Fabrication of a platform to isolate the influences of surface nanotopography from chemistry on bacterial attachment and growth.

PubMed

Pegalajar-Jurado, Adoracion; Easton, Christopher D; Crawford, Russell J; McArthur, Sally L

2015-03-26

Billions of dollars are spent annually worldwide to combat the adverse effects of bacterial attachment and biofilm formation in industries as varied as maritime, food, and health. While advances in the fabrication of antifouling surfaces have been reported recently, a number of the essential aspects responsible for the formation of biofilms remain unresolved, including the important initial stages of bacterial attachment to a substrate surface. The reduction of bacterial attachment to surfaces is a key concept in the prevention or minimization of biofilm formation. The chemical and physical characteristics of both the substrate and bacteria are important in understanding the attachment process, but substrate modification is likely the most practical route to enable the extent of bacterial attachment taking place to be effectively controlled. The microtopography and chemistry of the surface are known to influence bacterial attachment. The role of surface chemistry versus nanotopography and their interplay, however, remain unclear. Most methods used for imparting nanotopographical patterns onto a surface also induce changes in the surface chemistry and vice versa. In this study, the authors combine colloidal lithography and plasma polymerization to fabricate homogeneous, reproducible, and periodic nanotopographies with a controllable surface chemistry. The attachment of Escherichia coli bacteria onto carboxyl (plasma polymerized acrylic acid, ppAAc) and hydrocarbon (plasma polymerized octadiene, ppOct) rich plasma polymer films on either flat or colloidal array surfaces revealed that the surface chemistry plays a critical role in bacterial attachment, whereas the effect of surface nanotopography on the bacterial attachment appears to be more difficult to define. This platform represents a promising approach to allow a greater understanding of the role that surface chemistry and nanotopography play on bacterial attachment and the subsequent biofouling of the surface.

Thermal tuning the reversible optical band gap of self-assembled polystyrene photonic crystals

NASA Astrophysics Data System (ADS)

Vakili Tahami, S. H.; Pourmahdian, S.; Shirkavand Hadavand, B.; Azizi, Z. S.; Tehranchi, M. M.

2016-11-01

Nano-sized polymeric colloidal particles could undergo self-organization into three-dimensional structures to produce desired optical properties. In this research, a facile emulsifier-free emulsion polymerization method was employed to synthesize highly mono-disperse sub-micron polystyrene colloids. A high quality photonic crystal (PhC) structure was prepared by colloidal polystyrene. The reversible thermal tuning effect on photonic band gap position as well as the attenuation of the band gap was investigated in detail. The position of PBG can be tuned from 420 nm to 400 nm by varying the temperature of the PhC structure, reversibly. This reversible effect provides a reconfigurable PhC structure which could be used as thermo-responsive shape memory polymers.

Colloidal polyaniline

DOEpatents

Armes, Steven P.; Aldissi, Mahmoud

1990-01-01

Processable electrically conductive latex polymer compositions including colloidal particles of an oxidized, polymerized amino-substituted aromatic monomer, a stabilizing effective amount of a random copolymer containing amino-benzene type moieties as side chain constituents, and dopant anions, and a method of preparing such polymer compositions are provided.

Responsive polymer-based colloids for drug delivery and bioconversion

NASA Astrophysics Data System (ADS)

Kudina, Olena

Responsive polymer-based colloids (RPBC) are the colloidal structures containing responsive polymeric component which is able to adapt its physico-chemical properties to the environment by undergoing chemical and/or conformational changes. The goal of the dissertation is to develop and characterize several groups of RPBC with different morphological complexity and explore their potential in drug delivery and bioconversion. The role of RPBC morphology for these specific applications is discussed in details. Three groups of RPBC were fabricated: i. polymeric micelles; ii. mixed polymeric micelles; iii. hybrid polymer-inorganic particles. All fabricated RPBCs contain polymeric component in their structure. The dissertation investigates how the changes of the responsive polymeric component properties are reflected in morphologies of RPBC. The first group of RPBC, polymeric micelles, was formed by the self-assembly of amphiphilic invertible polymers (AIPs) synthesized in our group. AIPs self-assemble into invertible micellar assemblies (IMAs) in solvents of different polarity. In this work, IMAs ability to invert the structure as a response to the change in solvent polarity was demonstrated using 1H NMR spectroscopy and SANS. It was shown that the IMAs incorporate hydrophobic cargo either in the core or in the shell, depending on the chemical structure of cargo molecules. Following in vitro study demonstrates that loaded with drug (curcumin) IMAs are cytotoxic to osteosarcoma cells. Mixed polymeric micelles represent another, more complex, RPBC morphologies studied in the dissertation. Mixed micelles were fabricated from AIPs and amphiphilic oligomers synthesized from pyromellitic dianhydride, polyethylene glycol methyl ethers, and alkanols/cholesterol. The combination of selected AIP and oligomers based on cholesterol results in mixed micelles with an increased drug-loading capacity (from 10% w/w loaded curcumin in single component IMAs to 26%w/w in mixed micelles). Even more complex colloids are hybrid polymer-inorganic particles, the third RPBC group studied in dissertation. Material was designed as core--shell particles with superparamagnetic core engulfed by grafted polymer brushes. These particles were loaded with enzymes (cellulases), thus, are turned into enzymogels for cellulose bioconversion. The study demonstrates that such RPBCs can be used multiple times during hydrolysis and provide an about four-fold increase in glucose production in comparison to free enzymes.

Colloidal Covalent Organic Frameworks

PubMed Central

2017-01-01

Covalent organic frameworks (COFs) are two- or three-dimensional (2D or 3D) polymer networks with designed topology and chemical functionality, permanent porosity, and high surface areas. These features are potentially useful for a broad range of applications, including catalysis, optoelectronics, and energy storage devices. But current COF syntheses offer poor control over the material’s morphology and final form, generally providing insoluble and unprocessable microcrystalline powder aggregates. COF polymerizations are often performed under conditions in which the monomers are only partially soluble in the reaction solvent, and this heterogeneity has hindered understanding of their polymerization or crystallization processes. Here we report homogeneous polymerization conditions for boronate ester-linked, 2D COFs that inhibit crystallite precipitation, resulting in stable colloidal suspensions of 2D COF nanoparticles. The hexagonal, layered structures of the colloids are confirmed by small-angle and wide-angle X-ray scattering, and kinetic characterization provides insight into the growth process. The colloid size is modulated by solvent conditions, and the technique is demonstrated for four 2D boronate ester-linked COFs. The diameter of individual COF nanoparticles in solution is monitored and quantified during COF growth and stabilization at elevated temperature using in situ variable-temperature liquid cell transmission electron microscopy imaging, a new characterization technique that complements conventional bulk scattering techniques. Solution casting of the colloids yields a free-standing transparent COF film with retained crystallinity and porosity, as well as preferential crystallite orientation. Collectively this structural control provides new opportunities for understanding COF formation and designing morphologies for device applications. PMID:28149954

Colorimetric photonic hydrogel aptasensor for the screening of heavy metal ions.

PubMed

Ye, Bao-Fen; Zhao, Yuan-Jin; Cheng, Yao; Li, Ting-Ting; Xie, Zhuo-Ying; Zhao, Xiang-Wei; Gu, Zhong-Ze

2012-09-28

We have developed a robust method for the visual detection of heavy metal ions (such as Hg(2+) and Pb(2+)) by using aptamer-functionalized colloidal photonic crystal hydrogel (CPCH) films. The CPCHs were derived from a colloidal crystal array of monodisperse silica nanoparticles, which were polymerized within the polyacrylamide hydrogel. The heavy metal ion-responsive aptamers were then cross-linked in the hydrogel network. During detection, the specific binding of heavy metal ions and cross-linked single-stranded aptamers in the hydrogel network caused the hydrogel to shrink, which was detected as a corresponding blue shift in the Bragg diffraction peak position of the CPCHs. The shift value could be used to estimate, quantitatively, the amount of the target ion. It was demonstrated that our CPCH aptasensor could screen a wide concentration range of heavy metal ions with high selectivity and reversibility. In addition, these aptasensors could be rehydrated from dried gels for storage and aptamer protection. It is anticipated that our technology may also be used in the screening of a broad range of metal ions in food, drugs and the environment.

Integration of colloids into a semi-flexible network of fibrin.

PubMed

Bharadwaj, N Ashwin K; Kang, Jin Gu; Hatzell, Marta C; Schweizer, Kenneth S; Braun, Paul V; Ewoldt, Randy H

2017-02-15

Typical colloid-polymer composites have particle diameters much larger than the polymer mesh size, but successful integration of smaller colloids into a large-mesh network could allow for the realization of new colloidal states of spatial organization and faster colloid motion which can allow the possibility of switchable re-configuration of colloids or more dramatic stimuli-responsive property changes. Experimental realization of such composites requires solving non-trivial materials selection and fabrication challenges; key questions include composition regime maps of successful composites, the resulting structure and colloidal contact network, and the mechanical properties, in particular the ability to form a network and retain strain stiffening in the presence of colloids. Here, we study these fundamental questions by formulating composites with fluorescent (though not stimuli-responsive) carboxylate modified polystyrene/latex (CML) colloidal particles (diameters 200 nm and 1000 nm) in bovine fibrin networks (a semi-flexible biopolymer network with mesh size 1-5 μm). We describe and characterize two methods of composite preparation: adding colloids before fibrinogen polymerization (Method I), and electrophoretically driving colloids into a network already formed by fibrinogen polymerization (Method II). We directly image the morphology of colloidal and fibrous components with two-color fluorescent confocal microscopy under wet conditions and SEM of fixed dry samples. Mechanical properties are studied with shear and extensional rheology. Both fabrication methods are successful, though with trade-offs. Method I retains the nonlinear strain-stiffening and extensibility of the native fibrin network, but some colloid clustering is observed and fibrin network integrity is lost above a critical colloid concentration that depends on fibrinogen and thrombin concentration. Larger colloids can be included at higher volume fractions before massive aggregation occurs, indicating surface interactions as a limiting factor. Method II results in a loss of measurable strain-stiffening, but colloids are well dispersed and template along the fibrous scaffold. The results here, with insight into both structure and rheology, form a foundational understanding for the integration of other colloids, e.g. with stimuli-responsive functionalities, into semi-flexible networks.

Size dependence in tunneling spectra of PbSe quantum-dot arrays.

PubMed

Ou, Y C; Cheng, S F; Jian, W B

2009-07-15

Interdot Coulomb interactions and collective Coulomb blockade were theoretically argued to be a newly important topic, and experimentally identified in semiconductor quantum dots, formed in the gate confined two-dimensional electron gas system. Developments of cluster science and colloidal synthesis accelerated the studies of electron transport in colloidal nanocrystal or quantum-dot solids. To study the interdot coupling, various sizes of two-dimensional arrays of colloidal PbSe quantum dots are self-assembled on flat gold surfaces for scanning tunneling microscopy and scanning tunneling spectroscopy measurements at both room and liquid-nitrogen temperatures. The tip-to-array, array-to-substrate, and interdot capacitances are evaluated and the tunneling spectra of quantum-dot arrays are analyzed by the theory of collective Coulomb blockade. The current-voltage of PbSe quantum-dot arrays conforms properly to a scaling power law function. In this study, the dependence of tunneling spectra on the sizes (numbers of quantum dots) of arrays is reported and the capacitive coupling between quantum dots in the arrays is explored.

Plasmon-induced charge separation at two-dimensional gold semishell arrays on SiO2@TiO2 colloidal crystals

NASA Astrophysics Data System (ADS)

Wu, Ling; Nishi, Hiroyasu; Tatsuma, Tetsu

2015-10-01

Photoelectrodes based on plasmonic Au semishell (or halfshell) arrays are developed. A colloidal crystal consisting of SiO2@TiO2 core-shell particles is prepared on a TiO2-coated transparent electrode. A Au semishell (or halfshell) array is deposited by sputtering or evaporation on the colloidal crystal. An electrode with the semishell (or halfshell) array exhibits negative photopotential shifts and anodic photocurrents under visible light at 500-800 nm wavelengths in an aqueous electrolyte containing an electron donor. In particular, hydroquinone and ethanol are good electron donors. The photocurrents can be explained in terms of plasmon-induced charge separation at the Au-TiO2 interface.

Plasmon-induced charge separation at two-dimensional gold semishell arrays on SiO{sub 2}@TiO{sub 2} colloidal crystals

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

Wu, Ling; Nishi, Hiroyasu; Tatsuma, Tetsu, E-mail: tatsuma@iis.u-tokyo.ac.jp

2015-10-01

Photoelectrodes based on plasmonic Au semishell (or halfshell) arrays are developed. A colloidal crystal consisting of SiO{sub 2}@TiO{sub 2} core-shell particles is prepared on a TiO{sub 2}-coated transparent electrode. A Au semishell (or halfshell) array is deposited by sputtering or evaporation on the colloidal crystal. An electrode with the semishell (or halfshell) array exhibits negative photopotential shifts and anodic photocurrents under visible light at 500-800 nm wavelengths in an aqueous electrolyte containing an electron donor. In particular, hydroquinone and ethanol are good electron donors. The photocurrents can be explained in terms of plasmon-induced charge separation at the Au-TiO{sub 2} interface.

Autonomous colloidal crystallization in a galvanic microreactor

NASA Astrophysics Data System (ADS)

Punckt, Christian; Jan, Linda; Jiang, Peng; Frewen, Thomas A.; Saville, Dudley A.; Kevrekidis, Ioannis G.; Aksay, Ilhan A.

2012-10-01

We report on a technique that utilizes an array of galvanic microreactors to guide the assembly of two-dimensional colloidal crystals with spatial and orientational order. Our system is comprised of an array of copper and gold electrodes in a coplanar arrangement, immersed in a dilute hydrochloric acid solution in which colloidal micro-spheres of polystyrene and silica are suspended. Under optimized conditions, two-dimensional colloidal crystals form at the anodic copper with patterns and crystal orientation governed by the electrode geometry. After the aggregation process, the colloidal particles are cemented to the substrate by co-deposition of reaction products. As we vary the electrode geometry, the dissolution rate of the copper electrodes is altered. This way, we control the colloidal motion as well as the degree of reaction product formation. We show that particle motion is governed by a combination of electrokinetic effects acting directly on the colloidal particles and bulk electrolyte flow generated at the copper-gold interface.

Cocklebur-shaped colloidal dispersions.

PubMed

Lestage, David J; Urban, Marek W

2005-11-08

Unique cocklebur-shaped colloidal dispersions were prepared using a combination of a nanoextruder applied to the aqueous solution containing methyl methacrylate (MMA) and n-butyl acrylate (n-BA) with azo-bis-isobutyronitrile (AIBN) or potassium persulfate (KPS) initiators and stabilized by a mixture of sodium dioctyl sulfosuccinate (SDOSS) and 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine (DCPC) phospholipid. Upon extrusion and heating to 75 degrees C, methyl methacrylate/n-butyl acrylate (MMA/nBA) colloidal particles containing tubules pointing outward were obtained as a result of DCPC phospholipids present at the particle surfaces. The same cocklebur-shaped particles were obtained when classical polymerization was used without a nanoextruder under similar compositional and thermal conditions, giving a particle size of 159 nm. However, when Ca(2+) ions are present during polymerization, cocklebur morphologies are disrupted. Because DCPC tubules undergo a transition at 38 degrees C, such cocklebur morphologies may offer numerous opportunities for devices with stimuli-responsive characteristics.

Nanocomposites Based on Luminescent Colloidal Nanocrystals and Polymeric Ionic Liquids towards Optoelectronic Applications

PubMed Central

Panniello, Annamaria; Ingrosso, Chiara; Coupillaud, Paul; Tamborra, Michela; Binetti, Enrico; Curri, Maria Lucia; Agostiano, Angela; Taton, Daniel; Striccoli, Marinella

2014-01-01

Polymeric ionic liquids (PILs) are an interesting class of polyelectrolytes, merging peculiar physical-chemical features of ionic liquids with the flexibility, mechanical stability and processability typical of polymers. The combination of PILs with colloidal semiconducting nanocrystals leads to novel nanocomposite materials with high potential for batteries and solar cells. We report the synthesis and properties of a hybrid nanocomposite made of colloidal luminescent CdSe nanocrystals incorporated in a novel ex situ synthesized imidazolium-based PIL, namely, either a poly(N-vinyl-3-butylimidazolium hexafluorophosphate) or a homologous PIL functionalized with a thiol end-group exhibiting a chemical affinity with the nanocrystal surface. A capping exchange procedure has been implemented for replacing the pristine organic capping molecules of the colloidal CdSe nanocrystals with inorganic chalcogenide ions, aiming to disperse the nano-objects in the PILs, by using a common polar solvent. The as-prepared nanocomposites have been studied by TEM investigation, UV-Vis, steady-state and time resolved photoluminescence spectroscopy for elucidating the effects of the PIL functionalization on the morphological and optical properties of the nanocomposites. PMID:28788477

Lithographically patterned electrodeposition of gold, silver, and nickel nanoring arrays with widely tunable near-infrared plasmonic resonances.

PubMed

Halpern, Aaron R; Corn, Robert M

2013-02-26

A novel low-cost nanoring array fabrication method that combines the process of lithographically patterned nanoscale electrodeposition (LPNE) with colloidal lithography is described. Nanoring array fabrication was accomplished in three steps: (i) a thin (70 nm) sacrificial nickel or silver film was first vapor-deposited onto a plasma-etched packed colloidal monolayer; (ii) the polymer colloids were removed from the surface, a thin film of positive photoresist was applied, and a backside exposure of the photoresist was used to create a nanohole electrode array; (iii) this array of nanoscale cylindrical electrodes was then used for the electrodeposition of gold, silver, or nickel nanorings. Removal of the photoresist and sacrificial metal film yielded a nanoring array in which all of the nanoring dimensions were set independently: the inter-ring spacing was fixed by the colloidal radius, the radius of the nanorings was controlled by the plasma etching process, and the width of the nanorings was controlled by the electrodeposition process. A combination of scanning electron microscopy (SEM) measurements and Fourier transform near-infrared (FT-NIR) absorption spectroscopy were used to characterize the nanoring arrays. Nanoring arrays with radii from 200 to 400 nm exhibited a single strong NIR plasmonic resonance with an absorption maximum wavelength that varied linearly from 1.25 to 3.33 μm as predicted by a simple standing wave model linear antenna theory. This simple yet versatile nanoring array fabrication method was also used to electrodeposit concentric double gold nanoring arrays that exhibited multiple NIR plasmonic resonances.

Studies on photonic crystal composites: Fabrication and applications

NASA Astrophysics Data System (ADS)

Ying, Yurong

There is considerable interest in developing three-dimensional ordered dielectric structures because of their unique optical property, the photonic band gap. A material containing this photonic band gap can be used to control the propagation of electromagnetic waves. This characteristic can be utilized in fabricating a number of diffractive optical devices. A crystalline colloidal array (CCA) is one such three-dimensional ordered dielectric structure, formed through the self-assembly of monodispersed, surface-charged colloidal particles when they are dispersed in a polar liquid medium. Previous work has demonstrated that monodispersed, negatively charged polystyrene spheres can self-assemble into a face-centered cubic (fcc) structure when they are dispersed in a polar medium. This fee lattice can be locked in a hydrogel-based polymeric network and then encapsulated into a water-free elastomer network. These photonic crystal hydrogel films exhibit a solvatochromic effect. A method has been developed for creating patterns in photonic crystal hydrogel films based on this solvatochromic effect via a direct photopolymerization process. The multicolor pattern generation induced by this method resulted in macro- and micropatterns with a large color contrast, i.e. the difference between the patterned area and the background is greater than 150 nm. Unfortunately, CCA systems often exhibit intrinsic and extrinsic defects. To reduce the extrinsic defects incurred during the film fabrication process, a modified lithographic technique was developed to fabricate a high quality, large area, ca. 1 cm2 and a robust, water-free photonic band gap composite film having a thickness of 35 mum. The optical properties of these composite films change in response to their mechanical deformation. These robust films can change shape and recover after stretching or compression without destroying the order of the crystal. These thin films have a high sensitivity to a pressure variation when they are employed as a window in a pressure cell. In total, a 212 nm stop band shift was achieved as the pressure changed from 0 psi to 2.9 psi. Utilizing its mechanochromic response, this thin PBG composite film also has been employed as part of a resonant cavity to develop a thin film organic laser with a tunable emission wavelength of 32 nm. Since the refractive-index contrast between the polystyrene spheres and the polymeric matrix is relatively low, only a narrow stop band can be observed. To increase the contrast, CCA formed using organic dye doped polystyrene spheres and a crystalline colloidal array templated inverse opal was successfully synthesized.

Transferable ordered ni hollow sphere arrays induced by electrodeposition on colloidal monolayer.

PubMed

Duan, Guotao; Cai, Weiping; Li, Yue; Li, Zhigang; Cao, Bingqiang; Luo, Yuanyuan

2006-04-13

We report an electrochemical synthesis of two-dimensionally ordered porous Ni arrays based on polystyrene sphere (PS) colloidal monolayer. The morphology can be controlled from bowl-like to hollow sphere-like structure by changing deposition time under a constant current. Importantly, such ordered Ni arrays on a conducting substrate can be transferred integrally to any other desired substrates, especially onto an insulting substrate or curved surface. The magnetic measurements of the two-dimensional hollow sphere array show the coercivity values of 104 Oe for the applied field parallel to the film, and 87 Oe for the applied field perpendicular to the film, which is larger than those of bulk Ni and hollow Ni submicrometer-sized spheres. The formation of hollow sphere arrays is attributed to preferential nucleation on the interstitial sites between PS in the colloidal monolayer and substrate, and growth along PSs' surface. The transferability of the arrays originates from partial contact between the Ni hollow spheres and substrate. Such novel Ni ordered nanostructured arrays with transferability and high magnetic properties should be useful in applications such as data storage, catalysis, and magnetics.

A universal approach to fabricate ordered colloidal crystals arrays based on electrostatic self-assembly.

PubMed

Zhang, Xun; Zhang, Junhu; Zhu, Difu; Li, Xiao; Zhang, Xuemin; Wang, Tieqiang; Yang, Bai

2010-12-07

We present a novel and simple method to fabricate two-dimensional (2D) poly(styrene sulfate) (PSS, negatively charged) colloidal crystals on a positively charged substrate. Our strategy contains two separate steps: one is the three-dimensional (3D) assembly of PSS particles in ethanol, and the other is electrostatic adsorption in water. First, 3D assembly in ethanol phase eliminates electrostatic attractions between colloids and the substrate. As a result, high-quality colloidal crystals are easily generated, for electrostatic attractions are unfavorable for the movement of colloidal particles during convective self-assembly. Subsequently, top layers of colloidal spheres are washed away in the water phase, whereas well-packed PSS colloids that are in contact with the substrate are tightly linked due to electrostatic interactions, resulting in the formation of ordered arrays of 2D colloidal spheres. Cycling these processes leads to the layer-by-layer assembly of 3D colloidal crystals with controllable layers. In addition, this strategy can be extended to the fabrication of patterned 2D colloidal crystals on patterned polyelectrolyte surfaces, not only on planar substrates but also on nonplanar substrates. This straightforward method may open up new possibilities for practical use of colloidal crystals of excellent quality, various patterns, and controllable fashions.

Self-Assembled Colloidal Particle Clusters from In Situ Pickering-Like Emulsion Polymerization via Single Electron Transfer Mechanism.

PubMed

Yuan, Jinfeng; Zhao, Weiting; Pan, Mingwang; Zhu, Lei

2016-08-01

A simple route is reported to synthesize colloidal particle clusters (CPCs) from self-assembly of in situ poly(vinylidene fluoride)/poly(styrene-co-tert-butyl acrylate) [PVDF/P(St-co-tBA)] Janus particles through one-pot seeded emulsion single electron transfer radical polymerization. In the in situ Pickering-like emulsion polymerization, the tBA/St/PVDF feed ratio and polymerization temperature are important for the formation of well-defined CPCs. When the tBA/St/PVDF feed ratio is 0.75 g/2.5 g/0.5 g and the reaction temperature is 35 °C, relatively uniform raspberry-like CPCs are obtained. The hydrophobicity of the P(St-co-tBA) domains and the affinity of PVDF to the aqueous environment are considered to be the driving force for the self-assembly of the in situ formed PVDF/P(St-co-tBA) Janus particles. The resultant raspberry-like CPCs with PVDF particles protruding outward may be promising for superhydrophobic smart coatings. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioreduction of U(VI)-Phthalate to a Polymeric U(IV)-Phthalate Colloid

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

Vazquez, G.; Dodge, C; Francis, A

2009-01-01

Phthalic acid, a ubiquitous organic ligand, formed soluble mono- and biligand complexes with a uranyl ion that was then reduced to a U(IV)-phthalate by a Clostridium species under anaerobic conditions. We confirmed the reduction of the hexavalent uranium to the tetravalent oxidation state by UV-vis absorption and X-ray absorption near edge structure spectroscopy. Sequential micro- and ultrafiltration of the solution revealed that the bioreduced uranium was present as a colloid with particles between 0.03 and 0.45 {mu}m. Analysis with extended X-ray absorption fine structure revealed the association of the reduced uranium with the phthalic acid as a repeating biligand 1:2more » U(IV):phthalic acid polymer. This is the first report of the formation of a U(IV) complexed to two phthalic acid molecules in the form of a polymeric colloid. Although it was proposed that the bioreduction and the precipitation of uranium might be an invaluable strategy to immobilize uranium in contaminated environments, our results suggest that the organic ligands present there might hinder the precipitation of the bioreduced uranium under anaerobic conditions and, thereby, enhance its environmental mobility as uranium organic complexes or colloids.« less

Colloidal inverse bicontinuous cubic membranes of block copolymers with tunable surface functional groups

NASA Astrophysics Data System (ADS)

La, Yunju; Park, Chiyoung; Shin, Tae Joo; Joo, Sang Hoon; Kang, Sebyung; Kim, Kyoung Taek

2014-06-01

Analogous to the complex membranes found in cellular organelles, such as the endoplasmic reticulum, the inverse cubic mesophases of lipids and their colloidal forms (cubosomes) possess internal networks of water channels arranged in crystalline order, which provide a unique nanospace for membrane-protein crystallization and guest encapsulation. Polymeric analogues of cubosomes formed by the direct self-assembly of block copolymers in solution could provide new polymeric mesoporous materials with a three-dimensionally organized internal maze of large water channels. Here we report the self-assembly of amphiphilic dendritic-linear block copolymers into polymer cubosomes in aqueous solution. The presence of precisely defined bulky dendritic blocks drives the block copolymers to form spontaneously highly curved bilayers in aqueous solution. This results in the formation of colloidal inverse bicontinuous cubic mesophases. The internal networks of water channels provide a high surface area with tunable surface functional groups that can serve as anchoring points for large guests such as proteins and enzymes.

A Study of Functional Polymer Colloids Prepared Using Thiol-Ene/Yne Click Chemistry

NASA Astrophysics Data System (ADS)

Durham, Olivia Z.

This project demonstrates the first instance of thiol-ene chemistry as the polymerization method for the production of polymer colloids in two-phase heterogeneous suspensions, miniemulsions, and emulsions. This work was also expanded to thiol-yne chemistry for the production of polymer particles containing increased crosslinking density. The utility of thiol-ene and thiol-yne chemistries for polymerization and polymer modification is well established in bulk systems. These reactions are considered 'click' reactions, which can be defined as processes that are both facile and simple, offering high yields with nearly 100% conversion, no side products, easy product separation, compatibility with a diverse variety of commercially available starting materials, and orthogonality with other chemistries. In addition, thiol-ene and thiol-yne chemistry follow a step-growth mechanism for the development of highly uniform polymer networks, where polymer growth is dependent on the coupling of functional groups. These step-growth polymerization systems are in stark contrast to the chain-growth mechanisms of acrylic and styrenic monomers that have dominated the field of conventional heterogeneous polymerizations. Preliminary studies evaluated the mechanism of particle production in suspension and miniemulsion systems. Monomer droplets were compared to the final polymer particles to confirm that particle growth occurred through the polymerization of monomer droplets. Additional parameters examined include homogenization energy (mechanical mixing), diluent species and concentration, and monomer content. These reactions were conducted using photoinitiation to yield particles in a matter of minutes with diameters in the size range of several microns to hundreds of microns in suspensions or submicron particles in miniemulsions. Improved control over the particle size and size distribution was examined through variation of reaction parameters. In addition, a method of seeded suspension polymerization was attempted. This project was further expanded through an extensive evaluation of stabilizers in thiol-ene suspension polymerizations. The scope of stabilizers used included synthetic surfactants (ionic and nonionic), natural gums, and colloidal silica (Pickering stabilization). Suspension polymerizations were further expanded to include thiol-yne chemistry for the evaluation of polymer composition and thermal properties. In addition, polymer particles with excess ene, yne, or thiol functionality were successfully developed to demonstrate the potential for further functionalization. The self-limiting behavior of thiol-ene/yne reactions allows for successful synthesis of functional polymer colloids using off-stoichiometric amounts of monomers. This capacity to control functionality is illustrated through the creation of fluorescent polymer particles using both an in situ thiol-ene polymerization reaction with a vinyl chromophore as well as through post-polymerization modification of thiol-ene and thiol-yne polymers with excess thiol functionality via thiol-isocyanate chemistry. To produce smaller polymer particles without the need for intense homogenization energy or high stabilizer concentrations, an emulsion polymerization system was implemented using a water soluble-thermal initiator. It was found that unlike thiol-ene suspensions, which are limited to crosslinked systems, thiol-ene emulsion polymerizations allowed for the production of polymer particles comprised of either crosslinked or linear polymer networks. For the crosslinked systems, various anionic SDS surfactant concentrations were examined to observe the influence on particle size. In linear polymer systems, variations in polymer composition were examined. Preliminary studies performed with a monomer with an ethylene glycol-like structure indicated that the synthesis of polymer particles with narrower size distributions compared to any of the other emulsion compositions was possible. Finally, thiol-ene chemistry was also employed toward the synthesis of degradable polyanhydride polymer particles. Unlike the aforementioned studies, the approach to particle synthesis was conducted by using a premade thiol-ene polymer. Various linear thiol-ene polyanhydrides were emulsified in water or buffered solutions via sonication. Polymer latex was obtained upon solvent evaporation of the dichloromethane (DCM) solvent used to solubilize the polymer. In this work, variation of polymer composition as well as degradation was examined. Additional experiments included a study of the release of Rhodamine B dye, functionalization of the linear polymers, and studies involving the delay of degradation through the incorporation of crosslinking in the polymer particles. The projects presented herein provide an innovative approach to the synthesis of polymer colloids using thiol-ene and thiol-yne 'click' chemistry in both heterogeneous polymerizations as well as through solvent evaporation of premade polymer solutions. Polymer colloids prove to be an area of great interest for numerous applications that encompass various areas involving biomedical and industrial technologies including paints and coatings, cosmetics, diagnostics, and drug delivery. Improvements in methods of chemical synthesis as well as advances in the tailoring of material properties are of utmost importance for the ever increasing demands of new technologies and educational enlightenment.

Protein Corona Formation on Colloidal Polymeric Nanoparticles and Polymeric Nanogels: Impact on Cellular Uptake, Toxicity, Immunogenicity, and Drug Release Properties.

PubMed

Obst, Katja; Yealland, Guy; Balzus, Benjamin; Miceli, Enrico; Dimde, Mathias; Weise, Christoph; Eravci, Murat; Bodmeier, Roland; Haag, Rainer; Calderón, Marcelo; Charbaji, Nada; Hedtrich, Sarah

2017-06-12

The adsorption of biomolecules to the surface of nanoparticles (NPs) following administration into biological environments is widely recognized. In particular, the "protein corona" is well understood in terms of formation kinetics and impact upon the biological interactions of NPs. Its presence is an essential consideration in the design of therapeutic NPs. In the present study, the protein coronas of six polymeric nanoparticles of prospective therapeutic use were investigated. These included three colloidal NPs-soft core-multishell (CMS) NPs, plus solid cationic Eudragit RS (EGRS), and anionic ethyl cellulose (EC) nanoparticles-and three nanogels (NGs)-thermoresponsive dendritic-polyglycerol (dPG) nanogels (NGs) and two amino-functionalized dPG-NGs. Following incubation with human plasma, protein coronas were characterized and their biological interactions compared with pristine NPs. All NPs demonstrated protein adsorption and increased hydrodynamic diameters, although the solid EGRS and EC NPs bound notably more protein than the other tested particles. Shifts toward moderately negative surface charges were also observed for all corona bearing NPs, despite varied zeta potentials in their pristine states. While the uptake and cellular adhesion of the colloidal NPs in primary human keratinocytes and human umbilical vein endothelial cells were significantly decreased when bearing the protein corona, no obvious impact was seen in the NGs. By contrast, corona bearing NGs induced marked increases in cytokine release from primary human macrophages not seen with corona bearing colloidal NPs. Despite this, no apparent enhancement to in vitro toxicity was noted. Finally, drug release from EGRS and EC NPs was assessed, where a decrease was seen in the EGRS NPs alone. Together these results provide a direct comparison of the physical and biological impact the protein corona has on NPs of widely varied character and in particular highlights a distinction between the corona's effects on NGs and colloidal NPs.

Synthesis of Polymeric Microcapsule Arrays and Their Use for Enzyme Immobilization

DTIC Science & Technology

1994-04-01

Polymeric Microcapsule Arrays and Their Use for Enzyme Immobilization by R. Parthasarathy and C. R. Martin Prepared for publication in Nature DTICI...REPORT TYPE AND DATES COVERED April 1994 Interim 4. TITLE AND SUBTITLE S. FUNDING NUMBERS Synthesis of Polymeric Microcapsule Arrays and Their Contract...include adsorption or covalent attachment to a support, microencapsulation and entrapment within a membrane/film or gel. The ideal enzyme

Design of intelligent mesoscale periodic array structures utilizing smart hydrogel

NASA Technical Reports Server (NTRS)

Sunkara, H. B.; Penn, B. G.; Frazier, D. O.; Weissman, J. M.; Asher, S. A.

1996-01-01

Mesoscale Periodic Array Structures (MPAS, also known as crystalline colloidal arrays), composed of aqueous or nonaqueous dispersions of self-assembled submicron colloidal spheres are emerging toward the development of advanced optical devices for technological applications. This is because of their unique optical diffraction properties and the ease with which these intriguing properties can be modulated experimentally. Moreover our recent advancements in this area which include 'locking' the liquid MPAS into solid or semisolid polymer matrices for greater stability with longer life span, and incorporation of CdS quantum dots and laser dyes into colloidal spheres to obtain nonlinear optical (NLO) responses further corroborate the use of MPAS in optical technology. Our long term goal is fabrication of all-optical and electro-optical devices such as spatial light modulators for optical signal processing and flat panel display devices by utilizing intelligent nonlinear periodic array structural materials. Here we show further progress in the design of novel linear MPAS which have the ability to sense and respond to an external source such as temperature. This is achieved by combining the self-assembly properties of polymer colloidal spheres and thermoshrinking properties of smart polymer gels. At selected temperatures the periodic array efficiently Bragg diffracts light and transmits most of the light at other temperatures. Hence these intelligent systems are of potential use as fixed notch filters optical switches or limiters to protect delicate optical sensors from high intensity laser radiation.

The influence of gravity on the distribution of the deposit formed onto a substrate by sessile, hanging, and sandwiched hanging drop evaporation.

PubMed

Sandu, Ion; Fleaca, Claudiu Teodor

2011-06-15

The focus of the present article is the study of the influence of gravity on the particle deposition profiles on a solid substrate during the evaporation of sessile, hanging and sandwiched hanging drops of colloidal particle suspensions. For concentrations of nanoparticles in the colloidal solutions in the range 0.0001-1 wt.%, highly diluted suspensions will preferentially form rings while concentrated suspensions will preferentially form spots in both sessile and hanging drop evaporation. For intermediary concentrations, the particle deposition profiles will depend on the nanoparticle aggregation dynamics in the suspension during the evaporation process, gravity and on the detailed evaporation geometry. The evaporation of a drop of toluene/carbon nanoparticle suspension hanging from a pendant water drop will leave on the substrate a circular spot with no visible external ring. By contrast, a clear external ring is formed on the substrate by the sessile evaporation of a similar drop of suspension sandwiched between a water drop and the substrate. From the application viewpoint, these processes can be used to create preferential electrical conductive carbon networks and contacts for arrays of self-assembled nanostructures fabricated on solid substrates as well as on flexible polymeric substrates. Copyright © 2011 Elsevier Inc. All rights reserved.

New method for MBE growth of GaAs nanowires on silicon using colloidal Au nanoparticles

NASA Astrophysics Data System (ADS)

Bouravleuv, A.; Ilkiv, I.; Reznik, R.; Kotlyar, K.; Soshnikov, I.; Cirlin, G.; Brunkov, P.; Kirilenko, D.; Bondarenko, L.; Nepomnyaschiy, A.; Gruznev, D.; Zotov, A.; Saranin, A.; Dhaka, V.; Lipsanen, H.

2018-01-01

We present a new method for the deposition of colloidal Au nanoparticles on the surface of silicon substrates based on short-time Ar plasma treatment without the use of any polymeric layers. The elaborated method is compatible with molecular beam epitaxy, which allowed us to carry out the detailed study of GaAs nanowire synthesis on Si(111) substrates using colloidal Au nanoparticles as seeds for their growth. The results obtained elucidated the causes of the difference between the initial nanoparticle sizes and the diameters of the grown nanowires.

Artificial biofilms establish the role of matrix interactions in staphylococcal biofilm assembly and disassembly.

PubMed

Stewart, Elizabeth J; Ganesan, Mahesh; Younger, John G; Solomon, Michael J

2015-08-14

We demonstrate that the microstructural and mechanical properties of bacterial biofilms can be created through colloidal self-assembly of cells and polymers, and thereby link the complex material properties of biofilms to well understood colloidal and polymeric behaviors. This finding is applied to soften and disassemble staphylococcal biofilms through pH changes. Bacterial biofilms are viscoelastic, structured communities of cells encapsulated in an extracellular polymeric substance (EPS) comprised of polysaccharides, proteins, and DNA. Although the identity and abundance of EPS macromolecules are known, how these matrix materials interact with themselves and bacterial cells to generate biofilm morphology and mechanics is not understood. Here, we find that the colloidal self-assembly of Staphylococcus epidermidis RP62A cells and polysaccharides into viscoelastic biofilms is driven by thermodynamic phase instability of EPS. pH conditions that induce phase instability of chitosan produce artificial S. epidermidis biofilms whose mechanics match natural S. epidermidis biofilms. Furthermore, pH-induced solubilization of the matrix triggers disassembly in both artificial and natural S. epidermidis biofilms. This pH-induced disassembly occurs in biofilms formed by five additional staphylococcal strains, including three clinical isolates. Our findings suggest that colloidal self-assembly of cells and matrix polymers produces biofilm viscoelasticity and that biofilm control strategies can exploit this mechanism.

Artificial biofilms establish the role of matrix interactions in staphylococcal biofilm assembly and disassembly

PubMed Central

Stewart, Elizabeth J.; Ganesan, Mahesh; Younger, John G.; Solomon, Michael J.

2015-01-01

We demonstrate that the microstructural and mechanical properties of bacterial biofilms can be created through colloidal self-assembly of cells and polymers, and thereby link the complex material properties of biofilms to well understood colloidal and polymeric behaviors. This finding is applied to soften and disassemble staphylococcal biofilms through pH changes. Bacterial biofilms are viscoelastic, structured communities of cells encapsulated in an extracellular polymeric substance (EPS) comprised of polysaccharides, proteins, and DNA. Although the identity and abundance of EPS macromolecules are known, how these matrix materials interact with themselves and bacterial cells to generate biofilm morphology and mechanics is not understood. Here, we find that the colloidal self-assembly of Staphylococcus epidermidis RP62A cells and polysaccharides into viscoelastic biofilms is driven by thermodynamic phase instability of EPS. pH conditions that induce phase instability of chitosan produce artificial S. epidermidis biofilms whose mechanics match natural S. epidermidis biofilms. Furthermore, pH-induced solubilization of the matrix triggers disassembly in both artificial and natural S. epidermidis biofilms. This pH-induced disassembly occurs in biofilms formed by five additional staphylococcal strains, including three clinical isolates. Our findings suggest that colloidal self-assembly of cells and matrix polymers produces biofilm viscoelasticity and that biofilm control strategies can exploit this mechanism. PMID:26272750

Polymeric membranes: surface modification for minimizing (bio)colloidal fouling.

PubMed

Kochkodan, Victor; Johnson, Daniel J; Hilal, Nidal

2014-04-01

This paper presents an overview on recent developments in surface modification of polymer membranes for reduction of their fouling with biocolloids and organic colloids in pressure driven membrane processes. First, colloidal interactions such as London-van der Waals, electrical, hydration, hydrophobic, steric forces and membrane surface properties such as hydrophilicity, charge and surface roughness, which affect membrane fouling, have been discussed and the main goals of the membrane surface modification for fouling reduction have been outlined. Thereafter the recent studies on reduction of (bio)colloidal of polymer membranes using ultraviolet/redox initiated surface grafting, physical coating/adsorption of a protective layer on the membrane surface, chemical reactions or surface modification of polymer membranes with nanoparticles as well as using of advanced atomic force microscopy to characterize (bio)colloidal fouling have been critically summarized. Copyright © 2013 Elsevier B.V. All rights reserved.

Live Imaging of Cellular Internalization of Single Colloidal Particle by Combined Label-Free and Fluorescence Total Internal Reflection Microscopy.

PubMed

Byrne, Gerard D; Vllasaliu, Driton; Falcone, Franco H; Somekh, Michael G; Stolnik, Snjezana

2015-11-02

In this work we utilize the combination of label-free total internal reflection microscopy and total internal reflectance fluorescence (TIRM/TIRF) microscopy to achieve a simultaneous, live imaging of single, label-free colloidal particle endocytosis by individual cells. The TIRM arm of the microscope enables label free imaging of the colloid and cell membrane features, while the TIRF arm images the dynamics of fluorescent-labeled clathrin (protein involved in endocytosis via clathrin pathway), expressed in transfected 3T3 fibroblasts cells. Using a model polymeric colloid and cells with a fluorescently tagged clathrin endocytosis pathway, we demonstrate that wide field TIRM/TIRF coimaging enables live visualization of the process of colloidal particle interaction with the labeled cell structure, which is valuable for discerning the membrane events and route of colloid internalization by the cell. We further show that 500 nm in diameter model polystyrene colloid associates with clathrin, prior to and during its cellular internalization. This association is not apparent with larger, 1 μm in diameter colloids, indicating an upper particle size limit for clathrin-mediated endocytosis.

Kinetic of antigent-antibody reactions with scattering method

NASA Astrophysics Data System (ADS)

Bilyi, Olexander I.; Kiselyov, Yevgen M.; Novikov, Volodymyr P.

2001-07-01

The immune reactions of interaction antigen-antibody represent specific effect of an antigene with an antibody, which outcome are the complex immune aggregates forming precipitate in case of a soluble antigene, or agglutinate in case of a corpuscular antigene. Immunological methods which uses in the quality of carrier protein latex's polymeric microspheresis, gained name and method latex agglutination. Polymeric microspheresis have the array of advantages before biological carries, which consist in the opportunity of the variation of attributes surface and size microspheresis in the broad band of meanings with the preservation of narrow distribution particles behind measurements, the putting of functional groups, necessary for bunch with ligand on stage their synthesis, in ragidity at storage. The quantitative evaluation of parameters of a response of interaction antigen-antibody in immunology is possible by optical methods on a measurement of a modification of intensity of a light stream of a solution in an outcome of a course of a reaction. Concentration of immune complexes determine both on slacking a taking place stream of light, and on a modification of intensity of a stream of light scattering suspended particles in a solution. The process light scattering by colloidal aggregates are formed from suspension microspheresis with adsorbed on their surface protein is described. In report the physics principle of registration immune reaction by light scattering methods is concerned. The results of the effectiveness latex's preparation created on basis of the polymeric carries is described.

Interface colloidal robotic manipulator

DOEpatents

Aronson, Igor; Snezhko, Oleksiy

2015-08-04

A magnetic colloidal system confined at the interface between two immiscible liquids and energized by an alternating magnetic field dynamically self-assembles into localized asters and arrays of asters. The colloidal system exhibits locomotion and shape change. By controlling a small external magnetic field applied parallel to the interface, structures can capture, transport, and position target particles.

Preparation of poly(BMA-co-MMA) particles by soap-free emulsion polymerization and its optical properties as photonic crystals.

PubMed

Lee, Ki-Chang; Choo, Hun-Seung

2014-11-01

Narrowly dispersed poly(BMA-co-MMA) and PBMA latices with particle diameters ranging within 216-435 nm were synthesized successfully by surfactant-free emulsion polymerization with KPS and AIBA. The average particle diameter and particle size distribution, average molecular weight and its distribution, glass transition temperature, reflectance spectra in visible wavelength, and refractive indices for the respective poly(BMA-co-MMA) latices and their photonic crystals were systematically investigated in terms of BMA/MMA ratio, BMA content, polymerization temperature, and DVB effect. The rate of polymerization increased with increasing MMA concentration in BMA/MMA ratio. The particle diameter increased with BMA concentration in BMA/MMA ratio. The molecular weight increased with BMA concentration in BMA/MMA ratio and monomer concentration. The drying of the latices offered self-assembled shiny colloidal crystal films showing the characteristic structural colors in visible wavelength. All the poly(BMA-co-MMA) latices prepared in the study were fallen within the range of photonic grade microspheres. The reflectance measurement on the colloidal photonic crystals having different particle diameters clearly exhibited narrow stopbands. The reflection maxima (λ(max)) measured in this study were well close to the λ(max) calculated, derived from the Bragg's equation. The refractive indices of poly(BMA-co-MMA) photonic crystals were found to be almost same as the theoretical values and increased proportionally from 1.50 to 1.57 with BMA content in BMA/MMA ratios. It was, thus, found that the optical reflectance properties of the poly(BMA-co-MMA) colloidal photonic crystals can be controlled easily by adjusting the reaction conditions and BMA/MMA ratio in soap-free emulsion copolymerization of BMA and MMA.

Polymer-modified opal nanopores.

PubMed

Schepelina, Olga; Zharov, Ilya

2006-12-05

The surface of nanopores in opal films, assembled from 205 nm silica spheres, was modified with poly(acrylamide) brushes using surface-initiated atom transfer radical polymerization. The colloidal crystal lattice remained unperturbed by the polymerization. The polymer brush thickness was controlled by polymerization time and was monitored by measuring the flux of redox species across the opal film using cyclic voltammetry. The nanopore size and polymer brush thickness were calculated on the basis of the limiting current change. Polymer brush thickness increased over the course of 26 h of polymerization in a logarithmic manner from 1.3 to 8.5 nm, leading to nanopores as small as 7.5 nm.

Synthesis of silica-polymer core-shell nanoparticles by reversible addition-fragmentation chain transfer polymerization.

PubMed

Moraes, John; Ohno, Kohji; Maschmeyer, Thomas; Perrier, Sébastien

2013-10-14

Hybrid nanoparticles hold great promise for a range of applications such as drug-delivery vectors or colloidal crystal self-assemblies. The challenge of preparing highly monodisperse particles for these applications has recently been overcome by using living radical polymerization techniques. In particular, the use of reversible addition-fragmentation chain transfer (RAFT), initiated from silica surfaces, yields well-defined particles from a range of precursor monomers resulting in nanoparticles of tailored sizes that are accessible via the rational selection of polymerization conditions. Furthermore, using RAFT allows post-polymerization modification to afford multifunctional, monodisperse, nanostructures under mild and non-stringent reaction conditions.

