aptasensor based on the ternary self-assembled monolayer (SAM) layer. We show that anti-fouling properties depend on the type of gold surface used for biosensor construction, which was also confirmed by contact angle measurements. We further studied the ratio between aptamers and HDT, which can determine the specificity and selectivity of the sensing layer. We also report the influence of buffer pH and temperature used for incubation of electrodes with proteins on detection and anti-fouling properties. Finally, the stability of the aptasensor was studied by storage of modified electrodes for up to 28 days in different buffers and atmospheric conditions. Aptasensors based on ternary SAM layers are highly promising for clinical applications for detection of a range of proteins in real biological samples. PMID:26426017

Optimisation and Characterisation of Anti-Fouling Ternary SAM Layers for Impedance-Based Aptasensors.

PubMed

Miodek, Anna; Regan, Edward M; Bhalla, Nikhil; Hopkins, Neal A E; Goodchild, Sarah A; Estrela, Pedro

2015-09-29

An aptasensor with enhanced anti-fouling properties has been developed. As a case study, the aptasensor was designed with specificity for human thrombin. The sensing platform was developed on screen printed electrodes and is composed of a self-assembled monolayer made from a ternary mixture of 15-base thiolated DNA aptamers specific for human thrombin co-immobilised with 1,6-hexanedithiol (HDT) and further passivated with 1-mercapto-6-hexanol (MCH). HDT binds to the surface by two of its thiol groups forming alkyl chain bridges and this architecture protects from non-specific attachment of molecules to the electrode surface. Using Electrochemical Impedance Spectroscopy (EIS), the aptasensor is able to detect human thrombin as variations in charge transfer resistance (Rct) upon protein binding. After exposure to a high concentration of non-specific Bovine Serum Albumin (BSA) solution, no changes in the Rct value were observed, highlighting the bio-fouling resistance of the surface generated. In this paper, we present the optimisation and characterisation of the aptasensor based on the ternary self-assembled monolayer (SAM) layer. We show that anti-fouling properties depend on the type of gold surface used for biosensor construction, which was also confirmed by contact angle measurements. We further studied the ratio between aptamers and HDT, which can determine the specificity and selectivity of the sensing layer. We also report the influence of buffer pH and temperature used for incubation of electrodes with proteins on detection and anti-fouling properties. Finally, the stability of the aptasensor was studied by storage of modified electrodes for up to 28 days in different buffers and atmospheric conditions. Aptasensors based on ternary SAM layers are highly promising for clinical applications for detection of a range of proteins in real biological samples.

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.

Extreme Activity of Drug Nanocrystals Coated with A Layer of Non-Covalent Polymers from Self-Assembled Boric Acid

NASA Astrophysics Data System (ADS)

Zhan, Honglei; Liang, Jun F.

2016-12-01

Non-covalent polymers have remarkable advantages over synthetic polymers for wide biomedical applications. In this study, non-covalent polymers from self-assembled boric acid were used as the capping reagent to replace synthetic polymers in drug crystallization. Under acidic pH, boric acid self-assembled on the surface of drug nanocrystals to form polymers with network-like structures held together by hydrogen bonds. Coating driven by boric acid self-assembly had negligible effects on drug crystallinity and structure but resulted in drug nanocrystals with excellent dispersion properties that aided in the formation of a more stable suspension. Boric acid coating improved drug stability dramatically by preventing drug molecules from undergoing water hydrolysis in a neutral environment. More importantly, the specific reactivity of orthoboric groups to diols in cell glycocalyx facilitated a rapid cross-membrane translocation of drug nanocrystals, leading to efficient intracellular drug delivery, especially on cancer cells with highly expressed sialic acids. Boric acid coated nanocrystals of camptothecin, an anticancer drug with poor aqueous solubility and stability, demonstrated extreme cytotoxic activity (IC50 < 5.0 μg/mL) to cancer cells compared to synthetic polymer coated CPT nanocrystals and free CPT. Surface coating using non-covalent polymers from self-assembled boric acid will have wide biomedical applications especially in biomaterials and drug delivery field.

Extreme Activity of Drug Nanocrystals Coated with A Layer of Non-Covalent Polymers from Self-Assembled Boric Acid.

PubMed

Zhan, Honglei; Liang, Jun F

2016-12-09

Non-covalent polymers have remarkable advantages over synthetic polymers for wide biomedical applications. In this study, non-covalent polymers from self-assembled boric acid were used as the capping reagent to replace synthetic polymers in drug crystallization. Under acidic pH, boric acid self-assembled on the surface of drug nanocrystals to form polymers with network-like structures held together by hydrogen bonds. Coating driven by boric acid self-assembly had negligible effects on drug crystallinity and structure but resulted in drug nanocrystals with excellent dispersion properties that aided in the formation of a more stable suspension. Boric acid coating improved drug stability dramatically by preventing drug molecules from undergoing water hydrolysis in a neutral environment. More importantly, the specific reactivity of orthoboric groups to diols in cell glycocalyx facilitated a rapid cross-membrane translocation of drug nanocrystals, leading to efficient intracellular drug delivery, especially on cancer cells with highly expressed sialic acids. Boric acid coated nanocrystals of camptothecin, an anticancer drug with poor aqueous solubility and stability, demonstrated extreme cytotoxic activity (IC 50  < 5.0 μg/mL) to cancer cells compared to synthetic polymer coated CPT nanocrystals and free CPT. Surface coating using non-covalent polymers from self-assembled boric acid will have wide biomedical applications especially in biomaterials and drug delivery field.