Reinforcement of polymeric structures with asbestos fibrils

NASA Technical Reports Server (NTRS)

Rader, C. A.; Schwartz, A. M.

1970-01-01

Investigation determines structural potential of asbestos fibrils. Methods are developed for dispersing macrofibers of the asbestos into colloidal-sized ultimate fibrils and incorporating these fibrils in matrices without causing reagglomeration.

Electrohydrodynamically patterned colloidal crystals

NASA Technical Reports Server (NTRS)

Hayward, Ryan C. (Inventor); Poon, Hak F. (Inventor); Xiao, Yi (Inventor); Saville, Dudley A. (Inventor); Aksay, Ilhan A. (Inventor)

2003-01-01

A method for assembling patterned crystalline arrays of colloidal particles using ultraviolet illumination of an optically-sensitive semiconducting anode while using the anode to apply an electronic field to the colloidal particles. The ultraviolet illumination increases current density, and consequently, the flow of the colloidal particles. As a result, colloidal particles can be caused to migrate from non-illuminated areas of the anode to illuminated areas of the anode. Selective illumination of the anode can also be used to permanently affix colloidal crystals to illuminated areas of the anode while not affixing them to non-illuminated areas of the anode.

Continuous separation of colloidal particles using dielectrophoresis.

PubMed

Yunus, Nurul Amziah Md; Nili, Hossein; Green, Nicolas G

2013-04-01

Dielectrophoresis is the movement of particles in nonuniform electric fields and has been of interest for application to manipulation and separation at and below the microscale. This technique has the advantages of being noninvasive, nondestructive, and noncontact, with the movement of particle achieved by means of electric fields generated by miniaturized electrodes and microfluidic systems. Although the majority of applications have been above the microscale, there is increasing interest in application to colloidal particles around a micron and smaller. This paper begins with a review of colloidal and nanoscale dielectrophoresis with specific attention paid to separation applications. An innovative design of integrated microelectrode array and its application to flow-through, continuous separation of colloidal particles is then presented. The details of the angled chevron microelectrode array and the test microfluidic system are then discussed. The variation in device operation with applied signal voltage is presented and discussed in terms of separation efficiency, demonstrating 99.9% separation of a mixture of colloidal latex spheres. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultra-thin layer chromatography with integrated silver colloid-based SERS detection.

PubMed

Wallace, Ryan A; Lavrik, Nickolay V; Sepaniak, Michael J

2017-01-01

Simplified lab-on-a-chip techniques are desirable for quick and efficient detection of analytes of interest in the field. The following work involves the use of deterministic pillar arrays on the micro-scale as a platform to separate compounds, and the use of Ag colloid within the arrays as a source of increased signal via surface enhanced Raman spectroscopy (SERS). One problem traditionally seen with SERS surfaces containing Ag colloid is oxidation; however, our platforms are superhydrophobic, reducing the amount of oxidation taking place on the surface of the Ag colloid. This work includes the successful separation and SERS detection of a fluorescent dye compounds (resorufin and sulforhodamine 640), fluorescent anti-tumor drugs (Adriamycin and Daunomycin), and purine and pyrimidine bases (adenine, cytosine, guanine, hypoxanthine, and thymine). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermally Tunable Hydrogels Displaying Angle-Independent Structural Colors.

PubMed

Ohtsuka, Yumiko; Seki, Takahiro; Takeoka, Yukikazu

2015-12-14

We report the preparation of thermally tunable hydrogels displaying angle-independent structural colors. The porous structures were formed with short-range order using colloidal amorphous array templates and a small amount of carbon black (CB). The resultant porous hydrogels prepared using colloidal amorphous arrays without CB appeared white, whereas the hydrogels with CB revealed bright structural colors. The brightly colored hydrogels rapidly changed hues in a reversible manner, and the hues varied widely depending on the water temperature. Moreover, the structural colors were angle-independent under diffusive lighting because of the isotropic nanostructure generated from the colloidal amorphous arrays. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

Surface preparation of substances for continuous convective assembly of fine particles

DOEpatents

Rossi, Robert

2003-01-01

A method for producing periodic nanometer-scale arrays of metal or semiconductor junctions on a clean semiconductor substrate surface is provided comprising the steps of: etching the substrate surface to make it hydrophilic, forming, under an inert atmosphere, a crystalline colloid layer on the substrate surface, depositing a metal or semiconductor material through the colloid layer onto the surface of the substrate, and removing the colloid from the substrate surface. The colloid layer is grown on the clean semiconductor surface by withdrawing the semiconductor substrate from a sol of colloid particles.

Selective deposition and self-assembly of triblock copolymers into matrix arrays for membrane protein production.

PubMed

Andreasson-Ochsner, Mirjam; Fu, Zhikang; May, Sylvia; Xiu, Low Ying; Nallani, Madhavan; Sinner, Eva-Kathrin

2012-01-31

To improve the stability of cell membrane mimics, there has been growing interest in the use of block copolymers. Here, we present an easy approach to create an array of planar polymeric matrices capable of hosting membrane proteins. The array of polymeric matrices was formed by the selective deposition of triblock copolymers onto an array of hydrophilic islands situated within a hydrophobic background. The thickness of these matrices corresponds to the length of a single polymer chain. These polymeric matrices were used to host cell-free expressed membrane proteins, and offers a prototype from which a membrane protein array can be created for diagnostics or drug discovery purposes. © 2011 American Chemical Society

Photoinitiated Polymerization-Induced Self-Assembly of Glycidyl Methacrylate for the Synthesis of Epoxy-Functionalized Block Copolymer Nano-Objects.

PubMed

Tan, Jianbo; Liu, Dongdong; Huang, Chundong; Li, Xueliang; He, Jun; Xu, Qin; Zhang, Li

2017-08-01

Herein, a novel photoinitiated polymerization-induced self-assembly formulation via photoinitiated reversible addition-fragmentation chain transfer dispersion polymerization of glycidyl methacrylate (PGMA) in ethanol-water at room temperature is reported. It is demonstrated that conducting polymerization-induced self-assembly (PISA) at low temperatures is crucial for obtaining colloidal stable PGMA-based diblock copolymer nano-objects. Good control is maintained during the photo-PISA process with a high rate of polymerization. The polymerization can be switched between "ON" and "OFF" in response to visible light. A phase diagram is constructed by varying monomer concentration and degree of polymerization. The PGMA-based diblock copolymer nano-objects can be further cross-linked by using a bifunctional primary amine reagent. Finally, silver nanoparticles are loaded within cross-linked vesicles via in situ reduction, exhibiting good catalytic properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Poly(o-phenylenediamine) colloid-quenched fluorescent oligonucleotide as a probe for fluorescence-enhanced nucleic acid detection.

PubMed

Tian, Jingqi; Li, Hailong; Luo, Yonglan; Wang, Lei; Zhang, Yingwei; Sun, Xuping

2011-02-01

In this Letter, we demonstrate that chemical oxidation polymerization of o-phenylenediamine (OPD) by potassium bichromate at room temperature results in the formation of submicrometer-scale poly(o-phenylenediamine) (POPD) colloids. Such colloids can absorb and quench dye-labeled single-stranded DNA (ssDNA) very effectively. In the presence of a target, a hybridization event occurs, which produces a double-stranded DNA (dsDNA) that detaches from the POPD surface, leading to recovery of dye fluorescence. With the use of an oligonucleotide (OND) sequence associated with human immunodeficiency virus (HIV) as a model system, we demonstrate the proof of concept that POPD colloid-quenched fluorescent OND can be used as a probe for fluorescence-enhanced nucleic acid detection with selectivity down to single-base mismatch.

Asymmetrical Polyhedral Configuration of Giant Vesicles Induced by Orderly Array of Encapsulated Colloidal Particles

PubMed Central

Natsume, Yuno; Toyota, Taro

2016-01-01

Giant vesicles (GVs) encapsulating colloidal particles by a specific volume fraction show a characteristic configuration under a hypertonic condition. Several flat faces were formed in GV membrane with orderly array of inner particles. GV shape changed from the spherical to the asymmetrical polyhedral configuration. This shape deformation was derived by entropic interaction between inner particles and GV membrane. Because a part of inner particles became to form an ordered phase in the region neighboring the GV membrane, free volume for the other part of particles increased. Giant vesicles encapsulating colloidal particles were useful for the model of “crowding effect” which is the entropic interaction in the cell. PMID:26752650

Asymmetrical Polyhedral Configuration of Giant Vesicles Induced by Orderly Array of Encapsulated Colloidal Particles.

PubMed

Natsume, Yuno; Toyota, Taro

2016-01-01

Giant vesicles (GVs) encapsulating colloidal particles by a specific volume fraction show a characteristic configuration under a hypertonic condition. Several flat faces were formed in GV membrane with orderly array of inner particles. GV shape changed from the spherical to the asymmetrical polyhedral configuration. This shape deformation was derived by entropic interaction between inner particles and GV membrane. Because a part of inner particles became to form an ordered phase in the region neighboring the GV membrane, free volume for the other part of particles increased. Giant vesicles encapsulating colloidal particles were useful for the model of "crowding effect" which is the entropic interaction in the cell.

Polymeric hydrogels for novel contact lens-based ophthalmic drug delivery systems: a review.

PubMed

Xinming, Li; Yingde, Cui; Lloyd, Andrew W; Mikhalovsky, Sergey V; Sandeman, Susan R; Howel, Carol A; Liewen, Liao

2008-04-01

Only about 5% of drugs administrated by eye drops are bioavailable, and currently eye drops account for more than 90% of all ophthalmic formulations. The bioavailability of ophthalmic drugs can be improved by a soft contact lens-based ophthalmic drug delivery system. Several polymeric hydrogels have been investigated for soft contact lens-based ophthalmic drug delivery systems: (i) polymeric hydrogels for conventional contact lens to absorb and release ophthalmic drugs; (ii) polymeric hydrogels for piggyback contact lens combining with a drug plate or drug solution; (iii) surface-modified polymeric hydrogels to immobilize drugs on the surface of contact lenses; (iv) polymeric hydrogels for inclusion of drugs in a colloidal structure dispersed in the lens; (v) ion ligand-containing polymeric hydrogels; (vi) molecularly imprinted polymeric hydrogels which provide the contact lens with a high affinity and selectivity for a given drug. Polymeric hydrogels for these contact lens-based ophthalmic drug delivery systems, their advantages and drawbacks are critically analyzed in this review.

Relating structure and flow of soft colloids

NASA Astrophysics Data System (ADS)

Kundu, S. K.; Gupta, S.; Stellbrink, J.; Willner, L.; Richter, D.

2013-11-01

To relate the complex macroscopic flow of soft colloids to details of its microscopic equilibrium and non-equilibrium structure is still one big challenge in soft matter science. We investigated several well-defined colloidal model systems like star polymers or diblock copolymer micelles by linear/non-linear rheology, static/dynamic light scattering (SLS/DLS) and small angle neutron scattering (SANS). In addition, in-situ SANS experiments during shear (Rheo-SANS) revealed directly shear induced structural changes on a microscopic level. Varying the molecular architecture of the individual colloidal particle as well as particle-particle interactions and covering at the same time a broad concentration range from the very dilute to highly concentrated, glassy regime, we could separate contributions from intra- and inter-particle softness. Both can be precisely "tuned" by varying systematically the functionality, 6 ≤ f≤ 64, for star polymers or aggregation number, 30 ≤ N agg ≤ 1000 for diblock copolymer micelles, as well as the degree of polymerization of the individual polymer arm 100 ≤ D p ≤ 3000. In dilute solutions, the characteristic shear rate at which deformation of the soft colloid is observed can be related to the Zimm time of the polymeric corona. In concentrated solutions, we validated a generalized Stokes-Einstein approach to describe the increase in macroscopic viscosity and mesoscopic self diffusion coefficient on approaching the glassy regime. Both can be explained in terms of an ultra-soft interaction potential. Moreover, non-equilibrium structure factors are obtained by Rheo-SANS. All experimental results are in excellent quantitative agreement with recent theoretical predictions.

Fabrication and Characterization of Vertically Aligned ZnO Nanorod Arrays via Inverted Monolayer Colloidal Crystals Mask

NASA Astrophysics Data System (ADS)

Chen, Cheng; Ding, Taotao; Qi, Zhiqiang; Zhang, Wei; Zhang, Jun; Xu, Juan; Chen, Jingwen; Dai, Jiangnan; Chen, Changqing

2018-04-01

The periodically ordered ZnO nanorod (NR) arrays have been successfully synthesized via a hydrothermal approach on the silicon substrates by templating of the TiO2 ring deriving from the polystyrene (PS) nanosphere monolayer colloidal crystals (MCC). With the inverted MCC mask, sol-gel-derived ZnO seeds could serve as the periodic nucleation positions for the site-specific growth of ZnO NRs. The large-scale patterned arrays of single ZnO NR with good side-orientation can be readily produced. According to the experimental results, the as-integrated ZnO NR arrays showed an excellent crystal quality and optical property, very suitable for optoelectronic applications such as stimulated emitters and ZnO photonic crystal devices.

Two-dimensional patterning of colloidal crystals by means of lateral autocloning in edge-patterned cells

NASA Astrophysics Data System (ADS)

Emoto, Akira; Kamei, Tadayoshi; Shioda, Tatsutoshi; Kawatsuki, Nobuhiro; Ono, Hiroshi

2009-06-01

We report the experimental results of two-dimensional patterning of colloidal crystals using edge-patterned cells. Solvent evaporation of a colloidal suspension from the edge of the cell induces self-organized crystallization of spherical colloidal particles. From a reservoir of colloidal suspension in the cell, different colloidal suspensions are injected repetitively. An edge-patterned substrate is introduced into the cell as an upper substrate. As a result, different colloidal crystals are alternately stacked in the lateral direction according to the edge pattern. The characteristics of cloning formation are specifically showed including deformations from the original pattern. This two-dimensional patterning of three-dimensional colloidal crystals by means of lateral autocloning is promising for the development of photonic crystal arrays for use in optic and photonic devices.

Extracellular polymeric substances govern the surface charge of biogenic elemental selenium nanoparticles.

PubMed

Jain, Rohan; Jordan, Norbert; Weiss, Stephan; Foerstendorf, Harald; Heim, Karsten; Kacker, Rohit; Hübner, René; Kramer, Herman; van Hullebusch, Eric D; Farges, François; Lens, Piet N L

2015-02-03

The origin of the organic layer covering colloidal biogenic elemental selenium nanoparticles (BioSeNPs) is not known, particularly in the case when they are synthesized by complex microbial communities. This study investigated the presence of extracellular polymeric substances (EPS) on BioSeNPs. The role of EPS in capping the extracellularly available BioSeNPs was also examined. Fourier transform infrared (FT-IR) spectroscopy and colorimetric measurements confirmed the presence of functional groups characteristic of proteins and carbohydrates on the BioSeNPs, suggesting the presence of EPS. Chemical synthesis of elemental selenium nanoparticles in the presence of EPS, extracted from selenite fed anaerobic granular sludge, yielded stable colloidal spherical selenium nanoparticles. Furthermore, extracted EPS, BioSeNPs, and chemically synthesized EPS-capped selenium nanoparticles had similar surface properties, as shown by ζ-potential versus pH profiles and isoelectric point measurements. This study shows that the EPS of anaerobic granular sludge form the organic layer present on the BioSeNPs synthesized by these granules. The EPS also govern the surface charge of these BioSeNPs, thereby contributing to their colloidal properties, hence affecting their fate in the environment and the efficiency of bioremediation technologies.

Photoelectrochromism in Tungsten Trioxide Colloidal Solutions

ERIC Educational Resources Information Center

Chenthamarakshan, C. R.; Tacconi, N. R. de; Xu, Lucy; Rajeshwar, Krishnan

2004-01-01

Photophysical and photochemical properties of semiconductor metal oxide colloids are studied in the context of photoelectrochemical conversion and storage of solar energy. The experiment teaches the instrumental principles of UV-visible spectrophotometry, spectral acquisition and background subtraction strategies and diode array spectrometers.

Fabrication of magnetic field induced structural colored films with tunable colors and its application on security materials.

PubMed

Shang, Shenglong; Zhang, Qinghong; Wang, Hongzhi; Li, Yaogang

2017-01-01

A flexible, magnetic field induced structurally colored films with brilliant colors and high physical rigidity were reported in this article. Using an external magnetic field, the photocurable colloidal suspensions that containing superparamagnetic Fe 3 O 4 @C colloidal nanocrystal clusters (CNCs) could polymerize under UV light. After polymerization, the films with different colors (red, green, blue) were obtained. Through combination of suspensions which contains Fe 3 O 4 @C CNCs with different sizes, a series of multi-colored films were obtained. Moreover, these structural colors can be patterned easily by photolithography and various structural colored patterns were shown in the article. The structural colored patterns could conceal or display its color according to the changing of background which makes them hold significant potential applications for security materials. Copyright © 2016 Elsevier Inc. All rights reserved.

Surface morphology control of cross-linked polymer particles via dispersion polymerization.

PubMed

Peng, Bo; Imhof, Arnout

2015-05-14

Cross-linked polymer colloids (poly(methyl methacrylate) and polystyrene) with diverse shapes were prepared in polar solvents (ethanol, methanol and water) via dispersion polymerization, in which a linear addition of the cross-linker was used during reaction. Apart from spherical particles we found dented spheres or particles covered with nodules, or a combination of both. A comprehensive investigation was carried out, mainly concentrating on the effect of the experimental conditions (e.g., the addition start time and total addition time, cross-linker density and the solvency of the solvents) on particle morphologies. Consequently, we suggest a number of effective ways for the synthesis of regular (spherical) colloidal particles through maintaining a relatively low concentration of the cross-linker during the entire reaction, or forcing the co-polymerization (of monomer and cross-linker) locus to the continuous medium, or using a high quality or quantity of the stabilizer. Moreover, the size of the particles was also precisely manipulated by varying the polarity of the solvents, the concentration of the cross-linker, and the amount and average molecular weight of the stabilizer. In addition, the formation of the heavily dented particles with a very rough surface prepared under a pure or oxygen-'contaminated' nitrogen environment was monitored over time. The results accumulated in this article are of use for a better understanding of the mechanism of the polymerization and control over the structure and property of polymer particles.

Charge characteristics of humic and fulvic acids: comparative analysis by colloid titration and potentiometric titration with continuous pK-distribution function model.

PubMed

Bratskaya, S; Golikov, A; Lutsenko, T; Nesterova, O; Dudarchik, V

2008-09-01

Charge characteristics of humic and fulvic acids of a different origin (inshore soils, peat, marine sediments, and soil (lysimetric) waters) were evaluated by means of two alternative methods - colloid titration and potentiometric titration. In order to elucidate possible limitations of the colloid titration as an express method of analysis of low content of humic substances we monitored changes in acid-base properties and charge densities of humic substances with soil depth, fractionation, and origin. We have shown that both factors - strength of acidic groups and molecular weight distribution in humic and fulvic acids - can affect the reliability of colloid titration. Due to deviations from 1:1 stoichiometry in interactions of humic substances with polymeric cationic titrant, the colloid titration can underestimate total acidity (charge density) of humic substances with domination of weak acidic functional groups (pK>6) and high content of the fractions with molecular weight below 1kDa.

Anti-iridescent colloidal photonic nanostructure from thermal gradients and polymeric brush effects

NASA Astrophysics Data System (ADS)

Lee, Seung Yeol; Kim, Hyoungsoo; Kim, Shin-Hyun; Stone, Howard

2017-11-01

Colloidal nanostructures induced by self-assembly are important in reflective displays, plasmonic or photonic sensors, and color pigments. During the evaporation of droplets of colloidal suspension, due to the non-uniform evaporation rate along the droplet interface, a radially outward flow is created and it carries colloidal particles to the pinned contact line of the droplet. We document that the packing at the contact line is a face-center-cubic (fcc) colloidal nanostructure in a ring shape. The fcc structure of the colloidal nanoparticles exhibits angle-dependent color. In particular, we introduce a novel method to suppress the familiar coffee-ring effect and modify colloidal nanostructures to exhibit angle-independent optical properties. A suspension of polyethylene oxide (PEO)-coated silica nanoparticles dispersed in ethanol-water mixture is prepared. The droplet containing the nanoparticles dries on a heated substrate, which creates a thermal gradient along the interface of the droplet. This thermal gradient induces thermal-Marangoni stresses that suppress the coffee-ring effects. PEO adsorbed on the surface of silica nanoparticles produces an additional interaction between colloidal nanoparticles, which makes the final structure disordered. The disordered photonic nanostructures in our experiments exhibit angle-independent structural color. This technique can be applied to printing or optical filtering systems.

Poly(vinyl alcohol) stabilization of acrylic emulsion polymers using the miniemulsion approach

NASA Astrophysics Data System (ADS)

Kim, Noma

Miniemulsion approach was employed to obtain stable acrylic latexes of n-butyl acrylate and methyl methacrylate (50/50 wt%) stabilized with poly(vinyl alcohol) (PVA) and to enhance the grafting reaction between PVA and acrylic monomers at the water/droplet interface. The stability of miniemulsions were studied in terms of the type and concentration of' the stabilizer, and the PVA partitioning were determined as a function of the PVA concentration. Using the comparison of PVA partitioning at droplet surface and grafted PVA as a function of concentration, it was suggested that the water/monomer interface is the main grafting site in the miniemulsion polymerization. Seeded emulsion and miniemulsion copolymerizations initiated with water-soluble (hydrogen peroxide, HPO), partially water-soluble (t-butyl peroxide, TBHP), and oil-soluble (t-butyl peroxyoctoate, TBPO) initiators were carried out to further investigate the oil/water interface as the grafting site for PVA. The interaction between the capillary wall in the CHDF (capillary hydrodynamic fractionation) chromatographic particle sizer and the water-soluble polymers adsorbed on the particle surface was studied using different types of water-soluble polymers and eluants. Different grafting architectures depending on the initiation site were suggested based on the CHDF results. The amounts of grafted PVA produced in miniemulsion polymers initiated with TBHP and TBPO were substantially less than those in the corresponding seeded emulsion polymerizations. The effect on the internal viscosity at the interface was proposed to explain the difference in grafting in terms of polymerization methods. Aqueous phase and interface grafting were studied using the measurement of the degree of hydrolysis (DH) of the serum PVA and adsorbed PVA after miniemulsion polymerizations. Based on the results, it was found that aqueous phase and interface grafting occurred in the HPO system; however, interface grafting dominated the TBHP system. Colloidal instability in conventional emulsion polymerizations was investigated and compared with the corresponding miniemulsion polymerization. It was found that the grafted PVA in conventional emulsion polymerizations was more hydrophobic presumably due to a greater amount of grafted chains than that in similar miniemulsion polymerizations and this could be correlated with the colloidal instability during conventional emulsion polymerizations.

Centrifugation-assisted Assembly of Colloidal Silica into Crack-Free and Transferrable Films with Tunable Crystalline Structures

PubMed Central

Fan, Wen; Chen, Min; Yang, Shu; Wu, Limin

2015-01-01

Self-assembly of colloidal particles into colloidal films has many actual and potential applications. While various strategies have been developed to direct the assembly of colloidal particles, fabrication of crack-free and transferrable colloidal film with controllable crystal structures still remains a major challenge. Here we show a centrifugation-assisted assembly of colloidal silica spheres into free-standing colloidal film by using the liquid/liquid interfaces of three immiscible phases. Through independent control of centrifugal force and interparticle electrostatic repulsion, polycrystalline, single-crystalline and quasi-amorphous structures can be readily obtained. More importantly, by dehydration of silica particles during centrifugation, the spontaneous formation of capillary water bridges between particles enables the binding and pre-shrinkage of the assembled array at the fluid interface. Thus the assembled colloidal films are not only crack-free, but also robust and flexible enough to be easily transferred on various planar and curved substrates. PMID:26159121

Colloidal transport through trap arrays controlled by active microswimmers

NASA Astrophysics Data System (ADS)

Yang, Wen; Misko, Vyacheslav R.; Marchesoni, Fabio; Nori, Franco

2018-07-01

We investigate the dynamics of a binary mixture consisting of active and passive colloidal particles diffusing in a 2D array of truncated harmonic wells, or traps. We explore the possibility of using a small fraction of active particles to manipulate a much larger fraction of passive particles, for instance, to confine them in or extract them from the traps. The results of our study have potential application in biology and medical sciences, for example, to remove dead cells or undesired contaminants from biological systems by means of self-propelled nano-robots.

Progressive Transverse Microtubule Array Organization in Hormone-Induced Arabidopsis Hypocotyl Cells[W

PubMed Central

Vineyard, Laura; Elliott, Andrew; Dhingra, Sonia; Lucas, Jessica R.; Shaw, Sidney L.

2013-01-01

The acentriolar cortical microtubule arrays in dark-grown hypocotyl cells organize into a transverse coaligned pattern that is critical for axial plant growth. In light-grown Arabidopsis thaliana seedlings, the cortical array on the outer (periclinal) cell face creates a variety of array patterns with a significant bias (>3:1) for microtubules polymerizing edge-ward and into the side (anticlinal) faces of the cell. To study the mechanisms required for creating the transverse coalignment, we developed a dual-hormone protocol that synchronously induces ∼80% of the light-grown hypocotyl cells to form transverse arrays over a 2-h period. Repatterning occurred in two phases, beginning with an initial 30 to 40% decrease in polymerizing plus ends prior to visible changes in the array pattern. Transverse organization initiated at the cell’s midzone by 45 min after induction and progressed bidirectionally toward the apical and basal ends of the cell. Reorganization corrected the edge-ward bias in polymerization and proceeded without transiting through an obligate intermediate pattern. Quantitative comparisons of uninduced and induced microtubule arrays showed a limited deconstruction of the initial periclinal array followed by a progressive array reorganization to transverse coordinated between the anticlinal and periclinal cell faces. PMID:23444330

Collective mechanical behavior of multilayer colloidal arrays of hollow nanoparticles.

PubMed

Yin, Jie; Retsch, Markus; Thomas, Edwin L; Boyce, Mary C

2012-04-03

The collective mechanical behavior of multilayer colloidal arrays of hollow silica nanoparticles (HSNP) is explored under spherical nanoindentation through a combination of experimental, numerical, and theoretical approaches. The effective indentation modulus E(ind) is found to decrease with an increasing number of layers in a nonlinear manner. The indentation force versus penetration depth behavior for multilayer hollow particle arrays is predicted by an approximate analytical model based on the spring stiffness of the individual particles and the multipoint, multiparticle interactions as well as force transmission between the layers. The model is in good agreement with experiments and with detailed finite element simulations. The ability to tune the effective indentation modulus, E(ind), of the multilayer arrays by manipulating particle geometry and layering is revealed through the model, where E(ind) = (0.725m(-3/2) + 0.275)E(mon) and E(mon) is the monolayer modulus and m is number of layers. E(ind) is seen to plateau with increasing m to E(ind_plateau) = 0.275E(mon) and E(mon) scales with (t/R)(2), t being the particle shell thickness and R being the particle radius. The scaling law governing the nonlinear decrease in indentation modulus with an increase in layer number (E(ind) scaling with m(-3/2)) is found to be similar to that governing the indentation modulus of thin solid films E(ind_solid) on a stiff substrate (where E(ind_solid) scales with h(-1.4) and also decreases until reaching a plateau value) which also decreases with an increase in film thickness h. However, the mechanisms underlying this trend for the colloidal array are clearly different, where discrete particle-to-particle interactions govern the colloidal array behavior in contrast to the substrate constraint on deformation, which governs the thickness dependence of the continuous thin film indentation modulus.

Electrokinetic properties of polymer colloids

NASA Technical Reports Server (NTRS)

Micale, F. J.; Fuenmayor, D. Y.

1986-01-01

The surface of polymer colloids, especially polystyrene latexes, were modified for the purpose of controlling the electrokinetic properties of the resulting colloids. Achievement required a knowledge of electrical double layer charging mechanism, as a function of the electrolyte conditions, at the polymer/water interface. The experimental approach is to control the recipe formulation in the emulsion polymerization process so as to systematically vary the strong acid group concentration on the surface of the polymer particles. The electrophoretic mobility of these model particles will then be measured as a function of surface group concentration and as a function of electrolyte concentration and type. An effort was also made to evaluate the electrophoretic mobility of polystyrene latexes made in space and to compare the results with latexes made on the ground.

DELIVERY OF THERAPEUTIC PROTEINS

PubMed Central

Pisal, Dipak S.; Kosloski, Matthew P.; Balu-Iyer, Sathy V.

2009-01-01

The safety and efficacy of protein therapeutics are limited by three interrelated pharmaceutical issues, in vitro and in vivo instability, immunogenicity and shorter half-lives. Novel drug modifications for overcoming these issues are under investigation and include covalent attachment of poly(ethylene glycol) (PEG), polysialic acid, or glycolic acid, as well as developing new formulations containing nanoparticulate or colloidal systems (e.g. liposomes, polymeric microspheres, polymeric nanoparticles). Such strategies have the potential to develop as next generation protein therapeutics. This review includes a general discussion on these delivery approaches. PMID:20049941

From microscopic rules to macroscopic dynamics with active colloidal snakes

NASA Astrophysics Data System (ADS)

Zhang, Jie; Yan, Jing; Granick, Steve

Seeking to learn about self-assembly far from equilibrium, these imaging experiments inspect self-propelled colloidal particles whose heads and tails attract other particles reversibly as they swim. We observe processes akin to polymerization (short times) and chain scission and recombination (long times). The steady-state of dilute systems consists of discrete rings rotating in place with largely quenched dynamics, but when concentration is high, the system dynamics share features with turbulence. The dynamical rules of this model system appear to be scale-independent and hence potentially relevant more generally.

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.

Enhanced sub-micron colloidal particle separation with interdigitated microelectrode arrays using mixed AC/DC dielectrophoretic scheme.

PubMed

Swaminathan, Vikhram V; Shannon, Mark A; Bashir, Rashid

2015-04-01

Dielectrophoretic separation of particles finds a variety of applications in the capture of species such as cells, viruses, proteins, DNA from biological systems, as well as other organic and inorganic contaminants from water. The ability to capture particles is constrained by poor volumetric scaling of separation force with respect to particle diameter, as well as the weak penetration of electric fields in the media. In order to improve the separation of sub-micron colloids, we present a scheme based on multiple interdigitated electrode arrays under mixed AC/DC bias. The use of high frequency longitudinal AC bias breaks the shielding effects through electroosmotic micromixing to enhance electric fields through the electrolyte, while a transverse DC bias between the electrode arrays enables penetration of the separation force to capture particles from the bulk of the microchannel. We determine the favorable biasing conditions for field enhancement with the help of analytical models, and experimentally demonstrate the improved capture from sub-micron colloidal suspensions with the mixed AC/DC electrostatic excitation scheme over conventional AC-DEP methods.

Self assembled linear polymeric chains with tuneable semiflexibility using isotropic interactions.

PubMed

Abraham, Alex; Chatterji, Apratim

2018-04-21

We propose a two-body spherically symmetric (isotropic) potential such that particles interacting by the potential self-assemble into linear semiflexible polymeric chains without branching. By suitable control of the potential parameters, we can control the persistence length of the polymer and can even introduce a controlled number of branches. Thus we show how to achieve effective directional interactions starting from spherically symmetric potentials. The self-assembled polymers have an exponential distribution of chain lengths akin to what is observed for worm-like micellar systems. On increasing particle density, the polymeric chains self-organize to an ordered line-hexagonal phase where every chain is surrounded by six parallel chains, the transition is first order. On further increase in monomer density, the order is destroyed and we get a branched gel-like phase. This potential can be used to model semi-flexible equilibrium polymers with tunable semiflexibility and excluded volume. The use of the potential is computationally cheap and hence can be used to simulate and probe equilibrium polymer dynamics with long chains. The potential also gives a plausible method of tuning colloidal interactions in experiments such that one can obtain self-assembling polymeric chains made up of colloids and probe polymer dynamics using an optical microscope. Furthermore, we show how a modified potential leads to the observation of an intermediate nematic phase of self-assembled chains in between the low density disordered phase and the line-ordered hexagonal phase.

Self assembled linear polymeric chains with tuneable semiflexibility using isotropic interactions

NASA Astrophysics Data System (ADS)

Abraham, Alex; Chatterji, Apratim

2018-04-01

We propose a two-body spherically symmetric (isotropic) potential such that particles interacting by the potential self-assemble into linear semiflexible polymeric chains without branching. By suitable control of the potential parameters, we can control the persistence length of the polymer and can even introduce a controlled number of branches. Thus we show how to achieve effective directional interactions starting from spherically symmetric potentials. The self-assembled polymers have an exponential distribution of chain lengths akin to what is observed for worm-like micellar systems. On increasing particle density, the polymeric chains self-organize to an ordered line-hexagonal phase where every chain is surrounded by six parallel chains, the transition is first order. On further increase in monomer density, the order is destroyed and we get a branched gel-like phase. This potential can be used to model semi-flexible equilibrium polymers with tunable semiflexibility and excluded volume. The use of the potential is computationally cheap and hence can be used to simulate and probe equilibrium polymer dynamics with long chains. The potential also gives a plausible method of tuning colloidal interactions in experiments such that one can obtain self-assembling polymeric chains made up of colloids and probe polymer dynamics using an optical microscope. Furthermore, we show how a modified potential leads to the observation of an intermediate nematic phase of self-assembled chains in between the low density disordered phase and the line-ordered hexagonal phase.

Self-organized internal architectures of chiral micro-particles

NASA Astrophysics Data System (ADS)

Provenzano, Clementina; Mazzulla, Alfredo; Pagliusi, Pasquale; De Santo, Maria P.; Desiderio, Giovanni; Perrotta, Ida; Cipparrone, Gabriella

2014-02-01

The internal architecture of polymeric self-assembled chiral micro-particles is studied by exploring the effect of the chirality, of the particle sizes, and of the interface/surface properties in the ordering of the helicoidal planes. The experimental investigations, performed by means of different microscopy techniques, show that the polymeric beads, resulting from light induced polymerization of cholesteric liquid crystal droplets, preserve both the spherical shape and the internal self-organized structures. The method used to create the micro-particles with controlled internal chiral architectures presents great flexibility providing several advantages connected to the acquired optical and photonics capabilities and allowing to envisage novel strategies for the development of chiral colloidal systems and materials.

Mid-IR colloidal quantum dot detectors enhanced by optical nano-antennas

NASA Astrophysics Data System (ADS)

Yifat, Yuval; Ackerman, Matthew; Guyot-Sionnest, Philippe

2017-01-01

We report the fabrication of a colloidal quantum dot based photodetector designed for the 3-5 μm mid infrared wavelength range incorporated with optical nano-antenna arrays to enhance the photocurrent. The fabricated arrays exhibit a resonant behavior dependent on the length of the nano-antenna rods, in good agreement with numerical simulation. The device exhibits a three-fold increase in the spectral photoresponse compared to a photodetector device without antennas, and the resonance is polarized parallel to the antenna orientation. We numerically estimate the device quantum efficiency and investigate its bias dependence.

Utilization of hydroxypropyl carboxymethyl cellulose in synthesis of silver nanoparticles.

PubMed

Abdel-Halim, E S; Alanazi, Humaid H; Al-Deyab, Salem S

2015-04-01

Hydroxypropyl carboxymethyl cellulose samples having varying degrees of substitution and varying degrees of polymerization were used to reduce silver nitrate to silver nanoparticles. UV spectral analysis of silver nanoparticles colloidal solution reveal that increasing the pH of the reduction solution leads to improvement in the intensity of the absorption band for silver nanoparticles, to be maximum at pH 11. The absorption peak intensity also enhanced upon prolonging the reaction duration up to 60 min. The conversion of silver ions to metallic silver nanoparticles was found to be temperature-dependent and maximum transformation occurs at 60 °C. The reduction efficiency of hydroxypropyl carboxymethyl cellulose was found to be affected by its degree of polymerization. Colloidal solutions of silver nanoparticles having concentration up to 1000 ppm can be prepared upon fixing the ratio between silver nitrate and hydroxypropyl carboxymethyl cellulose at 0.017-0.3g per each 100ml of the reduction solution. Copyright © 2015 Elsevier B.V. All rights reserved.

Highly Monodisperse Microporous Polymeric and Carbonaceous Nanospheres with Multifunctional Properties

PubMed Central

Ouyang, Yi; Shi, Huimin; Fu, Ruowen; Wu, Dingcai

2013-01-01

Fabrication of monodisperse porous polymeric nanospheres with diameters below 500 nm remains a great challenge, due to serious crosslinking between neighboring nanospheres during pore-making process. Here we show how a versatile hypercrosslinking strategy can be used to prepare monodisperse microporous polystyrene nanospheres (MMPNSs) with diameters as low as ca. 190 nm. In our approach, an unreactive crosslinked PS outer skin as protective layer can be in-situ formed at the very beginning of hypercrosslinking treatment to minimize the undesired inter-sphere crosslinking. The as-prepared MMPNSs with a well-developed microporous network demonstrate unusual multifunctional properties, including remarkable colloidal stability in aqueous solution, good adsorption-release property for drug, and large adsorption capacity toward organic vapors. Surprisingly, MMPNSs can be directly transformed into high-surface-area monodisperse carbon nanospheres with good colloidal stability via a facile hydrothermal-assisted carbonization procedure. These findings provide a new benchmark for fabricating well-defined porous nanospheres with great promise for various applications. PMID:23478487

Dual soft-template system based on colloidal chemistry for the synthesis of hollow mesoporous silica nanoparticles.

PubMed

Li, Yunqi; Bastakoti, Bishnu Prasad; Imura, Masataka; Tang, Jing; Aldalbahi, Ali; Torad, Nagy L; Yamauchi, Yusuke

2015-04-20

A new dual soft-template system comprising the asymmetric triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) is used to synthesize hollow mesoporous silica (HMS) nanoparticles with a center void of around 17 nm. The stable PS-b-P2VP-b-PEO polymeric micelle serves as a template to form the hollow interior, while the CTAB surfactant serves as a template to form mesopores in the shells. The P2VP blocks on the polymeric micelles can interact with positively charged CTA(+) ions via negatively charged hydrolyzed silica species. Thus, dual soft-templates clearly have different roles for the preparation of the HMS nanoparticles. Interestingly, the thicknesses of the mesoporous shell are tunable by varying the amounts of TEOS and CTAB. This study provides new insight on the preparation of mesoporous materials based on colloidal chemistry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bacteriophage PRD1 and silica colloid transport and recovery in an iron oxide-coated sand aquifer

USGS Publications Warehouse

Ryan, J.N.; Elimelech, M.; Ard, R.A.; Harvey, R.W.; Johnson, P.R.

1999-01-01

Bacteriophage PRD1 and silica colloids were co-injected into sewage- contaminated and uncontaminated zones of an iron oxide-coated sand aquifer on Cape Cod, MA, and their transport was monitored over distances up to 6 m in three arrays. After deposition, the attached PRD1 and silica colloids were mobilized by three different chemical perturbations (elevated pH, anionic surfactant, and reductant). PRD1 and silica colloids experienced less attenuation in the contaminated zone where adsorbed organic matter and phosphate may be hindering attachment of PRD1 and silica colloids to the iron oxide coatings. The PRD1 collision efficiencies agree well with collision efficiencies predicted by assuming favorable PRD1 deposition on iron oxide coatings for which the surface area coverage was measured by microprobe analysis of sediment thin sections. ?? potentials of the PRD1, silica colloids, and aquifer grains corroborated the transport results, indicating that electrostatic forces dominated the attachment of PRD1 and silica colloids. Elevated pH was the chemical perturbation most effective at mobilizing the attached PRD1 and silica colloids. Elevated surfactant concentration mobilized the attached PRD1 and silica colloids more effectively in the contaminated zone than in the uncontaminated zone.Bacteriophage PRD1 and silica colloids were co-injected into sewage-contaminated and uncontaminated zones of an iron oxide-coated sand aquifer on Cape Cod, MA, and their transport was monitored over distances up to 6 m in three arrays. After deposition, the attached PRD1 and silica colloids were mobilized by three different chemical perturbations (elevated pH, anionic surfactant, and reductant). PRD1 and silica colloids experienced less attenuation in the contaminated zone where adsorbed organic matter and phosphate may be hindering attachment of PRD1 and silica colloids to the iron oxide coatings. The PRD1 collision efficiencies agree well with collision efficiencies predicted by assuming favorable PRD1 deposition on iron oxide coatings for which the surface area coverage was measured by microprobe analysis of sediment thin sections. ?? potentials of the PRD1, silica colloids, and aquifer grains corroborated the transport results, indicating that electrostatic forces dominated the attachment of PRD1 and silica colloids. Elevated pH was the chemical perturbation most effective at mobilizing the attached PRD1 and silica colloids. Elevated surfactant concentration mobilized the attached PRD1 and silica colloids more effectively in the contaminated zone than in the uncontaminated zone.

Ag colloids and arrays for plasmonic non-radiative energy transfer from quantum dots to a quantum well

NASA Astrophysics Data System (ADS)

Murphy, Graham P.; Gough, John J.; Higgins, Luke J.; Karanikolas, Vasilios D.; Wilson, Keith M.; Garcia Coindreau, Jorge A.; Zubialevich, Vitaly Z.; Parbrook, Peter J.; Bradley, A. Louise

2017-03-01

Non-radiative energy transfer (NRET) can be an efficient process of benefit to many applications including photovoltaics, sensors, light emitting diodes and photodetectors. Combining the remarkable optical properties of quantum dots (QDs) with the electrical properties of quantum wells (QWs) allows for the formation of hybrid devices which can utilize NRET as a means of transferring absorbed optical energy from the QDs to the QW. Here we report on plasmon-enhanced NRET from semiconductor nanocrystal QDs to a QW. Ag nanoparticles in the form of colloids and ordered arrays are used to demonstrate plasmon-mediated NRET from QDs to QWs with varying top barrier thicknesses. Plasmon-mediated energy transfer (ET) efficiencies of up to ˜25% are observed with the Ag colloids. The distance dependence of the plasmon-mediated ET is found to follow the same d -4 dependence as the direct QD to QW ET. There is also evidence for an increase in the characteristic distance of the interaction, thus indicating that it follows a Förster-like model with the Ag nanoparticle-QD acting as an enhanced donor dipole. Ordered Ag nanoparticle arrays display plasmon-mediated ET efficiencies up to ˜21%. To explore the tunability of the array system, two arrays with different geometries are presented. It is demonstrated that changing the geometry of the array allows a transition from overall quenching of the acceptor QW emission to enhancement, as well as control of the competition between the QD donor quenching and ET rates.

Polymeric Microcapsule Arrays.

DTIC Science & Technology

1995-03-24

support, microencapsulation and entrapment within a membrane/film or gel. The ideal enzyme immobilization method would (1) Employ mild chemical...yields hollow polymeric microcapsules of uniform diameter and length. These microcapsules are arranged in a high density array in which the...individual capsules protrude from a surface like the bristles of a brush. We have developed procedures for filling these microcapsules with high

Lateral separation of colloids or cells by dielectrophoresis augmented by AC electroosmosis.

PubMed

Zhou, Hao; White, Lee R; Tilton, Robert D

2005-05-01

Colloidal particles and biological cells are patterned and separated laterally adjacent to a micropatterned electrode array by applying AC electric fields that are principally oriented normally to the electrode array. This is demonstrated for yeast cells, red blood cells, and colloidal polystyrene particles of different sizes and zeta-potentials. The separation mechanism is observed experimentally to depend on the applied field frequency and voltage. At high frequencies, particles position themselves in a manner that is consistent with dielectrophoresis, while at low frequencies, the positioning is explained in terms of a strong coupling between gravity, the vertical component of the dielectrophoretic force, and the Stokes drag on particles induced by AC electroosmotic flow. Compared to high frequency dielectrophoretic separations, the low frequency separations are faster and require lower applied voltages. Furthermore, the AC electroosmosis coupling with dielectrophoresis may enable cell separations that are not feasible based on dielectrophoresis alone.

Nonaqueous polypyrrole colloids

DOEpatents

Armes, Steven P.; Aldissi, Mahmoud

1991-01-01

Processable conductive polymers including an oxidized, polymerized aromatic heterocyclic monomer, e.g., pyrrole, an stabilizing effective amount of a poly(vinyl acetate) and dopant anions, and a process of preparing said processable conductive polymers directly in a nonaqueous medium such as methyl acetate, methyl formate, ethyl formate, and propyl formate are disclosed.

Synthesis and Processing of Ultra-High Temperature Metal Carbide and Metal Diboride Nanocomposite Materials

DTIC Science & Technology

2008-04-15

cellulose acetate polymers, and diols. Common sol- uble metal/metal oxide-bearing materials are metal alkoxides, metal diketonates, and metal ... carboxylates . Metal-organic compounds are usually subjected to hydrolysis and condensa- tion reactions to produce polymeric or colloidal metal-oxide

Colloidal crystal beads composed of core-shell particles for multiplex bioassay.

PubMed

Xu, Hua; Zhu, Cun; Zhao, Yuanjin; Zhao, Xiangwei; Hu, Jing; Gu, Zhongze

2009-04-01

A convenient method was developed to fabricate colloidal crystal beads (CCBs) with tough mechanical strength, which was used as encoded carriers for multiplex bioassay. The latex particles used for the construction of the CCBs were designed with a rigid core PS and a elastomeric shell poly(MMA/EA/MAA), and were prepared via one-step soap-free emulsion polymerization. The as-above-prepared CCBs were thermo-treated to drive the elastomeric shells of adjacent latex particles joining together. It was found that the coalescence of latex particles can greatly improve the mechanical strength of the CCBs for multiplex bioassay.

ELECTROKINETIC DENSIFICATION OF COAL FINES IN WASTE PONDS

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

E. James Davis

1999-12-18

The objective of this research was to demonstrate that electrokinetics can be used to remove colloidal coal and mineral particles from coal-washing ponds and lakes without the addition of chemical additives such as salts and polymeric flocculants. The specific objectives were: Design and develop a scaleable electrophoresis apparatus to clarify suspensions of colloidal coal and clay particles; Demonstrate the separation process using polluted waste water from the coal-washing facilities at the coal-fired power plants in Centralia, WA; Develop a mathematical model of the process to predict the rate of clarification and the suspension electrical properties needed for scale up.

BACTERIOPHAGE PRD1 AND SILICA COLLOID TRANSPORT AND RECOVERY IN AN IRON OXIDE-COATED SAND AQUIFER. (R826179)

EPA Science Inventory

Bacteriophage PRD1 and silica colloids were co-injected into
sewage-contaminated and uncontaminated zones of an iron oxide-coated sand
aquifer on Cape Cod, MA, and their transport was monitored over distances up to
6 m in three arrays. After deposition, the attache...

Fabrication, Physicochemical Characterization, and Performance Evaluation of Biodegradable Polymeric Microneedle Patch System for Enhanced Transcutaneous Flux of High Molecular Weight Therapeutics.

PubMed

Shah, Viral; Choudhury, Bijaya Krushna

2017-11-01

A revolutionary paradigm shift is being observed currently, towards the use of therapeutic biologics for disease management. The present research was focused on designing an efficient dosage form for transdermal delivery of α-choriogonadotropin (high molecular weight biologic), through biodegradable polymeric microneedles. Polyvinylpyrrolidone-based biodegradable microneedle arrays loaded with high molecular weight polypeptide, α-choriogonadotropin, were fabricated for its systemic delivery via transdermal route. Varied process and formulation parameters were optimized for fabricating microneedle array, which in turn was expected to temporally rupture the stratum corneum layer of the skin, acting as a major barrier to drug delivery through transdermal route. The developed polymeric microneedles were optimized on the basis of quality attributes like mechanical strength, axial strength, insertion ratio, and insertion force analysis. The optimized polymeric microneedle arrays were characterized for in vitro drug release studies, ex vivo drug permeation studies, skin resealing studies, and in vivo pharmacokinetic studies. Results depicted that fabricated polymeric microneedle arrays with mechanical strength of above 5 N and good insertion ratio exhibited similar systemic bioavailability of α-choriogonadotropin in comparison to marketed subcutaneous injection formulation of α-choriogonadotropin. Thus, it was ultimately concluded that the designed drug delivery system can serve as an efficient tool for systemic delivery of therapeutic biologics, with an added benefit of overcoming the limitations of parenteral delivery, achieving better patient acceptability and compliance.

Plutonium partitioning in water-granite and water-α-FeOOH systems: from a viewpoint of a three-phase system.

PubMed

Lin, Jianfeng; Dang, Haijun; Xie, Jinchuan; Zhou, Guoqing; Li, Mei; Zhang, Jihong

2015-09-01

Traditional sorption experiments commonly treat the colloidal species of low-solubility contaminants as immobile species when separated by centrifugation or ultrafiltration. This study shows that, from a viewpoint of a three-phase system, the mobile Pu species, especially the colloidal species, play an important role in Pu partitioning in water-granite and water-α-FeOOH systems. A new distribution coefficient term Ks/(d+c) was defined to take the mobile colloidal species into consideration, and it differs to the traditional distribution coefficient Ks/d by orders of magnitude in the water-granite and water-α-FeOOH systems. This term, Ks/(d+c), can quantitatively describe Pu partitioning in the suspension, in particular the fraction of mobile species that dominate Pu migration in the environment. The effects of ionic strength (I) and pH on the Pu partitioning in water-granite and water-α-FeOOH systems are well interpreted with respect to the zeta potential change of granite grains, α-FeOOH colloid particles and polymeric Pu. It is concluded that the presence of the α-FeOOH colloid with a low concentration (<10 mg L(-1)) is favorable for the stability of colloidal Pu and leads to large proportion of mobile Pu, especially colloid-associated Pu, which will migrate much faster than dissolved Pu in groundwater.

Dynamic Colloidal Molecules Maneuvered by Light-Controlled Janus Micromotors.

PubMed

Gao, Yirong; Mou, Fangzhi; Feng, Yizheng; Che, Shengping; Li, Wei; Xu, Leilei; Guan, Jianguo

2017-07-12

In this work, we propose and demonstrate a dynamic colloidal molecule that is capable of moving autonomously and performing swift, reversible, and in-place assembly dissociation in a high accuracy by manipulating a TiO 2 /Pt Janus micromotor with light irradiation. Due to the efficient motion of the TiO 2 /Pt Janus motor and the light-switchable electrostatic interactions between the micromotor and colloidal particles, the colloidal particles can be captured and assembled one by one on the fly, subsequently forming into swimming colloidal molecules by mimicking space-filling models of simple molecules with central atoms. The as-demonstrated dynamic colloidal molecules have a configuration accurately controlled and stabilized by regulating the time-dependent intensity of UV light, which controls the stop-and-go motion of the colloidal molecules. The dynamic colloidal molecules are dissociated when the light irradiation is turned off due to the disappearance of light-switchable electrostatic interaction between the motor and the colloidal particles. The strategy for the assembly of dynamic colloidal molecules is applicable to various charged colloidal particles. The simulated optical properties of a dynamic colloidal molecule imply that the results here may provide a novel approach for in-place building functional microdevices, such as microlens arrays, in a swift and reversible manner.

Colloidal aspects and packing behaviour of charged microparticulates in high efficiency ion chromatography.

PubMed

Wahab, M Farooq; Pohl, Christopher A; Lucy, Charles A

2012-12-28

The development of small particles in ion chromatography (IC) is a recent phenomenon. Very few studies are available on packing polymeric particles bearing ionizable functional groups. This study explores the colloidal and rheological properties that govern slurry packing to form high efficiency IC columns. The polymeric substrate used was non-porous 4.4 μm sulfonated ethylvinylbenzene–divinylbenzene (1.4 mequiv. SO(3)H/g resin) with 55% crosslink. We developed simple tests optical microscopy and sedimentation tests for predicting the quality of packed columns. The negatively charged particles (zeta potential: −52 mV in water) behave like colloids. The influence of counter-ion charge (Al(3+), Mg(2+), Na(+)) and ionic strength on column efficiency followed the Schulze–Hardy rule. Highly flocculating slurries give poorly packed columns with N ~ 900 whereas under non-agglomerating slurry conditions efficiencies up to N > 10,000 can be achieved. A non-agglomerating slurry also shows non-Newtonian behaviour, specifically shear thickening. Packing at lower flow rate (<1 mL/min) or higher temperature (>50 °C) reduces the shear thickening and produces higher efficiency columns. The packed sulfonated resin column is coated with 72 nm quaternary ammonium bearing latex (AS4A) and used in the separation of F(−), Cl(−), NO(2)(−), Br(−), and NO(3)(−) yielding a reduced plate height of 1.9 under optimum conditions.

A comparison of tackified, miniemulsion core-shell acrylic latex films with corresponding particle-blend films: structure-property relationships.

PubMed

Canetta, Elisabetta; Marchal, Jeanne; Lei, Chun-Hong; Deplace, Fanny; König, Alexander M; Creton, Costantino; Ouzineb, Keltoum; Keddie, Joseph L

2009-09-15

Tackifying resins (TRs) are often added to pressure-sensitive adhesive films to increase their peel strength and adhesion energy. In waterborne adhesives, the TR is dispersed in water using surfactants and then blended with colloidal polymers in water (i.e., latex). In such waterborne systems, there are problems with the colloidal stability and difficulty in applying coatings of the particle blends; the films are often hydrophilic and subject to water uptake. Here, an alternative method of making waterborne, tackified adhesives is demonstrated. The TR is incorporated within the core of colloidal polymer particles via miniemulsion polymerization. Atomic force microscopy (AFM) combined with force spectroscopy analysis reveals there is heterogeneity in the distribution of the TR in films made from particle blends and also in films made from miniemulsion polymers. Two populations, corresponding to TR-rich and acrylic-rich components, were identified through analysis of the AFM force-displacement curves. The nanoscale maximum adhesion force and adhesion energy were found to be higher in a miniemulsion film containing 12 wt % tackifying resin in comparison to an equivalent blended film. The macroscale tack and viscoelasticity are interpreted by consideration of the nanoscale structure and properties. The incorporation of tackifying resin through a miniemulsion polymerization process not only offers clear benefits in the processing of the adhesive, but it also leads to enhanced adhesion properties.

Quantitative Phase Microscopy for Accurate Characterization of Microlens Arrays

NASA Astrophysics Data System (ADS)

Grilli, Simonetta; Miccio, Lisa; Merola, Francesco; Finizio, Andrea; Paturzo, Melania; Coppola, Sara; Vespini, Veronica; Ferraro, Pietro

Microlens arrays are of fundamental importance in a wide variety of applications in optics and photonics. This chapter deals with an accurate digital holography-based characterization of both liquid and polymeric microlenses fabricated by an innovative pyro-electrowetting process. The actuation of liquid and polymeric films is obtained through the use of pyroelectric charges generated into polar dielectric lithium niobate crystals.

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

Highly temperature responsive core-shell magnetic particles: synthesis, characterization and colloidal properties.

PubMed

Rahman, Md Mahbubor; Chehimi, Mohamed M; Fessi, Hatem; Elaissari, Abdelhamid

2011-08-15

Temperature responsive magnetic polymer submicron particles were prepared by two step seed emulsion polymerization process. First, magnetic seed polymer particles were obtained by emulsion polymerization of styrene using potassium persulfate (KPS) as an initiator and divinylbenzne (DVB) as a cross-linker in the presence of oil-in-water magnetic emulsion (organic ferrofluid droplets). Thereafter, DVB cross-linked magnetic polymer particles were used as seed in the precipitation polymerization of N-isopropylacrylamide (NIPAM) to induce thermosensitive PNIPAM shell onto the hydrophobic polymer surface of the cross-linked magnetic polymer particles. To impart cationic functional groups in the thermosensitive PNIPAM backbone, the functional monomer aminoethylmethacrylate hydrochloride (AEMH) was used to polymerize with NIPAM while N,N'-methylenebisacrylamide (MBA) and 2, 2'-azobis (2-methylpropionamidine) dihydrochloride (V-50) were used as a cross-linker and as an initiator respectively. The effect of seed to monomer (w/w) ratio along with seed nature on the final particle morphology was investigated. Dynamic light scattering (DLS) results demonstrated particles swelling at below volume phase transition temperature (VPTT) and deswelling above the VPTT. The perfect core (magnetic) shell (polymer) structure of the particles prepared was confirmed by Transmission Electron Microscopy (TEM). The chemical composition of the particles were determined by thermogravimetric analysis (TGA). The effect of temperature, pH, ionic strength on the colloidal properties such as size and zeta potential of the micron sized thermo-sensitive magnetic particles were also studied. In addition, a short mechanistic discussion on the formation of core-shell morphology of magnetic polymer particles has also been discussed. Copyright © 2011 Elsevier Inc. All rights reserved.

Synthesis and characterization of polyethylene glycol mediated silver nanoparticles by the green method.

PubMed

Shameli, Kamyar; Ahmad, Mansor Bin; Jazayeri, Seyed Davoud; Sedaghat, Sajjad; Shabanzadeh, Parvaneh; Jahangirian, Hossein; Mahdavi, Mahnaz; Abdollahi, Yadollah

2012-01-01

The roles of green chemistry in nanotechnology and nanoscience fields are very significant in the synthesis of diverse nanomaterials. Herein, we report a green chemistry method for synthesized colloidal silver nanoparticles (Ag NPs) in polymeric media. The colloidal Ag NPs were synthesized in an aqueous solution using silver nitrate, polyethylene glycol (PEG), and β-D-glucose as a silver precursor, stabilizer, and reducing agent, respectively. The properties of synthesized colloidal Ag NPs were studied at different reaction times. The ultraviolet-visible spectra were in excellent agreement with the obtained nanostructure studies performed by transmission electron microscopy (TEM) and their size distributions. The Ag NPs were characterized by utilizing X-ray diffraction (XRD), zeta potential measurements and Fourier transform infrared (FT-IR). The use of green chemistry reagents, such as glucose, provides green and economic features to this work.

Sustainable steric stabilization of colloidal titania nanoparticles

NASA Astrophysics Data System (ADS)

Elbasuney, Sherif

2017-07-01

A route to produce a stable colloidal suspension is essential if mono-dispersed particles are to be successfully synthesized, isolated, and used in subsequent nanocomposite manufacture. Dispersing nanoparticles in fluids was found to be an important approach for avoiding poor dispersion characteristics. However, there is still a great tendency for colloidal nanoparticles to flocculate over time. Steric stabilization can prevent coagulation by introducing a thick adsorbed organic layer which constitutes a significant steric barrier that can prevent the particle surfaces from coming into direct contact. One of the main features of hydrothermal synthesis technique is that it offers novel approaches for sustainable nanoparticle surface modification. This manuscript reports on the sustainable steric stabilization of titanium dioxide nanoparticles. Nanoparticle surface modification was performed via two main approaches including post-synthesis and in situ surface modification. The tuneable hydrothermal conditions (i.e. temperature, pressure, flow rates, and surfactant addition) were optimized to enable controlled steric stabilization in a continuous fashion. Effective post synthesis surface modification with organic ligand (dodecenyl succinic anhydride (DDSA)) was achieved; the optimum surface coating temperature was reported to be 180-240 °C to ensure DDSA ring opening and binding to titania nanoparticles. Organic-modified titania demonstrated complete change in surface properties from hydrophilic to hydrophobic and exhibited phase transfer from the aqueous phase to the organic phase. Exclusive surface modification in the reactor was found to be an effective approach; it demonstrated surfactant loading level 2.2 times that of post synthesis surface modification. Titania was also stabilized in aqueous media using poly acrylic acid (PAA) as polar polymeric dispersant. PAA-titania nanoparticles demonstrated a durable amorphous polymeric layer of 2 nm thickness. This manuscript revealed the state of the art for the real development of stable colloidal mono-dispersed particles with controlled surface properties.

Microbial Extracellular Polymeric Substances (EPSs) in Ocean Systems

PubMed Central

Decho, Alan W.; Gutierrez, Tony

2017-01-01

Microbial cells (i.e., bacteria, archaea, microeukaryotes) in oceans secrete a diverse array of large molecules, collectively called extracellular polymeric substances (EPSs) or simply exopolymers. These secretions facilitate attachment to surfaces that lead to the formation of structured ‘biofilm’ communities. In open-water environments, they also lead to formation of organic colloids, and larger aggregations of cells, called ‘marine snow.’ Secretion of EPS is now recognized as a fundamental microbial adaptation, occurring under many environmental conditions, and one that influences many ocean processes. This relatively recent realization has revolutionized our understanding of microbial impacts on ocean systems. EPS occur in a range of molecular sizes, conformations and physical/chemical properties, and polysaccharides, proteins, lipids, and even nucleic acids are actively secreted components. Interestingly, however, the physical ultrastructure of how individual EPS interact with each other is poorly understood. Together, the EPS matrix molecules form a three-dimensional architecture from which cells may localize extracellular activities and conduct cooperative/antagonistic interactions that cannot be accomplished efficiently by free-living cells. EPS alter optical signatures of sediments and seawater, and are involved in biogeomineral precipitation and the construction of microbial macrostructures, and horizontal-transfers of genetic information. In the water-column, they contribute to the formation of marine snow, transparent exopolymer particles (TEPs), sea-surface microlayer biofilm, and marine oil snow. Excessive production of EPS occurs during later-stages of phytoplankton blooms as an excess metabolic by product and releases a carbon pool that transitions among dissolved-, colloidal-, and gel-states. Some EPS are highly labile carbon forms, while other forms appear quite refractory to degradation. Emerging studies suggest that EPS contribute to efficient trophic-transfer of environmental contaminants, and may provide a protective refugia for pathogenic cells within marine systems; one that enhances their survival/persistence. Finally, these secretions are prominent in ‘extreme’ environments ranging from sea-ice communities to hypersaline systems to the high-temperatures/pressures of hydrothermal-vent systems. This overview summarizes some of the roles of exopolymer in oceans. PMID:28603518

Statistical interpretation of transient current power-law decay in colloidal quantum dot arrays

NASA Astrophysics Data System (ADS)

Sibatov, R. T.

2011-08-01

A new statistical model of the charge transport in colloidal quantum dot arrays is proposed. It takes into account Coulomb blockade forbidding multiple occupancy of nanocrystals and the influence of energetic disorder of interdot space. The model explains power-law current transients and the presence of the memory effect. The fractional differential analogue of the Ohm law is found phenomenologically for nanocrystal arrays. The model combines ideas that were considered as conflicting by other authors: the Scher-Montroll idea about the power-law distribution of waiting times in localized states for disordered semiconductors is applied taking into account Coulomb blockade; Novikov's condition about the asymptotic power-law distribution of time intervals between successful current pulses in conduction channels is fulfilled; and the carrier injection blocking predicted by Ginger and Greenham (2000 J. Appl. Phys. 87 1361) takes place.

Conducting polymer nanowire arrays for high performance supercapacitors.

PubMed

Wang, Kai; Wu, Haiping; Meng, Yuena; Wei, Zhixiang

2014-01-15

This Review provides a brief summary of the most recent research developments in the fabrication and application of one-dimensional ordered conducting polymers nanostructure (especially nanowire arrays) and their composites as electrodes for supercapacitors. By controlling the nucleation and growth process of polymerization, aligned conducting polymer nanowire arrays and their composites with nano-carbon materials can be prepared by employing in situ chemical polymerization or electrochemical polymerization without a template. This kind of nanostructure (such as polypyrrole and polyaniline nanowire arrays) possesses high capacitance, superior rate capability ascribed to large electrochemical surface, and an optimal ion diffusion path in the ordered nanowire structure, which is proved to be an ideal electrode material for high performance supercapacitors. Furthermore, flexible, micro-scale, threadlike, and multifunctional supercapacitors are introduced based on conducting polyaniline nanowire arrays and their composites. These prototypes of supercapacitors utilize the high flexibility, good processability, and large capacitance of conducting polymers, which efficiently extend the usage of supercapacitors in various situations, and even for a complicated integration system of different electronic devices. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation available encapsulation materials for low-cost long-life silicon photovoltaic arrays

NASA Technical Reports Server (NTRS)

Carmichael, D. C.; Gaines, G. B.; Noel, G. T.; Sliemers, F. A.; Nance, G. P.; Bunk, A. R.; Brockway, M. C.

1978-01-01

Experimental evaluation of selected encapsulation designs and materials based on an earlier study which have potential for use in low cost, long-life photovoltaic arrays are reported. The performance of candidate materials and encapsulated cells were evaluated principally for three types of encapsulation designs based on their potentially low materials and processing costs: (1) polymeric coatings, transparent conformal coatings over the cell with a structural-support substrate; (2) polymeric film lamination, cells laminated between two films or sheets of polymeric materials; and (3) glass-covered systems, cells adhesively bonded to a glass cover (superstrate) with a polymeric pottant and a glass or other substrate material. Several other design types, including those utilizing polymer sheet and pottant materials, were also included in the investigation.

Characterization of photonic colloidal crystals in real and reciprocal space

NASA Astrophysics Data System (ADS)

Thijssen, J. H. J.

2007-05-01

In this thesis, we present experimental work on the characterization of photonic colloidal crystals in real and reciprocal space. Photonic crystals are structures in which the refractive index varies periodically in space on the length scale of the wavelength of light. Self-assembly of colloidal particles is a promising route towards three-dimensional (3-D) photonic crystals. However, fabrication of photonic band-gap materials remains challenging, so calculations that predict their optical properties are indispensable. Our photonic band-structure calculations on binary Laves phases have led to a proposed route towards photonic colloidal crystals with a band gap in the visible region. Furthermore, contrary to results in literature, we found that there is no photonic band gap for inverse BCT crystals. Finally, optical spectra of colloidal crystals were analyzed using band-structure calculations. Self-assembled photonic crystals are fabricated in multiple steps. Each of these steps can significantly affect the 3-D structure of the resulting crystal. X-rays are an excellent probe of the internal structure of photonic crystals, even if the refractive-index contrast is large. In Chapter 3, we demonstrate that an angular resolution of 0.002 mrad is achievable at a third-generation synchrotron using compound refractive optics. As a result, the position and the width of Bragg reflections in 2D diffraction patterns can be resolved, even for lattice spacings larger than a micrometer (corresponding to approximately 0.1 mrad). X-ray diffraction patterns and electron-microscopy images are used in Chapter 4 to determine the orientation of hexagonal layers in convective-assembly colloidal crystals. Quantitative analysis revealed that, in our samples, the layers were not exactly hexagonal and the stacking sequence was that of face-centered cubic (FCC) crystals, though stacking faults may have been present. In Chapter 5, binary colloidal crystals of organic spheres (polystyrene, PMMA) and/or inorganic spheres (silica) are introduced as promising templates for strongly photonic crystals. To prevent melting of the template, we used atomic layer deposition (ALD) to infiltrate polystyrene and PMMA templates with alumina, after which chemical vapor deposition (CVD) was used to further enhance the refractive-index contrast. Binary colloidal crystals of silica spheres can be infiltrated by CVD directly, but they often have a layer of colloidal fluid on top. Preliminary etching experiments demonstrated that it may be possible to etch silica templates with plasmas or with adhesive tape. As described in Chapter 6, sedimentation of colloidal silica spheres in an external, high-frequency electric field lead to mm-scale BCT crystals with up to 25 layers. In addition, electric fields were used as an external control to switch between BCT and close-packed (CP) crystal structures within seconds. We also developed two procedures to invert BCT crystals without loss of structure - colloidal particles were immobilized by diffusion-polymerization or photo-induced polymerization of the surrounding solvent. Some BCT crystals were even infiltrated with silicon using CVD. We demonstrate in Chapter 7 that X-ray diffraction can be used to determine the 3-D structure of such photonic colloidal crystals at the various stages of their fabrication. Excellent agreement was found with confocal and electron-microscopy images.

Two-color beam improvement of the colloidal particle lens array assisted surface nanostructuring

NASA Astrophysics Data System (ADS)

Afanasiev, Andrei; Bredikhin, Vladimir; Pikulin, Alexander; Ilyakov, Igor; Shishkin, Boris; Akhmedzhanov, Rinat; Bityurin, Nikita

2015-05-01

We consider laser nanostructuring of the material surface by means of a colloidal particle lens array. Here, the monolayer of dielectric micro- or nanospheres placed on the surface acts as an array of near-field lenses that focus the laser radiation into the multitude of distinct spots, allowing the formation of many structures in a single stage. We show that conversion of a small part of the energy of the femtosecond beam into the second harmonic (SH) is an efficient way to increase the surface density of obtained nanostructures. By combining the fundamental frequency and the SH, one benefits both from the power of the former and from the focusing ability of the latter. This combination provides an efficient nanostructuring with sphere diameter close to the wavelength of the second harmonic. The possibility to create arrays of nanostructures with surface density above 5 × 10 8 cm - 2 with femtosecond Ti:sapphire laser operating at 800 nm was demonstrated by employing 0.45 μm spheres.

Crystalline Colloidal Arrays in Polymer Matrices

NASA Technical Reports Server (NTRS)

Sunkara, Hari B.; Penn, B. G.; Frazier, D. O.; Ramachandran, N.

1997-01-01

Crystalline Colloidal Arrays (CCA, also known as colloidal crystals), composed of aqueous or nonaqueous dispersions of self-assembled nanosized polymer colloidal spheres, are emerging toward the development of advanced optical devices for technological applications. The spontaneous self assembly of polymer spheres in a dielectric medium results from the electrostatic repulsive interaction between particles of uniform size and charge distribution. In a way similar to atomic crystals that diffract X-rays, CCA dispersions in thin quartz cells selectively and efficiently Bragg diffract the incident visible light. The reason for this diffraction is because the lattice (body or face centered cubic) spacing is on the order of the wavelength of visible light. Unlike the atomic crystals that diffract a fixed wavelength, colloidal crystals in principle, depending on the particle size, particle number and charge density, can diffract W, Vis or IR light. Therefore, the CCA dispersions can be used as laser filters. Besides, the diffraction intensity depends on the refractive index mismatch between polymer spheres and dielectric medium; therefore, it is possible to modulate incident light intensities by manipulating the index of either the spheres or the medium. Our interest in CCA is in the fabrication of all-optical devices such as optical switches, limiters, and spatial light modulators for optical signal processing. The two major requirements from a materials standpoint are the incorporation of suitable nonlinear optical materials (NLO) into polymer spheres which will allow us to alter the refractive index of the spheres by intense laser radiation, and preparation of solid CCA filters which can resist laser damage. The fabrication of solid composite filters not only has the advantage that the films are easier to handle, but also the arrays in solid films are more robust than in liquid media. In this paper, we report the photopolymerization process used to trap CCA in polymer matrices, the factors which affect the optical diffraction qualities of resulting polymer films, and methods to improve the efficiencies of solid optical filters. Before this, we also present the experimental demonstration, of controlling the optical diffraction intensities from aqueous CCA dispersions by varying the temperature, which establishes the feasibility of fabricating all-optical switching devices with nonlinear periodic array structures.

Large-area Co-silicide nanodot arrays produced by colloidal nanosphere lithography and thermal annealing.

PubMed

Cheng, S L; Wong, S L; Lu, S W; Chen, H

2008-09-01

We report here the successful fabrication of large-area size-tunable periodic arrays of cobalt and Co-silicide nanodots on silicon substrates by employing the colloidal nanosphere lithography (NSL) technique and heat treatments. The growth of low-resistivity epitaxial CoSi(2) was found to be more favorable for the samples with smaller Co nanodot sizes. The sizes of the epitaxial CoSi(2) nanodots can be tuned from 50 to 100 nm by varying the diameter of the colloidal spheres and annealing temperatures. The epitaxial CoSi(2) nanodots were found to grow with an epitaxial orientation with respect to the (001)Si substrates: [001]CoSi(2)//[001]Si and (200)CoSi(2)//(400)Si. From the results of planview HRTEM, XTEM, and SAED analysis, the epitaxial CoSi(2) nanodots were identified to be inverse pyramids in shape, and the average sizes of the faceted silicide nanodots were measured to decrease with annealing temperature. The observed results present the exciting prospect that with appropriate controls, the colloidal NSL technique promises to facilitate the growth of a variety of well-ordered silicide nanodots with selected shape, size, and periodicity.

The effect of high temperature sol-gel polymerization parameters on the microstructure and properties of hydrophobic phenol-formaldehyde/silica hybrid aerogels.

PubMed

Seraji, Mohamad Mehdi; Sameri, Ghasem; Davarpanah, Jamal; Bahramian, Ahmad Reza

2017-05-01

Phenol-formaldehyde/silica hybrid aerogels with different degree of hydrophobicity were successfully synthesized via high temperature sol-gel polymerization. Tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) were used as precursor and co-precursor of the hydrophobic silica-based phase, respectively. The hydrolysis step of silica based sols were conducted by acid catalyzed reactions and HCl was used as hydrolysis catalyst. The chemical structure of prepared hybrid aerogels was characterized by Fourier Transform Infrared spectroscopy (FT-IR). The effect of MTES/TEOS proportion and catalyst content on the morphology and microstructure of samples were investigated by FE-SEM and C, Si mapping analysis. The acid catalyzed hydrolysis of TEOS and MTES sols leads to formation of a sol with primarily silica particles in the organic-inorganic hybrid sol and varying colloid growth mechanisms were occurred with change in MTES and HCl molar ratio. With the increasing of MTES content, the microstructure of samples changed from uniform colloidal network, core-shell structure to polymeric structure with a huge phase separation. The increasing of HCl mole fraction leads to smaller particle size. Moreover, the shrinkage of samples was decreased and water contact angles of the resulted aerogels were increased from 40 to 156.8° with the increases of MTES content. Copyright © 2017 Elsevier Inc. All rights reserved.

Monodispersepoly[BMA-co-(COPS-I)] Particles by Soap-Free Emulsion Copolymerization and Its Optical Properties as Photonic Crystals.

PubMed

Lee, Ki Chang; Choo, Hun Seung

2015-10-01

In order to study the surfactant-free emulsion copolymerization of benzyl methacrylate (BMA) with sodium 1-allyloxy-2-hydroxypropane sulfonate (COPS-I) and the resulting optical properties, a series of experiments was carried out at various reaction conditions such as the changes of BMA concentration, COPS-I concentration, BMA concentration under a fixed COPS-I amount, initiator and divinyl benzene (DVB) concentration. All the latices showed highly monodispersed spherical particles in the size range of 144~435 nm and the respective shiny structural colors from their colloidal photonic crystals. It is found that the changes in such polymerization factors greatly affect the number of particles and particle diameter, polymerization rate, molecular weight, zeta-potential, and refractive indices. The increase of number of particles led to the increased rate of polymerization and zeta-potential of the latices, on the other hand, to the decreased molecular weight. Refractive indices and the reflectivity increased with COPS-I concentration, on the other hand, and decreased with DVB concentration. Especially, refractive indices of the resulting poly[BMA-co-(COPS-I)] colloidal photonic crystals showed much higher values of 1.65~2.21 than that of polystyrene, due to the formation of core-shell shaped morphology. Monodisperse and high refractive index of poly[BMA-co-(COPS-I)] particles prepared in this work could be used for the study in photonic crystals and electrophoretic display.

Quaternized polymeric microgels as metal free catalyst for H2 production from the methanolysis of sodium borohydride

NASA Astrophysics Data System (ADS)

Sahiner, Nurettin; Sengel, Sultan Butun

2016-12-01

Polymeric microgels derived from tris(2-amino ethyl)amine (TAEA) and glycerol diglycidyl ether as p(TAEA-co-GDE) via microemulsion polymerization techniques are protonated by 0.5 M HCl treatment as p(TAEA-co-GDE)-HCl). These microgels are then exposed to anion exchange reactions with differ ionic liquid forming salts, such as potassium thiocyanate (PTC), sodium dicyanamide (SDCA), ammonium hexafluorophosphate (AHFP), and sodium tetrafluoroborate (STFB) in aqueous medium for the preparation of p(TAEA-co-GDE) based ionic liquid colloidal microgels. These anions exchanged p(TAEA-co-GDE) ionic liquid colloids (ILCs) are directly used as catalyst for hydrogen (H2) generation from the methanol solution of sodium borohydride (NaBH4). Various parameters affecting the H2 production rate such as the catalyst types, NaBH4 amount, and the temperature are investigated. It is found that the methanolysis of NaBH4 catalyzed by p(TAEA-co-GDE)-HCl obeys the first order reaction kinetic. The activation energy, enthalpy and entropy of the protonated p(TAEA-co-GDE) microgels are calculated and found as the 30.37 kJ mol-1, 27.96 kJ mol-1, and -148.08 J mol-1 K-1, respectively. Furthermore, the hydrogen generation rate of 3018 mL min-1 g-1 catalyzed by p(TAEA-co-GDE)-HCl catalyst is attained.

Robust Plasma Polymerized-Titania/Silica Janus Microparticles

DTIC Science & Technology

2010-04-29

vladimir@mse.gatech.edu. (1) De Gennes, P. G. Rev. Mod. Phys. 1992, 64, 645. (2) Perro , A.; Reculusa, S.; Ravaine, S.; Bourgeat-Lami, E.; Duguet, E. J. Mater...Rubner,M. F.; Cohen, R. E.Macromolecules 2005, 38, 7876. (12) Perro ,A.;Meunier, F.; Schmitt, V.;Ravaine, S.Colloid. Surface.A. 2009, 332, 57. (13

Fabrication of polymeric nano-batteries array using anodic aluminum oxide templates.

PubMed

Zhao, Qiang; Cui, Xiaoli; Chen, Ling; Liu, Ling; Sun, Zhenkun; Jiang, Zhiyu

2009-02-01

Rechargeable nano-batteries were fabricated in the array pores of anodic aluminum oxide (AAO) template, combining template method and electrochemical method. The battery consisted of electropolymerized PPy electrode, porous TiO2 separator, and chemically polymerized PAn electrode was fabricated in the array pores of two-step anodizing aluminum oxide (AAO) membrane, based on three-step assembling method. It performs typical electrochemical battery behavior with good charge-discharge ability, and presents a capacity of 25 nAs. AFM results show the hexagonal array of nano-batteries' top side. The nano-battery may be a promising device for the development of Micro-Electro-Mechanical Systems (MEMS), and Nano-Electro-Mechanical Systems (NEMS).

Iron oxide/cassava starch-supported Ziegler-Natta catalysts for in situ ethylene polymerization.

PubMed

Chancharoenrith, Sittikorn; Kamonsatikul, Choavarit; Namkajorn, Montree; Kiatisevi, Supavadee; Somsook, Ekasith

2015-03-06

Iron oxide nanoparticles were used as supporters for in situ polymerization to produce polymer nanocomposites with well-dispersed fillers in polymer matrix. Iron oxide could be sustained as colloidal solutions by cassava starch to produce a good dispersion of iron oxide in the matrix. New supports based on iron oxide/cassava starch or cassava starch for Ziegler-Natta catalysts were utilized as heterogeneous supporters for partially hydrolyzed triethylaluminum. Then, TiCl4 was immobilized on the supports as catalysts for polymerization of ethylene. High-density polyethylene (HDPE) composites were obtained by the synthesized catalysts. A good dispersion of iron oxide/cassava starch particles was observed in the synthesized polymer matrix promoting to good mechanical properties of HDPE. Copyright © 2014 Elsevier Ltd. All rights reserved.

Rapid Prototyping of Polymeric Nanopillars by 3D Direct Laser Writing for Controlling Cell Behavior.

PubMed

Buch-Månson, Nina; Spangenberg, Arnaud; Gomez, Laura Piedad Chia; Malval, Jean-Pierre; Soppera, Olivier; Martinez, Karen L

2017-08-23

Mammalian cells have been widely shown to respond to nano- and microtopography that mimics the extracellular matrix. Synthetic nano- and micron-sized structures are therefore of great interest in the field of tissue engineering, where polymers are particularly attractive due to excellent biocompatibility and versatile fabrication methods. Ordered arrays of polymeric pillars provide a controlled topographical environment to study and manipulate cells, but processing methods are typically either optimized for the nano- or microscale. Here, we demonstrate polymeric nanopillar (NP) fabrication using 3D direct laser writing (3D DLW), which offers a rapid prototyping across both size regimes. The NPs are interfaced with NIH3T3 cells and the effect of tuning geometrical parameters of the NP array is investigated. Cells are found to adhere on a wide range of geometries, but the interface depends on NP density and length. The Cell Interface with Nanostructure Arrays (CINA) model is successfully extended to predict the type of interface formed on different NP geometries, which is found to correlate with the efficiency of cell alignment along the NPs. The combination of the CINA model with the highly versatile 3D DLW fabrication thus holds the promise of improved design of polymeric NP arrays for controlling cell growth.

Periodic assembly of nanoparticle arrays in disclinations of cholesteric liquid crystals.

PubMed

Li, Yunfeng; Prince, Elisabeth; Cho, Sangho; Salari, Alinaghi; Mosaddeghian Golestani, Youssef; Lavrentovich, Oleg D; Kumacheva, Eugenia

2017-02-28

An important goal of the modern soft matter science is to discover new self-assembly modalities to precisely control the placement of small particles in space. Spatial inhomogeneity of liquid crystals offers the capability to organize colloids in certain regions such as the cores of the topological defects. Here we report two self-assembly modes of nanoparticles in linear defects-disclinations in a lyotropic colloidal cholesteric liquid crystal: a continuous helicoidal thread and a periodic array of discrete beads. The beads form one-dimensional arrays with a periodicity that matches half a pitch of the cholesteric phase. The periodic assembly is governed by the anisotropic surface tension and elasticity at the interface of beads with the liquid crystal. This mode of self-assembly of nanoparticles in disclinations expands our ability to use topological defects in liquid crystals as templates for the organization of nanocolloids.

Evaporative lithographic patterning of binary colloidal films.

PubMed

Harris, Daniel J; Conrad, Jacinta C; Lewis, Jennifer A

2009-12-28

Evaporative lithography offers a promising new route for patterning a broad array of soft materials. In this approach, a mask is placed above a drying film to create regions of free and hindered evaporation, which drive fluid convection and entrained particles to regions of highest evaporative flux. We show that binary colloidal films exhibit remarkable pattern formation when subjected to a periodic evaporative landscape during drying.

Colloidal-gold electrosensor measuring device

DOEpatents

Wegner, S.; Harpold, M.A.; McCaffrey, T.M.; Morris, S.E.; Wojciechowski, M.; Zhao, J.; Henkens, R.W.; Naser, N.; O`Daly, J.P.

1995-11-21

The present invention provides a new device for use in measuring lead levels in biological and environmental samples. Using square wave coulometry and colloidal gold particles impregnated on carbon electrodes, the present invention provides a rapid, reliable, portable and inexpensive means of detecting low lead levels. The colloidal gold modified electrodes have microelectrode array characteristics and produce significantly higher stripping detection signals for lead than are produced at bulk gold electrode surfaces. The method is effective in determining levels of lead down to at least 5 {micro}g/dL in blood samples as small as 10 {micro}L. 9 figs.

Avalanches and plasticity for colloids in a time dependent optical trap

DOE PAGES

Olson Reichhardt, Cynthia Jane; McDermott, Danielle Marie; Reichhardt, Charles

2015-08-25

Here, with the use of optical traps it is possible to confine assemblies of colloidal particles in two-dimensional and quasi-one-dimensional arrays. Here we examine how colloidal particles rearrange in a quasi-one-dimensional trap with a time dependent confining potential. The particle motion occurs both through slow elastic uniaxial distortions as well as through abrupt large-scale two-dimensional avalanches associated with plastic rearrangements. During the avalanches the particle velocity distributions extend over a broad range and can be fit to a power law consistent with other studies of plastic events mediated by dislocations.

Colloidal-gold electrosensor measuring device

DOEpatents

Wegner, Steven; Harpold, Michael A.; McCaffrey, Terence M.; Morris, Susan E.; Wojciechowski, Marek; Zhao, Junguo; Henkens, Robert W.; Naser, Najih; O'Daly, John P.

1995-01-01

The present invention provides a new device for use in measuring lead levels in biological and environmental samples. Using square wave coulometry and colloidal gold particles impregnated on carbon electrodes, the present invention provides a rapid, reliable, portable and inexpensive means of detecting low lead levels. The colloidal gold modified electrodes have microelectrode array characteristics and produce significantly higher stripping detection signals for lead than are produced at bulk gold electrode surfaces. The method is effective in determining levels of lead down to at least 5 .mu.g/dL in blood samples as small as 10 .mu.L.

Fabrication of Polyhedral Particles from Spherical Colloids and Their Self-Assembly into Rotator Phases**

PubMed Central

Vutukuri, Hanumantha Rao; Imhof, Arnout; van Blaaderen, Alfons

2014-01-01

Particle shape is a critical parameter that plays an important role in self-assembly, for example, in designing targeted complex structures with desired properties. Over the last decades, an unprecedented range of monodisperse nanoparticle systems with control over the shape of the particles have become available. In contrast, the choice of micrometer-sized colloidal building blocks of particles with flat facets, that is, particles with polygonal shapes, is significantly more limited. This can be attributed to the fact that in contrast to nanoparticles, the larger colloids are significantly harder to synthesize as single crystals. It is now shown that a very simple building block, such as a micrometer-sized polymeric spherical colloidal particle, is already enough to fabricate particles with regularly placed flat facets, including completely polygonal shapes with sharp edges. As an illustration that the yields are high enough for further self-assembly studies, the formation of three-dimensional rotator phases of fluorescently labelled, micrometer-sized, and charged rhombic dodecahedron particles was demonstrated. This method for fabricating polyhedral particles opens a new avenue for designing new materials. PMID:25366869

Reversible switching of liquid crystalline order permits synthesis of homogeneous populations of dipolar patchy microparticles

DOE PAGES

Wang, Xiaoguang; Miller, Daniel S.; de Pablo, Juan J.; ...

2014-08-15

The spontaneous positioning of colloids on the surfaces of micrometer-sized liquid crystal (LC) droplets and their subsequent polymerization offers the basis of a general and facile method for the synthesis of patchy microparticles. The existence of multiple local energetic minima, however, can generate kinetic traps for colloids on the surfaces of the LC droplets and result in heterogeneous populations of patchy microparticles. To address this issue, in this paper it is demonstrated that adsorbate-driven switching of the internal configurations of LC droplets can be used to sweep colloids to a single location on the LC droplet surfaces, thus resulting inmore » the synthesis of homogeneous populations of patchy microparticles. The surface-driven switching of the LC can be triggered by addition of surfactant or salts, and permits the synthesis of dipolar microparticles as well as “Janus-like” microparticles. Finally, by using magnetic colloids, the utility of the approach is illustrated by synthesizing magnetically responsive patchy microdroplets of LC with either dipolar or quadrupolar symmetry that exhibit distinct optical responses upon application of an external magnetic field.« less

Design and Synthesis of Self-Assembled Polymeric Nanoparticles for Cancer Drug Delivery

NASA Astrophysics Data System (ADS)

Logie, Jennifer

Current chemotherapeutics are plagued by poor solubility and selectivity, requiring toxic excipients in formulations and causing a number of dose limiting side effects. Nanoparticle delivery has emerged as a strategy to more effectively deliver chemotherapeutics to the tumour site. Specifically, polymeric micelles enable the solubilization of hydrophobic small molecule drugs within the core and mitigate the necessity of excipients. Notwithstanding the significant progress made in polymeric micelle delivery, translation is limited by poor stability and low drug loading. In this work, a rational design approach is used to chemically modify poly(D,L-lactide-co-2-methyl-2-carboxytrimethylene carbonate)-graft-poly(ethylene glycol) (P(LA-co-TMCC)-g-PEG) in order to overcome these limitations and effectively deliver drug to tumours. The PEG density of the polymer system was optimized to enhance the stability of our polymeric micelles. Higher PEG densities permitted the lyophilization of micelles and enhanced the serum stability of the system. To increase the drug loading of our system, we facilitated specific intermolecular interactions within the micelle core. For drugs that form colloidal aggregates, such as pentyl-PABC doxazolidine, polymers were used to stabilize the colloidal core against aggregation and protein adsorption. For more challenging molecules, where self-assembly cannot be controlled, such as docetaxel, we modified the polymeric backbone with a peptide from the binding site of the drug to achieve loadings five times higher than those achieved in conventional micelle systems. This novel docetaxel nanoparticle was assessed in vivo in an orthotopic mouse model of breast cancer, where it showed a wider therapeutic index than the conventional ethanolic polysorbate 80 formulation. The improved tolerability of this formulation enabled higher dosing regimens and led to heightened efficacy and survival in this mouse model. Combined, these studies validated P(LA-co-TMCC)-g-PEG nanoparticles as an effective delivery vehicle for two chemotherapeutics, and presents approaches amenable to the delivery of many other clinically relevant hydrophobic drugs or drug combinations.

Colloidal silica films for high-capacity DNA arrays

NASA Astrophysics Data System (ADS)

Glazer, Marc Irving

The human genome project has greatly expanded the amount of genetic information available to researchers, but before this vast new source of data can be fully utilized, techniques for rapid, large-scale analysis of DNA and RNA must continue to develop. DNA arrays have emerged as a powerful new technology for analyzing genomic samples in a highly parallel format. The detection sensitivity of these arrays is dependent on the quantity and density of immobilized probe molecules. We have investigated substrates with a porous, "three-dimensional" surface layer as a means of increasing the surface area available for the synthesis of oligonucleotide probes, thereby increasing the number of available probes and the amount of detectable bound target. Porous colloidal silica films were created by two techniques. In the first approach, films were deposited by spin-coating silica colloid suspensions onto flat glass substrates, with the pores being formed by the natural voids between the solid particles (typically 23nm pores, 35% porosity). In the second approach, latex particles were co-deposited with the silica and then pyrolyzed, creating films with larger pores (36 nm), higher porosity (65%), and higher surface area. For 0.3 mum films, enhancements of eight to ten-fold and 12- to 14-fold were achieved with the pure silica films and the films "templated" with polymer latex, respectively. In gene expression assays for up to 7,000 genes using complex biological samples, the high-capacity films provided enhanced signals and performed equivalently or better than planar glass on all other functional measures, confirming that colloidal silica films are a promising platform for high-capacity DNA arrays. We have also investigated the kinetics of hybridization on planar glass and high-capacity substrates. Adsorption on planar arrays is similar to ideal Langmuir-type adsorption, although with an "overshoot" at high solution concentration. Hybridization on high-capacity films is controlled by traditional adsorption (ka) and desorption (kd) coefficients, as well as morphology factors and transient binding interactions between the target and probes. The strength of the transient probe/target binding interactions are on the order of 5--7 DNA base pairs, which suggests the formation of nucleation or other metastable complexes, rather than fully-zippered duplexes.

Hybrid nanostructures of well-organized arrays of colloidal quantum dots and a self-assembled monolayer of gold nanoparticles for enhanced fluorescence

NASA Astrophysics Data System (ADS)

Liu, Xiaoying; McBride, Sean P.; Jaeger, Heinrich M.; Nealey, Paul F.

2016-07-01

Hybrid nanomaterials comprised of well-organized arrays of colloidal semiconductor quantum dots (QDs) in close proximity to metal nanoparticles (NPs) represent an appealing system for high-performance, spectrum-tunable photon sources with controlled photoluminescence. Experimental realization of such materials requires well-defined QD arrays and precisely controlled QD-metal interspacing. This long-standing challenge is tackled through a strategy that synergistically combines lateral confinement and vertical stacking. Lithographically generated nanoscale patterns with tailored surface chemistry confine the QDs into well-organized arrays with high selectivity through chemical pattern directed assembly, while subsequent coating with a monolayer of close-packed Au NPs introduces the plasmonic component for fluorescence enhancement. The results show uniform fluorescence emission in large-area ordered arrays for the fabricated QD structures and demonstrate five-fold fluorescence amplification for red, yellow, and green QDs in the presence of the Au NP monolayer. Encapsulation of QDs with a silica shell is shown to extend the design space for reliable QD/metal coupling with stronger enhancement of 11 times through the tuning of QD-metal spatial separation. This approach provides new opportunities for designing hybrid nanomaterials with tailored array structures and multiple functionalities for applications such as multiplexed optical coding, color display, and quantum transduction.

Living Nanocrystals: Synthesis of Precisely Defined Metal Oxide Nanocrystals Through a Continuous Growth Process

NASA Astrophysics Data System (ADS)

Jansons, Adam Wayne

Colloidal nanocrystals offer new and improved performance in applications as well as less environmental impact when compared to traditional device fabrication methods. The important properties that enable improved applications are a direct result of nanocrystal structure. While there have been many great advances in the production of colloidal nanocrystals over the past three decades, precise, atomic-level control of the size, composition, and structure of the inorganic core remains challenging. Rather than dictate these material aspects through traditional synthetic routes, this dissertation details the development and exploitation of a colloidal nanocrystal synthetic method inspired by polymerization reactions. Living polymerization reactions offer precise control of polymer size and structure and have tremendously advanced polymer science, allowing the intuitive production of polymers and block co-polymers of well-defined molecular weights. Similarly, living nanocrystal synthetic methods allow an enhanced level of structural control, granting the synthesis of binary, doped, and core/shell nanocrystals of well-defined size, composition, and structure. This improved control in turn grants enhanced nanocrystal property performance and deepens our understanding of structure/property relationships. This dissertation defines living nanocrystal growth and demonstrates the potential of the living methods in the colloidal production of oxide nanocrystals. After a brief introduction, living growth is defined and discussed in the context of synthetic prerequisites, attributes, and outcomes. Living growth is also compared to more traditional colloidal nanocrystal synthetic methods. The following chapters then demonstrate the precise control living approaches offer in three separate studies; the first highlights sub-nanometer control of nanocrystal size from 2-22+ nm in diameter. Next the improvement in nanocrystal composition is illustrated using several transition metal dopants into an oxide nanocrystal matrix at near thermodynamically allowed compositions. Additionally, precise radial dopant placement is demonstrated, which has striking implications for material properties. The radial position of tin in tin-doped indium oxide nanocrystals and the resulting differences on the localized surface plasmon resonance are discussed. Finally, future opportunities are reviewed. This dissertation includes previously published co-authored material.

Chitosan doped with nanoparticles of copper, nickel and cobalt.