Extreme Activity of Drug Nanocrystals Coated with A Layer of Non-Covalent Polymers from Self-Assembled Boric Acid

PubMed Central

Zhan, Honglei; Liang, Jun F.

2016-01-01

Non-covalent polymers have remarkable advantages over synthetic polymers for wide biomedical applications. In this study, non-covalent polymers from self-assembled boric acid were used as the capping reagent to replace synthetic polymers in drug crystallization. Under acidic pH, boric acid self-assembled on the surface of drug nanocrystals to form polymers with network-like structures held together by hydrogen bonds. Coating driven by boric acid self-assembly had negligible effects on drug crystallinity and structure but resulted in drug nanocrystals with excellent dispersion properties that aided in the formation of a more stable suspension. Boric acid coating improved drug stability dramatically by preventing drug molecules from undergoing water hydrolysis in a neutral environment. More importantly, the specific reactivity of orthoboric groups to diols in cell glycocalyx facilitated a rapid cross-membrane translocation of drug nanocrystals, leading to efficient intracellular drug delivery, especially on cancer cells with highly expressed sialic acids. Boric acid coated nanocrystals of camptothecin, an anticancer drug with poor aqueous solubility and stability, demonstrated extreme cytotoxic activity (IC50 < 5.0 μg/mL) to cancer cells compared to synthetic polymer coated CPT nanocrystals and free CPT. Surface coating using non-covalent polymers from self-assembled boric acid will have wide biomedical applications especially in biomaterials and drug delivery field. PMID:27934922

Low-dimensional materials for organic electronic applications

NASA Astrophysics Data System (ADS)

Beniwal, Sumit

This thesis explores the self-assembly, surface interactions and electronic properties of functional molecules that have potential applications in electronics. Three classes of molecules - organic ferroelectric, spin-crossover complex, and molecules that assemble into a 2D semiconductor, have been studied through scanning tunneling microscopy and surfacesensitive spectroscopic methods. The scientific goal of this thesis is to understand the self-assembly of these molecules in low-dimensional (2D) configurations and the influence of substrate on their properties.

Driving self-assembly and emergent dynamics in colloidal suspensions by time-dependent magnetic fields

DOE PAGES

Martin, James E.; Snezhko, Alexey

2013-11-05

In this review we discuss recent research on driving self assembly of magnetic particle suspensions subjected to alternating magnetic fields. The variety of structures and effects that can be induced in such systems is remarkably broad due to the large number of variables involved. The alternating field can be uniaxial, biaxial or triaxial, the particles can be spherical or anisometric, and the suspension can be dispersed throughout a volume or confined to a soft interface. In the simplest case the field drives the static or quasi-static assembly of unusual particle structures, such as sheets, networks and open-cell foams. More complex,more » emergent collective behaviors evolve in systems that can follow the time-dependent field vector. In these cases energy is continuously injected into the system and striking °ow patterns and structures can arise. In fluid volumes these include the formation of advection and vortex lattices. At air-liquid and liquid-liquid interfaces striking dynamic particle assemblies emerge due to the particle-mediated coupling of the applied field to surface excitations. These out-of-equilibrium interface assemblies exhibit a number of remarkable phenomena, including self-propulsion and surface mixing. In addition to discussing various methods of driven self assembly in magnetic suspensions, some of the remarkable properties of these novel materials are described.« less

Self-assembly of protein-based biomaterials initiated by titania nanotubes.

PubMed

Forstater, Jacob H; Kleinhammes, Alfred; Wu, Yue

2013-12-03

Protein-based biomaterials are a promising strategy for creating robust highly selective biocatalysts. The assembled biomaterials must sufficiently retain the near-native structure of proteins and provide molecular access to catalytically active sites. These requirements often exclude the use of conventional assembly techniques, which rely on covalent cross-linking of proteins or entrapment within a scaffold. Here we demonstrate that titania nanotubes can initiate and template the self-assembly of enzymes, such as ribonuclease A, while maintaining their catalytic activity. Initially, the enzymes form multilayer thick ellipsoidal aggregates centered on the nanotube surface; subsequently, these nanosized entities assemble into a micrometer-sized enzyme material that has enhanced enzymatic activity and contains as little as 0.1 wt % TiO2 nanotubes. This phenomenon is uniquely associated with the active anatase (001)-like surface of titania nanotubes and does not occur on other anatase nanomaterials, which contain significantly fewer undercoordinated Ti surface sites. These findings present a nanotechnology-enabled mechanism of biomaterial growth and open a new route for creating stable protein-based biomaterials and biocatalysts without the need for chemical modification.

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.

Self-Assembly into Nanoparticles Is Essential for Receptor Mediated Uptake of Therapeutic Antisense Oligonucleotides.