PubMed

Cárdenas-Triviño, Galo; Elgueta, Carolina; Vergara, Luis; Ojeda, Javier; Valenzuela, Ariel; Cruzat, Christian

2017-11-01

Metal colloids in 2 propanol using nanoparticles (NPs) of copper, nickel and cobalt were prepared by Chemical Liquid Deposition (CLD) method. The resulting colloidal dispersions were characterized by Transmission Electron Microscopy (TEM). The colloids were supported in chitosan. Then, microbiological assays were performed using E. coli and S. aureus in order to determine the bactericide/bacteriostatic activity of nanoparticles (NPs) trapped or chelated with chitosan. Finally, the toxicity of the metal colloids Cu, Ni and Co was tested. Bio-assays were conducted in three different animal species. First of all on earth warms (Eisenia foetida) to evaluate the toxicity and the biocompatibility of chitosan in lactic acid (1% and 0.5%). Secondly bio-assay done in fishes (rainbow trout), the liver toxicity of NPs in vivo was evaluated. Finally, a bio-assay was conducted in Sprange-Dawley rats of 100g weight, which were injected intraperitoneally with different solutions of chitosan metal colloids. Then, the minimum and maximum concentration were determined for copper, nickel and cobalt. The purpose of the use of chitosan was acting as a carrier for some magnetic NPs, which toxicity would allow to obtain new polymeric materials with potential applications as magnet future drugs carrier. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of the Polymeric Stabilizer in the Aqueous Phase Fischer-Tropsch Synthesis Catalyzed by Colloidal Cobalt Nanocatalysts

PubMed Central

Delgado, Jorge A.; Claver, Carmen; Castillón, Sergio; Curulla-Ferré, Daniel; Godard, Cyril

2017-01-01

A series of small and well defined cobalt nanoparticles were synthesized by the chemical reduction of cobalt salts in water using NaBH4 as a reducing agent and using various polymeric stabilizers. The obtained nanocatalysts of similar mean diameters (ca. 2.6 nm) were fully characterized and tested in the aqueous phase Fischer-Tropsch Synthesis (AFTS). Interestingly, the nature and structure of the stabilizers used during the synthesis of the CoNPs affected the reduction degree of cobalt and the B-doping of these NPs and consequently, influenced the performance of these nanocatalysts in AFTS. PMID:28336892

Localized and delocalized motion of colloidal particles on a magnetic bubble lattice.

PubMed

Tierno, Pietro; Johansen, Tom H; Fischer, Thomas M

2007-07-20

We study the motion of paramagnetic colloidal particles placed above magnetic bubble domains of a uniaxial garnet film and driven through the lattice by external magnetic field modulation. An external tunable precessing field propels the particles either in localized orbits around the bubbles or in superdiffusive or ballistic motion through the bubble array. This motion results from the interplay between the driving rotating signal, the viscous drag force and the periodic magnetic energy landscape. We explain the transition in terms of the incommensurability between the transit frequency of the particle through a unit cell and the modulation frequency. Ballistic motion dynamically breaks the symmetry of the array and the phase locked particles follow one of the six crystal directions.

Functionalized poly(ethylene glycol) diacrylate microgels by microfluidics: In situ peptide encapsulation for in serum selective protein detection.

PubMed

Celetti, Giorgia; Natale, Concetta Di; Causa, Filippo; Battista, Edmondo; Netti, Paolo A

2016-09-01

Polymeric microparticles represent a robustly platform for the detection of clinically relevant analytes in biological samples; they can be functionalized encapsulating a multiple types of biologics entities, enhancing their applications as a new class of colloid materials. Microfluidic offers a versatile platform for the synthesis of monodisperse and engineered microparticles. In this work, we report microfluidic synthesis of novel polymeric microparticles endowed with specific peptide due to its superior specificity for target binding in complex media. A peptide sequence was efficiently encapsulated into the polymeric network and protein binding occurred with high affinity (KD 0.1-0.4μM). Fluidic dynamics simulation was performed to optimize the production conditions for monodisperse and stable functionalized microgels. The results demonstrate the easy and fast realization, in a single step, of functionalized monodisperse microgels using droplet-microfluidic technique, and how the inclusion of the peptide within polymeric network improve both the affinity and the specificity of protein capture. Copyright © 2016 Elsevier B.V. All rights reserved.

Adhesion of bacterial pathogens to soil colloidal particles: influences of cell type, natural organic matter, and solution chemistry.

PubMed

Zhao, Wenqiang; Walker, Sharon L; Huang, Qiaoyun; Cai, Peng

2014-04-15

Bacterial adhesion to granular soil particles is well studied; however, pathogen interactions with naturally occurring colloidal particles (<2 μm) in soil has not been investigated. This study was developed to identify the interaction mechanisms between model bacterial pathogens and soil colloids as a function of cell type, natural organic matter (NOM), and solution chemistry. Specifically, batch adhesion experiments were conducted using NOM-present, NOM-stripped soil colloids, Streptococcus suis SC05 and Escherichia coli WH09 over a wide range of solution pH (4.0-9.0) and ionic strength (IS, 1-100 mM KCl). Cell characterization techniques, Freundlich isotherm, and Derjaguin-Landau-Verwey-Overbeek (DLVO) theory (sphere-sphere model) were utilized to quantitatively determine the interactions between cells and colloids. The adhesion coefficients (Kf) of S. suis SC05 to NOM-present and NOM-stripped soil colloids were significantly higher than E. coli WH09, respectively. Similarly, Kf values of S. suis SC05 and E. coli WH09 adhesion to NOM-stripped soil colloids were greater than those colloids with NOM-present, respectively, suggesting NOM inhibits bacterial adhesion. Cell adhesion to soil colloids declined with increasing pH and enhanced with rising IS (1-50 mM). Interaction energy calculations indicate these adhesion trends can be explained by DLVO-type forces, with S. suis SC05 and E. coli WH09 being weakly adhered in shallow secondary energy minima via polymer bridging and charge heterogeneity. S. suis SC05 adhesion decreased at higher IS 100 mM, which is attributed to the change of hydrophobic effect and steric repulsion resulted from the greater presence of extracellular polymeric substances (EPS) on S. suis SC05 surface as compared to E. coli WH09. Hence, pathogen adhesion to the colloidal material is determined by a combination of DLVO, charge heterogeneity, hydrophobic and polymer interactions as a function of solution chemistry. Copyright © 2014 Elsevier Ltd. All rights reserved.

Armored Urease: Enzyme-Bioconjugated Poly(acrylamide) Hydrogel as a Storage and Sensing Platform.

PubMed

Kunduru, Konda R; Kutcherlapati, S N Raju; Arunbabu, Dhamodaran; Jana, Tushar

2017-01-01

Jack bean urease is an important enzyme not only because of its numerous uses in medical and other fields but also because of its historical significance-the first enzyme to be crystallized and also the first nickel metalloenzyme. This enzyme hydrolyzes urea into ammonia and carbon dioxide; however, the stability of this enzyme at ambient temperature is a bottleneck for its applicability. To improve urease stability, it was immobilized on different substrates, particularly on polymeric hydrogels. In this study, the enzyme was coupled covalently with poly(acrylamide) hydrogel with an yield of 18μmol/cm 3 . The hydrogel served as the nanoarmor and protected the enzyme against denaturation. The enzyme immobilized on the polymer hydrogel showed no loss in activity for more than 30 days at ambient temperature, whereas free enzyme lost its activity within a couple of hours. The Michaelis-Menten constant (K m ) for free and immobilized urease were 0.0256 and 0.2589mM, respectively, on the first day of the study. The K m of the immobilized enzyme was approximately 10 times higher than that of the free enzyme. The hydrogel technique was also used to prepare light diffracting polymerized colloidal crystal array in which urease enzyme was covalently immobilized. This system was applied for the detection of mercury (Hg 2+ ) with the lower limit as 1ppb, which is below the maximum contaminant limit (2ppb) for mercury ions in water. The experimental details of these studies are presented in this chapter. © 2017 Elsevier Inc. All rights reserved.

Inventions Utilizing Microfluidics and Colloidal Particles

NASA Technical Reports Server (NTRS)

Marr, David W.; Gong, Tieying; Oakey, John; Terray, Alexander V.; Wu, David T.

2009-01-01

Several related inventions pertain to families of devices that utilize microfluidics and/or colloidal particles to obtain useful physical effects. The families of devices can be summarized as follows: (1) Microfluidic pumps and/or valves wherein colloidal-size particles driven by electrical, magnetic, or optical fields serve as the principal moving parts that propel and/or direct the affected flows. (2) Devices that are similar to the aforementioned pumps and/or valves except that they are used to manipulate light instead of fluids. The colloidal particles in these devices are substantially constrained to move in a plane and are driven to spatially order them into arrays that function, variously, as waveguides, filters, or switches for optical signals. (3) Devices wherein the ultra-laminar nature of microfluidic flows is exploited to effect separation, sorting, or filtering of colloidal particles or biological cells in suspension. (4) Devices wherein a combination of confinement and applied electrical and/or optical fields forces the colloidal particles to become arranged into three-dimensional crystal lattices. Control of the colloidal crystalline structures could be exploited to control diffraction of light. (5) Microfluidic devices, incorporating fluid waveguides, wherein switching of flows among different paths would be accompanied by switching of optical signals.

An Experimental Study in the Mechanical Response of Polymer Modified Geopolymers

DTIC Science & Technology

2012-04-01

Compressive and Bending Strength of Fly ash Geopolymers ... 22 LIST OF TABLES Page Table 1. Chemical Composition of Aluminosilicates in Mass... geopolymer matrix composites .” Ceramic Transactions, 153, 227-250. 3. Davidovits J., 1991. “ Geopolymers , inorganic polymeric materials.” Journal of...Understanding the relationship between geopolymer composition , microstructure and mechanical properties.” Colloids and Surfaces.A, Physicochemical

Application of the solubility parameter concept to the design of chemiresistor arrays

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

Hughes, R.C.; Yelton, W.G.; Ricco, A.J.

1998-04-01

Arrays of unheated chemically sensitive resistors (chemiresistors) can serve as extremely small, low power consumption sensors with simple read out electronics. Most work has focused on the exotic polymeric organic metals, but here the authors report new results on carbon loaded polymer composites, as well as polymeric ionic conductors. They use the solubility parameter concept to understand and categorize the chemiresistor responses and, in particular, they compare chemiresistors fabricated from polyisobutylene (PIB) to results from PIB coated acoustic wave sensors.

Tethered fleximags: a physical model for ciliary propulsion.

NASA Astrophysics Data System (ADS)

Du Roure, Olivia; Babataheri, Avin; Jenffer, Patrice; Fermigier, Marc; Goubault, Cecile

2007-11-01

Fleximags are linear colloidal structures made of micron-sized superparamagnetic particles. Permanent links between colloids are established through molecules grafted on the particles. The elasticity of the linker bestows a flexibility to the filament. The fleximags have already been used to make one of the first artificial microswimmers (Dreyfus et al. Nature 2005) resembling a spermatozoon. They can also be anchored to a glass substrate isolated or as arrays. Those arrays build up experimental models of the array of cilia on paramecium for studying physical aspects of the propulsion. Here we'll show our first studies concerning anchored flexiamgs submitted to time-dependent field. The actuation is controlled by three electromagnets and allowing all types of 3-D movements: (a)symmetric beating in a plane, rotation... We first study one single anchored fleximag when the field is rotating on a cone. Only a part of the filament is moving reflecting the competition between magnetic interactions, elasticity and viscosity. The length of this mobile fraction decreases with frequency. We also study the induced flow by PIV.

Design of latex-layered double hydroxide composites by tuning the aggregation in suspensions.

PubMed

Pavlovic, Marko; Rouster, Paul; Bourgeat-Lami, Elodie; Prevot, Vanessa; Szilagyi, Istvan

2017-01-25

Colloidal stability of polymeric latex particles was studied in the presence of oppositely charged layered double hydroxide (LDH) platelets of different interlayer anions. Adsorption of the LDH particles led to charge neutralization and to overcharging of the latex at appropriate concentrations. Mixing stable colloidal suspensions of individual particles results in rapid aggregation once the LDH adsorption neutralizes the negative charges of the polymer spheres, while stable suspensions were observed at high and low LDH doses. The governing interparticle interactions included repulsive electrical double layer forces as well as van der Waals and patch-charge attractions, whose strength depended on the amount of LDH particles adsorbed on the latex surface. The type of the LDH interlayer anions did not affect the colloidal stability of the samples. Structural investigation of the obtained latex-LDH composites revealed that the polymer spheres were completely coated with the inorganic platelets once their concentration was sufficiently high. These results are especially important for designing synthetic routes for hybrid systems in suspensions, where stable colloids are required for uniform film-formation and for the homogeneous distribution of the inorganic filler within the composite materials.

Precise colloids with tunable interactions for confocal microscopy

PubMed Central

Kodger, Thomas E.; Guerra, Rodrigo E.; Sprakel, Joris

2015-01-01

Model colloidal systems studied with confocal microscopy have led to numerous insights into the physics of condensed matter. Though confocal microscopy is an extremely powerful tool, it requires a careful choice and preparation of the colloid. Uncontrolled or unknown variations in the size, density, and composition of the individual particles and interactions between particles, often influenced by the synthetic route taken to form them, lead to difficulties in interpreting the behavior of the dispersion. Here we describe the straightforward synthesis of copolymer particles which can be refractive index- and density-matched simultaneously to a non-plasticizing mixture of high dielectric solvents. The interactions between particles are accurately tuned by surface grafting of polymer brushes using Atom Transfer Radical Polymerization (ATRP), from hard-sphere-like to long-ranged electrostatic repulsion or mixed charge attraction. We also modify the buoyant density of the particles by altering the copolymer ratio while maintaining their refractive index match to the suspending solution resulting in well controlled sedimentation. The tunability of the inter-particle interactions, the low volatility of the solvents, and the capacity to simultaneously match both the refractive index and density of the particles to the fluid opens up new possibilities for exploring the physics of colloidal systems. PMID:26420044

Broadband optical antireflection enhancement by integrating antireflective nanoislands with silicon nanoconical-frustum arrays.

PubMed

Park, Haesung; Shin, Dongheok; Kang, Gumin; Baek, Seunghwa; Kim, Kyoungsik; Padilla, Willie J

2011-12-22

Based on conventional colloidal nanosphere lithography, we experimentally demonstrate novel graded-index nanostructures for broadband optical antireflection enhancement including the near-ultraviolet (NUV) region by integrating residual polystyrene antireflective (AR) nanoislands coating arrays with silicon nano-conical-frustum arrays. This is a feasible optimized integration method of two major approaches for antireflective surfaces: quarter-wavelength AR coating and biomimetic moth's eye structure. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Slab photonic crystals with dimer colloid bases

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

Riley, Erin K.; Liddell Watson, Chekesha M., E-mail: cliddell@ccmr.cornell.edu

2014-06-14

The photonic band gap properties for centered rectangular monolayers of asymmetric dimers are reported. Colloids in suspension have been organized into the phase under confinement. The theoretical model is inspired by the range of asymmetric dimers synthesized via seeded emulsion polymerization and explores, in particular, the band structures as a function of degree of lobe symmetry and degree of lobe fusion. These parameters are varied incrementally from spheres to lobe-tangent dimers over morphologies yielding physically realizable particles. The work addresses the relative scarcity of theoretical studies on photonic crystal slabs with vertical variation that is consistent with colloidal self-assembly. Odd,more » even and polarization independent gaps in the guided modes are determined for direct slab structures. A wide range of lobe symmetry and degree of lobe fusion combinations having Brillouin zones with moderate to high isotropy support gaps between odd mode band indices 3-4 and even mode band indices 1-2 and 2-3.« less

Nucleation of polystyrene latex particles in the presence of gamma-methacryloxypropyltrimethoxysilane: functionalized silica particles.

PubMed

Bourgeat-Lami, Elodie; Insulaire, Mickaelle; Reculusa, Stéphane; Perro, Adeline; Ravaine, Serge; Duguet, Etienne

2006-02-01

Silica/polystyrene nanocomposite particles with different morphologies were synthesized through emulsion polymerization of styrene in the presence of silica particles previously modified by gamma-methacryloxypropyltrimethoxysilane (MPS). Grafting of the silane molecule was performed by direct addition of MPS to the aqueous silica suspension in the presence of an anionic surfactant under basic conditions. The MPS grafting density on the silica surface was determined using the depletion method and plotted against the initial MPS concentration. The influence of the MPS grafting density, the silica particles size and concentration and the nature of the surfactant on the polymerization kinetics and the particles morphology was investigated. When the polymerization was performed in the presence of an anionic surfactant, transmission electron microscopy images showed the formation of polymer spheres around silica for MPS grafting densities lower than typically 1 micromole x m(-2) while the conversion versus time curves indicated a strong acceleration effect under such conditions. In contrast, polymerizations performed in the presence of a larger amount of MPS moieties or in the presence of a non ionic emulsifier resulted in the formation of "excentered" core-shell morphologies and lower polymerization rates. The paper identifies the parameters that allow to control particles morphology and polymerization kinetics and describes the mechanism of formation of the nanocomposite colloids.

Polymeric waveguide array with 45 degree slopes fabricated by bottom side tilted exposure

NASA Astrophysics Data System (ADS)

Lin, Xiaohui; Dou, Xinyuan; Wang, Alan X.; Chen, Ray T.

2011-01-01

This paper demonstrated a practical fabrication process of polymeric waveguide array (12 channels) with 50μm(W)×50μm(H)×23mm(L) dimension and mirror embedded 45° degree slopes for vertical coupling purpose. The entire process contained three main parts: a SU8 pre-mold with 45° slope, a PDMS mold and the final waveguide array device. The key step of fabricating the pre-mold included a bottom side tilted exposure of SU8 photo resist. By placing the sample upside down, tilting by 58.7° and immersing into DI water, the ultraviolet (UV) beam that shined vertically was directed to go through from the bottom of the glass substrate into top side SU8 resist with 45° angle to form the surface. This method was able to guarantee no-gap contact between the mask pattern and the photo resist when exposing. By comparing the process complexity and achieved structure of the top and bottom side exposure, the later was proved to be a promising method for making high quality tilted structure without any tailing effect. The reversed PDMS mold was then fabricated on the SU8 pre-mold. The PDMS mold was used to imprint the cladding layer of the waveguide array. After metal deposition, core filling and top cladding layer coating, the final polymeric waveguide array device was achieved. For performance evaluation, 850nm laser beam from VCSEL was modulated to 10Gbps signals and vertically coupled into the waveguide array. The eye diagrams revealed high Q factor when transmitting signals along these waveguide array.

A modular microfluidic platform for the synthesis of biopolymeric nanoparticles entrapping organic actives

NASA Astrophysics Data System (ADS)

Chronopoulou, Laura; Sparago, Carolina; Palocci, Cleofe

2014-11-01

Using a novel and versatile capillary microfluidic flow-focusing device we fabricated monodisperse drug-loaded nanoparticles from biodegradable polymers. A model amphiphilic drug (dexamethasone) was incorporated within the biodegradable matrix of the particles. The influence of flow rate ratio, polymer concentration, and microreactor-focusing channel dimensions on nanoparticles' size and drug loading has been investigated. The microfluidic approach resulted in the production of colloidal polymeric nanoparticles with a narrow size distribution (diameters ranging between 35 and 350 nm) and useful morphological characteristics. This technique allows the fast, low cost, easy, and automated synthesis of polymeric nanoparticles, therefore it may become a useful approach in the progression from laboratory scale to pilot-line scale processes.

Responsive etalon based on PNIPAM@SiO2 composite spacer with rapid response rate and excellent repeatability for sensing application

NASA Astrophysics Data System (ADS)

Wang, Tieqiang; Wang, Shuli; Zhang, Xun; Song, Guoshuai; Yu, Ye; Chen, Xinyang; Fu, Yu; Zhang, Junhu; Yang, Bai

2015-07-01

In this paper, we demonstrate a responsive etalon fabricated through combining colloidal lithography and surface-initiated atom-transfer radical polymerization (SI-ATRP). The responsive etalon is simply constructed with one responsive spacer sandwiched by two reflective layers, and the middle responsive spacer is constructed by grafting thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) brushes on a SiO2 nanosphere array. The etalon possesses one single interference peak in the visible region, and the interference peak changes sensitively against the concentration of the external stimulant (water vapor) or the temperature of the system, owing to the responsiveness of the PNIPAM brush. Importantly, the as-prepared etalon shows a rapid response rate and excellent stability, and it is also handy to realize the miniaturization and integration of the responsive etalon based on a conventional micro-fabrication method. These features all make the as-prepared responsive etalon an attractive candidate for future sensing applications. We believe such responsive etalons are promising for the fabrication of smart photonic materials and optical sensors that may be useful in tissue engineering, medical diagnosis, public security, and biochip areas.

Gels from soft hairy nanoparticles in polymeric matrices

NASA Astrophysics Data System (ADS)

Vlassopoulos, Dimitris

2013-03-01

Hairy particles represent a huge class of soft colloids with tunable interactions and properties. Advances in synthetic chemistry have enabled obtaining well-characterized such systems for specific needs. In this talk we present two model hairy soft particles with diameters of the order of tens of nanometers, star polymers and polymerically grafted spherical particles. In particular, we discuss design strategies for dispersing them in polymeric matrices and eventually creating and breaking gels. Control parameters are the matrix molar mass, the grafting density (or functionality) and the size of the grafts (or arms). The linear viscoelastic properties and slow time evolution of the gels are examined in view of the existing knowledge from colloidal gels consisting of micron-sized particles, and compared. In the case of stars we start from a concentrated glassy suspension in molecular solvent and add homopolymer at increasing concentration, and as a result of the induced osmotic pressure the stars shrink and a depletion gel is formed. For the grafted colloidal particles, they are added at low concentration to a polymer matrix, and it has been shown that under certain conditions the anisotropy of interactions gives rise to network formation. We then focus on the nonlinear rheological response and in particular the effect of shear flow in inducing a solid to liquid transition. Our studies show that the yielding process is gradual and shares many common features with that of flocculated colloidal suspensions, irrespectively of the shape of the building block of the gel. Whereas shear can melt such a gel, it cannot break it into its constituent blocks and hence fully disperse the hairy nanoparticles. On the other hand, the hairy particles are intrinsically hybrid. We show how this important feature is reflected on the heating of the gels. In that case, the mismatch of thermal expansion coefficients of core and shell appears to play a role on the particle response as it imposes and internal strain on the particle, which in turn changes the shell conformation and under some conditions can lead to thermal melting of the gel. These alternative avenues for manipulating the gel-to-liquid transition have potential implications in directing the properties of hairy nanoparticles and their assemblies in viscoelastic matrices. Parts of this work reflect collaboration with D. Truzzolillo (FORTH), J. F. Moll and S. K.Kumar (Columbia). R. H. Colby (Penn State), M. Gauthier (Waterloo) and B. C. Benicewicz (Univ. South Carolina).

Preparation of polymeric Janus particles by directional UV-induced reactions.

PubMed

Liu, Lianying; Ren, Mingwei; Yang, Wantai

2009-09-15

Polymeric Janus particles are obtained by UV-induced selective surface grafting polymerizations and coupling reactions, in virtue of the light-absorption of photoreactive materials such as the immobilized photoinitiator and spread photoinitiator solution on the surfaces exposed to UV light and the sheltering of densely arrayed immovable particles from light. Varying the monomers or macromolecules applied in photografting polymerization or coupling reaction, and choosing diverse polymeric particles of various size, bicolor and amphiphilic Janus particles could be successfully achieved. Observations by fluorescence microscope, scanning electron microscope ,and transmission electron microscope confirmed the asymmetrical morphology of the resultant Janus particles.

Fabrication of Novel Types of Colloidosome Microcapsules for Drug Delivery Applications

DTIC Science & Technology

2005-01-01

UNCLASSIFIED Defense Technical Information Center Compilation Part Notice ADP019733 TITLE: Fabrication of Novel Types of Colloidosome Microcapsules ...UNCLASSIFIED Mater. Res. Soc. Symp. Proc. Vol. 845 © 2005 Materials Research Society AA5.18 Fabrication of Novel Types of Colloidosome Microcapsules for Drug...Novel colloidosome microcapsules with aqueous gel cores and shells of different polymeric colloid particles have been prepared and characterized. Our

On the Failure of Upscaling the Single-Collector Efficiency to the Transport of Colloids in an Array of Collectors

NASA Astrophysics Data System (ADS)

Messina, F.; Tosco, T.; Sethi, R.

2017-12-01

Colloidal transport and deposition in saturated porous media are phenomena of considerable importance in a large number of natural processes and engineering applications, such as the contaminant and microorganism propagation in aquifer systems, the development of innovative groundwater remediation technologies, air and water filtration, and many others. Therefore, a thorough understanding of particle filtration is essential for predicting the transport and fate of colloids in the subsurface environment. The removal efficiency of a filter is a key aspect for colloid transport in porous media. Several efforts were devoted to derive accurate correlations for the single collector efficiency, one of the key concept in the filtration theory. However, up scaling this parameter to the entire porous medium is still a challenge. The common up-scaling approach assumes the deposition to be independent of the transport history, which means that the collector efficiency is considered uniform along the porous medium. However, previous works showed that this approach is inadequate under unfavorable deposition conditions. This study demonstrates that it is not adequate even in the simplest case of favorable deposition. Computational Fluid Dynamics simulations were run for a simplify porous media geometry, composed of a vertical array of 50 identical spherical collectors. A combination of Lagrangian and Eulerian simulations were performed to analyze the particle transport under a broad range of parameters (i.e., particle size, particle density, water velocity). The results show the limits of the existing models to interpret the experimental data. In fact, the outcome evidenced that when particle deposition is not controlled by Brownian diffusion, non-exponential concentration profiles are retrieved, in contrast with the assumption of uniform efficiency. Moreover, when the deposition mechanisms of sedimentation and interception dominate, the efficiency of the first sphere of the column is significantly higher compared to the others, and then it declines along the array down to an asymptotic value. A more rigorous procedure to evaluate the filtration processes in presence of a series of collectors was developed, and a new correlation for the up-scaled removal efficiency of the entire array was derived and proposed.

Optical parameters of ITO/TPD/Alq3/Al luminescent structures, containing arrays of CdSe/ZnS colloidal quantum dots

NASA Astrophysics Data System (ADS)

Mikhailov, I. I.; Tarasov, S. A.; Lamkin, I. A.; Tadtaev, P. O.; Kozlovich, L. I.; Solomonov, A. V.; Stepanov, E. M.

2016-08-01

The luminescent organic ITO/TPD/Alq3/Al structures and CdSe/ZnS quantum dots (QD) arrays were created. Electrical and optical properties of the samples were examined. The luminescence of the layers and QD arrays was shown in the range of wavelengths from 400 to 680 nm. Luminescent structures with phosphors corresponding to the emission standards with CRI>98 and with color temperature of 5500 K and 6504 K were created.

Patterned Colloidal Photonic Crystals.

PubMed

Hou, Jue; Li, Mingzhu; Song, Yanlin

2018-03-01

Colloidal photonic crystals (PCs) have been well developed because they are easy to prepare, cost-effective, and versatile with regards to modification and functionalization. Patterned colloidal PCs contribute a novel approach to constructing high-performance PC devices with unique structures and specific functions. In this review, an overview of the strategies for fabricating patterned colloidal PCs, including patterned substrate-induced assembly, inkjet printing, and selective immobilization and modification, is presented. The advantages of patterned PC devices are also discussed in detail, for example, improved detection sensitivity and response speed of the sensors, control over the flow direction and wicking rate of microfluidic channels, recognition of cross-reactive molecules through an array-patterned microchip, fabrication of display devices with tunable patterns, well-arranged RGB units, and wide viewing-angles, and the ability to construct anti-counterfeiting devices with different security strategies. Finally, the perspective of future developments and challenges is presented. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A guide to the synthesis of block copolymers using reversible-addition fragmentation chain transfer (RAFT) polymerization.

PubMed

Keddie, Daniel J

2014-01-21

The discovery of reversible-deactivation radical polymerization (RDRP) has provided an avenue for the synthesis of a vast array of polymers with a rich variety of functionality and architecture. The preparation of block copolymers has received significant focus in this burgeoning research field, due to their diverse properties and potential in a wide range of research environments. This tutorial review will address the important concepts behind the design and synthesis of block copolymers using reversible addition-fragmentation chain transfer (RAFT) polymerization. RAFT polymerization is arguably the most versatile of the RDRP methods due to its compatibility with a wide range of functional monomers and reaction media along with its relative ease of use. With an ever increasing array of researchers that possess a variety of backgrounds now turning to RDRP, and RAFT in particular, to prepare their required polymeric materials, it is pertinent to discuss the important points which enable the preparation of high purity functional block copolymers with targeted molar mass and narrow molar mass distribution using RAFT polymerization. The key principles of appropriate RAFT agent selection, the order of monomer addition in block synthesis and potential issues with maintaining high end-group fidelity are addressed. Additionally, techniques which allow block copolymers to be accessed using a combination of RAFT polymerization and complementary techniques are touched upon.

Surfactant-controlled polymerization of semiconductor clusters to quantum dots through competing step-growth and living chain-growth mechanisms.

PubMed

Evans, Christopher M; Love, Alyssa M; Weiss, Emily A

2012-10-17

This article reports control of the competition between step-growth and living chain-growth polymerization mechanisms in the formation of cadmium chalcogenide colloidal quantum dots (QDs) from CdSe(S) clusters by varying the concentration of anionic surfactant in the synthetic reaction mixture. The growth of the particles proceeds by step-addition from initially nucleated clusters in the absence of excess phosphinic or carboxylic acids, which adsorb as their anionic conjugate bases, and proceeds indirectly by dissolution of clusters, and subsequent chain-addition of monomers to stable clusters (Ostwald ripening) in the presence of excess phosphinic or carboxylic acid. Fusion of clusters by step-growth polymerization is an explanation for the consistent observation of so-called "magic-sized" clusters in QD growth reactions. Living chain-addition (chain addition with no explicit termination step) produces QDs over a larger range of sizes with better size dispersity than step-addition. Tuning the molar ratio of surfactant to Se(2-)(S(2-)), the limiting ionic reagent, within the living chain-addition polymerization allows for stoichiometric control of QD radius without relying on reaction time.

Switchable focus using a polymeric lenticular microlens array and a polarization rotator.

PubMed

Ren, Hongwen; Xu, Su; Liu, Yifan; Wu, Shin-Tson

2013-04-08

We demonstrate a flat polymeric lenticular microlens array using a mixture of rod-like diacrylate monomer and positive dielectric anisotropy nematic liquid crystal (LC). To create gradient refractive index profile in one microlens, we generate fringing fields from a planar top electrode and two striped bottom electrodes. After UV stabilization, the film is optically anisotropic and can stand alone. We then laminate this film on a 90° twisted-nematic LC cell, which works as a dynamic polarization rotator. The static polymeric lenticular lens exhibits focusing effect only to the extraordinary ray, but no optical effect to the ordinary ray. Such an integrated lens system offers several advantages, such as low voltage, fast response time, and temperature insensitivity, and can be used for switchable 2D/3D displays.

Dielectrophoretic levitation in the presence of shear flow: implications for colloidal fouling of filtration membranes.

PubMed

Molla, Shahnawaz; Bhattacharjee, Subir

2007-10-09

The ability of dielectrophoretic (DEP) forces created using a microelectrode array to levitate particles in a colloidal suspension is studied experimentally and theoretically. The experimental system employs microfabricated electrode arrays on a glass substrate to apply repulsive DEP forces on polystyrene latex particles suspended in an aqueous medium. A numerical model based on the convection-diffusion-migration equation is presented to calculate the concentration distribution of colloidal particles in shear flow under the influence of a repulsive DEP force field. The results obtained from the numerical simulations are compared against trajectory analysis results and experimental data. The results indicate that by incorporating ac electric field-induced DEP forces in a shear flow, particle accumulation and deposition on the flow channel surfaces can be significantly reduced or even completely averted. The mathematical model is then used to indicate how the deposition behavior is modified in the presence of a permeable substrate, representative of tangential flow membrane filtration operations. The results indicate that the repulsive dielectrophoretic (DEP) forces imparted to the particles suspended in the feed can be employed to mitigate membrane fouling in a cross-flow filtration process.

Design, Optimization and Characterisation of Polymeric Microneedle Arrays Prepared by a Novel Laser-Based Micromoulding Technique

PubMed Central

Donnelly, Ryan F.; Majithiya, Rita; Singh, Thakur Raghu Raj; Morrow, Desmond I. J.; Garland, Martin J.; Demir, Yusuf K.; Migalska, Katarzyna; Ryan, Elizabeth; Gillen, David; Scott, Christopher J.; Woolfson, A. David

2010-01-01

Purpose Design and evaluation of a novel laser-based method for micromoulding of microneedle arrays from polymeric materials under ambient conditions. The aim of this study was to optimise polymeric composition and assess the performance of microneedle devices that possess different geometries. Methods A range of microneedle geometries was engineered into silicone micromoulds, and their physicochemical features were subsequently characterised. Results Microneedles micromoulded from 20% w/w aqueous blends of the mucoadhesive copolymer Gantrez® AN-139 were surprisingly found to possess superior physical strength than those produced from commonly used pharma polymers. Gantrez® AN-139 microneedles, 600 μm and 900 μm in height, penetrated neonatal porcine skin with low application forces (>0.03 N per microneedle). When theophylline was loaded into 600 μm microneedles, 83% of the incorporated drug was delivered across neonatal porcine skin over 24 h. Optical coherence tomography (OCT) showed that drug-free 600 μm Gantrez® AN-139 microneedles punctured the stratum corneum barrier of human skin in vivo and extended approximately 460 μm into the skin. However, the entirety of the microneedle lengths was not inserted. Conclusion In this study, we have shown that a novel laser engineering method can be used in micromoulding of polymeric microneedle arrays. We are currently carrying out an extensive OCT-informed study investigating the influence of microneedle array geometry on skin penetration depth, with a view to enhanced transdermal drug delivery from optimised laser-engineered Gantrez® AN-139 microneedles. PMID:20490627

Micro-array versus nano-array platforms: a comparative study for ODN detection based on SPR enhanced ellipsometry

NASA Astrophysics Data System (ADS)

Celen, Burcu; Demirel, Gökhan; Piskin, Erhan

2011-04-01

The rapid and sensitive detection of DNA has recently attracted worldwide attention for a variety of disease diagnoses and detection of harmful bacteria in food and drink. In this paper, we carried out a comparative study based on surface plasmon resonance enhanced ellipsometry (SPREE) for the detection of oligodeoxynucleotides (ODNs) using micro- and nano-array platforms. The micro-arrayed surfaces were fabricated by a photolithography approach using different types of mask having varying size and shape. Well-ordered arrays of high aspect ratio polymeric nanotubes were also obtained using high molecular weight polystyrene (PS) and anodic aluminum oxide (AAO) membranes having 200 nm pore diameters. The SPREE sensors were then prepared by direct coupling of thiolated probe-ODNs, which contain suitable spacer arms, on gold-coated micro- and nano-arrayed surfaces. We experimentally demonstrated that, for the first time, gold-coated free standing polymeric nano-arrayed platforms can easily be produced and lead to a significant sensor sensitivity gain compared to that of the conventional SPREE surfaces of about four times. We believe that such an enhancement in sensor response could be useful for next generation sensor systems.

DNA Origami Patterned Colloids for Programmed Design and Chirality

NASA Astrophysics Data System (ADS)

Ben Zion, Matan Yah; He, Xiaojin; Maass, Corinna; Sha, Ruojie; Seeman, Ned; Chaikin, Paul

Micron size colloidal particles are scientifically important as model systems for equilibrium and active systems in physics, chemistry and biology and for technologies ranging from catalysis to photonics. The past decade has seen development of new particles with directional patches, lock and key reactions and specific recognition that guide assembly of structures such as complex crystalline arrays. What remains lacking is the ability to self-assemble structures of arbitrary shape with specific chirality, placement and orientation of neighbors. Here we demonstrate the adaptation of DNA origami nanotechnology to the micron colloidal scale with designed control of neighbor type, placement and dihedral angle. We use DNA origami belts with programmed flexibility, and functionality to pattern colloidal surfaces and bind particles to specific sites at specific angles and make uniquely right handed or left handed structures. The hybrid DNA origami colloid technology should allow the synthesis of designed functional structural and active materials. This work was supported as part of the Center for Bio-Inspired Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0000989.

Magnetic assembly route to colloidal responsive photonic nanostructures.

PubMed

He, Le; Wang, Mingsheng; Ge, Jianping; Yin, Yadong

2012-09-18

Responsive photonic structures can respond to external stimuli by transmitting optical signals. Because of their important technological applications such as color signage and displays, biological and chemical sensors, security devices, ink and paints, military camouflage, and various optoelectronic devices, researchers have focused on developing these functional materials. Conventionally, self-assembled colloidal crystals containing periodically arranged dielectric materials have served as the predominant starting frameworks. Stimulus-responsive materials are incorporated into the periodic structures either as the initial building blocks or as the surrounding matrix so that the photonic properties can be tuned. Although researchers have proposed various versions of responsive photonic structures, the low efficiency of fabrication through self-assembly, narrow tunability, slow responses to the external stimuli, incomplete reversibility, and the challenge of integrating them into existing photonic devices have limited their practical application. In this Account, we describe how magnetic fields can guide the assembly of superparamagnetic colloidal building blocks into periodically arranged particle arrays and how the photonic properties of the resulting structures can be reversibly tuned by manipulating the external magnetic fields. The application of the external magnetic field instantly induces a strong magnetic dipole-dipole interparticle attraction within the dispersion of superparamagnetic particles, which creates one-dimensional chains that each contains a string of particles. The balance between the magnetic attraction and the interparticle repulsions, such as the electrostatic force, defines the interparticle separation. By employing uniform superparamagnetic particles of appropriate sizes and surface charges, we can create one-dimensional periodicity, which leads to strong optical diffraction. Acting remotely over a large distance, magnetic forces drove the rapid formation of colloidal photonic arrays with a wide range of interparticle spacing. They also allowed instant tuning of the photonic properties because they manipulated the interparticle force balance, which changed the orientation of the colloidal assemblies or their periodicity. This magnetically responsive photonic system provides a new platform for chromatic applications: these colloidal particles assemble instantly into ordered arrays with widely, rapidly, and reversibly tunable structural colors, which can be easily and rapidly fixed in a curable polymer matrix. Based on these unique features, we demonstrated many applications of this system, such as structural color printing, the fabrication of anticounterfeiting devices, switchable signage, and field-responsive color displays. We also extended this idea to rapidly organize uniform nonmagnetic building blocks into photonic structures. Using a stable ferrofluid of highly charged magnetic nanoparticles, we created virtual magnetic moments inside the nonmagnetic particles. This "magnetic hole" strategy greatly broadens the scope of the magnetic assembly approach to the fabrication of tunable photonic structures from various dielectric materials.

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

PubMed

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

2008-02-01

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

Assembly of large-area, highly ordered, crack-free inverse opal films

PubMed Central

Hatton, Benjamin; Mishchenko, Lidiya; Davis, Stan; Sandhage, Kenneth H.; Aizenberg, Joanna

2010-01-01

Whereas considerable interest exists in self-assembly of well-ordered, porous “inverse opal” structures for optical, electronic, and (bio)chemical applications, uncontrolled defect formation has limited the scale-up and practicality of such approaches. Here we demonstrate a new method for assembling highly ordered, crack-free inverse opal films over a centimeter scale. Multilayered composite colloidal crystal films have been generated via evaporative deposition of polymeric colloidal spheres suspended within a hydrolyzed silicate sol-gel precursor solution. The coassembly of a sacrificial colloidal template with a matrix material avoids the need for liquid infiltration into the preassembled colloidal crystal and minimizes the associated cracking and inhomogeneities of the resulting inverse opal films. We discuss the underlying mechanisms that may account for the formation of large-area defect-free films, their unique preferential growth along the 〈110〉 direction and unusual fracture behavior. We demonstrate that this coassembly approach allows the fabrication of hierarchical structures not achievable by conventional methods, such as multilayered films and deposition onto patterned or curved surfaces. These robust SiO2 inverse opals can be transformed into various materials that retain the morphology and order of the original films, as exemplified by the reactive conversion into Si or TiO2 replicas. We show that colloidal coassembly is available for a range of organometallic sol-gel and polymer matrix precursors, and represents a simple, low-cost, scalable method for generating high-quality, chemically tailorable inverse opal films for a variety of applications. PMID:20484675

Synthesis of High Molecular Weight Poly(glycerol monomethacrylate) via RAFT Emulsion Polymerization of Isopropylideneglycerol Methacrylate

PubMed Central

2018-01-01

High molecular weight water-soluble polymers are widely used as flocculants or thickeners. However, synthesis of such polymers via solution polymerization invariably results in highly viscous fluids, which makes subsequent processing somewhat problematic. Alternatively, such polymers can be prepared as colloidal dispersions; in principle, this is advantageous because the particulate nature of the polymer chains ensures a much lower fluid viscosity. Herein we exemplify the latter approach by reporting the convenient one-pot synthesis of high molecular weight poly(glycerol monomethacrylate) (PGMA) via the reversible addition–fragmentation chain transfer (RAFT) aqueous emulsion polymerization of a water-immiscible protected monomer precursor, isopropylideneglycerol methacrylate (IPGMA) at 70 °C, using a water-soluble poly(glycerol monomethacrylate) (PGMA) chain transfer agent as a steric stabilizer. This formulation produces a low-viscosity aqueous dispersion of PGMA–PIPGMA diblock copolymer nanoparticles at 20% solids. Subsequent acid deprotection of the hydrophobic core-forming PIPGMA block leads to particle dissolution and affords a viscous aqueous solution comprising high molecular weight PGMA homopolymer chains with a relatively narrow molecular weight distribution. Moreover, it is shown that this latex precursor route offers an important advantage compared to the RAFT aqueous solution polymerization of glycerol monomethacrylate since it provides a significantly faster rate of polymerization (and hence higher monomer conversion) under comparable conditions. PMID:29805184

Colloidal micro- and nano-particles as templates for polyelectrolyte multilayer capsules.

PubMed

Parakhonskiy, Bogdan V; Yashchenok, Alexey M; Konrad, Manfred; Skirtach, Andre G

2014-05-01

Colloidal particles play an important role in various areas of material and pharmaceutical sciences, biotechnology, and biomedicine. In this overview we describe micro- and nano-particles used for the preparation of polyelectrolyte multilayer capsules and as drug delivery vehicles. An essential feature of polyelectrolyte multilayer capsule preparations is the ability to adsorb polymeric layers onto colloidal particles or templates followed by dissolution of these templates. The choice of the template is determined by various physico-chemical conditions: solvent needed for dissolution, porosity, aggregation tendency, as well as release of materials from capsules. Historically, the first templates were based on melamine formaldehyde, later evolving towards more elaborate materials such as silica and calcium carbonate. Their advantages and disadvantages are discussed here in comparison to non-particulate templates such as red blood cells. Further steps in this area include development of anisotropic particles, which themselves can serve as delivery carriers. We provide insights into application of particles as drug delivery carriers in comparison to microcapsules templated on them. Copyright © 2014 Elsevier B.V. All rights reserved.

[INDICES OF THE OXIDATIVE STATUS IN CHRONIC ADMINISTRATION OF COLLOID CARBONATE CALCIUM PRAPARATION WITH FAUCET AND LOW-MINERALIZED DRINKING WATER IN RATS].

PubMed

Khripach, L V; Mikhaylova, R I; Koganova, Z I; Knyazeva, T D; Alekseeva, A V; Savostikova, O N; Ryzhova, I N; Kruglova, E V; Revzova, T L

2015-01-01

There are discussed the changes of an array of indices of the oxidative status in chronic administration of colloidal calcium carbonate preparation with faucet and low-mineralized drinking water to rats. Slight differences between significant effects of administration of 3 and 30 mg/L of preparation permit to suggest that the process of its incoming delivery into organism of rats has a bottleneck in the nature of total capacity of macrophages of intestinal lymphoid tissue to absorption of particles.

Cell membrane-inspired polymeric micelles as carriers for drug delivery.

PubMed

Liu, Gongyan; Luo, Quanqing; Gao, Haiqi; Chen, Yuan; Wei, Xing; Dai, Hong; Zhang, Zongcai; Ji, Jian

2015-03-01

In cancer therapy, surface engineering of drug delivery systems plays an essential role in their colloidal stability, biocompatibility and prolonged blood circulation. Inspired by the cell membrane consisting of phospholipids and glycolipids, a zwitterionic phosphorylcholine functionalized chitosan oligosaccharide (PC-CSO) was first synthesized to mimic the hydrophilic head groups of those amphipathic lipids. Then hydrophobic stearic acid (SA) similar to lipid fatty acids was grafted onto PC-CSO to form amphiphilic PC-CSO-SA copolymers. Cell membrane-mimetic micelles with a zwitterionic surface and a hydrophobic SA core were prepared by the self-assembly of PC-CSO-SA copolymers, showing excellent stability under extreme conditions including protein containing media, high salt content or a wide pH range. Doxorubicin (DOX) was successfully entrapped into polymeric micelles through the hydrophobic interaction between DOX and SA segments. After fast internalization by cancer cells, sustained drug release from micelles to the cytoplasm and nucleus was achieved. This result suggests that these biomimetic polymeric micelles may be promising drug delivery systems in cancer therapy.

Design of Hybrid Nanostructural Arrays to Manipulate SERS-Active Substrates by Nanosphere Lithography.

PubMed

Zhao, Xiaoyu; Wen, Jiahong; Zhang, Mengning; Wang, Dunhui; Wang, Yaxin; Chen, Lei; Zhang, Yongjun; Yang, Jinghai; Du, Youwei

2017-03-01

An easy-handling and low-cost method is utilized to controllably fabricate nanopattern arrays as the surface-enhanced Raman scattering (SERS) active substrates with high density of SERS-active areas (hot spots). A hybrid silver array of nanocaps and nanotriangles are prepared by combining magnetron sputtering and plasma etching. By adjusting the etching time of polystyrene (PS) colloid spheres array in silver nanobowls, the morphology of the arrays can be easily manipulated to control the formation and distribution of hot spots. The experimental results show that the hybrid nanostructural arrays have large enhancement factor, which is estimated to be seven times larger than that in the array of nanocaps and three times larger than that in the array of nanorings and nanoparticles. According to the results of finite-difference time-domain simulation, the excellent SERS performance of this array is ascribed to the high density of hot spots and enhanced electromagnetic field.

Magnetic switching of optical reflectivity in nanomagnet/micromirror suspensions: colloid displays as a potential alternative to liquid crystal displays.

PubMed

Bubenhofer, S B; Athanassiou, E K; Grass, R N; Koehler, F M; Rossier, M; Stark, W J

2009-12-02

Two-particle colloids containing nanomagnets and microscale mirrors can be prepared from iron oxide nanoparticles, microscale metal flakes and high-density liquids stabilizing the mirror suspension against sedimentation by matching the constituent's density. The free Brownian rotation of the micromirrors can be magnetically controlled through an anisotropic change in impulse transport arising from impacts of the magnetic nanoparticles onto the anisotropic flakes. The resulting rapid mirror orientation allows large changes in light transmission and switchable optical reflectivity. The preparation of a passive display was conceptually demonstrated through colloid confinement in a planar cavity over an array of individually addressable solenoids and resulted in 4 x 4 digit displays with a reaction time of less than 100 ms.

Information storage and retrieval in a single levitating colloidal particle

NASA Astrophysics Data System (ADS)

Myers, Christopher J.; Celebrano, Michele; Krishnan, Madhavi

2015-10-01

The binary switch is a basic component of digital information. From phase-change alloys to nanomechanical beams, molecules and atoms, new strategies for controlled bistability hold great interest for emerging technologies. We present a generic methodology for precise and parallel spatiotemporal control of nanometre-scale matter in a fluid, and demonstrate the ability to attain digital functionalities such as switching, gating and data storage in a single colloid, with further implications for signal amplification and logic operations. This fluid-phase bit can be arrayed at high densities, manipulated by either electrical or optical fields, supports low-energy, high-speed operation and marks a first step toward ‘colloidal information’. The principle generalizes to any system where spatial perturbation of a particle elicits a differential response amenable to readout.

Information storage and retrieval in a single levitating colloidal particle.

PubMed

Myers, Christopher J; Celebrano, Michele; Krishnan, Madhavi

2015-10-01

The binary switch is a basic component of digital information. From phase-change alloys to nanomechanical beams, molecules and atoms, new strategies for controlled bistability hold great interest for emerging technologies. We present a generic methodology for precise and parallel spatiotemporal control of nanometre-scale matter in a fluid, and demonstrate the ability to attain digital functionalities such as switching, gating and data storage in a single colloid, with further implications for signal amplification and logic operations. This fluid-phase bit can be arrayed at high densities, manipulated by either electrical or optical fields, supports low-energy, high-speed operation and marks a first step toward 'colloidal information'. The principle generalizes to any system where spatial perturbation of a particle elicits a differential response amenable to readout.

Site-Specific Colloidal Crystal Nucleation by Template-enhanced Particle Transport

NASA Astrophysics Data System (ADS)

Mishra, Chandan K.; Sood, A. K.; Ganapathy, Rajesh

The deliberate positioning of nano- and microstructures on surfaces is often a prerequisite for fabricating functional devices. While template-assisted nucleation is a promising route to self-assemble these structures, its success hinges on particles reaching target sites prior to nucleation and for nano/microscale particles, this is hampered by their small surface mobilities. We tailored surface features, which in the presence of attractive depletion interactions not only directed micrometer-sized colloids to specific sites but also subsequently guided their growth into ordered crystalline arrays of well-defined size and symmetry. By following the nucleation kinetics with single-particle resolution, we demonstrate control over nucleation density in a growth regime that has hitherto remained inaccessible. Our findings pave the way towards realizing non-trivial surface architectures composed of complex colloids/nanoparticles as well.

2D mesoscale colloidal crystal patterns on polymer substrates

NASA Astrophysics Data System (ADS)

Bredikhin, Vladimir; Bityurin, Nikita

2018-05-01

The development of nanosphere lithography relies on the ability of depositing 2D colloidal crystals comprising micro- and nano-size elements on substrates of different materials. One of the most difficult problems here is deposition of coatings on hydrophobic substrates, e.g. polymers, from aqueous colloidal solutions. We use UV photooxidation for substrate hydrophilization. We demonstrate a new method of producing a two-dimensional ordered array of polymer microparticles (polystyrene microspheres ∼1 μm in diameter) on a polymer substrate (PMMA). We show that implementation of the new deposition technique for directed self-assembly of microspheres on an UV irradiated surface provides an opportunity to obtain coatings on a hydrophilized PMMA surface of large area (∼5 cm2). UV irradiation of the surface through masks allows creating 2D patterns consisting of mesoscale elements formed by the deposited self-assembled microparticles owing to the fact that the colloidal particles are deposited only on the irradiated area leaving the non-irradiated sections intact.

Solution-processed single-wall carbon nanotube transistor arrays for wearable display backplanes

NASA Astrophysics Data System (ADS)

Kang, Byeong-Cheol; Ha, Tae-Jun

2018-01-01

In this paper, we demonstrate solution-processed single-wall carbon nanotube thin-film transistor (SWCNT-TFT) arrays with polymeric gate dielectrics on the polymeric substrates for wearable display backplanes, which can be directly attached to the human body. The optimized SWCNT-TFTs without any buffer layer on flexible substrates exhibit a linear field-effect mobility of 1.5cm2/V-s and a threshold voltage of around 0V. The statistical plot of the key device metrics extracted from 35 SWCNT-TFTs which were fabricated in different batches at different times conclusively support that we successfully demonstrated high-performance solution-processed SWCNT-TFT arrays which demand excellent uniformity in the device performance. We also investigate the operational stability of wearable SWCNT-TFT arrays against an applied strain of up to 40%, which is the essential for a harsh degree of strain on human body. We believe that the demonstration of flexible SWCNT-TFT arrays which were fabricated by all solution-process except the deposition of metal electrodes at process temperature below 130oC can open up new routes for wearable display backplanes.

Adenosine Monophosphate Forms Ordered Arrays in Multilamellar Lipid Matrices: Insights into Assembly of Nucleic Acid for Primitive Life

PubMed Central

Toppozini, Laura; Dies, Hannah; Deamer, David W.; Rheinstädter, Maikel C.

2013-01-01

A fundamental question of biology is how nucleic acids first assembled and then were incorporated into the earliest forms of cellular life 4 billion years ago. The polymerization of nucleotides is a condensation reaction in which phosphodiester bonds are formed. This reaction cannot occur in aqueous solutions, but guided polymerization in an anhydrous lipid environment could promote a non-enzymatic condensation reaction in which oligomers of single stranded nucleic acids are synthesized. We used X-ray scattering to investigate 5′-adenosine monophosphate (AMP) molecules captured in a multilamellar phospholipid matrix composed of dimyristoylphosphatidylcholine. Bragg peaks corresponding to the lateral organization of the confined AMP molecules were observed. Instead of forming a random array, the AMP molecules are highly entangled, with the phosphate and ribose groups in close proximity. This structure may facilitate polymerization of the nucleotides into RNA-like polymers. PMID:23667523

Adenosine monophosphate forms ordered arrays in multilamellar lipid matrices: insights into assembly of nucleic acid for primitive life.

PubMed

Toppozini, Laura; Dies, Hannah; Deamer, David W; Rheinstädter, Maikel C

2013-01-01

A fundamental question of biology is how nucleic acids first assembled and then were incorporated into the earliest forms of cellular life 4 billion years ago. The polymerization of nucleotides is a condensation reaction in which phosphodiester bonds are formed. This reaction cannot occur in aqueous solutions, but guided polymerization in an anhydrous lipid environment could promote a non-enzymatic condensation reaction in which oligomers of single stranded nucleic acids are synthesized. We used X-ray scattering to investigate 5'-adenosine monophosphate (AMP) molecules captured in a multilamellar phospholipid matrix composed of dimyristoylphosphatidylcholine. Bragg peaks corresponding to the lateral organization of the confined AMP molecules were observed. Instead of forming a random array, the AMP molecules are highly entangled, with the phosphate and ribose groups in close proximity. This structure may facilitate polymerization of the nucleotides into RNA-like polymers.

NASA Tech Briefs, December 2009

NASA Technical Reports Server (NTRS)

2009-01-01

Topics include: A Deep Space Network Portable Radio Science Receiver; Detecting Phase Boundaries in Hard-Sphere Suspensions; Low-Complexity Lossless and Near-Lossless Data Compression Technique for Multispectral Imagery; Very-Long-Distance Remote Hearing and Vibrometry; Using GPS to Detect Imminent Tsunamis; Stream Flow Prediction by Remote Sensing and Genetic Programming; Pilotless Frame Synchronization Using LDPC Code Constraints; Radiometer on a Chip; Measuring Luminescence Lifetime With Help of a DSP; Modulation Based on Probability Density Functions; Ku Telemetry Modulator for Suborbital Vehicles; Photonic Links for High-Performance Arraying of Antennas; Reconfigurable, Bi-Directional Flexfet Level Shifter for Low-Power, Rad-Hard Integration; Hardware-Efficient Monitoring of I/O Signals; Video System for Viewing From a Remote or Windowless Cockpit; Spacesuit Data Display and Management System; IEEE 1394 Hub With Fault Containment; Compact, Miniature MMIC Receiver Modules for an MMIC Array Spectrograph; Waveguide Transition for Submillimeter-Wave MMICs; Magnetic-Field-Tunable Superconducting Rectifier; Bonded Invar Clip Removal Using Foil Heaters; Fabricating Radial Groove Gratings Using Projection Photolithography; Gratings Fabricated on Flat Surfaces and Reproduced on Non-Flat Substrates; Method for Measuring the Volume-Scattering Function of Water; Method of Heating a Foam-Based Catalyst Bed; Small Deflection Energy Analyzer for Energy and Angular Distributions; Polymeric Bladder for Storing Liquid Oxygen; Pyrotechnic Simulator/Stray-Voltage Detector; Inventions Utilizing Microfluidics and Colloidal Particles; RuO2 Thermometer for Ultra-Low Temperatures; Ultra-Compact, High-Resolution LADAR System for 3D Imaging; Dual-Channel Multi-Purpose Telescope; Objective Lens Optimized for Wavefront Delivery, Pupil Imaging, and Pupil Ghosting; CMOS Camera Array With Onboard Memory; Quickly Approximating the Distance Between Two Objects; Processing Images of Craters for Spacecraft Navigation; Adaptive Morphological Feature-Based Object Classifier for a Color Imaging System; Rover Slip Validation and Prediction Algorithm; Safety and Quality Training Simulator; Supply-Chain Optimization Template; Algorithm for Computing Particle/Surface Interactions; Cryogenic Pupil Alignment Test Architecture for Aberrated Pupil Images; and Thermal Transport Model for Heat Sink Design.

Impregnation of β-tricalcium phosphate robocast scaffolds by in situ polymerization.

PubMed

Martínez-Vázquez, Francisco J; Perera, Fidel H; van der Meulen, Inge; Heise, Andreas; Pajares, Antonia; Miranda, Pedro

2013-11-01

Ring-opening polymerization of ε-caprolactone (ε-CL) and L-lactide (LLA) was performed to impregnate β-tricalcium phosphate (β-TCP) scaffolds fabricated by robocasting. Concentrated colloidal inks prepared from β-TCP commercial powders were used to fabricate porous structures consisting of a 3D mesh of interpenetrating rods. ε-CL and LLA were in situ polymerized within the ceramic structure by using a lipase and stannous octanoate, respectively, as catalysts. The results show that both the macropores inside the ceramic mesh and the micropores within the ceramic rods are full of polymer in either case. The mechanical properties of scaffolds impregnated by in situ polymerization (ISP) are significantly increased over those of the bare structures, exhibiting similar values than those obtained by other, more aggressive, impregnation methods such as melt-immersion (MI). ISP using enzymatic catalysts requires a reduced processing temperature which could facilitate the incorporation of growth factors and other drugs into the polymer composition, thus enhancing the bioactivity of the composite scaffold. The implications of these results for the optimization of the mechanical and biological performance of scaffolds for bone tissue engineering applications are discussed. Copyright © 2013 Wiley Periodicals, Inc.

Sol processing of conjugated carbon nitride powders for thin-film fabrication.

PubMed

Zhang, Jinshui; Zhang, Mingwen; Lin, Lihua; Wang, Xinchen

2015-05-18

The chemical protonation of graphitic carbon nitride (CN) solids with strong oxidizing acids, for example HNO3, is demonstrated as an efficient pathway for the sol processing of a stable CN colloidal suspension, which can be translated into thin films by dip/disperse-coating techniques. The unique features of CN colloids, such as the polymeric matrix and the reversible hydrogen bonding, result in the thin-film electrodes derived from the sol solution exhibiting a high mechanical stability with improved conductivity for charge transport, and thus show a remarkably enhanced photo-electrochemical performance. The polymer system can in principle be broadly tuned by hybridization with desired functionalities, thus paving the way for the application of CN for specific tasks, as exemplified here by coupling with carbon nanotubes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ZnO/perovskite core–shell nanorod array based monolithic catalysts with enhanced propane oxidation and material utilization efficiency at low temperature

DOE PAGES

Wang, Sibo; Ren, Zheng; Song, Wenqiao; ...

2015-04-24

Here, a hydrothermal strategy combined with colloidal deposition synthesis was successfully used to grow ZnO/perovskite (LaBO 3, B=Mn, Co, Ni) core-shell nanorod arrays within three dimensional (3-D) honeycomb cordierite substrates. A facile sonication assisted colloidal wash coating process is able to coat a uniformly dispersed perovskite nanoparticles onto the large scale ZnO nanorod arrays rooted on the channel surfaces of the 3D cordierite substrate achieved by hydrothermal synthesis. Compared to traditional wash-coated perovskite catalysts, an enhanced catalytic performance was observed for propane oxidation with 25°C lower light-off temperature than wash-coated perovskite catalyst of similar LaMnO 3 loading (4.3mg). Temperature programmedmore » reduction and desorption under H 2 and O 2 atmosphere, respectively, were used to study the reducibility and oxygen activity of these core-shell nanorod arrays based monolithic catalysts, revealing a catalytic activity sequence of LaCoO 3>LaMnO 3>La 2NiO 4 at the initial stage of catalytic reaction. The good dispersion and size control in La-based perovskite nanoparticles and their interfaces to ZnO nanorod arrays support may contribute to the enhancement of catalytic performance. Lastly, this work may provide a new type of Pt-group metals (PGM) free catalysts with improved catalytic performance for hydrocarbon oxidations at low temperatures.« less

Solid-Lubricant, Polymer - Polymeric and Functionalized Fiber- and Powder Reinforced Composites of Ultra-High Molecular Weight Polyethylene

NASA Astrophysics Data System (ADS)

Panin, S. V.; Alexenko, V. O.; Buslovich, D. G.; Anh, Nguyen Duc; Qitao, Huang

2018-01-01

Mechanical and tribotechnical characteristics of solid-lubricant and polymer-polymeric composites of UHMWPE were studied for the sake of design extrudable, wear-resistant, self-lubricant polymer mixtures for Additive Manufacturing (AM). Tribotechnical properties of UHMWPE blends with the optimized content of solid lubricant fillers (polytetrafluoroethylene, calcium stearate, molybdenum disulphide, colloidal graphite, boron nitride) were studied under dry sliding friction at different velocities (V = 0.3 and 0.5 m/s) and loads (P = 60 and 140 N). Also, in order to increase strength and wear-resistance of UHMWPE composites they were reinforced with wollastonite microfibers and aluminum metahydroxide AlO (OH) microparticles preliminary treated (functionalized) in polyorganosiloxane. The comparison on measured mechanical and tribotechnical properties are given with interpretation of the mechanisms of observed phenomenon.

Covalent Organic Frameworks as a Platform for Multidimensional Polymerization.

PubMed

Bisbey, Ryan P; Dichtel, William R

2017-06-28

The simultaneous polymerization and crystallization of monomers featuring directional bonding designs provides covalent organic frameworks (COFs), which are periodic polymer networks with robust covalent bonds arranged in two- or three-dimensional topologies. The range of properties characterized in COFs has rapidly expanded to include those of interest for heterogeneous catalysis, energy storage and photovoltaic devices, and proton-conducting membranes. Yet many of these applications will require materials quality, morphological control, and synthetic efficiency exceeding the capabilities of contemporary synthetic methods. This level of control will emerge from an improved fundamental understanding of COF nucleation and growth processes. More powerful characterization of structure and defects, improved syntheses guided by mechanistic understanding, and accessing diverse isolated forms, ranging from single crystals to thin films to colloidal suspensions, remain important frontier problems.

Covalent Organic Frameworks as a Platform for Multidimensional Polymerization

PubMed Central

2017-01-01

The simultaneous polymerization and crystallization of monomers featuring directional bonding designs provides covalent organic frameworks (COFs), which are periodic polymer networks with robust covalent bonds arranged in two- or three-dimensional topologies. The range of properties characterized in COFs has rapidly expanded to include those of interest for heterogeneous catalysis, energy storage and photovoltaic devices, and proton-conducting membranes. Yet many of these applications will require materials quality, morphological control, and synthetic efficiency exceeding the capabilities of contemporary synthetic methods. This level of control will emerge from an improved fundamental understanding of COF nucleation and growth processes. More powerful characterization of structure and defects, improved syntheses guided by mechanistic understanding, and accessing diverse isolated forms, ranging from single crystals to thin films to colloidal suspensions, remain important frontier problems. PMID:28691064

Large-Scale Noniridescent Structural Color Printing Enabled by Infiltration-Driven Nonequilibrium Colloidal Assembly.

PubMed

Bai, Ling; Mai, Van Cuong; Lim, Yun; Hou, Shuai; Möhwald, Helmuth; Duan, Hongwei

2018-03-01

Structural colors originating from interaction of light with intricately arranged micro-/nanostructures have stimulated considerable interest because of their inherent photostability and energy efficiency. In particular, noniridescent structural color with wide viewing angle has been receiving increasing attention recently. However, no method is yet available for rapid and large-scale fabrication of full-spectrum structural color patterns with wide viewing angles. Here, infiltration-driven nonequilibrium assembly of colloidal particles on liquid-permeable and particle-excluding substrates is demonstrated to direct the particles to form amorphous colloidal arrays (ACAs) within milliseconds. The infiltration-assisted (IFAST) colloidal assembly opens new possibilities for rapid manufacture of noniridescent structural colors of ACAs and straightforward structural color mixing. Full-spectrum noniridescent structural colors are successfully produced by mixing primary structural colors of red, blue, and yellow using a commercial office inkjet printer. Rapid fabrication of large-scale structural color patterns with sophisticated color combination/layout by IFAST printing is realized. The IFAST technology is versatile for developing structural color patterns with wide viewing angles, as colloidal particles, inks, and substrates are flexibly designable for diverse applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-organized colloidal quantum dots and metal nanoparticles for plasmon-enhanced intermediate-band solar cells.

PubMed

Mendes, Manuel J; Hernández, Estela; López, Esther; García-Linares, Pablo; Ramiro, Iñigo; Artacho, Irene; Antolín, Elisa; Tobías, Ignacio; Martí, Antonio; Luque, Antonio

2013-08-30

A colloidal deposition technique is presented to construct long-range ordered hybrid arrays of self-assembled quantum dots and metal nanoparticles. Quantum dots are promising for novel opto-electronic devices but, in most cases, their optical transitions of interest lack sufficient light absorption to provide a significant impact in their implementation. A potential solution is to couple the dots with localized plasmons in metal nanoparticles. The extreme confinement of light in the near-field produced by the nanoparticles can potentially boost the absorption in the quantum dots by up to two orders of magnitude.In this work, light extinction measurements are employed to probe the plasmon resonance of spherical gold nanoparticles in lead sulfide colloidal quantum dots and amorphous silicon thin-films. Mie theory computations are used to analyze the experimental results and determine the absorption enhancement that can be generated by the highly intense near-field produced in the vicinity of the gold nanoparticles at their surface plasmon resonance.The results presented here are of interest for the development of plasmon-enhanced colloidal nanostructured photovoltaic materials, such as colloidal quantum dot intermediate-band solar cells.

Synthesis of polymer nanostructures via the use of surfactant surface aggregates as templates

NASA Astrophysics Data System (ADS)

Marquez, Maricel

The subject of this work is the synthesis of polymer nanostructures via the use of surfactant surface aggregates as templates, also termed Template Assisted Admicellar Polymerization (TAAP). The first chapter reviews some of the most current nanopatterning techniques (including both top-down and bottom-up approaches), with particular emphasis on the fabrication of organic and inorganic patterned nanostructures via particle lithography. In chapter 2, highly ordered hexagonal arrays of latex spheres were prepared on highly ordered pyrolytic graphite (HOPG) from a variation of the Langmuir Blodgett technique, using an anionic surfactant (SDS), and a low molecular weight (ca. 10000) polyacrylamide as spreading agents. When a nonionic polyethoxylated (EO = 9) surfactant was used as the spreading agent, no ordered arrays were observed. Based on the correlation found between the surface tension in the presence of the latex particles and the critical concentration at which hexagonal arrangements of latex spheres occurs; a model was proposed to explain the role of the spreading agent in forming stable monolayers at the air/liquid interface, which in turn are necessary for the formation of well-ordered monolayers on a solid substrate from the LB technique. According to this model, solid-like regions of small numbers of latex spheres form at the liquid-air interface, which are then transferred to the substrate. These ordered regions then act as nuclei for the formation of 2D arrays of latex spheres on the surface upon water evaporation. The role of other factors such as relative humidity, substrate and solvent choice, and pulling vs. compression speed were also found to affect the quality of the monolayers formed. Finally, a simple, easy to automate, yet effective surface tension method was proposed to predict the optimal conditions for the formation of ordered monolayers using a variation of the LB deposition method from any monodisperse set of spheres. In chapter 3, a novel method for the formation of nanometer-scale polymer structures on solid surfaces via template assisted admicellar polymerization (TAAP) is described. Admicellar polymerization uses a surfactant layer adsorbed on a surface to localize monomer to the surface prior to polymerization of the monomer. TAAP refers to nanostructures that form by restricting adsorption to the uncovered sites of an already-templated surface. In this case, the interstitial sites between adsorbed latex spheres were used as the template. Unlike most other process that form polymer nanostructures, polymer dimensions can be significantly smaller than the interstitial size because of sphere-surfactant-monomer interactions. As a proof of concept, nanostructures formed via TAAP were compared to structures prepared by others via adsorption of three different proteins (Bovine serum albumin, fibrinogen, and anti-mouse IgG) in the interstitial sites of colloidal monolayers. The size and shape of the nanostructures formed (honeycomb vs. pillars) was dependent upon the size of the spheres utilized and the method of polymer deposition (i.e. admicellar polymerization vs. polymer adsorption). Thinner honeycomb walls, and larger separation distances between the template and the nanostructures were consistently found for TAAP. In chapter 4, an in-depth study of the factors affecting TAAP is presented for three different monomers: aniline, pyrrole and methyl methacrylate; and three different surfaces: highly ordered pyrolytic graphite (HOPG), gold, and SiO2. Among the parameters discussed are the effect of monomer and surfactant concentration, surfactant chain length, polymerization time and temperature, solution ionic strength, substrate choice and surface treatment. Control over these parameters allowed the synthesis of polymer nanopillars, nanorings, honeycombs, and "honeytubes." Experimental results showed that the nanostructures' morphology can be effectively modified by changing the length of the hydrophobic chain of the surfactant. Nanostructures with fewer defects were found for surfactants with the longest hydrophobic tails (i.e. 12 carbon atoms). The hydrophobic nature of the monomer also seemed to affect the morphology of the nanostructure; poly(methyl methacrylate) (PMMA) honeycombs showed thicker walls compared to polyaniline (PANI) and polypyrrole (Ppy). In general, HOPG seems to be a better choice of substrate for TAAP compared to gold-coated glass and SiO2 wafers. Preliminary results on the formation of layered polymer nanostructures via multiple TAAP sequences were also presented.

Structure and properties of nanostructured ZnO arrays and ZnO/Ag nanocomposites fabricated by pulsed electrodeposition

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

Kopach, V. R.; Klepikova, K. S.; Klochko, N. P., E-mail: klochko-np@mail.ru

We investigate the structure, surface morphology, and optical properties of nanostructured ZnO arrays fabricated by pulsed electrodeposition, Ag nanoparticles precipitated from colloidal solutions, and a ZnO/Ag nanocomposite based on them. The electronic and electrical parameters of the ZnO arrays and ZnO/Ag nanocomposites are analyzed by studying the I–V and C–V characteristics. Optimal modes for fabricating the ZnO/Ag heterostructures with the high stability and sensitivity to ultraviolet radiation as promising materials for use in photodetectors, gas sensors, and photocatalysts are determined.

Superhydrophobic Analyte Concentration Utilizing Colloid-Pillar Array SERS Substrates

DOE PAGES

Wallace, Ryan A.; Charlton, Jennifer J.; Kirchner, Teresa B.; ...

2014-11-04

In order to detect a few molecules present in a large sample it is important to know the trace components in the medicinal and environmental sample. Surface enhanced Raman spectroscopy (SERS) is a technique that can be utilized to detect molecules at very low absolute numbers. However, detection at trace concentration levels in real samples requires properly designed delivery and detection systems. Moreover, the following work involves superhydrophobic surfaces that includes silicon pillar arrays formed by lithographic and dewetting protocols. In order to generate the necessary plasmonic substrate for SERS detection, simple and flow stable Ag colloid was added tomore » the functionalized pillar array system via soaking. The pillars are used native and with hydrophobic modification. The pillars provide a means to concentrate analyte via superhydrophobic droplet evaporation effects. A 100-fold concentration of analyte was estimated, with a limit of detection of 2.9 10-12 M for mitoxantrone dihydrochloride. Additionally, analytes were delivered to the surface via a multiplex approach in order to demonstrate an ability to control droplet size and placement for scaled-up applications in real world applications. Finally, a concentration process involving transport and sequestration based on surface treatment selective wicking is demonstrated.« less

Superhydrophobic Analyte Concentration Utilizing Colloid-Pillar Array SERS Substrates

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

Wallace, Ryan A.; Charlton, Jennifer J.; Kirchner, Teresa B.

In order to detect a few molecules present in a large sample it is important to know the trace components in the medicinal and environmental sample. Surface enhanced Raman spectroscopy (SERS) is a technique that can be utilized to detect molecules at very low absolute numbers. However, detection at trace concentration levels in real samples requires properly designed delivery and detection systems. Moreover, the following work involves superhydrophobic surfaces that includes silicon pillar arrays formed by lithographic and dewetting protocols. In order to generate the necessary plasmonic substrate for SERS detection, simple and flow stable Ag colloid was added tomore » the functionalized pillar array system via soaking. The pillars are used native and with hydrophobic modification. The pillars provide a means to concentrate analyte via superhydrophobic droplet evaporation effects. A 100-fold concentration of analyte was estimated, with a limit of detection of 2.9 10-12 M for mitoxantrone dihydrochloride. Additionally, analytes were delivered to the surface via a multiplex approach in order to demonstrate an ability to control droplet size and placement for scaled-up applications in real world applications. Finally, a concentration process involving transport and sequestration based on surface treatment selective wicking is demonstrated.« less

The development and characterization of stimuli-responsive systems for performance materials

NASA Astrophysics Data System (ADS)

Gordon, Melissa B.

In nature, living organisms adjust to their surroundings by responding to environmental cues, such as light, temperature or force. Stimuli-triggered processes, such as the contraction of eyes in response to bright light or wound healing in skin after a cut, motivate the design of "smart" materials which are designed to respond to environmental stimuli. Responsive materials are used as self-healing materials, shape memory polymers and responsive coatings; moreover, responsive materials may also be employed as model systems, which enhance understanding of complex behavior. The overall goal of this work is to design a material that offers self-healing functionality, which will allow for self-repair following material fatigue or failure, and increased strength in response to ballistic or puncture threats through the incorporation of colloidal particles. The target application for this material is as a protective barrier in extreme environments, such as outer space. Towards this end, the dissertation is focused on the development and characterization of each component of the protective material by (1) designing and testing novel light- and force-sensitive polymers for self-healing applications and (2) examining and characterizing long-time behavior (i.e., aging) in model thermoreversible colloidal gels and glasses. Towards the development of novel stimuli-responsive materials, a photo-responsive polymer network is developed in which a dynamic bond is incorporated into the network architecture to enable a light-triggered, secondary polymerization, which increases the modulus by two orders of magnitude while strengthening the network by over 100%. Unlike traditional two-stage polymerization systems, in which the secondary polymerization is triggered by a leachable photoinitiator, the dynamic nature is imparted by the material itself via the dissociation of its own crosslinks to become stronger in response to light. Several attributes of the photo-responsive network are shown including: (1) photo-induced healing and strengthening of a specimen after it has been severed, (2) photopatterning for effecting spatially confined property changes on demand, and (3) locking in the film's 3D geometry using light after reshaping. The utility of the photo-responsive dynamic bond is enhanced by demonstrating that it is also responsive to mechanical force. Force-responsive materials are activated by the energy from the damage event itself, thereby enabling healing without human intervention. Specifically, selective cleavage of a polymer containing a dynamic trithiocarbonate group initiates a force-driven radical polymerization, thus enabling the material to constructively respond to force via gelation on an experimentally relevant timescale. To enhance the stress response of the self-healing materials described above, a protective material composed of colloidal particles is proposed. Toward this goal, the second half of this dissertation investigates the microstructural basis of rheological aging in colloidal gels and glasses using a model thermoreversible colloidal dispersion. In this work, rheological aging is quantitatively related to microstructural aging in glasses and gels by simultaneously measuring the bulk properties and sample microstructure using rheometry and small angle neutron scattering (Rheo-SANS), respectively. A one-to-one correspondence between the evolution in storage modulus and microstructure as the sample ages is observed, which is investigated as a function of thermal and shear history. The microstructural measurements are consistent with the hypothesis of aging as a trajectory in a free energy landscape, which combined with analysis with mode coupling theory, support local particle rearrangements as the mechanism of aging. Moreover, by using a system that is fully rejuvenated by thermal cycling, the effectiveness of shear as a rejuvenation method is investigated by directly comparing microstructure and bulk properties following thermal and mechanical rejuvenation. The conclusions of this study may be industrially relevant to products that age on commercial timescales, such as pharmaceuticals, applicable to other dynamically arrested systems, such as metallic glasses, and provide pathways to advanced composite materials such as those envisioned in this work.

General route for the assembly of functional inorganic capsules.

PubMed

Akartuna, Ilke; Tervoort, Elena; Studart, André R; Gauckler, Ludwig J

2009-11-03

Semipermeable, hollow capsules are attractive materials for the encapsulation and delivery of active agents in food processing, pharmaceutical and agricultural industries, and biomedicine. These capsules can be produced by forming a solid shell of close packed colloidal particles, typically polymeric particles, at the surface of emulsion droplets. However, current methods to prepare such capsules may involve multistep chemical procedures to tailor the surface chemistry of particles or are limited to particles that exhibit inherently the right hydrophobic-hydrophilic balance to adsorb around emulsion droplets. In this work, we describe a general and simple method to fabricate semipermeable, inorganic capsules from emulsion droplets stabilized by a wide variety of colloidal metal oxide particles. The assembly of particles at the oil-water interface is induced by the in situ hydrophobization of the particle surface through the adsorption of short amphiphilic molecules. The adsorption of particles at the interface leads to stable capsules comprising a single layer of particles in the outer shell. Such capsules can be used in the wet state or can be further processed into dry capsules. The permeability of the capsules can be modified by filling the interstices between the shell particles with polymeric or inorganic species. Functional capsules with biocompatible, bioresorbable, heat-resistant, chemical-resistant, and magnetic properties were prepared using alumina, silica, iron oxide, or tricalcium phosphate as particles in the shell.

Tunable TiO2 Nanotube Arrays for Flexible Bio-Sensitized Solar Cells

DTIC Science & Technology

2012-08-01

microid extender followed by a colloidal silica /wetted imperial cloth. The foil was then cut into 1- × 2-cm samples. Then, the substrates were...17. Lei, B.; Liao, J.; Wang, R. J.; Su, C.; Kuang, D. Ordered Crystalline Ti02 Nanotube Arrays on Transparent FTO Glass for Efficient Dye...combined with a transparent , Indium Tin Dioxide coated PET film are attractive candidates for efficient, flexible DSSC’s. Flexible solar cells offer

Self-assembled biomimetic antireflection coatings

NASA Astrophysics Data System (ADS)

Linn, Nicholas C.; Sun, Chih-Hung; Jiang, Peng; Jiang, Bin

2007-09-01

The authors report a simple self-assembly technique for fabricating antireflection coatings that mimic antireflective moth eyes. Wafer-scale, nonclose-packed colloidal crystals with remarkable large hexagonal domains are created by a spin-coating technology. The resulting polymer-embedded colloidal crystals exhibit highly ordered surface modulation and can be used directly as templates to cast poly(dimethylsiloxane) (PDMS) molds. Moth-eye antireflection coatings with adjustable reflectivity can then be molded against the PDMS master. The specular reflection of replicated nipple arrays matches the theoretical prediction using a thin-film multilayer model. These biomimetic films may find important technological application in optical coatings and solar cells.

Smart photonic coating as a new visualization technique of strain deformation of metal plates

NASA Astrophysics Data System (ADS)

Fudouzi, Hiroshi; Sawada, Tsutomu; Tanaka, Yoshikazu; Ario, Ichiro; Hyakutake, Tsuyoshi; Nishizaki, Itaru

2012-04-01

We will present a simple and low cost method to visualize local strain distribution in deformed aluminum plates. In this study, aluminum plates were coated with opal photonic crystal film with tunable structural color. The photonic crystal films consist of a silicone elastomer that contains an array of submicron polystyrene colloidal particles. When the aluminum sheets were stretched, the change in the spacing of the colloidal particles in the opal film alters the color of the film. This approach could be useful as a new strain gauge having a visual indicator to detect mechanical deformation.

Surface Modification of Nanocellulose Substrates

NASA Astrophysics Data System (ADS)

Zoppe, Justin Orazio

Cellulose fibers constitute an important renewable raw material that is utilized in many commercial applications in non-food, paper, textiles and composite materials. Chemical functionalization is an important approach for improving the properties of cellulose based materials. Different approaches are used to graft polymeric chains onto cellulose substrates, which can be classified by two principal routes, namely 'grafting onto' or 'grafting from' methods. Never-dried cellulose nanocrystals (CNCs) or nanowhiskers produced from sulfuric acid hydrolysis of ramie fibers were used as substrates for surface chemical functionalization with various macromolecules. In addition, the use of cellulose nanocrystals to reinforce poly(epsilon-caprolactone) (PCL) nanofibers was studied. Chemical grafting with low molecular weight polycaprolactone diol onto cellulose nanocrystals was carried out in an attempt to improve the interfacial adhesion with the fiber matrix. Significant improvements in the mechanical properties of the nanofibers after reinforcement with unmodified cellulose nanocrystals were confirmed. Fiber webs from PCL reinforced with 2.5% unmodified CNCs showed ca. 1.5-fold increase in Young's modulus and ultimate strength compared to PCL webs. The CNCs were also grafted with poly(N-isopropylacrylamide) (poly(NiPAAm)) brushes via surface-initiated single-electron transfer living radical polymerization (SI-SETLRP) under various conditions at room temperature. The grafting process depended on the initiator and/or monomer concentrations used. No observable damage occurred to the CNCs after grafting, as determined by X-ray diffraction. Size exclusion chromatography analyses of polymer chains cleaved from the cellulose nanocrystals indicated that a higher degree of polymerization was achieved by increasing initiator or monomer loading, most likely caused by local heterogeneities yielding higher rates of polymerization. In addition, the colloidal stability and thermo-responsive behavior of poly(NiPAAm) brushes grafted from nanoparticles of CNCs of varying graft densities and molecular weights was investigated. Halo areas surrounding grafted CNCs that were adsorbed on silica and imaged with an AFM were indicative of the grafted polymer brushes. Aggregation of nanoparticles carrying grafts of high degree of polymerization was observed. The responsiveness of CNCs in liquid medium and as spin-coated films was determined by using light scattering, viscometry and Colloidal Probe Microscopy (CPM). Light transmittance measurements showed temperaturedependent aggregation originating from the different graft densities and molecular weights and a sharp increase in dispersion viscosity as the temperature approached the LCST. The lower critical solution temperature (LCST) of grafted poly(NiPAAm) brushes was found to decrease with the ionic strength as is the case of neat poly(NiPAAm) in aqueous solution. CPM in aqueous media for asymmetric systems consisting of thin films of CNCs and a colloidal silica probe showed the distinctive effects of the grafted polymer brushes on the interaction (repulsive and adhesive) forces. The origin of such forces was mainly electrostatic and steric in the case of bare and grafted CNCs, respectively. A decrease in the onset of attractive and adhesion forces of grafted CNCs films was observed with the ionic strength of the aqueous solution medium. The decreased mobility of polymer brushes upon partial collapse and decreased availability of hydrogen bonding sites with higher electrolyte concentration were hypothesized as main reasons for the less prominent polymer bridging between interacting surfaces. Finally, poly(NiPAAm)-g-CNCs were utilized as a Pickering emulsions stabilizer. All emulsions formed were oil-in-water confirmed by a drop test. Various drop sizes were obtained as characterized by laser scattering particle size analysis and optical microscopy. Anisotropic colloidal assemblies of grafted CNCs at the oil-water interface were observed in freeze-fractured samples via Transmission Electron Microscopy. Emulsions were stable for over three months at the time of writing this thesis, however rapidly broke above the LCST as determined by rheometry.

Sputtering-growth of seeded Au nanoparticles for nanogap-assisted surface-enhanced Raman scattering (SERS) biosensing

NASA Astrophysics Data System (ADS)

Fu, Chit Yaw; U. S., Dinish; Rautela, Shashi; Goh, Douglas Wenda; Olivo, Malini

2011-12-01

Gold-coated array patterned with tightly-packed nanospheres was developed as a substrate base for constructing SERSenriched nanogaps with Au-nanoparticles (GNPs). Using 1,2-ethanedithiol as a linker, Au-NPs (=17-40nm) were anchored covalently on the sphere-array. Thin Au layer was sputtered on the substrate to mask the citrate coating of GNPs that could demote the sensing mechanism. The negatively-charged GNP surface warrants the colloidal stability, but the resulting repulsive force keeps the immobilized NPs apart by about 40nm. The attained gap size is inadequately narrow to sustain any intense enhancement owing to the near-field nature of SERS. Minimal amount of NaCl was then added to slightly perturb the colloidal stability by reducing their surface charge. Notably, the interparticle-gap reduces at increasing amount of salt, giving rise to increased packing density of GNPs. The SERS enhancement is also found to exponentially increase at decreasing gap size. Nevertheless, the minimum gap achieved is limited to merely 7nm. Excessive addition of salt would eventually induce complete aggregation of particles, forming clustered NPs on the array. A simple sputtering-growth approach is therefore proposed to further minimize the interparticle gap by enlarging the seeded NPs based on mild sputtering. The SEM images confirm that the gap below 7nm is achievable. With advent of the colloidal chemistry, the combined salt-induced aggregation and sputtering-growth techniques can be applied to engineer interparticle gap that is crucial to realize an ultrasensitive SERS biosensor. The proposed two-step preparation can be potentially adopted to fabricate the SERS-enriched nanogaps on the microfluidics platform.

Colloidal Synthesis of Silicon-Carbon Composite Material for Lithium-Ion Batteries.

PubMed

Su, Haiping; Barragan, Alejandro A; Geng, Linxiao; Long, Donghui; Ling, Licheng; Bozhilov, Krassimir N; Mangolini, Lorenzo; Guo, Juchen

2017-08-28

We report colloidal routes to synthesize silicon@carbon composites for the first time. Surface-functionalized Si nanoparticles (SiNPs) dissolved in styrene and hexadecane are used as the dispersed phase in oil-in-water emulsions, from which yolk-shell and dual-shell hollow SiNPs@C composites are produced via polymerization and subsequent carbonization. As anode materials for Li-ion batteries, the SiNPs@C composites demonstrate excellent cycling stability and rate performance, which is ascribed to the uniform distribution of SiNPs within the carbon hosts. The Li-ion anodes composed of 46 wt % of dual-shell SiNPs@C, 46 wt % of graphite, 5 wt % of acetylene black, and 3 wt % of carboxymethyl cellulose with an areal loading higher than 3 mg cm -2 achieve an overall specific capacity higher than 600 mAh g -1 , which is an improvement of more than 100 % compared to the pure graphite anode. These new colloidal routes present a promising general method to produce viable Si-C composites for Li-ion batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Colloidal polymer particles as catalyst carriers and phase transfer agents in multiphasic hydroformylation reactions.

PubMed

Peral, D; Stehl, D; Bibouche, B; Yu, H; Mardoukh, J; Schomäcker, R; Klitzing, R von; Vogt, D

2018-03-01

Colloidal particles have been used to covalently bind ligands for the heterogenization of homogeneous catalysts. The replacement of the covalent bonds by electrostatic interactions between particles and the catalyst could preserve the selectivity of a truly homogeneous catalytic process. Functionalized polymer particles with trimethylammonium moieties, dispersed in water, with a hydrophobic core and a hydrophilic shell have been synthesized by emulsion polymerization and have been thoroughly characterized. The ability of the particles with different monomer compositions to act as catalyst carriers has been studied. Finally, the colloidal dispersions have been applied as phase transfer agents in the multiphasic rhodium-catalyzed hydroformylation of 1-octene. The hydrodynamic radius of the particles has been shown to be around 100 nm, and a core-shell structure could be observed by atomic force microscopy. The polymer particles were proven to act as carriers for the water-soluble hydroformylation catalyst, due to electrostatic interaction between the functionalized particles bearing ammonium groups and the sulfonated ligands of the catalyst. The particles were stable under the hydroformylation conditions and the aqueous catalyst phase could be recycled three times. Copyright © 2017 Elsevier Inc. All rights reserved.

Thermophoretically induced large-scale deformations around microscopic heat centers

NASA Astrophysics Data System (ADS)

Puljiz, Mate; Orlishausen, Michael; Köhler, Werner; Menzel, Andreas M.

2016-05-01

Selectively heating a microscopic colloidal particle embedded in a soft elastic matrix is a situation of high practical relevance. For instance, during hyperthermic cancer treatment, cell tissue surrounding heated magnetic colloidal particles is destroyed. Experiments on soft elastic polymeric matrices suggest a very long-ranged, non-decaying radial component of the thermophoretically induced displacement fields around the microscopic heat centers. We theoretically confirm this conjecture using a macroscopic hydrodynamic two-fluid description. Both thermophoretic and elastic effects are included in this theory. Indeed, we find that the elasticity of the environment can cause the experimentally observed large-scale radial displacements in the embedding matrix. Additional experiments confirm the central role of elasticity. Finally, a linearly decaying radial component of the displacement field in the experiments is attributed to the finite size of the experimental sample. Similar results are obtained from our theoretical analysis under modified boundary conditions.

Two-photon polymerization of a three dimensional structure using beams with orbital angular momentum

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

Zhang, Shi-Jie; Li, Yan, E-mail: li@pku.edu.cn; Liu, Zhao-Pei

The focus of a beam with orbital angular momentum exhibits internal structure instead of an elliptical intensity distribution of a Gaussian beam, and the superposition of Gauss-Laguerre beams realized by two-dimensional phase modulation can generate a complex three-dimensional (3D) focus. By taking advantage of the flexibility of this 3D focus tailoring, we have fabricated a 3D microstructure with high resolution by two-photon polymerization with a single exposure. Furthermore, we have polymerized an array of double-helix structures that demonstrates optical chirality.

Real-time monitoring of surface-initiated atom transfer radical polymerization using silicon photonic microring resonators: implications for combinatorial screening of polymer brush growth conditions.

PubMed

Limpoco, F Ted; Bailey, Ryan C

2011-09-28

We directly monitor in parallel and in real time the temporal profiles of polymer brushes simultaneously grown via multiple ATRP reaction conditions on a single substrate using arrays of silicon photonic microring resonators. In addition to probing relative polymerization rates, we show the ability to evaluate the dynamic properties of the in situ grown polymers. This presents a powerful new platform for studying modified interfaces that may allow for the combinatorial optimization of surface-initiated polymerization conditions.

Ultra-high-aspect-orthogonal and tunable three dimensional polymeric nanochannel stack array for BioMEMS applications

NASA Astrophysics Data System (ADS)

Heo, Joonseong; Kwon, Hyukjin J.; Jeon, Hyungkook; Kim, Bumjoo; Kim, Sung Jae; Lim, Geunbae

2014-07-01

Nanofabrication technologies have been a strong advocator for new scientific fundamentals that have never been described by traditional theory, and have played a seed role in ground-breaking nano-engineering applications. In this study, we fabricated ultra-high-aspect (~106 with O(100) nm nanochannel opening and O(100) mm length) orthogonal nanochannel array using only polymeric materials. Vertically aligned nanochannel arrays in parallel can be stacked to form a dense nano-structure. Due to the flexibility and stretchability of the material, one can tune the size and shape of the nanochannel using elongation and even roll the stack array to form a radial-uniformly distributed nanochannel array. The roll can be cut at discretionary lengths for incorporation with a micro/nanofluidic device. As examples, we demonstrated ion concentration polarization with the device for Ohmic-limiting/overlimiting current-voltage characteristics and preconcentrated charged species. The density of the nanochannel array was lower than conventional nanoporous membranes, such as anodic aluminum oxide membranes (AAO). However, accurate controllability over the nanochannel array dimensions enabled multiplexed one microstructure-on-one nanostructure interfacing for valuable biological/biomedical microelectromechanical system (BioMEMS) platforms, such as nano-electroporation.Nanofabrication technologies have been a strong advocator for new scientific fundamentals that have never been described by traditional theory, and have played a seed role in ground-breaking nano-engineering applications. In this study, we fabricated ultra-high-aspect (~106 with O(100) nm nanochannel opening and O(100) mm length) orthogonal nanochannel array using only polymeric materials. Vertically aligned nanochannel arrays in parallel can be stacked to form a dense nano-structure. Due to the flexibility and stretchability of the material, one can tune the size and shape of the nanochannel using elongation and even roll the stack array to form a radial-uniformly distributed nanochannel array. The roll can be cut at discretionary lengths for incorporation with a micro/nanofluidic device. As examples, we demonstrated ion concentration polarization with the device for Ohmic-limiting/overlimiting current-voltage characteristics and preconcentrated charged species. The density of the nanochannel array was lower than conventional nanoporous membranes, such as anodic aluminum oxide membranes (AAO). However, accurate controllability over the nanochannel array dimensions enabled multiplexed one microstructure-on-one nanostructure interfacing for valuable biological/biomedical microelectromechanical system (BioMEMS) platforms, such as nano-electroporation. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00350k

Tunable Nanoantennas for Surface Enhanced Infrared Absorption Spectroscopy by Colloidal Lithography and Post-Fabrication Etching

NASA Astrophysics Data System (ADS)

Chen, Kai; Duy Dao, Thang; Nagao, Tadaaki

2017-03-01

We fabricated large-area metallic (Al and Au) nanoantenna arrays on Si substrates using cost-effective colloidal lithography with different micrometer-sized polystyrene spheres. Variation of the sphere size leads to tunable plasmon resonances in the middle infrared (MIR) range. The enhanced near-fields allow us to detect the surface phonon polaritons in the natural SiO2 thin layers. We demonstrated further tuning capability of the resonances by employing dry etching of the Si substrates with the nanoantennas acting as the etching masks. The effective refractive index of the nanoantenna surroundings is efficiently decreased giving rise to blueshifts of the resonances. In addition, partial removal of the Si substrates elevates the nanoantennas from the high-refractive-index substrates making more enhanced near-fields accessible for molecular sensing applications as demonstrated here with surface-enhanced infrared absorption (SEIRA) spectroscopy for a thin polymer film. We also directly compared the plasmonic enhancement from the Al and Au nanoantenna arrays.

Transparent arrays of silver nanowire rings driven by evaporation of sessile droplets

NASA Astrophysics Data System (ADS)

Wang, Xiaofeng; Kang, Giho; Seong, Baekhoon; Chae, Illkyeong; Teguh Yudistira, Hadi; Lee, Hyungdong; Kim, Hyunggun; Byun, Doyoung

2017-11-01

A coffee-ring pattern can be yielded on the three-phase contact line following evaporation of sessile droplets with suspended insoluble solutes, such as particles, DNA molecules, and mammalian cells. The formation of such coffee-ring, together with their suppression has been applied in printing and coating technologies. We present here an experimental study on the assembly of silver nanowires inside an evaporating droplet of a colloidal suspension. The effects of nanowire length and concentration on coffee-ring formation of the colloidal suspension were investigated. Several sizes of NWs with an aspect ratio between 50 and 1000 were systematically investigated to fabricate coffee-ring patterns. Larger droplets containing shorter nanowires formed clearer ring deposits after evaporation. An order-to-disorder transition of the nanowires’ alignment was found inside the rings. A printing technique with the evaporation process enabled fabrication of arrays of silver nanowire rings. We could manipulate the patterns silver nanowire rings, which might be applied to the transparent and flexible electrode.

Process for preparing fine grain silicon carbide powder

DOEpatents

Wei, G.C.