PubMed

Ezzat, Kariem; Aoki, Yoshitsugu; Koo, Taeyoung; McClorey, Graham; Benner, Leif; Coenen-Stass, Anna; O'Donovan, Liz; Lehto, Taavi; Garcia-Guerra, Antonio; Nordin, Joel; Saleh, Amer F; Behlke, Mark; Morris, John; Goyenvalle, Aurelie; Dugovic, Branislav; Leumann, Christian; Gordon, Siamon; Gait, Michael J; El-Andaloussi, Samir; Wood, Matthew J A

2015-07-08

Antisense oligonucleotides (ASOs) have the potential to revolutionize medicine due to their ability to manipulate gene function for therapeutic purposes. ASOs are chemically modified and/or incorporated within nanoparticles to enhance their stability and cellular uptake, however, a major challenge is the poor understanding of their uptake mechanisms, which would facilitate improved ASO designs with enhanced activity and reduced toxicity. Here, we study the uptake mechanism of three therapeutically relevant ASOs (peptide-conjugated phosphorodiamidate morpholino (PPMO), 2'Omethyl phosphorothioate (2'OMe), and phosphorothioated tricyclo DNA (tcDNA) that have been optimized to induce exon skipping in models of Duchenne muscular dystrophy (DMD). We show that PPMO and tcDNA have high propensity to spontaneously self-assemble into nanoparticles. PPMO forms micelles of defined size and their net charge (zeta potential) is dependent on the medium and concentration. In biomimetic conditions and at low concentrations, PPMO obtains net negative charge and its uptake is mediated by class A scavenger receptor subtypes (SCARAs) as shown by competitive inhibition and RNAi silencing experiments in vitro. In vivo, the activity of PPMO was significantly decreased in SCARA1 knockout mice compared to wild-type animals. Additionally, we show that SCARA1 is involved in the uptake of tcDNA and 2'OMe as shown by competitive inhibition and colocalization experiments. Surface plasmon resonance binding analysis to SCARA1 demonstrated that PPMO and tcDNA have higher binding profiles to the receptor compared to 2'OMe. These results demonstrate receptor-mediated uptake for a range of therapeutic ASO chemistries, a mechanism that is dependent on their self-assembly into nanoparticles.

The Molecular Boat: A Hands-On Experiment to Demonstrate the Forces Applied to Self-Assembled Monolayers at Interfaces

ERIC Educational Resources Information Center

Chan, Charlene J.; Salaita, Khalid

2012-01-01

Demonstrating how surface chemistry and self-assembled monolayers (SAMs) control the macroscopic properties of materials is challenging as it often necessitates the use of specialized instrumentation. In this hands-on experiment, students directly measure a macroscopic property, the floatation of glass coverslips on water as a function of…

Synthetic approaches to construct viral capsid-like spherical nanomaterials.

PubMed

Matsuura, Kazunori

2018-06-06

This feature article describes recent progress in synthetic strategies to construct viral capsid-like spherical nanomaterials using the self-assembly of peptides and/or proteins. By mimicking the self-assembly of spherical viral capsids and clathrin, trigonal peptide conjugates bearing β-sheet-forming peptides, glutathiones, or coiled-coil-forming peptides were developed to construct viral capsid-like particles. β-Annulus peptides from tomato bushy stunt virus self-assembled into viral capsid-like nanocapsules with a size of 30-50 nm, which could encapsulate various guest molecules and be decorated with different molecules on their surface. Rationally designed fusion proteins bearing symmetric assembling units afforded precise viral capsid-like polyhedral assemblies. These synthetic approaches to construct artificial viruses could become useful guidelines to develop novel drug carriers, vaccine platforms, nanotemplates and nanoreactors.

Self-assembly of ordered nanostructures

NASA Astrophysics Data System (ADS)

Yin, Jinsong

2000-10-01

Several different kinds of nanostructure materials were studied in this thesis: self-assembled monodispersive nanocrystals, photonic crystals, ordered mesoporous silica and hierarchically ordered nanostructured materials. Tetrahedral nanocrystals of CoO, with edge-lengths of 4.4 +/- 0.2 nm, were synthesized at high purity and monodispersity. The size, shape and phase selections of the nanocrystals were performed using a novel magnetic field separation technique. These nanocrystals behave like molecules, forming a face-centered cubic self-assembly of nanocrystal superlattices. In-situ behavior of self-assembled CoO nanocrystal arrays was also analyzed using transmission electron microscopy and associated techniques. The surface passivation layer started to evaporate/decompose at temperatures as low as ˜200°C, but the exposed cores of nanocrystals preserved the geometrical configuration of the assembly due to the strong adhesion of the carbon substrate. As the temperature is further increased from 300 to 600°C, the intrinsic crystal structure of the CoO nanoparticles experiences a replacement reaction, resulting in the formation of cobalt carbides. Two-dimensional self-assembling of cobalt nanocrystals with an average particle size of 9.2 nm and polydispersity of 9% is processed. Phtonic crystals were processed by a template-assisted method. Ordered self-assembly of pores of titania nanocrystals formed a face-centered cubic packing structure. The walls of the pores were made of anatase nanocrystals of ˜8 nm in diameter. Cobalt can be doped into the walls of the pores by solution infiltration of cobalt carbonyl. Cobalt titanium oxide may be formed on the internal surface of the ordered pore structure. This type of structure is likely to be an excellent supporting material for catalysis. The experimental results suggest that transition metal elements can be incorporated into porous titania without blocking the interconnected pores. Hierarchically ordered nanostructured materials with high porosity at dual length-scale were prepared by a single annealing procedure. The plasma energy of this porous materials shifts about 1.2 eV to lower energy, compared to the fully densed silica spheres. This type of material is expected to have not only large surface area for catalysis, but also low dielectric constant for low-loss dielectric applications.

Monolayers of the lipid derivatives of isoniazid at the air/water interface and the formation of self-assembled nanostructures in water.