Finely divided silicon carbide powder is obtained by mixing colloidal silica and unreacted phenolic resin in either acetone or methanol, evaporating solvent from the obtained solution to form a gel, drying and calcining the gel to polymerize the phenolic resin therein, pyrolyzing the dried and calcined gel at a temperature in the range of 500 to 1000/sup 0/C, and reacting silicon and carbon in the pyrolyzed gel at a temperature in the range of 1550 to 1700/sup 0/C to form the powder.

Synthesis of amphipathic block copolymers based on polyisobutylene and polyoxyethylene and their application in emulsion polymerization

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

Sar, B.

1992-12-31

Polymer colloids stabilized by polymeric surfactants are of great interest both commercially and academically. It has been found that these materials enhance latex stabilization in a number of applications. The polymeric surfactants are amphipathic block and graft copolymers containing both hydrophilic and hydrophobic moieties. The current study involved the synthesis of a series of amphipathic triblock copolymers, polyisobutylene-block-polyoxyethylene-block-polyisobutylene (PIB-b-POE-b-PIB), for use in the emulsion polymerization of styrene (STY), methyl methacrylate (MMA), and vinyl acetate (VAc). The stabilizing effectiveness of these triblock copolymers was studied as a function of their blocklength. When the molecular weight of the POE center block wasmore » changed from M{sub n} = 2,000 to 20,000 g/mole, stable lattices were obtained in emulsion polymerization with MMA, STY, and VAc as the monomers. In all cases, the polymerization rates remained constant, while the number of particles/volume decreased with increasing POE chain length. When the molecular weight of the PIB end blocks was changed from M{sub n} = 400 to 2,600 g/mole keeping the molecular weight of the POE center block constant at M{sub n} = 20,000 g/mole, the poly(methyl methacrylate) and poly(vinyl acetate) lattices exhibited similar behavior, i.e., the number of particles and particle sizes remained the same, but the rate of polymerization reached a maximum at 87 wt% POE content. In the case of poly(styrene) both the rate of polymerization and the number of particles remained constant. The emulsion polymerization of other monomers such as butadiene, acrylonitrile, methyl acrylate, ethyl acrylate, and butyl acrylate was carried out by using one triblock copolymer, i.e., PIB(400)-b-POE (8,000)-b-PIB-(400). Stable lattices were also formed in all cases.« less

Characterization of polymerized liposomes using a combination of dc and cyclical electrical field-flow fractionation.

PubMed

Sant, Himanshu J; Chakravarty, Siddharth; Merugu, Srinivas; Ferguson, Colin G; Gale, Bruce K

2012-10-02

Characterization of polymerized liposomes (PolyPIPosomes) was carried out using a combination of normal dc electrical field-flow fractionation and cyclical electrical field-flow fractionation (CyElFFF) as an analytical technique. The constant nature of the carrier fluid and channel configuration for this technique eliminates many variables associated with multidimensional analysis. CyElFFF uses an oscillating field to induce separation and is performed in the same channel as standard dc electrical field-flow fractionation separation. Theory and experimental methods to characterize nanoparticles in terms of their sizes and electrophoretic mobilities are discussed in this paper. Polystyrene nanoparticles are used for system calibration and characterization of the separation performance, whereas polymerized liposomes are used to demonstrate the applicability of the system to biomedical samples. This paper is also the first to report separation and a higher effective field when CyElFFF is operated at very low applied voltages. The technique is shown to have the ability to quantify both particle size and electrophoretic mobility distributions for colloidal polystyrene nanoparticles and PolyPIPosomes.

Tunable photonic crystals with partial bandgaps from blue phase colloidal crystals and dielectric-doped blue phases.

PubMed

Stimulak, Mitja; Ravnik, Miha

2014-09-07

Blue phase colloidal crystals and dielectric nanoparticle/polymer doped blue phases are demonstrated to combine multiple components with different symmetries in one photonic material, creating a photonic crystal with variable and micro-controllable photonic band structure. In this composite photonic material, one contribution to the band structure is determined by the 3D periodic birefringent orientational profile of the blue phases, whereas the second contribution emerges from the regular array of the colloidal particles or from the dielectric/nanoparticle-doped defect network. Using the planewave expansion method, optical photonic bands of the blue phase I and II colloidal crystals and related nanoparticle/polymer doped blue phases are calculated, and then compared to blue phases with no particles and to face-centred-cubic and body-centred-cubic colloidal crystals in isotropic background. We find opening of local band gaps at particular points of Brillouin zone for blue phase colloidal crystals, where there were none in blue phases without particles or dopants. Particle size and filling fraction of the blue phase defect network are demonstrated as parameters that can directly tune the optical bands and local band gaps. In the blue phase I colloidal crystal with an additionally doped defect network, interestingly, we find an indirect total band gap (with the exception of one point) at the entire edge of SC irreducible zone. Finally, this work demonstrates the role of combining multiple - by symmetry - differently organised components in one photonic crystal material, which offers a novel approach towards tunable soft matter photonic materials.

Analytical instrumentation infrastructure for combinatorial and high-throughput development of formulated discrete and gradient polymeric sensor materials arrays

NASA Astrophysics Data System (ADS)

Potyrailo, Radislav A.; Hassib, Lamyaa

2005-06-01

Multicomponent polymer-based formulations of optical sensor materials are difficult and time consuming to optimize using conventional approaches. To address these challenges, our long-term goal is to determine relationships between sensor formulation and sensor response parameters using new scientific methodologies. As the first step, we have designed and implemented an automated analytical instrumentation infrastructure for combinatorial and high-throughput development of polymeric sensor materials for optical sensors. Our approach is based on the fabrication and performance screening of discrete and gradient sensor arrays. Simultaneous formation of multiple sensor coatings into discrete 4×6, 6×8, and 8×12 element arrays (3-15μL volume per element) and their screening provides not only a well-recognized acceleration in the screening rate, but also considerably reduces or even eliminates sources of variability, which are randomly affecting sensors response during a conventional one-at-a-time sensor coating evaluation. The application of gradient sensor arrays provides additional capabilities for rapid finding of the optimal formulation parameters.

Disintegration of nano-embedded microparticles after deposition on mucus: A mechanistic study.

PubMed

Ruge, Christian A; Bohr, Adam; Beck-Broichsitter, Moritz; Nicolas, Valérie; Tsapis, Nicolas; Fattal, Elias

2016-03-01

The conversion of colloidal drug carriers/polymeric nanoparticles into dry microparticulate powders (e.g., by spray-drying) is a prominent approach to overcome the aerodynamic limitations of these formulations for delivery via inhalation. However, to what extent such nano-embedded microparticles disintegrate into individual/intact nanoparticles after contacting relevant physiological media has so far not been addressed. Polymeric nanoparticles were spray-dried into nano-embedded microparticles (NEMs) using different amounts of trehalose as embedding matrix excipient. Formulations were characterized and then evaluated for their disintegration behavior after aerosolization onto model mucus. Although a rapid and complete aqueous redispersion was observed for specific excipient/nanoparticle weight ratios (i.e., greater than 1/1), the same formulations revealed no disintegration after deposition onto a static mucus layer. Double-labeled NEMs powders (i.e., dual color staining of polymeric nanoparticles and trehalose) demonstrated rapid matrix dissolution, while the nanoparticle aggregates persisted. When deposited onto agitated mucus, however, sufficient disintegration of NEMs into individual polymeric nanoparticles was observed. These findings indicate that mechanical forces are necessary to overcome the attraction between individual nanoparticles found within the NEMs. Thus, it remains questionable whether the lung mechanics (e.g., breathing, mucociliary clearance) acting on these formulations will contribute to the overall disintegration process. Copyright © 2015 Elsevier B.V. All rights reserved.

Doped colloidal artificial spin ice

DOE PAGES

Libál, A.; Reichhardt, C. J. Olson; Reichhardt, C.

2015-10-07

We examine square and kagome artificial spin ice for colloids confined in arrays of double-well traps. Conversely, magnetic artificial spin ices, unlike colloidal and vortex artificial spin ice realizations, allow creation of doping sites through double occupation of individual traps. We find that doping square and kagome ice geometries produces opposite effects. For square ice, doping creates local excitations in the ground state configuration that produce a local melting effect as the temperature is raised. In contrast, the kagome ice ground state can absorb the doping charge without generating non-ground-state excitations, while at elevated temperatures the hopping of individual colloidsmore » is suppressed near the doping sites. Our results indicate that in the square ice, doping adds degeneracy to the ordered ground state and creates local weak spots, while in the kagome ice, which has a highly degenerate ground state, doping locally decreases the degeneracy and creates local hard regions.« less

Doped colloidal artificial spin ice

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

Libál, A.; Reichhardt, C. J. Olson; Reichhardt, C.

We examine square and kagome artificial spin ice for colloids confined in arrays of double-well traps. Conversely, magnetic artificial spin ices, unlike colloidal and vortex artificial spin ice realizations, allow creation of doping sites through double occupation of individual traps. We find that doping square and kagome ice geometries produces opposite effects. For square ice, doping creates local excitations in the ground state configuration that produce a local melting effect as the temperature is raised. In contrast, the kagome ice ground state can absorb the doping charge without generating non-ground-state excitations, while at elevated temperatures the hopping of individual colloidsmore » is suppressed near the doping sites. Our results indicate that in the square ice, doping adds degeneracy to the ordered ground state and creates local weak spots, while in the kagome ice, which has a highly degenerate ground state, doping locally decreases the degeneracy and creates local hard regions.« less

Polymeric Janus Nanoparticles: Recent Advances in Synthetic Strategies, Materials Properties, and Applications.

PubMed

Fan, Xiaoshan; Yang, Jing; Loh, Xian Jun; Li, Zibiao

2018-06-13

Polymeric Janus nanoparticles with two sides of incompatible chemistry have received increasing attention due to their tunable asymmetric structure and unique material characteristics. Recently, with the rapid progress in controlled polymerization combined with novel fabrication techniques, a large array of functional polymeric Janus particles are diversified with sophisticated architecture and applications. In this review, the most recently developed strategies for controlled synthesis of polymeric Janus nanoparticles with well-defined size and complex superstructures are summarized. In addition, the pros and cons of each approach in mediating the anisotropic shapes of polymeric Janus particles as well as their asymmetric spatial distribution of chemical compositions and functionalities are discussed and compared. Finally, these newly developed structural nanoparticles with specific shapes and surface functions orientated applications in different domains are also discussed, followed by the perspectives and challenges faced in the further advancement of polymeric Janus nanoparticles as high performance materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymers as directing agents for motions of chemical and biological species

NASA Astrophysics Data System (ADS)

Tanyeri, Nihan Yonet

This thesis involves descriptions of solid surface modifications with various polymeric materials which were used as a guiding agent for motion of chemical and biological species. Quasi-two dimensional poly(oligoethylene glycol) acrylate polymer brush based molecular conduits have been designed with the goal of regulating and controlling the diffusive transport of molecular, e.g. organic dyes, and ionic species, e.g. AuCl4-, and Cu2+ ions, along predefined 2-D pathways. The transport of these chemical species has been examined by both fluorescence and dark field microscopy. The polymer brushes were formed through microcontact printing of an initiator, followed by surface-initiated Atom Transfer Radical Polymerization (SI-ATRP). SI-ATRP enables both 2-D patterning with a resolution of about 1 micrometer, and control over the resultant polymer brush thickness (which was varied from 10-100 nm). A hydrophilic poly(oligoethylene glycol) acrylate brushe was selected because of its potential to dissolve a wide range of hydrophilic species. The transport of fluorescent species can be directly followed. A non-lithographic fabrication method was developed for mufluidic devices used in the diffusion studies. Singular channel mufluidic device was utilized to study the directed organic dye diffusion. The AuCl4-, and Cu 2+ ion transport was studied by designing molecular devices with two mufluidic channels. We have demonstrated that the various species of interest diffuse much more rapidly along the predefined pathway than along the bare (polymer brush free) regions of the substrate, demonstrating that diffusive conduits for molecular transport can indeed be formed. The protein resistance of poly(N-isopropylacrylamide) (PNIPAM) brushes grafted from silicon wafers was investigated as a function of the chain molecular weight, grafting density, and temperature. Above the lower critical solution temperature (LCST) of 32°C, the collapse of the water swollen chains, determined by ellipsometry, depends on the grafting density and molecular weight. Ellipsometry, radio assay, and fluorescence imaging demonstrated that, below the LCST, the brushes repel protein as effectively as oligoethylene oxide terminated monolayers. Above 32°C, very low levels of protein adsorb on densely grafted brushes, and the amounts of adsorbed protein increase with decreasing brush grafting densities. Brushes that do not exhibit a collapse transition also bind protein, even though the chains remain extended above the LCST. These findings suggest possible mechanisms underlying protein interactions with end-grafted PNIPAM brushes. 3D porous materials on solid surfaces were built to mimic the corneal basement membrane so that we can monitor direction of the corneal epithelia cells behaviors as the surface topography changes. We have used colloidal crystal templating approach to build the 3D porous structures. Polystyrene (PS) colloids were crystallized in a flow cell. The crystals were filled with acrylamide precursor (including photoinitiator, crosslinker) in the oxygen free aqueous solution. After polymerization of acrylamide under UV exposure, PS colloids were dissolved in chloroform. Thus, 3D porous polyacrylamide hydrogels have been fabricated. The various pore sizes at the 3D porous surface have been obtained by using PS colloids with the colloid diameters ranging from 450 nm to 4 mum. Human corneal epithelial cell growth, morphology change and adhesion studies have been conducted on the porous polyacrylamide scaffolds. The effect of pore size on human corneal epithelial cell function has been investigated.

3D investigation on polystyrene colloidal crystals by floatage self-assembly with mixed solvent via synchrotron radiation x-ray phase-contrast computed tomography

NASA Astrophysics Data System (ADS)

Fu, Yanan; Xie, Honglan; Deng, Biao; Du, Guohao; Xiao, Tiqiao

2017-06-01

The floatage self-assembly method was introduced with mixed solvent as the medium of polystyrene sphere suspension to fabricate the colloidal crystal. The three dimensional (3D) void system of the colloidal crystal was noninvasively characterized by synchrotron radiation phase-contrast computed tomography, and the quantitative image analysis was implemented aiming to the polystyrene sphere colloidal crystal. Comparing with gravity sedimentation method, the three samples fabricated from floatage self-assembly with mixed solvents have the lowest porosity, and when ethylene glycol and water were mixed with ratio of 1:1, the lowest porosity of 27.49% could be achieved, that has been very close to the minimum porosity of ordered 3D monodisperse sphere array (26%). In single slices, the porosities and fractal dimension for the voids were calculated. The results showed that two factors would significantly influence the porosity of the whole colloidal crystal: the first deposited sphere layer's orderliness and the sedimentation speed of the spheres. The floatage self-assembly could induce a stable close-packing process, resulted from the powerful nucleation force-lateral capillary force coupled with the mixed solvent to regulate the floating upward speed for purpose of matching the assembly rate.

Aggregative stability of fungicidal nanomodifier based on zinc hydrosilicates

NASA Astrophysics Data System (ADS)

Grishina, Anna; Korolev, Evgeniy

2018-03-01

Currently, there is a strong need of high performance multi functional materials in high-rise construction. Obviously, such materials should be characterized by high strength; but for interior rooms biosafety is important as well. The promising direction to obtain both high strength and maintain biosafety in buildings and structures is to manage the structure of mineral binders by means of fungicidal nanomodifier based on zinc hydrosilicates. In the present work the aggregative stability of colloidal solutions of zinc hydrosilicates after one year of storage was studied. It has been established that the concentration of iron (III) hydroxide used to prepare the precursor of zinc hydrosilicates has a significant effect on the long-term aggregative stability: as the concentration of iron (III) hydroxide increases, the resistance of the fungicidal nanomodifier increases. It was found that, despite the minimal concentration of nano-sized zinc hydrosilicates (0.028%), the colloidal solution possesses a low long-term aggregative stability; while in the initial period (not less than 14 days) the colloidal solution of the nanomodifier is aggregatively stable. It is shown that when the ratio in the colloidal solution of the amount of the substance CH3COOH / SiO2 = 0.43 is reached, an increase in the polymerization rate is observed, which is the main cause of low aggregative stability. Colloidal solutions containing zinc hydrosilicates synthesized at a concentration of iron (III) hydroxide used to produce a precursor equal to 0.7% have a long-term aggregative stability and do not significantly change the reduced particle. Such compositions are to be expediently used for the nanomodifying of building composites in order to control their structure formation and to create conditions that impede the development of various mycelial fungi.

Transparent anodic TiO2 nanotube arrays on plastic substrates for disposable biosensors and flexible electronics.

PubMed

Farsinezhad, Samira; Mohammadpour, Arash; Dalrymple, Ashley N; Geisinger, Jared; Kar, Piyush; Brett, Michael J; Shankar, Karthik

2013-04-01

Exploitation of anodically formed self-organized TiO2 nanotube arrays in mass-manufactured, disposable biosensors, rollable electrochromic displays and flexible large-area solar cells would greatly benefit from integration with transparent and flexible polymeric substrates. Such integration requires the vacuum deposition of a thin film of titanium on the desired substrate, which is then anodized in suitable media to generate TiO2 nanotube arrays. However the challenges associated with control of Ti film morphology, nanotube array synthesis conditions, and film adhesion and transparency, have necessitated the use of substrate heating during deposition to temperatures of at least 300 degrees C and as high as 500 degrees C to generate highly ordered open-pore nanotube arrays, thus preventing the use of polymeric substrates. We report on a film growth technique that exploits atomic peening to achieve high quality transparent TiO2 nanotube arrays with lengths up to 5.1 microm at room temperature on polyimide substrates without the need for substrate heating or substrate biasing or a Kauffman ion source. The superior optical quality and uniformity of the nanotube arrays was evidenced by the high specular reflectivity and the smooth pattern of periodic interferometric fringes in the transmission spectra of the nanotube arrays, from which the wavelength-dependent effective refractive index was extracted for the air-TiO2 composite medium. A fluorescent immunoassay biosensor constructed using 5.1 microm-long transparent titania nanotube arrays (TTNAs) grown on Kapton substrates detected human cardiac troponin I at a concentration of 0.1 microg ml(-1).

Dynamic colloidal sorting on a magnetic bubble lattice

NASA Astrophysics Data System (ADS)

Tierno, Pietro; Soba, Alejandro; Johansen, Tom H.; Sagués, Francesc

2008-11-01

We use a uniaxial garnet film with a magnetic bubble lattice to sort paramagnetic colloidal particles with different diameters, i.e., 1.0 and 2.8μm. We apply an external magnetic field which precesses around an axis normal to the film with a frequency Ω =62.8s-1 and intensity 3120A/m

Superhydrophobic analyte concentration utilizing colloid-pillar array SERS substrates.

PubMed

Wallace, Ryan A; Charlton, Jennifer J; Kirchner, Teresa B; Lavrik, Nickolay V; Datskos, Panos G; Sepaniak, Michael J

2014-12-02

The ability to detect a few molecules present in a large sample is of great interest for the detection of trace components in both medicinal and environmental samples. Surface enhanced Raman spectroscopy (SERS) is a technique that can be utilized to detect molecules at very low absolute numbers. However, detection at trace concentration levels in real samples requires properly designed delivery and detection systems. The following work involves superhydrophobic surfaces that have as a framework deterministic or stochastic silicon pillar arrays formed by lithographic or metal dewetting protocols, respectively. In order to generate the necessary plasmonic substrate for SERS detection, simple and flow stable Ag colloid was added to the functionalized pillar array system via soaking. Native pillars and pillars with hydrophobic modification are used. The pillars provide a means to concentrate analyte via superhydrophobic droplet evaporation effects. A ≥ 100-fold concentration of analyte was estimated, with a limit of detection of 2.9 × 10(-12) M for mitoxantrone dihydrochloride. Additionally, analytes were delivered to the surface via a multiplex approach in order to demonstrate an ability to control droplet size and placement for scaled-up uses in real world applications. Finally, a concentration process involving transport and sequestration based on surface treatment selective wicking is demonstrated.

Camptothecin prodrug nanomicelle based on a boronate ester-linked diblock copolymer as the carrier of doxorubicin with enhanced cellular uptake.

PubMed

Gao, Ya; Xiao, Yi; Liu, Shiyuan; Yu, Jiahui

2018-02-01

A novel pH-sensitive polymeric prodrug of camptothecin (CPT) by polymerizing γ-camptothecin-glutamate N-carboxyanhydride (Glu (CPT)-NCA) on boronate ester-linked poly (ethyleneglycol) (PEG) directly via the amine-initiated ring open polymerization (ROP) has been developed. The resulting amphiphilic prodrug (mPEG-BC-PGluCPT) could self-assemble into nanoparticles and encapsulate doxorubicin (Dox) simultaneously in aqueous solution for dual-drug delivery. The formation of polymeric prodrug micelles (mPEG-BC@PGluCPT) was confirmed by the measurements of critical aggregation concentration (CAC), particle size, and morphology observations. The mPEG-BC@PGluCPT micelles were colloidally stable in solutions for two weeks. Polymeric prodrug micelles mPEG-BC@PGluCPT and Dox-loaded micelles mPEG-BC@PGluCPT⋅Dox showed sustained drug release profiles over 48 h. As expected, drug release was accelerated by the decreasement of pH value from 7.4 to 6.0, which demonstrated pH-dependent manner of drug release. Additionally, it was found that cellular uptake of mPEG-BC@PGluCPT⋅Dox micelles on HepG2 cells was higher than that on HL-7702 cells, especially in culture medium at pH 6.0. The enhanced cellular uptake of mPEG-BC@PGluCPT⋅Dox micelles under acidic condition on HepG2 cells resulted in the higher cytotoxicity of mPEG-BC@PGluCPT⋅Dox micelles at acidic pH than that at pH 7.4.

Investigation of Proposed Process Sequence for the Array Automated Assembly Task, Phase 2. [low cost silicon solar array fabrication

NASA Technical Reports Server (NTRS)

Mardesich, N.; Garcia, A.; Bunyan, S.; Pepe, A.

1979-01-01

The technological readiness of the proposed process sequence was reviewed. Process steps evaluated include: (1) plasma etching to establish a standard surface; (2) forming junctions by diffusion from an N-type polymeric spray-on source; (3) forming a p+ back contact by firing a screen printed aluminum paste; (4) forming screen printed front contacts after cleaning the back aluminum and removing the diffusion oxide; (5) cleaning the junction by a laser scribe operation; (6) forming an antireflection coating by baking a polymeric spray-on film; (7) ultrasonically tin padding the cells; and (8) assembling cell strings into solar circuits using ethylene vinyl acetate as an encapsulant and laminating medium.

Polymeric spatial resolution test patterns for mass spectrometry imaging using nano-thermal analysis with atomic force microscopy

DOE PAGES

Tai, Tamin; Kertesz, Vilmos; Lin, Ming -Wei; ...

2017-05-11

As the spatial resolution of mass spectrometry imaging technologies has begun to reach into the nanometer regime, finding readily available or easily made resolution reference materials has become particularly challenging for molecular imaging purposes. This study describes the fabrication, characterization and use of vertical line array polymeric spatial resolution test patterns for nano-thermal analysis/atomic force microscopy/mass spectrometry chemical imaging.

Polymeric spatial resolution test patterns for mass spectrometry imaging using nano-thermal analysis with atomic force microscopy

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

Tai, Tamin; Kertesz, Vilmos; Lin, Ming -Wei

As the spatial resolution of mass spectrometry imaging technologies has begun to reach into the nanometer regime, finding readily available or easily made resolution reference materials has become particularly challenging for molecular imaging purposes. This study describes the fabrication, characterization and use of vertical line array polymeric spatial resolution test patterns for nano-thermal analysis/atomic force microscopy/mass spectrometry chemical imaging.

Magnetic properties of the Fe{sup II} spin crossover complex in emulsion polymerization of trifluoroethylmethacrylate using poly(vinyl alcohol)

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

Suzuki, Atsushi, E-mail: suzuki@mat.usp.ac.j; Iguchi, Motoi; Oku, Takeo

2010-04-15

Influence of chemical substitution in the Fe{sup II} spin crossover complex on magnetic properties in emulsion polymerization of trifluoroethylmethacrylate using poly(vinyl alcohol) as a protective colloid was investigated near its high spin/low spin (HS/LS) phase transition. The obvious bi-stability of the HS/LS phase transition was considered by the identification of multiple spin states between the quintet (S=2) states to single state (S=0) across the excited triplet state (S=1). Magnetic parameters of gradual shifts of anisotropy g-tensor supported by the molecular distortion of the spin crossover complex would arise from a Jahn-Teller effect regarding ligand field theory on the basis ofmore » a B3LYP density functional theory using electron spin resonance (ESR) spectrum and X-ray powder diffraction. - Graphical abstract: AFM surface image of the emulsion particles with the spin crossover complex.« less

Polymer functionalized nanocomposites for metals removal from water and wastewater: An overview.

PubMed

Lofrano, Giusy; Carotenuto, Maurizio; Libralato, Giovanni; Domingos, Rute F; Markus, Arjen; Dini, Luciana; Gautam, Ravindra Kumar; Baldantoni, Daniela; Rossi, Marco; Sharma, Sanjay K; Chattopadhyaya, Mahesh Chandra; Giugni, Maurizio; Meric, Sureyya

2016-04-01

Pollution by metal and metalloid ions is one of the most widespread environmental concerns. They are non-biodegradable, and, generally, present high water solubility facilitating their environmental mobilisation interacting with abiotic and biotic components such as adsorption onto natural colloids or even accumulation by living organisms, thus, threatening human health and ecosystems. Therefore, there is a high demand for effective removal treatments of heavy metals, making the application of adsorption materials such as polymer-functionalized nanocomposites (PFNCs), increasingly attractive. PFNCs retain the inherent remarkable surface properties of nanoparticles, while the polymeric support materials provide high stability and processability. These nanoparticle-matrix materials are of great interest for metals and metalloids removal thanks to the functional groups of the polymeric matrixes that provide specific bindings to target pollutants. This review discusses PFNCs synthesis, characterization and performance in adsorption processes as well as the potential environmental risks and perspectives. Copyright © 2016 Elsevier Ltd. All rights reserved.

Multifractal detrended fluctuation analysis of intensity time series of photons scattered by tracer particles within a polymeric gel

NASA Astrophysics Data System (ADS)

Telesca, Luciano; Haro-Pérez, Catalina; Moreno-Torres, L. Rebeca; Ramirez-Rojas, Alejandro

2018-01-01

Some properties of spatial confinement of tracer colloidal particles within polyacrylamide dispersions are studied by means of the well-known dynamic light scattering (DLS) technique. DLS allows obtaining sequences of elapsed times of scattered photons. In this work, the aqueous polyacrylamide dispersion has no crosslinking and the volume fraction occupied by the tracer particles is 0.02 %. Our experimental setup provides two sequences of photons scattered by the same scattering volume that corresponds to two simultaneous experiments (Channel A and Channel B). By integration of these sequences, the intensity time series are obtained. We find that both channels are antipersistent with Hurst exponent, H ∼0.43 and 0.36, respectively. The antipersistence of the intensity time series indicates a subdiffusive dynamics of the tracers in the polymeric network, which is in agreement with the time dependence of the tracer's mean square displacement.

DNA-imprinted polymer nanoparticles with monodispersity and prescribed DNA-strand patterns

NASA Astrophysics Data System (ADS)

Trinh, Tuan; Liao, Chenyi; Toader, Violeta; Barłóg, Maciej; Bazzi, Hassan S.; Li, Jianing; Sleiman, Hanadi F.

2018-02-01

As colloidal self-assembly increasingly approaches the complexity of natural systems, an ongoing challenge is to generate non-centrosymmetric structures. For example, patchy, Janus or living crystallization particles have significantly advanced the area of polymer assembly. It has remained difficult, however, to devise polymer particles that associate in a directional manner, with controlled valency and recognition motifs. Here, we present a method to transfer DNA patterns from a DNA cage to a polymeric nanoparticle encapsulated inside the cage in three dimensions. The resulting DNA-imprinted particles (DIPs), which are 'moulded' on the inside of the DNA cage, consist of a monodisperse crosslinked polymer core with a predetermined pattern of different DNA strands covalently 'printed' on their exterior, and further assemble with programmability and directionality. The number, orientation and sequence of DNA strands grafted onto the polymeric core can be controlled during the process, and the strands are addressable independently of each other.

Probing actin polymerization by intermolecular cross-linking.

PubMed

Millonig, R; Salvo, H; Aebi, U

1988-03-01

We have used N,N'-1,4-phenylenebismaleimide, a bifunctional sulfhydryl cross-linking reagent, to probe the oligomeric state of actin during the early stages of its polymerization into filaments. We document that one of the first steps in the polymerization of globular monomeric actin (G-actin) under a wide variety of ionic conditions is the dimerization of a significant fraction of the G-actin monomer pool. As polymerization proceeds, the yield of this initial dimer ("lower" dimer with an apparent molecular mass of 86 kD by SDS-PAGE [LD]) is attenuated, while an actin filament dimer ("upper" dimer with an apparent molecular mass of 115 kD by SDS-PAGE [UD] as characterized [Elzinga, M., and J. J. Phelan. 1984. Proc. Natl. Acad. Sci. USA. 81:6599-6602]) is formed. This shift from LD to UD occurs concomitant with formation of filaments as assayed by N-(1-pyrenyl)iodoacetamide fluorescence enhancement and electron microscopy. Isolated cross-linked LD does not form filaments, while isolated cross-linked UD will assemble into filaments indistinguishable from those polymerized from unmodified G-actin under typical filament-forming conditions. The presence of cross-linked LD does not effect the kinetics of polymerization of actin monomer, whereas cross-linked UD shortens the "lag phase" of the polymerization reaction in a concentration-dependent fashion. Several converging lines of evidence suggest that, although accounting for a significant oligomeric species formed during early polymerization, the LD is incompatible with the helical symmetry defining the mature actin filament; however, it could represent the interfilament dimer found in paracrystalline arrays or filament bundles. Furthermore, the LD is compatible with the unit cell structure and symmetry common to various types of crystalline actin arrays (Aebi, U., W. E. Fowler, G. Isenberg, T. D. Pollard, and P. R. Smith. 1981. J. Cell Biol. 91:340-351) and might represent the major structural state in which a mutant beta-actin (Leavitt, J., G. Bushar, T. Kakunaga, H. Hamada, T. Hirakawa, D. Goldman, and C. Merril. 1982. Cell. 28:259-268) is arrested under polymerizing conditions.

Construction of near-infrared photonic crystal glucose-sensing materials for ratiometric sensing of glucose in tears.

PubMed

Hu, Yumei; Jiang, Xiaomei; Zhang, Laiying; Fan, Jiao; Wu, Weitai

2013-10-15

Noninvasive monitoring of glucose in tears is highly desirable in tight glucose control. The polymerized crystalline colloidal array (PCCA) that can be incorporated into contact lens represents one of the most promising materials for noninvasive monitoring of glucose in tears. However, low sensitivity and slow time response of the PCCA reported in previous arts has limited its clinical utility. This paper presents a new PCCA, denoted as NIR-PCCA, comprising a CCA of glucose-responsive sub-micrometered poly(styrene-co-acrylamide-co-3-acrylamidophenylboronic acid) microgels embedded within a slightly positive charged hydrogel matrix of poly(acrylamide-co-2-(dimethylamino)ethyl acrylate). This newly designed NIR-PCCA can reflect near-infrared (NIR) light, whose intensity (at 1722 nm) would decrease evidently with increasing glucose concentration over the physiologically relevant range in tears. The lowest glucose concentration reliably detectable was as low as ca. 6.1 μg/dL. The characteristic response time τ(sensing) was 22.1±0.2s when adding glucose to 7.5 mg/dL, and the higher the glucose concentration is, the faster the time response. Such a rationally designed NIR-PCCA is well suited for ratiometric NIR sensing of tear glucose under physiological conditions, thereby likely to bring this promising glucose-sensing material to the forefront of analytical devices for diabetes. Copyright © 2013 Elsevier B.V. All rights reserved.

Fabrication of all-inorganic nanocrystal solids through matrix encapsulation of nanocrystal arrays.

PubMed

Kinder, Erich; Moroz, Pavel; Diederich, Geoffrey; Johnson, Alexa; Kirsanova, Maria; Nemchinov, Alexander; O'Connor, Timothy; Roth, Dan; Zamkov, Mikhail

2011-12-21

A general strategy for low-temperature processing of colloidal nanocrystals into all-inorganic films is reported. The present methodology goes beyond the traditional ligand-interlinking scheme and relies on encapsulation of morphologically defined nanocrystal arrays into a matrix of a wide-band gap semiconductor, which preserves optoelectronic properties of individual nanoparticles while rendering the nanocrystal film photoconductive. Fabricated solids exhibit excellent thermal stability, which is attributed to the heteroepitaxial structure of nanocrystal-matrix interfaces, and show compelling light-harvesting performance in prototype solar cells. © 2011 American Chemical Society

Pentacene-based organic thin film transistors, integrated circuits, and active matrix displays on polymeric substrates

NASA Astrophysics Data System (ADS)

Sheraw, Christopher Duncan

2003-10-01

Organic thin film transistors are attractive candidates for a variety of low cost, large area commercial electronics including smart cards, RF identification tags, and flat panel displays. Of particular interest are high performance organic thin film transistors (TFTs) that can be fabricated on flexible polymeric substrates allowing low-cost, lightweight, rugged electronics such as flexible active matrix displays. This thesis reports pentacene organic thin film transistors fabricated on flexible polymeric substrates with record performance, the fastest photolithographically patterned organic TFT integrated circuits on polymeric substrates reported to date, and the fabrication of the organic TFT backplanes used to build the first organic TFT-driven active matrix liquid crystal display (AMLCD), also the first AMLCD on a flexible substrate, ever reported. In addition, the first investigation of functionalized pentacene derivatives used as the active layer in organic thin film transistors is reported. A low temperature (<110°C) process technology was developed allowing the fabrication of high performance organic TFTs, integrated circuits, and large TFT arrays on flexible polymeric substrates. This process includes the development of a novel water-based photolithographic active layer patterning process using polyvinyl alcohol that allows the patterning of organic semiconductor materials for elimination of active layer leakage current without causing device degradation. The small molecule aromatic hydrocarbon pentacene was used as the active layer material to fabricate organic TFTs on the polymeric material polyethylene naphthalate with field-effect mobility as large as 2.1 cm2/V-s and on/off current ratio of 108. These are the best values reported for organic TFTs on polymeric substrates and comparable to organic TFTs on rigid substrates. Analog and digital integrated circuits were also fabricated on polymeric substrates using pentacene TFTs with propagation delay as low as 38 musec and clocked digital circuits that operated at 1.1 kHz. These are the fastest photolithographically patterned organic TFT circuits on polymeric substrates reported to date. Finally, 16 x 16 pentacene TFT pixel arrays were fabricated on polymeric substrates and integrated with polymer dispersed liquid crystal to build an AMLCD. The pixel arrays showed good optical response to changing data signals when standard quarter-VGA display waveforms were applied. This result marks the first organic TFT-driven active matrix liquid crystal display ever reported as well as the first active matrix liquid crystal display on a flexible polymeric substrate. Lastly, functionalized pentacene derivatives were used as the active layer in organic thin film transistor materials. Functional groups were added to the pentacene molecule to influence the molecular ordering so that the amount of pi-orbital overlap would be increased allowing the potential for improved field-effect mobility. The functionalization of these materials also improves solubility allowing for the possibility of solution-processed devices and increased oxidative stability. Organic thin film transistors were fabricated using five different functionalized pentacene active layers. Devices based on the pentacene derivative triisopropylsilyl pentacene were found to have the best performance with field-effect mobility as large as 0.4 cm 2/V-s.

Mechanism of in situ surface polymerization of gallic acid in an environmental-inspired preparation of carboxylated core-shell magnetite nanoparticles.

PubMed

Tóth, Ildikó Y; Szekeres, Márta; Turcu, Rodica; Sáringer, Szilárd; Illés, Erzsébet; Nesztor, Dániel; Tombácz, Etelka

2014-12-30

Magnetite nanoparticles (MNPs) with biocompatible coatings are good candidates for MRI (magnetic resonance imaging) contrasting, magnetic hyperthermia treatments, and drug delivery systems. The spontaneous surface induced polymerization of dissolved organic matter on environmental mineral particles inspired us to prepare carboxylated core-shell MNPs by using a ubiquitous polyphenolic precursor. Through the adsorption and in situ surface polymerization of gallic acid (GA), a polygallate (PGA) coating is formed on the nanoparticles (PGA@MNP) with possible antioxidant capacity. The present work explores the mechanism of polymerization with the help of potentiometric acid-base titration, dynamic light scattering (for particle size and zeta potential determination), UV-vis (UV-visible light spectroscopy), FTIR-ATR (Fourier-transformed infrared spectroscopy by attenuated total reflection), and XPS (X-ray photoelectron spectroscopy) techniques. We observed the formation of ester and ether linkages between gallate monomers both in solution and in the adsorbed state. Higher polymers were formed in the course of several weeks both on the surface of nanoparticles and in the dispersion medium. The ratio of the absorbances of PGA supernatants at 400 and 600 nm (i.e., the E4/E6 ratio commonly used to characterize the degree of polymerization of humic materials) was determined to be 4.3, similar to that of humic acids. Combined XPS, dynamic light scattering, and FTIR-ATR results revealed that, prior to polymerization, the GA monomers became oxidized to poly(carboxylic acid)s due to ring opening while Fe(3+) ions reduced to Fe(2+). Our published results on the colloidal and chemical stability of PGA@MNPs are referenced thoroughly in the present work. Detailed studies on biocompatibility, antioxidant property, and biomedical applicability of the particles will be published.

Solution-processed phase-change VO(2) metamaterials from colloidal vanadium oxide (VO(x)) nanocrystals.

PubMed

Paik, Taejong; Hong, Sung-Hoon; Gaulding, E Ashley; Caglayan, Humeyra; Gordon, Thomas R; Engheta, Nader; Kagan, Cherie R; Murray, Christopher B

2014-01-28

We demonstrate thermally switchable VO2 metamaterials fabricated using solution-processable colloidal nanocrystals (NCs). Vanadium oxide (VOx) NCs are synthesized through a nonhydrolytic reaction and deposited from stable colloidal dispersions to form NC thin films. Rapid thermal annealing transforms the VOx NC thin films into monoclinic, nanocrystalline VO2 thin films that show a sharp, reversible metal-insulator phase transition. Introduction of precise concentrations of tungsten dopings into the colloidal VOx NCs enables the still sharp phase transition of the VO2 thin films to be tuned to lower temperatures as the doping level increases. We fabricate "smart", differentially doped, multilayered VO2 films to program the phase and therefore the metal-insulator behavior of constituent vertically structured layers with temperature. With increasing temperature, we tailored the optical response of multilayered films in the near-IR and IR regions from that of a strong light absorber, in a metal-insulator structure, to that of a Drude-like reflector, characteristic of a pure metallic structure. We demonstrate that nanocrystal-based nanoimprinting can be employed to pattern multilayered subwavelength nanostructures, such as three-dimensional VO2 nanopillar arrays, that exhibit plasmonic dipolar responses tunable with a temperature change.

Mechanistic principles of colloidal crystal growth by evaporation-induced convective steering.

PubMed

Brewer, Damien D; Allen, Joshua; Miller, Michael R; de Santos, Juan M; Kumar, Satish; Norris, David J; Tsapatsis, Michael; Scriven, L E

2008-12-02

We simulate evaporation-driven self-assembly of colloidal crystals using an equivalent network model. Relationships between a regular hexagonally close-packed array of hard, monodisperse spheres, the associated pore space, and selectivity mechanisms for face-centered cubic microstructure propagation are described. By accounting for contact line rearrangement and evaporation at a series of exposed menisci, the equivalent network model describes creeping flow of solvent into and through a rigid colloidal crystal. Observations concerning colloidal crystal growth are interpreted in terms of the convective steering hypothesis, which posits that solvent flow into and through the pore space of the crystal may play a major role in colloidal self-assembly. Aspects of the convective steering and deposition of high-Peclet-number rigid spherical particles at a crystal boundary are inferred from spatially resolved solvent flow into the crystal. Gradients in local flow through boundary channels were predicted due to the channels' spatial distribution relative to a pinned free surface contact line. On the basis of a uniform solvent and particle flux as the criterion for stability of a particular growth plane, these network simulations suggest the stability of a declining {311} crystal interface, a symmetry plane which exclusively propagates fcc microstructure. Network simulations of alternate crystal planes suggest preferential growth front evolution to the declining {311} interface, in consistent agreement with the proposed stability mechanism for preferential fcc microstructure propagation in convective assembly.

Improvement in glucose biosensing response of electrochemically grown polypyrrole nanotubes by incorporating crosslinked glucose oxidase.

PubMed

Palod, Pragya Agar; Singh, Vipul

2015-10-01

In this paper a novel enzymatic glucose biosensor has been reported in which platinum coated alumina membranes (Anodisc™s) have been employed as templates for the growth of polypyrrole (PPy) nanotube arrays using electrochemical polymerization. The PPy nanotube arrays were grown on Anodisc™s of pore diameter 100 nm using potentiostatic electropolymerization. In order to optimize the polymerization time, immobilization of glucose oxidase (GOx) was first performed using physical adsorption followed by measuring its biosensing response which was examined amperometrically for increasing concentrations of glucose. In order to further improve the sensing performance of the biosensor fabricated for optimum polymerization duration, enzyme immobilization was carried out using cross-linking with glutaraldehyde and bovine serum albumin (BSA). Approximately six fold enhancement in the sensitivity was observed in the fabricated electrodes. The biosensors also showed a wide range of linear operation (0.2-13 mM), limit of detection of 50 μM glucose concentration, excellent selectivity for glucose, notable reliability for real sample detection and substantially improved shelf life. Copyright © 2015 Elsevier B.V. All rights reserved.

Laser polymerization-based novel lift-off technique

NASA Astrophysics Data System (ADS)

Bhuian, B.; Winfield, R. J.; Crean, G. M.

2009-03-01

The fabrication of microstructures by two-photon polymerization has been widely reported as a means of directly writing three-dimensional nanoscale structures. In the majority of cases a single point serial writing technique is used to form a polymer model. Single layer writing can also be used to fabricate two-dimensional patterns and we report an extension of this capability by using two-photon polymerization to form a template that can be used as a sacrificial layer for a novel lift-off process. A Ti:sapphire laser, with wavelength 795 nm, 80 MHz repetition rate, 100 fs pulse duration and an average power of 700 mW, was used to write 2D grid patterns with pitches of 0.8 and 1.0 μm in a urethane acrylate resin that was spun on to a lift-off base layer. This was overcoated with gold and the grid lifted away to leave an array of gold islands. The optical transmission properties of the gold arrays were measured and found to be in agreement with a rigorous coupled-wave analysis simulation.

DHS Internship Summary-Crystal Assembly at Different Length Scales

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

Mishchenko, L

2009-08-06

I was part of a project in which in situ atomic force microscopy (AFM) was used to monitor growth and dissolution of atomic and colloidal crystals. At both length scales, the chemical environment of the system greatly altered crystal growth and dissolution. Calcium phosphate was used as a model system for atomic crystals. A dissolution-reprecipitation reaction was observed in this first system, involving the conversion of brushite (DCPD) to octacalcium phosphate (OCP). In the second system, polymeric colloidal crystals were dissolved in an ionic solvent, revealing the underlying structure of the crystal. The dissolved crystal was then regrown through anmore » evaporative step method. Recently, we have also found that colloids can be reversibly deposited in situ onto an ITO (indium tin oxide) substrate via an electrochemistry setup. The overall goal of this project was to develop an understanding of the mechanisms that control crystallization and order, so that these might be controlled during material synthesis. Controlled assembly of materials over a range of length scales from molecules to nanoparticles to colloids is critical for designing new materials. In particular, developing materials for sensor applications with tailorable properties and long range order is important. In this work, we examine two of these length scales: small molecule crystallization of calcium phosphate (whose crystal phases include DCPD, OCP, and HAP) and colloidal crystallization of Poly(methyl methacrylate) beads. Atomic Force Microscopy is ideal for this line of work because it allows for the possibility of observing non-conducting samples in fluid during growth with high resolution ({approx} 10 nm). In fact, during atomic crystal growth one can observe changes in atomic steps, and with colloidal crystals, one can monitor the individual building blocks of the crystal. Colloids and atoms crystallize under the influence of different forces acting at different length scales as seen in Table 1. In particular, molecular crystals, which are typically dominated by ionic and covalent bonding, are an order of magnitude more strongly bonded than colloidal crystals. In molecular crystals, ordering is driven by the interaction potentials between molecules. By contrast, colloidal assembly is a competition between the repulsive electrostatic forces that prevent aggregation in solution (due to surface charge), and short-range van der Waals and entropic forces that leads to ordering. Understanding atomic crystallization is fundamentally important for fabrication of tailorable crystalline materials, for example for biological or chemical sensors. The transformation of brushite to OCP not only serves as a model system for atomic crystal growth (applicable to many other crystal growth processes), but is also important in bone cements. Colloidal crystals have unique optical properties which respond to chemical and mechanical stimuli, making them very important for sensing applications. The mechanism of colloidal crystal assembly is thus fundamentally important. Our in situ dissolution and regrowth experiments are one good method of analyzing how these crystals pack under different conditions and how defect sites are formed and filled. In these experiments, a silica additive was used to strengthen the colloidal crystal during initial assembly (ex situ) and to increase domain size and long range order. Reversible electrodeposition of colloids onto a conductive substrate (ITO in our case) is another system which can further our knowledge of colloidal assembly. This experiment holds promise of allowing in situ observation of colloidal crystal growth and the influence of certain additives on crystal order. The ultimate goal would be to achieve long range order in these crystals by changing the surface charge or the growth environment.« less

Fractionation of Exosomes and DNA using Size-Based Separation at the Nanoscale

NASA Astrophysics Data System (ADS)

Wunsch, Benjamin; Smith, Joshua; Wang, Chao; Gifford, Stacey; Brink, Markus; Bruce, Robert; Solovitzky, Gustavo; Austin, Robert; Astier, Yann

Exosomes, a key target of ``liquid biopsies'', are nano-vesicles found in nearly all biological fluids. Exosomes are secreted by eukaryotic and prokaryotic cells alike, and contain information about their originating cells, including surface proteins, cytoplasmic proteins, and nucleic acids. One challenge in studying exosome morphology is the difficulty of sorting exosomes by size and surface markers. Common separation techniques for exosomes include ultracentrifugation and ultrafiltration, for preparation of large volume samples, but these techniques often show contamination and significant heterogeneity between preparations. To date, deterministic lateral displacement (DLD) pillar arrays in silicon have proven an efficient technology to sort, separate, and enrich micron-scale particles including human parasites, eukaryotic cells, blood cells, and circulating tumor cells in blood; however, the DLD technology has never been translated to the true nanoscale, where it could function on bio-colloids such as exosomes. We have fabricated nanoscale DLD (nanoDLD) arrays capable of rapidly sorting colloids down to 20 nm in continuous flow, and demonstrated size sorting of individual exosome vesicles and dsDNA polymers, opening the potential for on-chip biomolecule separation and diagnosti

Rheotaxis of elongated platinum-gold nanoswimmers

NASA Astrophysics Data System (ADS)

Brosseau, Quentin; Wu, Yang; Ristroph, Leif; Zhang, Jun; Ward, Michael; Shelley, Michael

2017-11-01

Directed motion of self-propelled colloids has attracted much attention as a possible means to transport microscopic cargo to desired locations. However, active colloids, such as our gold-platinum (Au-Pt) bi-metallic motors ( 2 micrometers) that are powered by hydrogen peroxide (H2O2), are subjected to Brownian motion and move diffusively. These swimmers can be directed via interactions with structured substrates, e.g. within an array of asymmetric pillars. Our current study focuses on realizing the directed motion in an imposed open flow, of these active nanorods. This dynamic response, often referred to as ``rheotaxis'', is found in many marine organisms. The effect of flow geometry and flow characteristics will be discussed in more details.

High-definition polymeric membranes: construction of 3D lithographed channel arrays through control of natural building blocks dynamics.

PubMed

Speranza, Valentina; Trotta, Francesco; Drioli, Enrico; Gugliuzza, Annarosa

2010-02-01

The fabrication of well-defined interfaces is in high demand in many fields of biotechnologies. Here, high-definition membrane-like arrays are developed through the self-assembly of water droplets, which work as natural building blocks for the construction of ordered channels. Solution viscosity together with the dynamics of the water droplets can decide the final formation of three-dimensional well-ordered patterns resembling anodic structures, especially because solvents denser than water are used. Particularly, the polymer solution viscosity is demonstrated to be a powerful tool for control of the mobility of submerged droplets during the microfabrication process. The polymeric patterns are structured at very high levels of organization and exhibit well-established transport-surface property relationships, considered basics for any types of advanced biotechnologies.

Thermally Stable Gold Nanoparticles with a Crosslinked Diblock Copolymer Shell

NASA Astrophysics Data System (ADS)

Jang, Se Gyu; Khan, Anzar; Hawker, Craig J.; Kramer, Edward J.

2010-03-01

The use of polymer-coated Au nanoparticles prepared using oligomeric- or polymeric-ligands tethered by Au-S bonds for incorporation into block copolymer templates under thermal processing has been limited due to dissociation of the Au-S bond at T > 100^oC where compromises their colloidal stability. We report a simple route to prepare sub-5nm gold nanoparticles with a thermally stable polymeric shell. An end-functional thiol ligand consisting of poly(styrene-b-1,2&3,4-isoprene-SH) is synthesized by anionic polymerization. After a standard thiol ligand synthesis of Au nanoparticles, the inner PI block is cross-linked through reaction with 1,1,3,3-tetramethyldisiloxane. Gold nanoparticles with the cross-linked shell are stable in organic solvents at 160^oC as well as in block copolymer films of PS-b-P2VP annealed in vacuum at 170^oC for several days. These nanoparticles can be designed to strongly segregate to the PS-P2VP interface resulting in very large Au nanoparticle volume fractions φp without macrophase separation as well as transitions between lamellar and bicontinuous morphologies as φp increases.

A solid colloidal drug delivery system for the eye: encapsulation of pilocarpin in nanoparticles.

PubMed

Harmia, T; Speiser, P; Kreuter, J

1986-01-01

The present study was undertaken in order to encapsulate pilocarpin into nanoparticles. Two principally different methods for manufacturing these particles were investigated. Firstly, pilocarpin was dissolved in an aqueous medium in which the polymerization was carried out, and secondly, the polymerizing monomer was kept saturated with the drug solution under acidic conditions resulting in an incorporation into the nanoparticles in an aqueous environment. The amount of pilocarpin that could be incorporated into the nanoparticles was found to be largely influenced by the temperature at which the nanoparticles were produced and by the stabilizers used. At low temperatures, up to 60 per cent of pilocarpin nitrate could be encapsulated into butylcyanoacrylate nanoparticles using emulsion polymerization techniques. Larger amounts of pilocarpin could not be incorporated because of the hydrophilicity of the salts of this drug. The physico-chemical characteristics of the nanoparticles are reported: the particle size and morphology were determined by scanning and transmission electron microscopy and photon correlation spectrometry. The average particle size was about 100 nm. The results obtained in this study show that photon correlation spectrometry is a suitable method for the sizing of nanoparticles.

Physico-chemical strategies to enhance stability and drug retention of polymeric micelles for tumor-targeted drug delivery

PubMed Central

Shi, Yang; Lammers, Twan; Storm, Gert; Hennink, Wim E.

2017-01-01

Polymeric micelles (PM) have been extensively used for tumor-targeted delivery of hydrophobic anti-cancer drugs. The lipophilic core of PM is naturally suitable for loading hydrophobic drugs and the hydrophilic shell endows them with colloidal stability and stealth properties. Decades of research on PM have resulted in tremendous numbers of PM-forming amphiphilic polymers, and approximately a dozen micellar nanomedicines have entered the clinic. The first generation of PM can be considered solubilizers of hydrophobic drugs, with short circulation times resulting from poor micelle stability and unstable drug entrapment. To more optimally exploit the potential of PM for targeted drug delivery, several physical (e.g. π-π stacking, stereocomplexation, hydrogen bonding, host-guest complexation and coordination interaction) and chemical (e.g. free radical polymerization, click chemistry, disulfide and hydrazone bonding) strategies have been developed to improve micelle stability and drug retention. In this review, we describe the most promising physico-chemical approaches to enhance micelle stability and drug retention, and we summarize how these strategies have resulted in systems with promising therapeutic efficacy in animal models, paving the way for clinical translation. PMID:27413999

3-Dimensional Colloidal Crystals From Hollow Spheres

NASA Astrophysics Data System (ADS)

Zhang, Jian; Work, William J.; Sanyal, Subrata; Lin, Keng-Hui; Yodh, A. G.

2000-03-01

We have succeeded in synthesizing submicron-sized, hollow PMMA spheres and self-assembling them into colloidal crystalline structures using the depletion force. The resulting structures can be used as templates to make high refractive-index contrast, porous, inorganic structures without the need to use calcination or chemical-etching. With the method of emulsion polymerization, we managed to coat a thin PMMA shell around a swellable P(MMA/MAA/EGDMA) core. After neutralization and heating above the glass transition temperature of PMMA, we obtained water-swollen hydrogel particles encapsulated in PMMA shells. These composite particles become hollow spheres after drying. We characterized the particles with both transmission electron microscopy (TEM) and dynamic light scattering (DLS). The TEM results confirmed that each sphere has a hollow core. The DLS results showed that our hollow spheres are submicron-sized, with a swelling ratio of at least 25%, and with a polydispersity less than 5%. We anticipate using this method in the near-future to encapsulate ferrofluid emulsion droplets and liquid crystal droplets.

Molecular engineering of fracture energy dissipating sacrificial bonds into cellulose nanocrystal nanocomposites.

PubMed

McKee, Jason R; Huokuna, Johannes; Martikainen, Lahja; Karesoja, Mikko; Nykänen, Antti; Kontturi, Eero; Tenhu, Heikki; Ruokolainen, Janne; Ikkala, Olli

2014-05-12

Even though nanocomposites have provided a plethora of routes to increase stiffness and strength, achieving increased toughness with suppressed catastrophic crack growth has remained more challenging. Inspired by the concepts of mechanically excellent natural nanomaterials, one-component nanocomposites were fabricated involving reinforcing colloidal nanorod cores with polymeric grafts containing supramolecular binding units. The concept is based on mechanically strong native cellulose nanocrystals (CNC) grafted with glassy polymethacrylate polymers, with side chains that contain 2-ureido-4[1H]-pyrimidone (UPy) pendant groups. The interdigitation of the grafts and the ensuing UPy hydrogen bonds bind the nanocomposite network together. Under stress, UPy groups act as sacrificial bonds: simultaneously providing adhesion between the CNCs while allowing them to first orient and then gradually slide past each other, thus dissipating fracture energy. We propose that this architecture involving supramolecular binding units within side chains of polymer grafts attached to colloidal reinforcements opens generic approaches for tough nanocomposites. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Particulate Coacervation of Associative Polymer Brushes-Grafted Nanoparticles To Produce Structurally Stable Pickering Emulsions.

PubMed

Yang, Taeseung; Choi, Sang Koo; Park, Daehwan; Lee, Yea Ram; Chung, Chan Bok; Kim, Jin Woong

2016-12-20

This study introduces a new type of associative nanoparticle (ANP) that provides controlled chain-to-chain attraction with an associative polymer rheology modifier (APRM) to produce highly stable Pickering emulsions. The ANPs were synthesized by grafting hydrophobically modified hygroscopic zwitterionic poly(2-methacryloyloxyethyl phosphorylcholine-co-stearyl methacrylate) brushes onto 20 nm sized silica NPs via surface-mediated living radical polymerization. The ANP-stabilized Pickering emulsions show significant viscosity enhancement in the presence of the APRM. This indicates that the ANPs act as particulate concentration agents at the interface owing to their hydrophobic association with the APRM in the aqueous phase, which leads to the generation of an ANP-mediated complex colloidal film. Consequently, the described ANP-reinforced Pickering emulsion system exhibits improved resistance to pH and salinity changes. This coacervation approach is advantageous because the complex colloidal layer at the interface provides the emulsion drops with a mechanically robust barrier, thus guaranteeing the improved Pickering emulsion stability against harsh environmental factors.

Determination of Hamaker constants of polymeric nanoparticles in organic solvents by asymmetrical flow field-flow fractionation.

PubMed

Noskov, Sergey; Scherer, Christian; Maskos, Michael

2013-01-25

Interaction forces between all objects are either of repulsive or attractive nature. Concerning attractive interactions, the determination of dispersion forces are of special interest since they appear in all colloidal systems and have a crucial influence on the properties and processes in these systems. One possibility to link theory and experiment is the description of the London-Van der Waals forces in terms of the Hamaker constant, which leads to the challenging problem of calculating the van der Waals interaction energies between colloidal particles. Hence, the determination of a Hamaker constant for a given material is needed when interfacial phenomena such as adhesion are discussed in terms of the total potential energy between particles and substrates. In this work, the asymmetrical flow field-flow fractionation (AF-FFF) in combination with a Newton algorithm based iteration process was used for the determination of Hamaker constants of different nanoparticles in toluene. Copyright © 2012 Elsevier B.V. All rights reserved.

Patterning of colloidal particles in the galvanic microreactor

NASA Astrophysics Data System (ADS)

Jan, Linda

A Cu-Au galvanic microreactor is used to demonstrate the autonomous patterning of two-dimensional colloidal crystals with spatial and orientational order which are adherent to the electrode substrate. The microreactor is comprised of a patterned array of copper and gold microelectrodes in a coplanar arrangement that is immersed in a dilute hydrochloric acid solution in which colloidal polystyrene microspheres are suspended. During the electrochemical dissolution of copper, polystyrene colloids are transported to the copper electrodes. The spatial arrangement of the electrodes determines whether the colloids initiate aggregation at the edges or centers of the copper electrodes. Depending on the microreactor parameters, two-dimensional colloidal crystals can form and adhere to the electrode. This thesis investigates the mechanisms governing the autonomous particle motion, the directed particle trajectory (inner- versus edge-aggregation) as affected by the spatial patterning of the electrodes, and the adherence of the colloidal particles onto the substrate. Using in situ current density measurements, particle velocimetry, and order-of-magnitude arguments, it is shown that particle motion is governed by bulk fluid motion and electrophoresis induced by the electrochemical reactions. Bulk electrolyte flow is most likely driven by electrochemical potential gradients of reaction products formed during the inhomogeneous copper dissolution, particularly due to localized high current density at the electrode junction. Preferential aggregation of the colloidal particles resulting in inner- and edge-aggregation is influenced by changes to the flow pattern in response to difference in current density profiles as affected by the spatial patterning of the electrode. Finally, by determining the onset of particle cementation through particle tracking analysis, and by monitoring the deposition of reaction products through the observation of color changes of the galvanic electrodes in situ, it is shown that particle cementation coincides with the precipitation and deposition of reaction products. The precipitation process is caused by shifts in the chemical equilibria of the microreactor due to changes in the composition of the electrolyte during the reactions, which can be used to control particle cementation. The corrosion driven transport, deposition and adherence of colloidal particles at corrosion sites have implications for the development of autonomous self-healing materials.

Self-Consistent Physical Properties of Carbon Nanotubes in Composite Materials

NASA Technical Reports Server (NTRS)

Pipes, R. B.; Frankland, S. J. V.; Hubert, P.; Saether, E.; Bushnell, Dennis M. (Technical Monitor)

2002-01-01

A set of relationships is developed for selected physical properties of single-walled carbon nanotubes (SWCN) and their hexagonal arrays as a function of nanotube size in terms of the chiral vector integer pair, (n,m). Properties include density, principal Young's modulus, and specific Young's modulus. Relationships between weight fraction and volume fraction of SWCN and their arrays are developed for polymeric mixtures.

Characterization of polymeric nanoparticles for intravenous delivery: Focus on stability.

PubMed

Oliveira, Claudia L; Veiga, Francisco; Varela, Carla; Roleira, Fernanda; Tavares, Elisiário; Silveira, Isabel; Ribeiro, Antonio J

2017-02-01

The nano-bio interaction has been of increased focus in the past years but very limited results have been obtained for polymeric nanoparticles (NP). Not only is needed to broaden the results obtained with model NP towards other nano-materials used for clinical application but the colloidal stability of NP as a variable consequence of the formation of the protein corona has been significantly understated. The lack and heterogeneity of assays to study NP stability and represent the biological environment call for the standardization of assays to improve the representativeness and comparability of results. In this paper, uncoated and PAH-coated PLGA NP have been prepared and characterized in regard to their potential for intravenous administration. The comparative study of the stability of NP in three media used to represent the biological environment-bovine serum albumin (BSA) solution, mouse and human plasma - revealed that both formulations were unstable in human plasma as opposed to the results obtained for other media. This unexpected behavior in plasmas of different origins could be correlated with a significant variation of the amount of proteins adsorbed to NP and, ultimately, with an approximately 6-fold difference in total protein concentration between the plasma samples. These results suggest that inter-species variation could impact on the colloidal stability of NP and enhance the need to understand the correlation between biological media and identify protocol-related interferences which, altogether, may evidence a relevant factor compromising in vitro- in vivo correlation and the translation of delivery systems aimed at intravenous administration. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis and photoluminescence properties of ZnS nanobowl arrays via colloidal monolayer template

PubMed Central

2014-01-01

Two-dimensional Zinc sulfide (ZnS) nanobowl arrays were synthesized via self-assembled monolayer polystyrene sphere template floating on precursor solution surface. A facile approach was proposed to investigate the morphology evolution of nanobowl arrays by post-annealing procedure. Photoluminescence (PL) measurement of as-grown nanoarrays shows that the spectrum mainly includes two parts: a purple emission peak at 382 nm and a broad blue emission band centering at 410 nm with a shoulder around 459 nm, and a blue emission band at 440 nm was obtained after the annealing procedure. ZnS nanoarrays with special morphologies and PL emission are benefits to their promising application in novel photoluminescence nanodevice. PMID:25246857

Amorphous silicon thin film transistor active-matrix organic light-emitting diode displays fabricated on flexible substrates

NASA Astrophysics Data System (ADS)

Nichols, Jonathan A.

Organic light-emitting diode (OLED) displays are of immense interest because they have several advantages over liquid crystal displays, the current dominant flat panel display technology. OLED displays are emissive and therefore are brighter, have a larger viewing angle, and do not require backlights and filters, allowing thinner, lighter, and more power efficient displays. The goal of this work was to advance the state-of-the-art in active-matrix OLED display technology. First, hydrogenated amorphous silicon (a-Si:H) thin film transistor (TFT) active-matrix OLED pixels and arrays were designed and fabricated on glass substrates. The devices operated at low voltages and demonstrated that lower performance TFTs could be utilized in active-matrix OLED displays, possibly allowing lower cost processing and the use of polymeric substrates. Attempts at designing more control into the display at the pixel level were also made. Bistable (one bit gray scale) active-matrix OLED pixels and arrays were designed and fabricated. Such pixels could be used in novel applications and eventually help reduce the bandwidth requirements in high-resolution and large-area displays. Finally, a-Si:H TFT active-matrix OLED pixels and arrays were fabricated on a polymeric substrate. Displays fabricated on a polymeric substrates would be lightweight; flexible, more rugged, and potentially less expensive to fabricate. Many of the difficulties associated with fabricating active-matrix backplanes on flexible substrates were studied and addressed.

Synthesis of polymeric microcapsule arrays and their use for enzyme immobilization

NASA Astrophysics Data System (ADS)

Parthasarathy, Ranjani V.; Martin, Charles R.

1994-05-01

CURRENT methods for immobilizing enzymes for use in bioreactors and biosensors1-20 include adsorption on or covalent attachment to a support2-4, micro-encapsulation5,6, and entrapment within a membrane/film7,8,11-20 or gel9. The ideal immobilization method should employ mild chemical conditions, allow for large quantities of enzyme to be immobilized, provide a large surface area for enzyme-substrate contact within a small total volume, minimize barriers to mass transport of substrate and product, and provide a chemically and mechanically robust system. Here we describe a method for enzyme immobilization that satisfies all of these criteria. We have developed a template-based synthetic method that yields hollow polymeric microcapsules of uniform diameter and length. These microcapsules are arranged in a high-density array in which the individual capsules protrude from a surface like the bristles of a brush. We have developed procedures for filling these microcapsules with high concentrations of enzymes. The enzyme-loaded microcapsule arrays function as enzymatic bioreactors in both aqueous solution and organic solvents.

Highly Tunable Complementary Micro/Submicro-Nanopatterned Surfaces Combining Block Copolymer Self-Assembly and Colloidal Lithography.

PubMed

Chang, Tongxin; Du, Binyang; Huang, Haiying; He, Tianbai

2016-08-31

Two kinds of large-area ordered and highly tunable micro/submicro-nanopatterned surfaces in a complementary manner were successfully fabricated by elaborately combining block copolymer self-assembly and colloidal lithography. Employing a monolayer of polystyrene (PS) colloidal spheres assembled on top as etching mask, polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) or polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) micelle films were patterned into micro/submicro patches by plasma etching, which could be further transferred into micropatterned metal nanoarrays by subsequent metal precursor loading and a second plasma etching. On the other hand, micro/submicro-nanopatterns in a complementary manner were generated via preloading a metal precursor in initial micelle films before the assembly of PS colloidal spheres on top. Both kinds of micro/submicro-nanopatterns showed good fidelity at the micro/submicroscale and nanoscale; meanwhile, they could be flexibly tuned by the sample and processing parameters. Significantly, when the PS colloidal sphere size was reduced to 250 nm, a high-resolution submicro-nanostructured surface with 3-5 metal nanoparticles in each patch or a single-nanoparticle interconnected honeycomb network was achieved. Moreover, by applying gold (Au) nanoparticles as anchoring points, micronanopatterned Au arrays can serve as a flexible template to pattern bovine serum albumin (BSA) molecules. This facile and cost-effective approach may provide a novel platform for fabrication of micropatterned nanoarrays with high tunability and controllability, which are promising in the applications of biological and microelectronic fields.

Microtubule self-organisation by reaction-diffusion processes causes collective transport and organisation of cellular particles

PubMed Central

Glade, Nicolas; Demongeot, Jacques; Tabony, James

2004-01-01

Background The transport of intra-cellular particles by microtubules is a major biological function. Under appropriate in vitro conditions, microtubule preparations behave as a 'complex' system and show 'emergent' phenomena. In particular, they form dissipative structures that self-organise over macroscopic distances by a combination of reaction and diffusion. Results Here, we show that self-organisation also gives rise to a collective transport of colloidal particles along a specific direction. Particles, such as polystyrene beads, chromosomes, nuclei, and vesicles are carried at speeds of several microns per minute. The process also results in the macroscopic self-organisation of these particles. After self-organisation is completed, they show the same pattern of organisation as the microtubules. Numerical simulations of a population of growing and shrinking microtubules, incorporating experimentally realistic reaction dynamics, predict self-organisation. They forecast that during self-organisation, macroscopic parallel arrays of oriented microtubules form which cross the reaction space in successive waves. Such travelling waves are capable of transporting colloidal particles. The fact that in the simulations, the aligned arrays move along the same direction and at the same speed as the particles move, suggest that this process forms the underlying mechanism for the observed transport properties. Conclusions This process constitutes a novel physical chemical mechanism by which chemical energy is converted into collective transport of colloidal particles along a given direction. Self-organisation of this type provides a new mechanism by which intra cellular particles such as chromosomes and vesicles can be displaced and simultaneously organised by microtubules. It is plausible that processes of this type occur in vivo. PMID:15176973

Tunable plasmon resonances in anisotropic metal nanostructures

NASA Astrophysics Data System (ADS)

Penninkhof, J. J.

2006-09-01

Coherent oscillations of free electrons in a metal, localized in a small volume or at an interface between a metal and a dielectric medium, have attracted a lot of attention in the past decades. These so-called surface plasmons have special optical properties that can be used in many applications ranging from optoelectronics to sensing of small quantities of molecules. One of the key issues is that electromagnetic energy can be confined to a relatively small volume close to the metal surface. This field enhancement and the resonance frequency strongly depend on the shape and size of the metal structures. In this thesis, several fabrication methods to create these metal structures on the nanometer to micrometer scale are presented. The optical properties are studied with a special emphasis on the effect of shape anisotropy. Self-assembled 2D colloidal crystals are used as mask to fabricate arrays of metal triangles on a substrate. One of the limitations of this nanosphere lithography technique is that the size of the holes in the colloidal mask (through which the metal is evaporated) is determined by the size of the colloids in the mask. The masks, however, can be modified by use of MeV ion beams and/or wet-chemical growth of a thin layer of silica, resulting in a reduced hole size. Arbitrary symmetry and spacing can be obtained by use of optical tweezers and angle-resolved metal deposition. In contrast to pure metals, amorphous materials like silica are known to show anisotropic plastic deformation at constant volume when subject to MeV ion irradiation. Gold cores embedded in a silica matrix, however, show an elongation along the direction of the ion beam, whereas silver cores rather disintegrate. Silver nanocrystals in an ion-exchanged soda-lime glass redistribute themselves in arrays along the ion beam direction. The optical extinction becomes polarization-dependent, with red- and blue-shifts of the plasmon resonances for polarizations longitudinal and transverse to the arrays, respectively. The band splitting is attributed to near-field electromagnetic plasmon coupling within the arrays. Finite difference time domain simulations indicate that the combination of particle center-to-center spacing and diameter, rather than inter-particle spacing alone, is the key parameter determining the coupling strength. The resonant electric field is concentrated in the very small gaps between the particles in the array. With the MeV ion beam technique, it is possible to fabricate large substrates with relatively monodisperse oblate ellipsoidal silica-core/metal-shell colloids, with the short axis aligned in the direction of the ion beam. The optical extinction of these particles, is a complex function of the core radius and the shell thickness, due to a competition between phase retardation effects and the coupling between the surface plasmons at the inner and outer surfaces of the shell. After deformation, the extinction is angle- and polarization-dependent. Calculations indicate that large Au-shell particles can sustain cavity modes, for which the electric field is enhanced in almost the full volume of the dielectric core. The resonance frequency is sensitive to the size, shape and dielectric constant of the core, and the polarization direction.

Patterned assembly of colloidal particles by confined dewetting lithography.

PubMed

Celio, Hugo; Barton, Emily; Stevenson, Keith J

2006-12-19

We report the assembly of colloidal particles into confined arrangements and patterns on various cleaned and chemically modified solid substrates using a method which we term "confined dewetting lithography" or CDL for short. The experimental setup for CDL is a simple deposition cell where an aqueous suspension of colloidal particles (e.g., polystyrene spheres) is placed between a floating deposition template (i.e., metal microgrid) and the solid substrate. The voids of the deposition template serve as an array of micrometer-sized reservoirs where several hydrodynamic processes are confined. These processes include water evaporation, meniscus formation, convective flow, rupturing, dewetting, and capillary-bridge formation. We discuss the optimal conditions where the CDL has a high efficiency to deposit intricate patterns of colloidal particles using polystyrene spheres (PS; 4.5, 2.0, 1.7, 0.11, 0.064 microm diameter) and square and hexagonal deposition templates as model systems. We find that the optimization conditions of the CDL method, when using submicrometer, sulfate-functionalized PS particles, are primarily dependent on minimizing attractive particle-substrate interactions. The CDL methodology described herein presents a relatively simple and rapid method to assemble virtually any geometric pattern, including more complex patterns assembled using PS particles with different diameters, from aqueous suspensions by choosing suitable conditions and materials.

Cell adhesion and guidance by micropost-array chemical sensors

NASA Astrophysics Data System (ADS)

Pantano, Paul; Quah, Soo-Kim; Danowski, Kristine L.

2002-06-01

An array of ~50,000 individual polymeric micropost sensors was patterned across a glass coverslip by a photoimprint lithographic technique. Individual micropost sensors were ~3-micrometers tall and ~8-micrometers wide. The O2-sensitive micropost array sensors (MPASs) comprised a ruthenium complex encapsulated in a gas permeable photopolymerizable siloxane. The pH-sensitive MPASs comprised a fluorescein conjugate encapsulated in a photocrosslinkable poly(vinyl alcohol)-based polymer. PO2 and pH were quantitated by acquiring MPAS luminescence images with an epifluorescence microscope/charge coupled device imaging system. O2-sensitive MPASs displayed linear Stern-Volmer quenching behavior with a maximum Io/I of ~8.6. pH-sensitive MPASs displayed sigmoidal calibration curves with a pKa of ~5.8. The adhesion of undifferentiated rat pheochromocytoma (PC12) cells across these two polymeric surface types was investigated. The greatest PC12 cell proliferation and adhesion occurred across the poly(vinyl alcohol)-based micropost arrays relative to planar poly(vinyl alcohol)-based surfaces and both patterned and planar siloxane surfaces. An additional advantage of the patterned MPAS layers relative to planar sensing layers was the ability to direct the growth of biological cells. Preliminary data is presented whereby nerve growth factor-differentiated PC12 cells grew neurite-like processes that extended along paths defined by the micropost architecture.

Wettability and friction coefficient of micro-magnet arrayed surface

NASA Astrophysics Data System (ADS)

Huang, Wei; Liao, Sijie; Wang, Xiaolei

2012-01-01

Surface coating is an important part of surface engineering and it has been successfully used in many applications to improve the performance of surfaces. In this paper, magnetic arrayed films with different thicknesses were fabricated on the surface of 316 stainless steel disks. Controllable colloid - ferrofluids (FF) was chosen as lubricant, which can be adsorbed on the magnetic surface. The wettability of the micro-magnet arrayed surface was evaluated by measuring the contract angle of FF drops on surface. Tribological experiments were carried out to investigate the effects of magnetic film thickness on frictional properties when lubricated by FF under plane contact condition. It was found that the magnetic arrayed surface with thicker magnetic films presented larger contract angle. The frictional test results showed that samples with thicker magnetic films could reduce friction and wear more efficiently at higher sliding velocity under the lubrication of FF.

Plasmonic nanoantenna arrays for surface-enhanced Raman spectroscopy of lipid molecules embedded in a bilayer membrane.

PubMed

Kühler, Paul; Weber, Max; Lohmüller, Theobald

2014-06-25

We demonstrate a strategy for surface-enhanced Raman spectroscopy (SERS) of supported lipid membranes with arrays of plasmonic nanoantennas. Colloidal lithography refined with plasma etching is used to synthesize arrays of triangular shaped gold nanoparticles. Reducing the separation distance between the triangle tips leads to plasmonic coupling and to a strong enhancement of the electromagnetic field in the nanotriangle gap. As a result, the Raman scattering intensity of molecules that are located at this plasmonic "hot-spot" can be increased by several orders of magnitude. The nanoantenna array is then embedded with a supported phospholipid membrane which is fluid at room temperature and spans the antenna gap. This configuration offers the advantage that molecules that are mobile within the bilayer membrane can enter the "hot-spot" region via diffusion and can therefore be measured by SERS without static entrapment or adsorption of the molecules to the antenna itself.

Physics of Hard Spheres Experiment (PhaSE) or "Making Jello in Space"

NASA Technical Reports Server (NTRS)

Ling, Jerri S.; Doherty, Michael P.

1998-01-01

The Physics of Hard Spheres Experiment (PHaSE) is a highly successful experiment that flew aboard two shuttle missions to study the transitions involved in the formation of jellolike colloidal crystals in a microgravity environment. A colloidal suspension, or colloid, consists of fine particles, often having complex interactions, suspended in a liquid. Paint, ink, and milk are examples of colloids found in everyday life. In low Earth orbit, the effective force of gravity is thousands of times less than at the Earth's surface. This provides researchers a way to conduct experiments that cannot be adequately performed in an Earth-gravity environment. In microgravity, colloidal particles freely interact without the complications of settling that occur in normal gravity on Earth. If the particle interactions within these colloidal suspensions could be predicted and accurately modeled, they could provide the key to understanding fundamental problems in condensed matter physics and could help make possible the development of wonderful new "designer" materials. Industries that make semiconductors, electro-optics, ceramics, and composites are just a few that may benefit from this knowledge. Atomic interactions determine the physical properties (e.g., weight, color, and hardness) of ordinary matter. PHaSE uses colloidal suspensions of microscopic solid plastic spheres to model the behavior of atomic interactions. When uniformly sized hard spheres suspended in a fluid reach a certain concentration (volume fraction), the particle-fluid mixture changes from a disordered fluid state, in which the spheres are randomly organized, to an ordered "crystalline" state, in which they are structured periodically. The thermal energy of the spheres causes them to form ordered arrays, analogous to crystals. Seven of the eight PHaSE samples ranged in volume fraction from 0.483 to 0.624 to cover the range of interest, while one sample, having a concentration of 0.019, was included for instrument calibration.

Carbon dioxide-assisted fabrication of highly uniform submicron-sized colloidal carbon spheres via hydrothermal carbonization using soft drink

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

Moon, Gun-Hee; Shin, Yongsoon; Arey, Bruce W.

An eco-friendly and economical method for the formation of uniform-sized carbon spheres by hydrothermal dehydration/condensation of a commercial carbonated beverage at 200 oC is reported. CO2 dissolved in the beverage accelerates the dehydration kinetics of the dissolved sugar molecules leading to production of homogeneous carbon spheres having a diameter less than 850 nm. In the presence of CO2, the rough surface of these carbon spheres likely results from continuous Ostwald ripening of constituent microscopic carbon-containing spheres that are formed by subsequent polymerization of intermediate HMF molecules.

Amphiphilic Soft Janus Particles as Interfacial Stabilizers

NASA Astrophysics Data System (ADS)

Wang, Wenda; Niu, Sunny; Sosa, Chris; Prud'Homme, Robert; Priestley, Rodney; Priestley Polymer Group Team; Prud'homme Research Group Team

Janus particles, which incorporate two or more ``faces'' with different chemical functionality, have attracted great attention in scientific research. Amphiphilic Janus particles have two faces with distinctly different hydrophobicity. This can be thought of as colloidal surfactants. Theoretical studies on the stabilization of emulsions using Janus particles have confirmed higher efficiency. Herein we synthesize the narrow distributed amphiphilic polymeric Janus particles via Precipitation-Induced Self-Assembly (PISA). The efficiency of the amphiphilic Janus particles are tested on different oil/water systems. Biocompatible polymers can also be used on this strategy and may potentially have wide application for food emulsion, cosmetics and personal products.

Growth of arrays of oriented epitaxial platinum nanoparticles with controlled size and shape by natural colloidal lithography

DOE PAGES

Komanicky, Vladimir; Barbour, Andi; Lackova, Miroslava; ...

2014-07-05

Here, we developed a method for production of arrays of platinum nanocrystals of controlled size and shape using templates from ordered silica bead monolayers. Silica beads with nominal sizes of 150 and 450 nm were self-assembl into monolayers over strontium titanate single crystal substrates. The monolayers were used as shadow masks for platinum metal deposition on the substrate using the three-step evaporation technique. Produced arrays of epitaxial platinum islands were transformed into nanocrystals by annealing in a quartz tube in nitrogen flow. The shape of particles is determined by the substrate crystallography, while the size of the particles and theirmore » spacing are controlled by the size of the silica beads in the mono- layer mask. As a proof of concept, arrays of platinum nanocrystals of cubooctahedral shape were prepared on (100) strontium titanate substrates. We also characterized the nanocrystal arrays by atomic force microscopy, scanning electron microscopy, and synchrotron X-ray diffraction techniques.« less

Brownian cluster dynamics with short range patchy interactions: Its application to polymers and step-growth polymerization

NASA Astrophysics Data System (ADS)

Prabhu, A.; Babu, S. B.; Dolado, J. S.; Gimel, J.-C.

2014-07-01

We present a novel simulation technique derived from Brownian cluster dynamics used so far to study the isotropic colloidal aggregation. It now implements the classical Kern-Frenkel potential to describe patchy interactions between particles. This technique gives access to static properties, dynamics and kinetics of the system, even far from the equilibrium. Particle thermal motions are modeled using billions of independent small random translations and rotations, constrained by the excluded volume and the connectivity. This algorithm, applied to a single polymer chain leads to correct static and dynamic properties, in the framework where hydrodynamic interactions are ignored. By varying patch angles, various local chain flexibilities can be obtained. We have used this new algorithm to model step-growth polymerization under various solvent qualities. The polymerization reaction is modeled by an irreversible aggregation between patches while an isotropic finite square-well potential is superimposed to mimic the solvent quality. In bad solvent conditions, a competition between a phase separation (due to the isotropic interaction) and polymerization (due to patches) occurs. Surprisingly, an arrested network with a very peculiar structure appears. It is made of strands and nodes. Strands gather few stretched chains that dip into entangled globular nodes. These nodes act as reticulation points between the strands. The system is kinetically driven and we observe a trapped arrested structure. That demonstrates one of the strengths of this new simulation technique. It can give valuable insights about mechanisms that could be involved in the formation of stranded gels.

Influence of membrane material on the production of colloidal emulsions by premix membrane emulsification.

PubMed

Gehrmann, Sandra; Bunjes, Heike

2018-05-01

Premix membrane emulsification is a possibility to produce colloidal emulsions as carrier systems for poorly water soluble drugs. During the extrusion of a coarse pre-emulsion through a porous membrane, the emulsion droplets are disrupted into smaller droplets. The influence of the membrane material on the emulsification success was investigated in dependence on the emulsifier. Premixed medium chain triglyceride (MCT) emulsions stabilized with five different emulsifiers were extruded through seven different hydrophilic polymeric membrane materials with pore sizes of 200nm. The resulting emulsions differed strongly in particle size and particle size distribution with a range of median particle sizes between 0.08μm and 11μm. The particle size of the emulsions did not depend mainly on the structure or thickness of the membrane but on the combination of emulsifier and membrane material. Contact angle measurements indicated that the wetting of the membrane with the continuous phase of the emulsion was decisive for achieving emulsions with colloidal particle sizes. The type of dispersed phase was of minor importance as basically the same results were obtained with peanut oil instead of MCT. To prove the assumption that only sufficiently hydrophilic membrane materials led to emulsions with colloidal particle sizes, two membrane materials were hydrophilized by plasma treatment. After hydrophilization, the emulsifying process led to emulsions with smaller particle sizes. The use of an alumina membrane (Anodisc®) improved the process even more. With this type of membrane, emulsions with a median particle size below 250nm and a narrow particle size distribution could be obtained with all investigated emulsifiers. Copyright © 2016 Elsevier B.V. All rights reserved.

Nanowires and Nanostructures That Grow Like Polymer Molecules

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

Shaw, Santosh; Cademartiri, Ludovico

Unique properties (e.g., rubber elasticity, viscoelasticity, folding, reptation) determine the utility of polymer molecules and derive from their morphology (i.e., one-dimensional connectivity and large aspect ratios) and flexibility. Crystals do not display similar properties because they have smaller aspect ratios, they are rigid, and they are often too large and heavy to be colloidally stable. We argue, with the support of recent experimental studies, that these limitations are not fundamental and that they might be overcome by growth processes that mimic polymerization. Furthermore, we (i) discuss the similarities between crystallization and polymerization, (ii) critically review the existing experimental evidence ofmore » polymer-like growth kinetic and behavior in crystals and nanostructures, and (iii) propose heuristic guidelines for the synthesis of “polymer-like” crystals and assemblies. Understanding these anisotropic materials at the boundary between molecules and solids will determine whether we can confer the unique properties of polymer molecules to crystals, expanding them with topology, dynamics, and information and not just tuning them with size.« less

Cyclodextrin-Modified Porous Silicon Nanoparticles for Efficient Sustained Drug Delivery and Proliferation Inhibition of Breast Cancer Cells.

PubMed

Correia, Alexandra; Shahbazi, Mohammad-Ali; Mäkilä, Ermei; Almeida, Sérgio; Salonen, Jarno; Hirvonen, Jouni; Santos, Hélder A

2015-10-21

Over the past decade, the potential of polymeric structures has been investigated to overcome many limitations related to nanosized drug carriers by modulating their toxicity, cellular interactions, stability, and drug-release kinetics. In this study, we have developed a successful nanocomposite consisting of undecylenic acid modified thermally hydrocarbonized porous silicon nanoparticles (UnTHCPSi NPs) loaded with an anticancer drug, sorafenib, and surface-conjugated with heptakis(6-amino-6-deoxy)-β-cyclodextrin (HABCD) to show the impact of the surface polymeric functionalization on the physical and biological properties of the drug-loaded nanoparticles. Cytocompatibility studies showed that the UnTHCPSi-HABCD NPs were not toxic to breast cancer cells. HABCD also enhanced the suspensibility and both the colloidal and plasma stabilities of the UnTHCPSi NPs. UnTHCPSi-HABCD NPs showed a significantly increased interaction with breast cancer cells compared to bare NPs and also sustained the drug release. Furthermore, the sorafenib-loaded UnTHCPSi-HABCD NPs efficiently inhibited cell proliferation of the breast cancer cells.

Strong thin membrane structure. [solar sails

NASA Technical Reports Server (NTRS)

Frazer, R. E. (Inventor)

1979-01-01

A continuous process is described for producing strong lightweight structures for use as solar sails for spacecraft propulsion by radiation pressure. A thin reflective coating, such as aluminum, is applied to a rotating cylinder. A nylon mesh, applied over the aluminum coating, is then coated with a polymerizing material such as a para-xylylene monomer gas to polymerize as a film bound to the mesh and the aluminum. An emissivity increasing material such as chromium or silicon monoxide is applied to the polymer film to disperse such material colloidally into the growing polymer film, or to the final polymer film. The resulting membrane structure is then removed from the cylinder. Alternately, the membrane structure can be formed by etching a substrate in the form of an organic film such as a polymide, or a metal foil, to remove material from the substrate and reduce its thickness. A thin reflective coating (aluminum) is applied on one side of the substrate, and an emissivity increasing coating is applied on the reverse side of the substrate.

Ethanol-assisted multi-sensitive poly(vinyl alcohol) photonic crystal sensor.

PubMed

Chen, Cheng; Zhu, Yihua; Bao, Hua; Shen, Jianhua; Jiang, Hongliang; Peng, Liming; Yang, Xiaoling; Li, Chunzhong; Chen, Guorong

2011-05-21

An ethanol-assisted method is utilized to generate a robust gelated crystalline colloidal array (GCCA) photonic crystal sensor. The functionalized sensor efficiently diffracts the visible light and responds to various stimuli involving solvent, pH, cation, and compressive strain; the related color change can be easily distinguished by the naked eye. © The Royal Society of Chemistry 2011

Rapid Engineering of Three-Dimensional, Multicellular Tissues With Polymeric Scaffolds

NASA Technical Reports Server (NTRS)

Gonda, Steve R.; Jordan, Jacqueline; Fraga, Denise N.

2007-01-01

A process has been developed for the rapid tissue engineering of multicellular-tissue-equivalent assemblies by the controlled enzymatic degradation of polymeric beads in a low-fluid-shear bioreactor. In this process, the porous polymeric beads serve as temporary scaffolds to support the assemblies of cells in a tissuelike 3D configuration during the critical initial growth phases of attachment of anchorage-dependent cells, aggregation of the cells, and formation of a 3D extracellular matrix. Once the cells are assembled into a 3D array and enmeshed in a structural supportive 3D extracellular matrix (ECM), the polymeric scaffolds can be degraded in the low-fluid-shear environment of the NASA-designed bioreactor. The natural 3D tissuelike assembly, devoid of any artificial support structure, is maintained in the low-shear bioreactor environment by the newly formed natural cellular/ECM. The elimination of the artificial scaffold allows normal tissue structure and function.

Synthesis of nanostructured bio-related materials by hybridization of synthetic polymers with polysaccharides or saccharide residues.

PubMed

Kaneko, Yoshiro; Kadokawa, Jun-Ichi

2006-01-01

In the first part of this review, we describe the synthesis of nanostructured hybrid materials composed of polysaccharides and synthetic polymers. Amylose-synthetic polymer inclusion complexes were synthesized by amylose-forming polymerization using phosphorylase enzyme in the presence of synthetic polymers such as polyethers and polyesters. Alginate-polymethacrylate hybrid materials were prepared by free-radical polymerization of cationic methacrylate in the presence of sodium alginate. These methods allow the simultaneous control of the nanostructure with polymerization, giving well-defined hybrid materials. In the second part of this review, we describe the synthesis of novel glycopolymers with rigid structures. Polyaniline-based glycopolymers were synthesized by means of oxidative polymerization of N-glycosylaniline. Polysiloxane-based glycopolymers were prepared by means of introduction of sugar-lactone to the rodlike polysiloxane. These glycopolymers had regular higher-ordered structures due to their rigid polymer backbones, resulting in control of the three-dimensional array of sugar-residues.

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

Li Hong.

A new technique was developed and demonstrated for combining carbon fibers with aromatic thermoplastic matrices to form a high-quality towpreg. The developed technique utilizes an in-situ electrochemical process (Electrochemical polymerization - ECP) to create the entire polymer matrix surrounding the fiber array by direct polymerization of monomer. Poly-paraxylylene (PPX) and derivatives are successfully polymerized in-situ on carbon fiber surfaces through ECP. A PPX/carbon-fiber towpreg with 40 vol % of matrix is achieved in a fairly short reaction time with a high polymer-coating efficiency. Vapor deposition polymerization (VDP) was also studied. PPX and carbon-fiber towpreg were made successfully by this process.more » A comparison between ECP and VDP was conducted. A study on electrochemical oxidation (ECO) of carbon fibers was also performed. The ECO treatment may be suitable for carbon fibers incorporated in composites with high-temperature curing resins and thermoplastic matrices.« less

A CMOS Time-Resolved Fluorescence Lifetime Analysis Micro-System

PubMed Central

Rae, Bruce R.; Muir, Keith R.; Gong, Zheng; McKendry, Jonathan; Girkin, John M.; Gu, Erdan; Renshaw, David; Dawson, Martin D.; Henderson, Robert K.

2009-01-01

We describe a CMOS-based micro-system for time-resolved fluorescence lifetime analysis. It comprises a 16 × 4 array of single-photon avalanche diodes (SPADs) fabricated in 0.35 μm high-voltage CMOS technology with in-pixel time-gated photon counting circuitry and a second device incorporating an 8 × 8 AlInGaN blue micro-pixellated light-emitting diode (micro-LED) array bump-bonded to an equivalent array of LED drivers realized in a standard low-voltage 0.35 μm CMOS technology, capable of producing excitation pulses with a width of 777 ps (FWHM). This system replaces instrumentation based on lasers, photomultiplier tubes, bulk optics and discrete electronics with a PC-based micro-system. Demonstrator lifetime measurements of colloidal quantum dot and Rhodamine samples are presented. PMID:22291564

Lithographically Patterned Nanoscale Electrodeposition of Plasmonic, Bimetallic, Semiconductor, Magnetic, and Polymer Nanoring Arrays

PubMed Central

2015-01-01

Large area arrays of magnetic, semiconducting, and insulating nanorings were created by coupling colloidal lithography with nanoscale electrodeposition. This versatile nanoscale fabrication process allows for the independent tuning of the spacing, diameter, and width of the nanorings with typical values of 1.0 μm, 750 nm, and 100 nm, respectively, and was used to form nanorings from a host of materials: Ni, Co, bimetallic Ni/Au, CdSe, and polydopamine. These nanoring arrays have potential applications in memory storage, optical materials, and biosensing. A modified version of this nanoscale electrodeposition process was also used to create arrays of split gold nanorings. The size of the split nanoring opening was controlled by the angle of photoresist exposure during the fabrication process and could be varied from 50% down to 10% of the ring circumference. The large area (cm2 scale) gold split nanoring array surfaces exhibited strong polarization-dependent plasmonic absorption bands for wavelengths from 1 to 5 μm. Plasmonic nanoscale split ring arrays are potentially useful as tunable dichroic materials throughout the infrared and near-infrared spectral regions. PMID:25553204

Evaluations of candidate encapsulation designs and materials for low-cost silicon photovoltaic arrays

NASA Technical Reports Server (NTRS)

Gaines, G. B.; Carmichael, D. C.; Sliemers, F. A.; Brockway, M. C.; Bunk, A. R.; Nance, G. P.

1978-01-01

Three encapsulation designs for silicon photovoltaic arrays based on cells with silk-screened Ag metallization have been evaluated: transparent polymeric coatings over cells laminated between two films or sheets of polymeric materials; cells adhesively bonded to a glass cover with a polymer pottant and a glass or other substrate component. Silicone and acrylic coatings were assessed, together with acrylic sheet, 0.635 mm fiberglass-reinforced polyester sheet, 0.102 mm polycarbonate/acrylic dual-layer film, 0.127 mm fluorocarbon film, soda-lime glass, borosilicate glass, low-iron glass, and several adhesives. The encapsulation materials were characterized by light transmittance measurements, determination of moisture barrier properties and bond strengths, and by the performance of cells before and after encapsulation. Silicon and acrylic coatings provided inadequate protection. Acrylic and fluorocarbon films displayed good weatherability and acceptable optical transmittance. Borosilicate, low-iron and soda-lime-float glasses were found to be acceptable candidate encapsulants for most environments.

Effect of the polymeric coating thickness on the photocurrent performance of titanium dioxide nanorod arrays-polyaniline composite-based UV photosensor

NASA Astrophysics Data System (ADS)

Yusoff, M. M.; Mamat, M. H.; Malek, M. F.; Othman, , N.; Ismail, A. S.; Saidi, S. A.; Mohamed, R.; Suriani, A. B.; Khusaimi, Z.; Rusop, M.

2018-05-01

Titanium dioxide (TiO2) nanorod arrays (TNAs) were synthesized and deposited on fluorine tin oxide (FTO)-coated glass substrate using a one-step immersion method in a glass container. The effect of the polymeric coating thickness of p-type polyaniline (PANI) on the n-type TNAs was investigated in the p-n heterojunction photodiode (PD) for the application of ultraviolet (UV) photosensor. The fabricated photosensor demonstrated an increased photocurrent under UV irradiation in correlation with the thickness layer of PANI. The measured UV response showed the highest photocurrent of 0.014 µA at 1.0 V of reverse bias with low dark current under the UV radiation (365 nm, 750 µW/cm2). The thickness of the PANI film improved the photocurrent of the fabricated TNAs/PANI composite-based UV photosensor.

Sonochemically Fabricated Microelectrode Arrays for Use as Sensing Platforms

PubMed Central

Collyer, Stuart D.; Davis, Frank; Higson, Séamus P.J.