PubMed

Jin, Yiguang; Chen, Shufeng; Xin, Rui; Zhou, Yisheng

2008-07-15

Isoniazid (INH, isonicotinic acid hydrazide) is one of the most commonly used anti-tubercular drugs. However, resistance of Mycobacterium tuberculosis strains to anti-mycobacterial agents including INH is an increasing problem worldwide. Development of new anti-mycobacterial agents thus has attracted attention. Five lipid derivatives of INH were prepared in this study. They formed monolayers at the air/water interface, and some nanostructures with different morphologies were obtained through molecular self-assembly in water. The derivatives included one fatty acyl derivative containing a 12-C hydrocarbon-long chain (1), three fatty alcohol derivatives with a succinyl as spacer and an 8, 12 or 16-C hydrocarbon-long chain (2, 3 and 4), and one tetrahydro-2H-1,3,5-thiadiazine-2-thione (THTT) derivative containing a 12-C hydrocarbon-long chain (5). The surface pressure-area isotherms depended on the volume and configuration of heads and the length of tails of derivatives. Compound 2 had a relatively large head and a short tail, easily standing uprightly at the interface. Under a certain surface pressure, the linear polar head groups of 3 could be partly squeezed out and insert into subphase because the length of heads were comparable to the one of tails. The very long tails of 4 always maintained above the interface and led to a high collapse pressure. Compound 5 possessed an extended and large head consisting of the THTT and INH groups so that the relatively short tails tilted at the interface and difficultly contact with each other. The THTT rings might be partly squeezed out and enter into air under a certain surface pressure. The self-assembly behaviours of derivatives in water depended on the molecular configuration and agreed with the corresponding monolayer behaviours. The flexible and medium-long tails (1 and 3) led to the derivatives to form nanoscale vesicles, though the short or very long tails did not (2 and 4). Interestingly, intermolecular hydrogen bonding could occur between the molecules of 5, and improve the derivative forming helical nanofibres other than vesicles. The molecular self-assembly of INH's lipid derivatives was explored in details in this study. The formation mechanisms of self-assembled nanostructures were analyzed. Various types of self-assembled nanostructures were obtained and the formation mechanisms were analyzed. The relationship between the self-assembly and the molecular configuration of amphiphilic derivatives was also revealed. The lipid derivatives of INH show promising anti-Mycobacterium action because the amphiphilic prodrugs allow for better penetration of the bacterial cells. The self-assembled nanostructures may likely be the potential self-assembled drug delivery systems for tuberculosis therapy.

Understanding Peptide Oligomeric State in Langmuir Monolayers of Amphiphilic 3-Helix Bundle-Forming Peptide-PEG Conjugates

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

Lund, Reidar; Ang, JooChuan; Shu, Jessica Y.

Coiled-coil peptide-polymer conjugates are an emerging class of biomaterials. Fundamental understanding of the coiled-coil oligomeric state and assembly process of these hybrid building blocks is necessary to exert control over their assembly into well-defined structures. Here in this paper, we studied the effect of peptide structure and PEGylation on the self-assembly process and oligomeric state of a Langmuir monolayer of amphiphilic coiled-coil peptide-polymer conjugates using X-ray reflectivity (XR) and grazing-incidence X-ray diffraction (GIXD). Our results show that the oligomeric state of PEGylated amphiphiles based on 3-helix bundle-forming peptide is surface pressure dependent, a mixture of dimers and trimers was formedmore » at intermediate surface pressure but transitions into trimers completely upon increasing surface pressure. Moreover, the interhelical distance within the coiled-coil bundle of 3-helix peptide-PEG conjugate amphiphiles was not perturbed under high surface pressure. Present studies provide valuable insights into the self-assembly process of hybrid peptide-polymer conjugates and guidance to develop biomaterials with controlled multivalency of ligand presentation.« less

Understanding Peptide Oligomeric State in Langmuir Monolayers of Amphiphilic 3-Helix Bundle-Forming Peptide-PEG Conjugates

DOE PAGES

Lund, Reidar; Ang, JooChuan; Shu, Jessica Y.; ...

2016-10-26

Coiled-coil peptide-polymer conjugates are an emerging class of biomaterials. Fundamental understanding of the coiled-coil oligomeric state and assembly process of these hybrid building blocks is necessary to exert control over their assembly into well-defined structures. Here in this paper, we studied the effect of peptide structure and PEGylation on the self-assembly process and oligomeric state of a Langmuir monolayer of amphiphilic coiled-coil peptide-polymer conjugates using X-ray reflectivity (XR) and grazing-incidence X-ray diffraction (GIXD). Our results show that the oligomeric state of PEGylated amphiphiles based on 3-helix bundle-forming peptide is surface pressure dependent, a mixture of dimers and trimers was formedmore » at intermediate surface pressure but transitions into trimers completely upon increasing surface pressure. Moreover, the interhelical distance within the coiled-coil bundle of 3-helix peptide-PEG conjugate amphiphiles was not perturbed under high surface pressure. Present studies provide valuable insights into the self-assembly process of hybrid peptide-polymer conjugates and guidance to develop biomaterials with controlled multivalency of ligand presentation.« less

Directed surface attachment of nanomaterials via coiled-coil-driven self-assembly

NASA Astrophysics Data System (ADS)

White, Simon J.; Johnson, Steven; Szymonik, Michal; Wardingley, Richard A.; Pye, Douglas; Davies, A. Giles; Wälti, Christoph; Stockley, Peter G.

2012-12-01

Numerous nanoscale devices and materials have been fabricated in recent years using a variety of biological scaffolds. However, the interfacing of these devices and materials into existing circuits and ordered arrays has proved problematic. Here, we describe a simple solution to this problem using self-assembly of the peptide coiled-coil heterodimer ACID:BASE to immobilize M13 bacteriophage particles to specific locations on a patterned gold surface. Surface plasmon resonance demonstrated that free ACID peptides will assemble onto a surface derivatized with BASE. We then displayed the ACID peptide on the pIX coat protein of M13 and showed that these phage particles permit formation of the coiled-coil resulting in specific surface attachment. The ACID:immobilized BASE affinities appear to be similar for free peptide and phage-displayed ACID. Finally, we fabricated two gold electrodes, separated by a 200 nm gap, coated one of them with BASE and showed that this allows localization of the M13:ACID onto the functionalized electrode.

Time-resolved viscoelastic properties of self-assembling iron oxide nanocube superlattices probed by quartz crystal microbalance with dissipation monitoring.

PubMed

Kapuscinski, Martin; Agthe, Michael; Bergström, Lennart

2018-07-15

Self-assembly of nanoparticles into superlattices can be used to create hierarchically structured materials with tailored functions. We have used the surface sensitive quartz crystal microbalance with dissipation monitoring (QCM-D) technique in combination with video microscopy (VM) to obtain time-resolved information on the mass increase and rheological properties of evaporation-induced self-assembly of nanocubes. We have recorded the frequency and dissipation shifts during growth and densification of superlattices formed by self-assembly of oleic acid capped, truncated iron oxide nanocubes and analyzed the time-resolved QCM-D data using a Kelvin-Voigt viscoelastic model. We show that the nanoparticles first assemble into solvent-containing arrays dominated by a viscous response followed by a solvent-releasing step that results in the formation of rigid and well-ordered superlattices. Our findings demonstrate that QCM-D can be successfully used to follow self-assembly and assist in the design of optimized routes to produce well-ordered superlattices. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

Micro/nano-particles and Cells: Manipulation, Transport, and Self-assembly

DTIC Science & Technology

2014-10-23

SECURITY CLASSIFICATION OF: Technologies that control nano- and micron- sized inert as well as biological materials are crucial to realizing engineered...that control nano- and micron- sized inert as well as biological materials are crucial to realizing engineered systems that can assemble, transport, and...nano-scale particles offer several advantages as building blocks of artificial materials . The relative ease of modifying their charge states

Time-resolved spectroscopy of self-assembly of CCMV protein capsids

NASA Astrophysics Data System (ADS)

Moore, Jelyn; Aronzon, Dina; Manoharan, V. N.

2008-10-01

In order to gain a deeper understanding of the process a virus undergoes to assemble; the purpose of this study to time resolve the self-assembly of a virus. Cowpea Chlorotic Mottle virus (CCMV), an icosahedral type virus, can assemble without its genetic code (RNA) depending on its chemical and physical surroundings. The surface plasmon resonance (SPR) of colloidal gold particles is known to display a shift when the gold interacts with the proteins of a virus. Surface plasmon resonance is the free electron oscillation occurring at the surface of the gold particle resulting in a characteristic peak location at maximal absorbance and peak width. The shift results from the change in the refractive index of the particles as induced by the presence of the proteins. We hope to detect this shift through total internal reflection microscopy (TIRM). The accomplishments of this research are the completion of the TIR setup and the purification of the virus and its proteins.

One-Dimensional Multichromophor Arrays Based on DNA: From Self-Assembly to Light-Harvesting.

PubMed

Ensslen, Philipp; Wagenknecht, Hans-Achim

2015-10-20

Light-harvesting complexes collect light energy and deliver it by a cascade of energy and electron transfer processes to the reaction center where charge separation leads to storage as chemical energy. The design of artificial light-harvesting assemblies faces enormous challenges because several antenna chromophores need to be kept in close proximity but self-quenching needs to be avoided. Double stranded DNA as a supramolecular scaffold plays a promising role due to its characteristic structural properties. Automated DNA synthesis allows incorporation of artificial chromophore-modified building blocks, and sequence design allows precise control of the distances and orientations between the chromophores. The helical twist between the chromophores, which is induced by the DNA framework, controls energy and electron transfer and thereby reduces the self-quenching that is typically observed in chromophore aggregates. This Account summarizes covalently multichromophore-modified DNA and describes how such multichromophore arrays were achieved by Watson-Crick-specific and DNA-templated self-assembly. The covalent DNA systems were prepared by incorporation of chromophores as DNA base substitutions (either as C-nucleosides or with acyclic linkers as substitutes for the 2'-deoxyribofuranoside) and as DNA base modifications. Studies with DNA base substitutions revealed that distances but more importantly relative orientations of the chromophores govern the energy transfer efficiencies and thereby the light-harvesting properties. With DNA base substitutions, duplex stabilization was faced and could be overcome, for instance, by zipper-like placement of the chromophores in both strands. For both principal structural approaches, DNA-based light-harvesting antenna could be realized. The major disadvantages, however, for covalent multichromophore DNA conjugates are the poor yields of synthesis and the solubility issues for oligonucleotides with more than 5-10 chromophore modifications in a row. A logical alternative approach is to leave out the phosphodiester bridges between the chromophores and let chromophore-nucleoside conjugates self-assemble specifically along single stranded DNA as template. The self-organization of chromophores along the DNA template based on canonical base pairing would be advantageous because sequence selective base pairing could provide a structural basis for programmed complexity within the chromophore assembly. The self-assembly is governed by two interactions. The chromophore-nucleoside conjugates as guest molecules are recognized via hydrogen bonds to the corresponding counter bases in the single stranded DNA template. Moreover, the π-π interactions between the stacked chromophores stabilize these self-assembled constructs with increasing length. Longer DNA templates are more attractive for self-assembled antenna. The helicity in the stack of porphyrins as guest molecules assembled on the DNA template can be switched by environmental changes, such as pH variations. DNA-templated stacks of ethynyl pyrene and nile red exhibit left-handed chirality, which stands in contrast to similar covalent multichromophore-DNA conjugates with enforced right-handed helicity. With ethynyl nile red, it is possible to occupy every available binding site on the templates. Mixed assemblies of ethynyl pyrene and nile red show energy transfer and thereby provide a proof-of-principle that simple light-harvesting antennae can be obtained in a noncovalent and self-assembled fashion. With respect to the next important step, chemical storage of the absorbed light energy, future research has to focus on the coupling of sophisticated DNA-based light-harvesting antenna to reaction centers.

Ordered Array of Gold Nanoparticles Promoted by Functional Peptides

NASA Astrophysics Data System (ADS)

Matsukawa, Nozomu; Yamashita, Ichiro

2011-05-01

It was successfully demonstrated that 5-nm-diameter gold nanoparticles (GNPs) with 15% size distribution, the surface of which was modified by the synthesized peptides composed of the carbonaceous material affinity peptide (NHBP-1), linker of 11 amino acids and C-terminal cysteine, self-assembled into a two-dimensional (2D) ordered array on a silicon substrate in a spin drying process. NHBP-1 generated an attractive force large enough for the GNP to make 2D collections of GNPs in the course of the spin drying process, and the long linker of 11 amino acids cancelled out the ill effect of size distribution of GNP on the 2D ordered array formation.

Synthesis of photothermal nanocomposites and their application to antibacterial assays

NASA Astrophysics Data System (ADS)

Yang, Ning; Wang, Chun; Wang, Xiaoyu; Li, Lidong

2018-04-01

In this work, we report a novel gold nanorod (AuNR)-based nanocomposite that shows strong binding to bacterium and high antibacterial efficiency. The AuNRs were used as a photothermal material to transform near-infrared radiation (NIR) into heat. We selected poly (acrylic acid) to modify the surface of the AuNRs based on a simple self-assembly method. After conjugation of the bacterium-binding molecule vancomycin, the nanocomposites were capable of efficiently gathering on the cell walls of bacteria. The nanocomposites exhibited a high bacterial inhibition capability owing to NIR-induced heat generation in situ. Therefore, the prepared photothermal nanocomposites show great potential for use in antibacterial assays.

Directed self-assembly of mesoscopic components for led applications

NASA Astrophysics Data System (ADS)

Tkachenko, Anton

Light-emitting diodes (LEDs) constitute a rapidly evolving and fast growing technology that promises to replace incandescent bulbs and compact fluorescent lights in many illumination applications. Large-area LED luminaires have a capability to transform lighting by providing a venue for development of smart lighting systems with additional benefits, such as visible light communications, sensing, health and productivity improvement through color temperature control, capability of creating "virtual sky" ceiling, and many others. The objective of this work is to explore directed self-assembly (DSA) approaches suitable for cost-effective assembly of large amount of LEDs and other mesoscopic (i.e. millimeter and sub-millimeter) electronic components and thus to enable manufacturing of smart lighting luminaires. Existing alternative approaches for assembly of semiconductor dies are examined including transfer printing, laser-assisted die transfer, and various directed self-assembly approaches using shape-recognition, magnetic and capillary forces, etc. After comparing their advantages and limitations, we developed two approaches to magnetic force-assisted DSA of LEDs on a large-area substrate in liquid and air medium. The first approach involves pick-up of buoyant and magnetic dies from the liquid surface onto the flexible substrate in a roll-to-roll process. The possibility of high-speed assembly of LED dies is demonstrated, but with a low yield due to the influence of the capillary force of the carrier liquid and the difficulty in ensuring reliable supply of dies to the assembly interface. To overcome the aforementioned challenges this process was modified to assemble the dies by sinking them onto the receiving substrate with a stencil mask on top, demonstrating LED assembly with a very low error rate but at a lower speed. A solder-assisted self-alignment is used to further improve placement precision and to ensure the proper orientation of the dies. The second approach involves self-assembly of dies in an air medium by levitating them in a periodic magnetic field. Using only vibration in z-direction with properly selected waveforms, both high-yield and high-speed DSA was demonstrated. Magnetostatic simulations were used to demonstrate scaling of DSA process with the die size while a model based on a 2D random walk was used to show how the assembly time scales with the number of dies and how this scaling law can be improved. These results indicate that this process can scale well both with the die size and with the number of assembled dies. Through this thesis work, it was demonstrated that assembly in liquid using ferromagnetic dies can be done either with high speed or with high yield, but not with both at the same time. DSA using diamagnetic levitation offers a way to achieve both through a careful design of magnetic field, thickness and quality of diamagnetic material (graphite) as well as proper selection of vibration pattern. This DSA process can enable large-area parallel assembly of millimeter and sub-millimeter components for manufacturing of LED panels, displays and microcell photovoltaics.

Supramolecular self-assembly on the B-Si(111)-(√3x√3) R30° surface: From single molecules to multicomponent networks

NASA Astrophysics Data System (ADS)

Makoudi, Younes; Jeannoutot, Judicaël; Palmino, Frank; Chérioux, Frédéric; Copie, Guillaume; Krzeminski, Christophe; Cleri, Fabrizio; Grandidier, Bruno

2017-09-01

Understanding the physical and chemical processes in which local interactions lead to ordered structures is of particular relevance to the realization of supramolecular architectures on surfaces. While spectacular patterns have been demonstrated on metal surfaces, there have been fewer studies of the spontaneous organization of supramolecular networks on semiconductor surfaces, where the formation of covalent bonds between organics and adatoms usually hamper the diffusion of molecules and their subsequent interactions with each other. However, the saturation of the dangling bonds at a semiconductor surface is known to make them inert and offers a unique way for the engineering of molecular patterns on these surfaces. This review describes the physicochemical properties of the passivated B-Si(111)-(√3x√3) R30° surface, that enable the self-assembly of molecules into a rich variety of extended and regular structures on silicon. Particular attention is given to computational methods based on multi-scale simulations that allow to rationalize the relative contribution of the dispersion forces involved in the self-assembled networks observed with scanning tunneling microscopy. A summary of state of the art studies, where a fine tuning of the molecular network topology has been achieved, sheds light on new frontiers for exploiting the construction of supramolecular structures on semiconductor surfaces.

A virus-based biocatalyst

NASA Astrophysics Data System (ADS)

Carette, Noëlle; Engelkamp, Hans; Akpa, Eric; Pierre, Sebastien J.; Cameron, Neil R.; Christianen, Peter C. M.; Maan, Jan C.; Thies, Jens C.; Weberskirch, Ralf; Rowan, Alan E.; Nolte, Roeland J. M.; Michon, Thierry; van Hest, Jan C. M.

2007-04-01

Virus particles are probably the most precisely defined nanometre-sized objects that can be formed by protein self-assembly. Although their natural function is the storage and transport of genetic material, they have more recently been applied as scaffolds for mineralization and as containers for the encapsulation of inorganic compounds. The reproductive power of viruses has been used to develop versatile analytical methods, such as phage display, for the selection and identification of (bio)active compounds. To date, the combined use of self-assembly and reproduction has not been used for the construction of catalytic systems. Here we describe a self-assembled system based on a plant virus that has its coat protein genetically modified to provide it with a lipase enzyme. Using single-object and bulk catalytic studies, we prove that the virus-anchored lipase molecules are catalytically active. This anchored biocatalyst, unlike man-made supported catalysts, has the capability to reproduce itself in vivo, generating many independent catalytically active copies.

High yield recombinant production of a self-assembling polycationic peptide for silica biomineralization.

PubMed

Zerfaß, Christian; Braukmann, Sandra; Nietzsche, Sandor; Hobe, Stephan; Paulsen, Harald

2015-04-01

We report the recombinant bacterial expression and purification at high yields of a polycationic oligopeptide, P5S3. The sequence of P5S3 was inspired by a diatom silaffin, a silica precipitating peptide. Like its native model, P5S3 exhibits silica biomineralizing activity, but furthermore has unusual self-assembling properties. P5S3 is efficiently expressed in Escherichia coli as fusion with ketosteroid isomerase (KSI), which causes deposition in inclusion bodies. After breaking the fusion by cyanogen bromide reaction, P5S3 was purified by cation exchange chromatography, taking advantage of the exceptionally high content of basic amino acids. The numerous cationic charges do not prevent, but may even promote counterion-independent self-assembly which in turn leads to silica precipitation. Enzymatic phosphorylation, a common modification in native silica biomineralizing peptides, can be used to modify the precipitation activity. Copyright © 2015 Elsevier Inc. All rights reserved.

Aryl diazonium for biomolecules immobilization onto SPRi chips.

PubMed

Mandon, Céline A; Blum, Loïc J; Marquette, Christophe A

2009-12-21

A method for the immobilization of proteins at the surface of surface plasmon resonance imaging (SPRi) chips is presented. The technology, based on the electro-deposition of a 4-carboxymethyl aryl diazonium (CMA) monolayer is compared to a classical thioctic acid self-assembled monolayer. SPRi live recording experiments followed by the quantification of the diazonium surface coverage demonstrate the presence of a monolayer of electro-deposited molecules (11*10(12) molecules mm(-2)). This monolayer, when activated through a classical carbodiimide route, generates a surface suitable for the protein immobilization. In the present study, protein A and BSA are immobilized as specific and control spots (150 microm id), respectively. The AFM characterization of the spots deposited onto CMA or thioctic acid modified chips prove the presence of 4.7 nm protein monolayers. Finally, the SPRi detection capabilities of the two surface chemistries are compared according to specific signal, non-specific interaction and regeneration possibilities. Advantages are given to the CMA surface modification since no measurable non-specific signal is obtained while reaching a higher specific signal.

Self-folding polymeric containers for encapsulation and delivery of drugs

PubMed Central

Fernandes, Rohan; Gracias, David H.

2012-01-01

Self-folding broadly refers to self-assembly processes wherein thin films or interconnected planar templates curve, roll-up or fold into three dimensional (3D) structures such as cylindrical tubes, spirals, corrugated sheets or polyhedra. The process has been demonstrated with metallic, semiconducting and polymeric films and has been used to curve tubes with diameters as small as 2 nm and fold polyhedra as small as 100 nm, with a surface patterning resolution of 15 nm. Self-folding methods are important for drug delivery applications since they provide a means to realize 3D, biocompatible, all-polymeric containers with well-tailored composition, size, shape, wall thickness, porosity, surface patterns and chemistry. Self-folding is also a highly parallel process, and it is possible to encapsulate or self-load therapeutic cargo during assembly. A variety of therapeutic cargos such as small molecules, peptides, proteins, bacteria, fungi and mammalian cells have been encapsulated in self-folded polymeric containers. In this review, we focus on self-folding of all-polymeric containers. We discuss the mechanistic aspects of self-folding of polymeric containers driven by differential stresses or surface tension forces, the applications of self-folding polymers in drug delivery and we outline future challenges. PMID:22425612

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.

Self-assembly of cationic multidomain peptide hydrogels: supramolecular nanostructure and rheological properties dictate antimicrobial activity

NASA Astrophysics Data System (ADS)

Jiang, Linhai; Xu, Dawei; Sellati, Timothy J.; Dong, He

2015-11-01

Hydrogels are an important class of biomaterials that have been widely utilized for a variety of biomedical/medical applications. The biological performance of hydrogels, particularly those used as wound dressing could be greatly advanced if imbued with inherent antimicrobial activity capable of staving off colonization of the wound site by opportunistic bacterial pathogens. Possessing such antimicrobial properties would also protect the hydrogel itself from being adversely affected by microbial attachment to its surface. We have previously demonstrated the broad-spectrum antimicrobial activity of supramolecular assemblies of cationic multi-domain peptides (MDPs) in solution. Here, we extend the 1-D soluble supramolecular assembly to 3-D hydrogels to investigate the effect of the supramolecular nanostructure and its rheological properties on the antimicrobial activity of self-assembled hydrogels. Among designed MDPs, the bactericidal activity of peptide hydrogels was found to follow an opposite trend to that in solution. Improved antimicrobial activity of self-assembled peptide hydrogels is dictated by the combined effect of supramolecular surface chemistry and storage modulus of the bulk materials, rather than the ability of individual peptides/peptide assemblies to penetrate bacterial cell membrane as observed in solution. The structure-property-activity relationship developed through this study will provide important guidelines for designing biocompatible peptide hydrogels with built-in antimicrobial activity for various biomedical applications.Hydrogels are an important class of biomaterials that have been widely utilized for a variety of biomedical/medical applications. The biological performance of hydrogels, particularly those used as wound dressing could be greatly advanced if imbued with inherent antimicrobial activity capable of staving off colonization of the wound site by opportunistic bacterial pathogens. Possessing such antimicrobial properties would also protect the hydrogel itself from being adversely affected by microbial attachment to its surface. We have previously demonstrated the broad-spectrum antimicrobial activity of supramolecular assemblies of cationic multi-domain peptides (MDPs) in solution. Here, we extend the 1-D soluble supramolecular assembly to 3-D hydrogels to investigate the effect of the supramolecular nanostructure and its rheological properties on the antimicrobial activity of self-assembled hydrogels. Among designed MDPs, the bactericidal activity of peptide hydrogels was found to follow an opposite trend to that in solution. Improved antimicrobial activity of self-assembled peptide hydrogels is dictated by the combined effect of supramolecular surface chemistry and storage modulus of the bulk materials, rather than the ability of individual peptides/peptide assemblies to penetrate bacterial cell membrane as observed in solution. The structure-property-activity relationship developed through this study will provide important guidelines for designing biocompatible peptide hydrogels with built-in antimicrobial activity for various biomedical applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05233e

Electrochemical growth of CoNi and Pt-CoNi soft magnetic composites on an alkanethiol monolayer-modified ITO substrate.

PubMed

Escalera-López, D; Gómez, E; Vallés, E

2015-07-07

CoNi and Pt-CoNi magnetic layers on indium-tin oxide (ITO) substrates modified by an alkanethiol self-assembled monolayer (SAM) have been electrochemically obtained as an initial stage to prepare semiconducting layer-SAM-magnetic layer hybrid structures. The best conditions to obtain the maximum compactness of adsorbed layers of dodecanethiol (C12-SH) on ITO substrate have been studied using contact angle, AFM, XPS and electrochemical tests. The electrochemical characterization (electrochemical probe or voltammetric response in blank solutions) is fundamental to ensure the maximum blocking of the substrate. Although the electrodeposition process on the SAM-modified ITO substrate is very slow if the blocking of the surface is significant, non-cracked metallic layers of CoNi, with or without a previously electrodeposited seed-layer of platinum, have been obtained by optimizing the deposition potentials. Initial nucleation is expected to take place at the pinhole defects of the C12-SH SAM, followed by a mushroom-like growth regime through the SAM interface that allows the formation of a continuous metallic layer electrically connected to the ITO surface. Due to the potential of the methodology, the preparation of patterned metallic deposits on ITO substrate using SAMs with different coverage as templates is feasible.

A Modified Gibson Assembly Method for Cloning Large DNA Fragments with High GC Contents.

PubMed

Li, Lei; Jiang, Weihong; Lu, Yinhua

2018-01-01

Gibson one-step, isothermal assembly method (Gibson assembly) can be used to efficiently assemble large DNA molecules by in vitro recombination involving a 5'-exonuclease, a DNA polymerase and a DNA ligase. In the past few years, this robust DNA assembly method has been widely applied to seamlessly construct genes, genetic pathways and even entire genomes. Here, we expand this method to clone large DNA fragments with high GC contents, such as antibiotic biosynthetic gene clusters from Streptomyces . Due to the low isothermal condition (50 °C) in the Gibson reaction system, the complementary overlaps with high GC contents are proposed to easily form mismatched linker pairings, which leads to low assembly efficiencies mainly due to vector self-ligation. So, we modified this classic method by the following two steps. First, a pair of universal terminal single-stranded DNA overhangs with high AT contents are added to the ends of the BAC vector. Second, two restriction enzyme sites are introduced into the respective sides of the designed overlaps to achieve the hierarchical assembly of large DNA molecules. The optimized Gibson assembly method facilitates fast acquisition of large DNA fragments with high GC contents from Streptomyces.