2010-01-01

The development, manufacture, modification and subsequent utilisation of sonochemically-formed microelectrode arrays is described for a range of applications. Initial fabrication of the sensing platform utilises ultrasonic ablation of electrochemically insulating polymers deposited upon conductive carbon substrates, forming an array of up to 70,000 microelectrode pores cm−2. Electrochemical and optical analyses using these arrays, their enhanced signal response and stir-independence area are all discussed. The growth of conducting polymeric “mushroom” protrusion arrays with entrapped biological entities, thereby forming biosensors is detailed. The simplicity and inexpensiveness of this approach, lending itself ideally to mass fabrication coupled with unrivalled sensitivity and stir independence makes commercial viability of this process a reality. Application of microelectrode arrays as functional components within sensors include devices for detection of chlorine, glucose, ethanol and pesticides. Immunosensors based on microelectrode arrays are described within this monograph for antigens associated with prostate cancer and transient ischemic attacks (strokes). PMID:22399926

Self-Assembled Polymeric Ionic Liquid-Functionalized Cellulose Nano-crystals: Constructing 3D Ion-conducting Channels Within Ionic Liquid-based Composite Polymer Electrolytes.

PubMed

Shi, Qing Xuan; Xia, Qing; Xiang, Xiao; Ye, Yun Sheng; Peng, Hai Yan; Xue, Zhi Gang; Xie, Xiao Lin; Mai, Yiu-Wing

2017-09-04

Composite polymeric and ionic liquid (IL) electrolytes are some of the most promising electrolyte systems for safer battery technology. Although much effort has been directed towards enhancing the transport properties of polymer electrolytes (PEs) through nanoscopic modification by incorporating nano-fillers, it is still difficult to construct ideal ion conducting networks. Here, a novel class of three-dimensional self-assembled polymeric ionic liquid (PIL)-functionalized cellulose nano-crystals (CNC) confining ILs in surface-grafted PIL polymer chains, able to form colloidal crystal polymer electrolytes (CCPE), is reported. The high-strength CNC nano-fibers, decorated with PIL polymer chains, can spontaneously form three-dimensional interpenetrating nano-network scaffolds capable of supporting electrolytes with continuously connected ion conducting networks with IL being concentrated in conducting domains. These new CCPE have exceptional ionic conductivities, low activation energies (close to bulk IL electrolyte with dissolved Li salt), high Li + transport numbers, low interface resistances and improved interface compatibilities. Furthermore, the CCPE displays good electrochemical properties and a good battery performance. This approach offers a route to leak-free, non-flammable and high ionic conductivity solid-state PE in energy conversion devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Physics of Hard Sphere Experiment: Scattering, Rheology and Microscopy Study of Colloidal Particles

NASA Technical Reports Server (NTRS)

Cheng, Z.-D.; Zhu, J.; Phan, S.-E.; Russel, W. B.; Chaikin, P. M.; Meyer, W. V.

2002-01-01

The Physics of Hard Sphere Experiment has two incarnations: the first as a scattering and rheology experiment on STS-83 and STS-94 and the second as a microscopy experiment to be performed in the future on LMM on the space station. Here we describe some of the quantitative and qualitative results from previous flights on the dynamics of crystallization in microgravity and especially the observed interaction of growing crystallites in the coexistance regime. To clarify rheological measurements we also present ground based experiments on the low shear rate viscosity and diffusion coefficient of several hard sphere experiments at high volume fraction. We also show how these experiments will be performed with confocal microscopy and laser tweezers in our lab and as preparation for the phAse II experiments on LMM. One of the main aims of the microscopy study will be the control of colloidal samples using an array of applied fields with an eye toward colloidal architectures. Temperature gradients, electric field gradients, laser tweezers and a variety of switchable imposed surface patterns are used toward this control.

Broadband moth-eye antireflection coatings on silicon

NASA Astrophysics Data System (ADS)

Sun, Chih-Hung; Jiang, Peng; Jiang, Bin

2008-02-01

We report a bioinspired templating technique for fabricating broadband antireflection coatings that mimic antireflective moth eyes. Wafer-scale, subwavelength-structured nipple arrays are directly patterned on silicon using spin-coated silica colloidal monolayers as etching masks. The templated gratings exhibit excellent broadband antireflection properties and the normal-incidence specular reflection matches with the theoretical prediction using a rigorous coupled-wave analysis (RCWA) model. We further demonstrate that two common simulation methods, RCWA and thin-film multilayer models, generate almost identical prediction for the templated nipple arrays. This simple bottom-up technique is compatible with standard microfabrication, promising for reducing the manufacturing cost of crystalline silicon solar cells.

Bioinspired broadband antireflection coatings on GaSb

NASA Astrophysics Data System (ADS)

Min, Wei-Lun; Betancourt, Amaury P.; Jiang, Peng; Jiang, Bin

2008-04-01

We report an inexpensive yet scalable templating technique for fabricating moth-eye antireflection gratings on gallium antimonide substrates. Non-close-packed colloidal monolayers are utilized as etching masks to pattern subwavelength-structured nipple arrays on GaSb. The resulting gratings exhibit superior broadband antireflection properties and thermal stability than conventional multilayer dielectric coatings. The specular reflection of the templated nipple arrays match with the theoretical predictions using a rigorous coupled-wave analysis model. The effect of the nipple shape and size on the antireflection properties has also been investigated by the same model. These biomimetic coatings are of great technological importance in developing efficient thermophotovoltaic cells.

Two Photon Polymerization of Microneedles for Transdermal Drug Delivery

PubMed Central

Gittard, Shaun D.; Ovsianikov, Aleksandr; Chichkov, Boris N.; Doraiswamy, Anand; Narayan, Roger J.

2010-01-01

Importance of the field Microneedles are small-scale devices that are finding use for transdermal delivery of protein-based pharmacologic agents and nucleic acid-based pharmacologic agents; however, microneedles prepared using conventional microelectronics-based technologies have several shortcomings, which have limited translation of these devices into widespread clinical use. Areas covered in this review Two photon polymerization is a laser-based rapid prototyping technique that has been recently used for direct fabrication of hollow microneedles with a wide variety of geometries. In addition, an indirect rapid prototyping method that involves two photon polymerization and polydimethyl siloxane micromolding has been used for fabrication of solid microneedles with exceptional mechanical properties. What the reader will gain In this review, the use of two photon polymerization for fabricating in-plane and out-of-plane hollow microneedle arrays is described. The use of two photon polymerization-micromolding for fabrication of solid microneedles is also reviewed. In addition, fabrication of microneedles with antimicrobial properties is discussed; antimicrobial microneedles may reduce the risk of infection associated with formation of channels through the stratum corneum. Take home message It is anticipated that the use of two photon polymerization as well as two photon polymerization-micromolding for fabrication of microneedles and other microstructured drug delivery devices will increase over the coming years. PMID:20205601

Improving the performance of membrane bioreactors by powdered activated carbon dosing with cost considerations.

PubMed

Yang, W; Paetkau, M; Cicek, N

2010-01-01

Effects of powdered activated carbon (PAC) dosing on the overall performance of membrane bioreactors (MBR) were investigated in two bench-scale submerged MBRs. Positive impacts of PAC dosing on membrane fouling and the removal of 17beta-estradiol (E2) and 17alpha-ethyinylestradiol (EE2) were demonstrated over a six-month stable operational period. PAC dosing in the MBR increased the removal rates of E2 and EE2 by 3.4% and 15.8%, respectively. The average soluble extracellular polymeric substances (EPS) and colloidal total organic carbon (TOC) concentrations in the PAC-MBR sludge was 60.1% and 61.8% lower than the control MBR sludge, respectively. Lower soluble EPS and colloidal TOC concentrations in the PAC-MBR sludge resulted in a slower rate of trans-membrane pressure (TMP) increase during MBRs operation, which could prolong the lifespan of membranes. Cost assessment showed that PAC dosing could reduce the operating cost for membrane cleaning and/or membrane replacement by about 25%. The operating cost for PAC dosing could be offset by the benefit from its reducing the cost for membrane maintenance.

Study of the self-organization processes in lead sulfide quantum dots

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

Tarasov, S. A., E-mail: SATarasov@mail.ru; Aleksandrova, O. A.; Maksimov, A. I.

A procedure is described for the synthesis of nanoparticles based on lead chalcogenides. The procedure combines the synthesis of colloidal quantum dots (QDs) in aqueous solutions with simultaneous organization of the QDs into ordered arrays. The processes of the self-organization of QDs are analyzed at the nano- and microscopic levels by the photoluminescence method, atomic-force microscopy, and optical microscopy.

Creation of antifouling microarrays by photopolymerization of zwitterionic compounds for protein assay and cell patterning.

PubMed

Sun, Xiuhua; Wang, Huaixin; Wang, Yuanyuan; Gui, Taijiang; Wang, Ke; Gao, Changlu

2018-04-15

Nonspecific binding or adsorption of biomolecules presents as a major obstacle to higher sensitivity, specificity and reproducibility in microarray technology. We report herein a method to fabricate antifouling microarray via photopolymerization of biomimetic betaine compounds. In brief, carboxybetaine methacrylate was polymerized as arrays for protein sensing, while sulfobetaine methacrylate was polymerized as background. With the abundant carboxyl groups on array surfaces and zwitterionic polymers on the entire surfaces, this microarray allows biomolecular immobilization and recognition with low nonspecific interactions due to its antifouling property. Therefore, low concentration of target molecules can be captured and detected by this microarray. It was proved that a concentration of 10ngmL -1 bovine serum albumin in the sample matrix of bovine serum can be detected by the microarray derivatized with anti-bovine serum albumin. Moreover, with proper hydrophilic-hydrophobic designs, this approach can be applied to fabricate surface-tension droplet arrays, which allows surface-directed cell adhesion and growth. These light controllable approaches constitute a clear improvement in the design of antifouling interfaces, which may lead to greater flexibility in the development of interfacial architectures and wider application in blood contact microdevices. Copyright © 2017 Elsevier B.V. All rights reserved.

Board-to-board optical interconnection using novel optical plug and slot

NASA Astrophysics Data System (ADS)

Cho, In K.; Yoon, Keun Byoung; Ahn, Seong H.; Kim, Jin Tae; Lee, Woo Jin; Shin, Kyoung Up; Heo, Young Un; Park, Hyo Hoon

2004-10-01

A novel optical PCB with transmitter/receiver system boards and optical bakcplane was prepared, which is board-to-board interconnection by optical plug and slot. We report an 8Gb/s PRBS NRZ data transmission between transmitter system board and optical backplane embedded multimode polymeric waveguide arrays. The basic concept of ETRI's optical PCB is as follows; 1) Metal optical bench is integrated with optoelectronic devices, driver and receiver circuits, polymeric waveguide and access line PCB module. 2) Multimode polymeric waveguide inside an optical backplane, which is embedded into PCB. 3) Optical slot and plug for high-density(channel pitch : 500um) board-to-board interconnection. The polymeric waveguide technology can be used for transmission of data on transmitter/ receiver system boards and for backplane interconnections. The main components are low-loss tapered polymeric waveguides and a novel optical plug and slot for board-to-board interconnections, respectively. The optical PCB is characteristic of low coupling loss, easy insertion/extraction of the boards and, especially, reliable optical coupling unaffected from external environment after board insertion.

Reproducible, high-throughput synthesis of colloidal nanocrystals for optimization in multidimensional parameter space.

PubMed

Chan, Emory M; Xu, Chenxu; Mao, Alvin W; Han, Gang; Owen, Jonathan S; Cohen, Bruce E; Milliron, Delia J

2010-05-12

While colloidal nanocrystals hold tremendous potential for both enhancing fundamental understanding of materials scaling and enabling advanced technologies, progress in both realms can be inhibited by the limited reproducibility of traditional synthetic methods and by the difficulty of optimizing syntheses over a large number of synthetic parameters. Here, we describe an automated platform for the reproducible synthesis of colloidal nanocrystals and for the high-throughput optimization of physical properties relevant to emerging applications of nanomaterials. This robotic platform enables precise control over reaction conditions while performing workflows analogous to those of traditional flask syntheses. We demonstrate control over the size, size distribution, kinetics, and concentration of reactions by synthesizing CdSe nanocrystals with 0.2% coefficient of variation in the mean diameters across an array of batch reactors and over multiple runs. Leveraging this precise control along with high-throughput optical and diffraction characterization, we effectively map multidimensional parameter space to tune the size and polydispersity of CdSe nanocrystals, to maximize the photoluminescence efficiency of CdTe nanocrystals, and to control the crystal phase and maximize the upconverted luminescence of lanthanide-doped NaYF(4) nanocrystals. On the basis of these demonstrative examples, we conclude that this automated synthesis approach will be of great utility for the development of diverse colloidal nanomaterials for electronic assemblies, luminescent biological labels, electroluminescent devices, and other emerging applications.

Flexible Teflon nanocone array surfaces with tunable superhydrophobicity for self-cleaning and aqueous droplet patterning.

PubMed

Toma, Mana; Loget, Gabriel; Corn, Robert M

2014-07-23

Tunable hydrophobic/hydrophilic flexible Teflon nanocone array surfaces were fabricated over large areas (cm(2)) by a simple two-step method involving the oxygen plasma etching of a colloidal monolayer of polystyrene beads on a Teflon film. The wettability of the nanocone array surfaces was controlled by the nanocone array dimensions and various additional surface modifications. The resultant Teflon nanocone array surfaces were hydrophobic and adhesive (a "gecko" type of surface on which a water droplet has a high contact angle but stays in place) with a contact angle that correlated with the aspect ratio/sharpness of the nanocones. The surfaces switched to a superhydrophobic or "lotus" type of surface when hierarchical nanostructures were created on Teflon nanocones by modifying them with a gold nanoparticle (AuNPs) film. The nanocone array surfaces could be made superhydrophobic with a maximum contact angle of 160° by the further modification of the AuNPs with an octadecanethiol (C18SH) monolayer. Additionally, these nanocone array surfaces became hydrophilic when the nanocone surfaces were sequentially modified with AuNPs and hydrophilic polydopamine (PDA) layers. The nanocone array surfaces were tested for two potential applications: self-cleaning superhydrophobic surfaces and for the passive dispensing of aqueous droplets onto hybrid superhydrophobic/hydrophilic microarrays.

Utilizing stretch-tunable thermochromic elastomeric opal films as novel reversible switchable photonic materials.

PubMed

Schäfer, Christian G; Lederle, Christina; Zentel, Kristina; Stühn, Bernd; Gallei, Markus

2014-11-01

In this work, the preparation of highly thermoresponsive and fully reversible stretch-tunable elastomeric opal films featuring switchable structural colors is reported. Novel particle architectures based on poly(diethylene glycol methylether methacrylate-co-ethyl acrylate) (PDEGMEMA-co-PEA) as shell polymer are synthesized via seeded and stepwise emulsion polymerization protocols. The use of DEGMEMA as comonomer and herein established synthetic strategies leads to monodisperse soft shell particles, which can be directly processed to opal films by using the feasible melt-shear organization technique. Subsequent UV crosslinking strategies open access to mechanically stable and homogeneous elastomeric opal films. The structural colors of the opal films feature mechano- and thermoresponsiveness, which is found to be fully reversible. Optical characterization shows that the combination of both stimuli provokes a photonic bandgap shift of more than 50 nm from 560 nm in the stretched state to 611 nm in the fully swollen state. In addition, versatile colorful patterns onto the colloidal crystal structure are produced by spatial UV-induced crosslinking by using a photomask. This facile approach enables the generation of spatially cross-linked switchable opal films with fascinating optical properties. Herein described strategies for the preparation of PDEGMEMA-containing colloidal architectures, application of the melt-shear ordering technique, and patterned crosslinking of the final opal films open access to novel stimuli-responsive colloidal crystal films, which are expected to be promising materials in the field of security and sensing applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembly of resins and asphaltenes facilitates asphaltene dissolution by an organic acid.

PubMed

Hashmi, Sara M; Firoozabadi, Abbas

2013-03-15

Asphaltene precipitation occurs in petroleum fluids under certain unfavorable conditions, but can be controlled by tuning composition. Aromatic solvents in large quantities can prevent precipitation entirely and can dissolve already precipitated asphaltenes. Some polymeric surfactants can dissolve asphaltenes when added at much lower concentrations than required by aromatic solvents. Other dispersants can truncate asphaltene precipitation at the sub-micron length scale, creating stable colloidal asphaltene dispersants. One particular asphaltene dispersant, dodecylbenzene sulfonic acid (DBSA), can do both, namely: (1) stabilize asphaltene colloids and (2) dissolve asphaltenes to the molecular scale. Acid-base interactions are responsible for the efficiency of DBSA in dissolving asphaltenes compared to aromatic solvents. However, many details remain to be quantified regarding the action of DBSA on asphaltenes, including the effect of petroleum fluid composition. For instance, resins, naturally amphiphilic components of petroleum fluids, can associate with asphaltenes, but it is unknown whether they cooperate or compete with DBSA. Similarly, the presence of metals is known to hinder asphaltene dissolution by DBSA, but its effect on colloidal asphaltene stabilization has yet to be considered. We introduce the concepts of cooperativity and competition between petroleum fluid components and DBSA in stabilizing and dissolving asphaltenes. Notably, we find that resins cooperatively interact with DBSA in dissolving asphaltenes. We use UV-vis spectroscopy to investigate the interactions responsible for the phase transitions between unstable suspensions, stable suspensions, and molecular solutions of asphaltenes. Copyright © 2012 Elsevier Inc. All rights reserved.

β-Cyclodextrin polymer brushes decorated magnetic colloidal nanocrystal clusters for the release of hydrophobic drugs

NASA Astrophysics Data System (ADS)

Lv, Shaonan; Zhao, Meiqin; Cheng, Changjing; Zhao, Zhigang

2014-05-01

β-Cyclodextrin (β-CD) polymer brushes decorated magnetic Fe3O4 colloidal nanocrystal clusters (Fe3O4@PG-CD) were fabricated by a combination of surface-initiated atom transfer radical polymerization on the surface of Br-anchored Fe3O4 colloidal nanocrystal clusters (Fe3O4-Br) and ring-opening reaction of epoxy groups. The resulted Fe3O4@PG-CD hybrid nanoparticles were characterized by several methods including Fourier transform infrared, transmission electron microscope, dynamic light scattering instrument, X-ray diffraction, thermogravimetric analysis, and vibrating sample magnetometer. Moreover, the potential of as-synthesized Fe3O4@PG-CD as a carrier of hydrophobic anticancer drug 5-fluorouracil (5-FU) was also investigated. The results showed that the prepared Fe3O4@PG-CD have core/shell structure and high saturated magnetism. 5-FU could be loaded into the Fe3O4@PG-CD via the formation of β-CD/5-FU inclusion complex. Furthermore, the Fe3O4@PG-CD displayed a high loading capacity and pH-dependent release behavior for 5-FU. The release behavior demonstrated a simple Fickian diffusion in the acidic environment (pH 2.0 and 4.0) but neither non-Fickian nor anomalous when neutral. The results reveal that this nanosystem seems to be a very promising vehicle for the hydrophobic drugs for pH-dependent controlled release.

Ultraflexible nanostructures and implications for future nanorobots

NASA Astrophysics Data System (ADS)

Cohn, Robert W.; Panchapakesan, Balaji

2016-05-01

Several high aspect ratio nanostructures have been made by capillary force directed self-assembly including polymeric nanofiber air-bridges, trampoline-like membranes, microsphere-beaded nanofibers, and intermetallic nanoneedles. Arrays of polymer air-bridges form in seconds by simply hand brushing a bead of polymeric liquid over an array of micropillars. The domination of capillary force that is thinning unstable capillary bridges leads to uniform arrays of nanofiber air-bridges. Similarly, arrays of vertically oriented Ag2Ga nanoneedles have been formed by dipping silvercoated arrays of pyramidal silicon into melted gallium. Force-displacement measurements of these structures are presented. These nanostructures, especially when compressively or torsionally buckled, have extremely low stiffnesses, motion due to thermal fluctuations that is relatively easily detected, and the ability to move great distances for very small changes in applied force. Nanofibers with bead-on-a-string structure, where the beads are micron diameter and loaded with magnetic iron oxide (maghemite), are shown to be simply viewable under optical microscopes, have micronewton/ m stiffness, and have ultralow torsional stiffnesses enabling the bead to be rotated numerous revolutions without breaking. Combination of these high aspect ratio structures with stretched elastomers offer interesting possibilities for robotic actuation and locomotion. Polydimethylsiloxane loaded with nanomaterials, e.g. nanotubes, graphene or MoS2, can be efficiently heated with directed light. Heating produces considerable force through the thermoelastic effect, and this force can be used for continuous translation or to trigger reversible elastic buckling of the nanostructures. The remote stimulation of motion with light provides a possible mechanism for producing cooperative behavior between swarms of semiautonomous nanorobots.

Form and stability of aluminum hydroxide complexes in dilute solution

USGS Publications Warehouse

Hem, John David; Roberson, Charles Elmer

1967-01-01

Laboratory studies of solutions 4.53 x 10 -4 to 4.5 x 10 -5 molal (12.2-1.2 ppm) in aluminum, in 0.01 molal sodium perchlorate, were conducted to obtain information as to the probable behavior of aluminum in natural water. When the solutions were brought to pH 7.5-9.5 and allowed to stand for 24 hours, a precipitate was obtained which was virtually amorphous as shown by X-rays, and which had a solubility equivalent to that of boehmite. This precipitate had a hydrolysis constant (*Ks4) of 1.93 x 10 -13a. When solutions were allowed to stead at this pH range for 10 days, their precipitates gave the X-ray pattern of bayerite (*Ks4 = 1.11 > (10- 4). These hydrolysis constants were obtained at 25?C. and corrected to zero ionic strength and are in close agreement with other published values. The predominant dissolved form in this pH range is Al(OH) -4. Below neutral pH (7.0) the dissolved aluminum species consist of octahedral units in which each aluminum ion is surrounded by six water molecules or hydroxide ions. Single units such as Al(OH2)6 + 3 and AlOH(OH2)5+2 are most abundant below pH 5.0, and where the molar ratio (r) of combined hydroxide to total dissolved aluminum is low. When r is greater than 1.0, polymerization of the octahedral units occurs. When r is between 2.0 and 3.0, solutions aged for 10 days or more contained colloidal particles between 0.10 and 0.45 ? in diameter. Particles whose diameters were greater than 0.10 ? were identified by X-ray diffraction as gibbsite. Particles smaller than 0.10 ? were also present and were shown by means of the electron microscope to have a hexagonal crystal pattern. Structured material consisting of sheets of coalesced six-membered rings of aluminum ions held together by double OH bridges has a distinctive kinetic behavior. This property was used to determine amounts of polymerized material in solutions having r between 1.0 and 3.0 after aging times ranging from a few hours to more than 4 months. Aging increased the size and orderliness of the polymeric aggregates and was accompanied by a decrease in the pH of the solution. The kinetic experiments and stoichiometric data for solutions aged for long periods provided a means of determining activities of polymerized aluminum. From these values the solubility product for microcrystalline gibbsite was determined to be 2.24 x 10 -3, and its free energy of formation, -? 272.3 0.4 kcal per mole. Where polymerization was observed, the process did not stop with small polynuclear complexes containing a few aluminum ions, but proceeded with aging until macromolecules or colloidal-sized particles were formed.

Confined surface plasmon sensors based on strongly coupled disk-in-volcano arrays.

PubMed

Ai, Bin; Wang, Limin; Möhwald, Helmuth; Yu, Ye; Zhang, Gang

2015-02-14

Disk-in-volcano arrays are reported to greatly enhance the sensing performance due to strong coupling in the nanogaps between the nanovolcanos and nanodisks. The designed structure, which is composed of a nanovolcano array film and a disk in each cavity, is fabricated by a simple and efficient colloidal lithography method. By tuning structural parameters, the disk-in-volcano arrays show greatly enhanced resonances in the nanogaps formed by the disks and the inner wall of the volcanos. Therefore they respond to the surrounding environment with a sensitivity as high as 977 nm per RIU and with excellent linear dependence on the refraction index. Moreover, through mastering the fabrication process, biological sensing can be easily confined to the cavities of the nanovolcanos. The local responsivity has the advantages of maximum surface plasmon energy density in the nanogaps, reducing the sensing background and saving expensive reagents. The disk-in-volcano arrays also possess great potential in applications of optical and electrical trapping and single-molecule analysis, because they enable establishment of electric fields across the gaps.

Application of the Solubility Parameter Concept to the Design of Chemiresistor Arrays

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

Eastman, M.P.; Hughes, R.C.; Jenkins, M.W.

1999-01-11

Arrays of unheated chemically sensitive resistors (chemiresistors) can serve as extremely small, low-power-consumption sensors with simple read-out electronics. We report here results on carbon-loaded polymer composites, as well as polymeric ionic conductors, as chemiresistor sensors. We use the volubility parameter concept to understand and categorize the chemiresistor responses and, in particular, we compare chemiresistors fabricated from polyisobutylene (PIB) to results from PIB-coated acoustic wave sensors. One goal is to examine the possibility that a small number of diverse chemiresistors can sense all possible solvents-the "Universal Solvent Sensor Array". keywords: chemiresistor, volubility parameter, chemical sensor

Plasmonic Photovoltaic Cells with Dual-Functional Gold, Silver, and Copper Half-Shell Arrays.

PubMed

Wu, Ling; Kim, Gyu Min; Nishi, Hiroyasu; Tatsuma, Tetsu

2017-09-12

Solid-state photovoltaic cells based on plasmon-induced charge separation (PICS) have attracted growing attention during the past decade. However, the power conversion efficiency (PCE) of the previously reported devices, which are generally loaded with dispersed metal nanoparticles as light absorbers, has not been sufficiently high. Here we report simpler plasmonic photovoltaic cells with interconnected Au, Ag, and Cu half-shell arrays deposited on SiO 2 @TiO 2 colloidal crystals, which serve both as a plasmonic light absorber and as a current collector. The well-controlled and easily prepared plasmonic structure allows precise comparison of the PICS efficiency between different plasmonic metal species. The cell with the Ag half-shell array has higher photovoltaic performance than the cells with Au and Cu half-shell arrays because of the high population of photogenerated energetic electrons, which gives a high electron injection efficiency and suppressed charge recombination probability, achieving the highest PCE among the solid-state PICS devices even without a hole transport layer.

Strong light extraction enhancement using TiO2 nanoparticles-based microcone arrays embossed on III-Nitride light emitting diodes

NASA Astrophysics Data System (ADS)

Désières, Yohan; Chen, Ding Yuan; Visser, Dennis; Schippers, Casper; Anand, Srinivasan

2018-06-01

Colloidal TiO2 nanoparticles were used for embossing of composite microcone arrays on III-Nitride vertical-thin-film blue light emitting diodes (LEDs) as well as on silicon, glass, gallium arsenide, and gallium nitride surfaces. Ray tracing simulations were performed to optimize the design of microcones for light extraction and to explain the experimental results. An optical power enhancement of ˜2.08 was measured on III-Nitride blue LEDs embossed with a hexagonal array of TiO2 microcones of ˜1.35 μm in height and ˜2.6 μm in base width, without epoxy encapsulation. A voltage increase in ˜70 mV at an operating current density of ˜35 A/cm2 was measured for the embossed LEDs. The TiO2 microcone arrays were embossed on functioning LEDs, using low pressures (˜100 g/cm2) and temperatures ≤100 °C.

Programmable Matter

DTIC Science & Technology

2012-01-03

over it (Fig. 3d). The hydrogel prepolymer is then photopolymerized using a mask to align the electrical array with the polymer shape’s design. In...order to sandwich the electronic mesh into the receiving hydrogel, a second hydrogel prepolymer solution is then added and polymerized in registry

Bioinspired polyethylene terephthalate nanocone arrays with underwater superoleophobicity and anti-bioadhesion properties

NASA Astrophysics Data System (ADS)

Liu, Wendong; Liu, Xueyao; Fangteng, Jiaozi; Wang, Shuli; Fang, Liping; Shen, Huaizhong; Xiang, Siyuan; Sun, Hongchen; Yang, Bai

2014-10-01

This paper presents a facile method to fabricate bioinspired polyethylene terephthalate (PET) nanocone arrays via colloidal lithography. The aspect ratio (AR) of the nanocones can be finely modulated ranging from 1 to 6 by regulating the etching time. The samples with the AR value of 6 can present underwater superoleophobicity with the underwater oil contact angle (OCA) of 171.8°. The as-prepared PET nanocone arrays perform anti-bioadhesion behavior, which inhibits the formation of the actin cytoskeleton when it used as the substrate for cell culture. Moreover, the oil wettability is temperature controlled after modifying the PET nanocone arrays with PNIPAAm film, and the oil wettability of the functionalized nanocone arrays can be transformed from the superoleophobic state with OCA about 151° to the oleophilic state with OCA about 25° reversibly. Due to the high-throughput, parallel fabrication and cost-efficiency of this method, it will be favourable for researchers to introduce oleophobic properties to various substrate and device surfaces. Due to the superoleophobicity and simple functionalizing properties, the PET nanocone arrays are very promising surfaces for anti-adhesion, self-cleaning and have potential applications in material, medical, and biological fields.This paper presents a facile method to fabricate bioinspired polyethylene terephthalate (PET) nanocone arrays via colloidal lithography. The aspect ratio (AR) of the nanocones can be finely modulated ranging from 1 to 6 by regulating the etching time. The samples with the AR value of 6 can present underwater superoleophobicity with the underwater oil contact angle (OCA) of 171.8°. The as-prepared PET nanocone arrays perform anti-bioadhesion behavior, which inhibits the formation of the actin cytoskeleton when it used as the substrate for cell culture. Moreover, the oil wettability is temperature controlled after modifying the PET nanocone arrays with PNIPAAm film, and the oil wettability of the functionalized nanocone arrays can be transformed from the superoleophobic state with OCA about 151° to the oleophilic state with OCA about 25° reversibly. Due to the high-throughput, parallel fabrication and cost-efficiency of this method, it will be favourable for researchers to introduce oleophobic properties to various substrate and device surfaces. Due to the superoleophobicity and simple functionalizing properties, the PET nanocone arrays are very promising surfaces for anti-adhesion, self-cleaning and have potential applications in material, medical, and biological fields. Electronic supplementary information (ESI) available: The optical microscopy image of the self-assembled 2D PS microspheres over a large area, the diameter of the PS microsphere is 580 nm; The top-view SEM image of the PET nanocone arrays over a large area, the AR of the nanocone is 6; The SEM image of the PET nanocone arrays obtained after 30 min etching; The optical image of the water droplet on the PET nanocone arrays with an AR of 6; The schematic illustration of the nanocone arrays modification with PNIPAAm; High resolution XPS spectra of the PNIPAAm modified PET nanocone arrays. See DOI: 10.1039/c4nr04471a

Segregation of colloidal swimmers by their activity

NASA Astrophysics Data System (ADS)

Ferrari, Melissa; Youssef, Mena; Driscoll, Michelle; Sacanna, Stefano; Pine, David; Chaikin, Paul

We study a system of micron sized self-propelled colloidal swimmers whose activity can be switched on or off with the flick of a light switch. We have designed a system where an external LED source reflects light off of an array with hundreds of thousands of independently controlled tiny mirrors, through an optical microscope, and onto the plane of the swimmers. By exposing a collection of particles to a spatial or dynamic light field, we have the ability to control the speed of a particle based on its position, and therefore the density of the collection of particles in space. Theoreticians in the field have been building a framework that describes systems which are out-of-equilibrium and we will show how our system can be useful tool in mapping these theories to experiment. Center for Bio-inspired Energy Science.

The Growth-Suppressive Function of the Polycomb Group Protein Polyhomeotic Is Mediated by Polymerization of Its Sterile Alpha Motif (SAM) Domain*

PubMed Central

Robinson, Angela K.; Leal, Belinda Z.; Chadwell, Linda V.; Wang, Renjing; Ilangovan, Udayar; Kaur, Yogeet; Junco, Sarah E.; Schirf, Virgil; Osmulski, Pawel A.; Gaczynska, Maria; Hinck, Andrew P.; Demeler, Borries; McEwen, Donald G.; Kim, Chongwoo A.

2012-01-01

Polyhomeotic (Ph), a member of the Polycomb Group (PcG), is a gene silencer critical for proper development. We present a previously unrecognized way of controlling Ph function through modulation of its sterile alpha motif (SAM) polymerization leading to the identification of a novel target for tuning the activities of proteins. SAM domain containing proteins have been shown to require SAM polymerization for proper function. However, the role of the Ph SAM polymer in PcG-mediated gene silencing was uncertain. Here, we first show that Ph SAM polymerization is indeed required for its gene silencing function. Interestingly, the unstructured linker sequence N-terminal to Ph SAM can shorten the length of polymers compared with when Ph SAM is individually isolated. Substituting the native linker with a random, unstructured sequence (RLink) can still limit polymerization, but not as well as the native linker. Consequently, the increased polymeric Ph RLink exhibits better gene silencing ability. In the Drosophila wing disc, Ph RLink expression suppresses growth compared with no effect for wild-type Ph, and opposite to the overgrowth phenotype observed for polymer-deficient Ph mutants. These data provide the first demonstration that the inherent activity of a protein containing a polymeric SAM can be enhanced by increasing SAM polymerization. Because the SAM linker had not been previously considered important for the function of SAM-containing proteins, our finding opens numerous opportunities to manipulate linker sequences of hundreds of polymeric SAM proteins to regulate a diverse array of intracellular functions. PMID:22275371

Novel anti-reflection technology for GaAs single-junction solar cells using surface patterning and Au nanoparticles.

PubMed

Kim, Youngjo; Lam, Nguyen Dinh; Kim, Kangho; Kim, Sangin; Rotermund, Fabian; Lim, Hanjo; Lee, Jaejin

2012-07-01

Single-junction GaAs solar cell structures were grown by low-pressure MOCVD on GaAs (100) substrates. Micro-rod arrays with diameters of 2 microm, 5 microm, and 10 microm were fabricated on the surfaces of the GaAs solar cells via photolithography and wet chemical etching. The patterned surfaces were coated with Au nanoparticles using an Au colloidal solution. Characteristics of the GaAs solar cells with and without the micro-rod arrays and Au nanoparticles were investigated. The short-circuit current density of the GaAs solar cell with 2 microm rod arrays and Au nanoparticles increased up to 34.9% compared to that of the reference cell without micro-rod arrays and Au nanoparticles. The conversion efficiency of the GaAs solar cell that was coated with Au nanoparticles on the patterned surface with micro-rod arrays can be improved from 14.1% to 19.9% under 1 sun AM 1.5G illumination. These results show that micro-rod arrays and Au nanoparticle coating can be applied together in surface patterning to achieve a novel cost-effective anti-reflection technology.

Analysis of polymeric phenolics in red wines using different techniques combined with gel permeation chromatography fractionation.

PubMed

Guadalupe, Zenaida; Soldevilla, Alberto; Sáenz-Navajas, María-Pilar; Ayestarán, Belén

2006-04-21

A multiple-step analytical method was developed to improve the analysis of polymeric phenolics in red wines. With a common initial step based on the fractionation of wine phenolics by gel permeation chromatography (GPC), different analytical techniques were used: high-performance liquid chromatography-diode array detection (HPLC-DAD), HPLC-mass spectrometry (MS), capillary zone electrophoresis (CZE) and spectrophotometry. This method proved to be valid for analyzing different families of phenolic compounds, such as monomeric phenolics and their derivatives, polymeric pigments and proanthocyanidins. The analytical characteristics of fractionation by GPC were studied and the method was fully validated, yielding satisfactory statistical results. GPC fractionation substantially improved the analysis of polymeric pigments by CZE, in terms of response, repeatability and reproducibility. It also represented an improvement in the traditional vanillin assay used for proanthocyanidin (PA) quantification. Astringent proanthocyanidins were also analyzed using a simple combined method that allowed these compounds, for which only general indexes were available, to be quantified.

The competing effects of microbially derived polymeric and low molecular-weight substances on the dispersibility of CeO2 nanoparticles

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

Nakano, Yuriko; Ochiai, Asumi; Kawamoto, Keisuke

To understand the competing effects of the components in extracellular substances (ES), polymeric substances (PS) and low-molecular-weight small substances (SS) <1 kDa derived from microorganisms, on the colloidal stability of cerium dioxide nanoparticles (CeNPs), we investigated their adsorption to sparingly soluble CeNPs at room temperature at pH 6.0. The ES was extracted from the fungus S. cerevisiae. The polypeptides and phosphates in all components preferentially adsorbed onto the CeNPs. The zeta potentials of ES + CeNPs, PS + CeNPs, and SS + CeNPs overlapped on the plot of PS itself, indicating the surface charge of the polymeric substances controls themore » zeta potentials. The sizes of the CeNP aggregates, 100–1300 nm, were constrained by the zeta potentials. The steric barrier derived from the polymers, even in SS, enhanced the CeNP dispersibility at pH 1.5–10. Consequently, the PS and SS had similar effects on modifying the CeNP surfaces. The adsorption of ES, which contains PS + SS, can suppress the aggregation of CeNPs over a wider pH range than that for PS only. The present study addresses the non-negligible effects of small-sized molecules derived from microbial activity on the migration of CeNP in aquatic environments, especially where bacterial consortia prevail.« less

Development of an immunochromatographic kit for rapid detection of human influenza B virus infection.

PubMed

Zhang, Peirui; Duan, Yueqiang; Zhang, Dexi; Zhang, Shaogeng; Li, Zhiwei; Wang, Xiliang; Yang, Penghui

2014-01-01

Type B influenza virus is a major epidemic strain responsible for considerable mortality and morbidity. A colloidal gold immunochromatographic strip for the rapid detection of human influenza B virus was developed. This test is based on membrane chromatography and uses colloidal gold conjugated with influenza B virus anti-NP monoclonal antibody as the tracer. The assembled test strip was housed in a plastic case. The colloid gold strip (CGS) specifically detected all influenza B viruses tested and did not react with other respiratory viruses. Compared with SYBR Green real-time PCR, the sensitivity and specificity of the CGS test was 89.76% and 99.56%, respectively, and the consistency ratio between CGS and real-time PCR was 96.06% in detecting influenza B virus in 710 nasopharyngeal swabs from patients with influenza-like illness in the hospital. The CGS array developed in this study enabled typing of influenza B viruses in human clinical specimens. Thus, together with the advantages of rapid detection and easy operation without requiring specialized personnel and equipment, this technique is a convenient and relatively inexpensive diagnostic tool for large-scale screening of clinical samples.

Folding dynamics of linear emulsion polymers into 3D architectures

NASA Astrophysics Data System (ADS)

McMullen, Angus; Bargteil, Dylan; Brujic, Jasna

Colloidal polymers have been limited to inflexible, solid colloids. Here we show that the fluidity of emulsion droplets allows for the self-assembly of flexible droplet chains, which can subsequently be folded into 3D structures via secondary interactions. We achieve this using DNA-guided interactions, to initially form the chain, and then program its folding pathways. When two emulsion droplets labeled with complementary DNA meet, the balance of hybridization energy and droplet deformation yields an equilibrium patch size. Therefore, the concentration of DNA on the surface determines the number of droplet-droplet bonds in the assembly. We find that 96 % of bound droplets successfully self-assemble into chains. Droplet binding is a stochastic process, following a Poisson distribution of lengths. Since the fluid droplets can rearrange, we compare the dynamics of emulsion chains to that of polymers. We also trigger secondary interactions along the chain, causing the formation of specific loops or compact clusters. This approach will allow us to fold our emulsion polymers into a wide array of soft structures, giving us a powerful biomimetic colloidal system to investigate protein folding on the mesoscopic scale. This work was supported by the NSF MRSEC Program (DMR-0820341).

Synthesis of Dispersible Mesoporous Nitrogen-Doped Hollow Carbon Nanoplates with Uniform Hexagonal Morphologies for Supercapacitors.

PubMed

Cao, Jie; Jafta, Charl J; Gong, Jiang; Ran, Qidi; Lin, Xianzhong; Félix, Roberto; Wilks, Regan G; Bär, Marcus; Yuan, Jiayin; Ballauff, Matthias; Lu, Yan

2016-11-02

In this study, dispersible mesoporous nitrogen-doped hollow carbon nanoplates have been synthesized as a new anisotropic carbon nanostructure using gibbsite nanoplates as templates. The gibbsite-silica core-shell nanoplates were first prepared before the gibbsite core was etched away. Dopamine as carbon precursor was self-polymerized on the hollow silica nanoplates surface assisted by sonification, which not only favors a homogeneous polymer coating on the nanoplates but also prevents their aggregation during the polymerization. Individual silica-polydopamine core-shell nanoplates were immobilized in a silica gel in an insulated state via a silica nanocasting technique. After pyrolysis in a nanoconfine environment and elimination of silica, discrete and dispersible hollow carbon nanoplates are obtained. The resulted hollow carbon nanoplates bear uniform hexagonal morphology with specific surface area of 460 m 2 ·g -1 and fairly accessible small mesopores (∼3.8 nm). They show excellent colloidal stability in aqueous media and are applied as electrode materials for symmetric supercapacitors. When using polyvinylimidazolium-based nanoparticles as a binder in electrodes, the hollow carbon nanoplates present superior performance in parallel to polyvinylidene fluoride (PVDF) binder.

Excimers from stable and persistent supramolecular radical-pairs in red/NIR-emitting organic nanoparticles and polymeric films.

PubMed

Blasi, Davide; Nikolaidou, Domna M; Terenziani, Francesca; Ratera, Imma; Veciana, Jaume

2017-03-29

In this work, the luminescence properties of new materials based on open-shell molecular systems are studied. In particular, we prepared polymeric films and organic nanoparticles (ONPs) doped with triphenylmethyl radical molecules. ONPs exhibit a uniform size distribution, spherical morphology and high colloidal stability. The emission spectrum of low-doped ONP suspensions and low-doped films is very similar to the emission spectrum of TTM in solution, while the luminescence lifetime and the luminescence quantum yield (LQY) are highly increased. Increasing the radical doping leads to a progressive decrease of the LQY and the appearance of a new broad excimeric band at longer wavelengths, both for ONPs and films. Thus, not only the luminescence properties were improved, but also the formation of excimers from stable and persistent supramolecular radical-pairs was observed for the first time. The good stability and luminescence properties with emission in the red-NIR region (650-800 nm), together with the open-shell nature of the emitter, make these free-radical excimer-forming materials promising candidates for optoelectronic and bioimaging applications.

Super-enhanced particle nucleation in styrene emulsion polymerization in the presence of sodium styrene sulfonate.

PubMed

Farias-Cepeda, Lorena; Herrera-Ordonez, Jorge; Hernandez-Martinez, Angel R; Estevez, Miriam; Rosales-Marines, Lucero

2017-08-15

The styrene (St) emulsion polymerization using Aerosol MA80 as surfactant and in the presence of sodium styrene sulfonate (NaSS) was studied. The effect of NaSS content was assessed using MA80 concentrations below and at the critical micellar concentration. It was found that at the higher NaSS and MA80 contents, the number of particles (N) reaches a maximum of the order of 10 17 particles/cm 3 water, a huge value that has never been reported. In this work an explanation for this super-enhanced particle nucleation phenomenon is proposed. Such hypothesis is based on the role of St-NaSS oligomers formed in the aqueous phase and their synergy with MA80 molecules to provide colloidal stability to the system. The proposal seems to be consistent with the experimental data obtained for the evolution of monomer conversion, N, particles size distribution and the wideness of this latter as well as with a theoretical estimation of the N. Copyright © 2017 Elsevier Inc. All rights reserved.

New thiol-responsive mono-cleavable block copolymer micelles labeled with single disulfides.

PubMed

Sourkohi, Behnoush Khorsand; Schmidt, Rolf; Oh, Jung Kwon

2011-10-18

Thiol-responsive symmetric triblock copolymers having single disulfide linkages in the middle blocks (called mono-cleavable block copolymers, ss-ABP(2)) were synthesized by atom transfer radical polymerization in the presence of a disulfide-labeled difunctional Br-initiator. These brush-like triblock copolymers consist of a hydrophobic polyacrylate block having pendent oligo(propylene oxide) and a hydrophilic polymethacrylate block having pendent oligo(ethylene oxide). Gel permeation chromatography and (1)H NMR results confirmed the synthesis of well-defined mono-cleavable block copolymers and revealed that polymerizations were well controlled. Because of amphiphilic nature, these copolymers self-assembled to form colloidally stable micelles above critical micellar concentration of 0.032 mg · mL(-1). In response to reductive reactions, disulfides in thiol-responsive micelles were cleaved. Atomic force microscopy and dynamic light scattering analysis suggested that the cleavage of disulfides caused dissociation of micelles to smaller-sized assembled structures in water. Moreover, in a biomedical perspective, the mono-cleavable block copolymer micelles are not cytotoxic and thus biocompatible. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface-enhanced Raman scattering from metal and transition metal nano-caped arrays

NASA Astrophysics Data System (ADS)

Sun, Huanhuan; Gao, Renxian; Zhu, Aonan; Hua, Zhong; Chen, Lei; Wang, Yaxin; Zhang, Yongjun

2018-03-01

The metal and transition metal cap-shaped arrays on polystyrene colloidal particle (PSCP) templates were fabricated to study the surface-enhanced Raman scattering (SERS) effect. We obtained the Ag and Fe complex film by a co-sputtering deposition method. The size of the deposited Fe particle was changed by the sputtering power. We also study the SERS enhancement mechanism by decorating the PATP probe molecule on the different films. The SERS signals increased firstly, and then decreased as the size of Fe particles grows gradually. The finite-difference time domain (FDTD) simulation and experimental Raman results manifest that SERS enhancement was mainly attributed to surface plasma resonance (SPR) between Ag and Ag nanoparticles. The SERS signals of PATP molecule were enhanced to reach a lowest detectable concentration of 10-8 mol/L. The research demonstrates that the SERS substrates with Ag-Fe cap-shaped arrays have a high sensitivity.

Synthesis and characterization of novel polyacid-stabilized latexes.

PubMed

Yang, Pengcheng; Armes, S P

2012-09-18

A series of novel polyacid macromonomers based on 2-hydroxypropyl methacrylate (HPMA) were prepared by atom transfer radical polymerization (ATRP) via a two-step route. First, a range of well-defined PHPMA homopolymer precursors were synthesized by ATRP using a tertiary amine-functionalized initiator, 2-(dimethylamino)ethyl-2-bromoisobutyrylamide, and a CuCl/2, 2'-bipyridine (bpy) catalyst in alcoholic media at 50 °C. ATRP polymerizations were relatively slow and poorly controlled in pure isopropanol (IPA), especially when targeting higher degrees of polymerization (DP > 30). Improved control was achieved by addition of water: low polydispersity (M(w)/M(n) < 1.25) PHPMA homopolymers of DP = 30, 40, 50, 60, or 70 were successfully prepared using a 9:1 w/w % IPA/water mixture at 50 °C. These PHPMA homopolymer precursors were then derivatized to produce the corresponding poly(2-(succinyloxy)propyl methacrylate) (PSPMA) macromonomers by quaternizing the tertiary amine end-group with excess 4-vinylbenzyl chloride, followed by esterification of the pendent hydroxyl groups using excess succinic anhydride at 20 °C. These polyacid macromonomers were evaluated as reactive steric stabilizers for polystyrene latex synthesis under either aqueous emulsion polymerization or alcoholic dispersion polymerization conditions. Near-monodisperse polystyrene latexes were obtained via aqueous emulsion polymerization using 10 wt % PSPMA macromonomer (with respect to styrene monomer) with various initiators as evidenced by scanning electron microscopy, disk centrifuge photosedimentometry and light scattering studies. PSPMA macromomer concentrations as low as 1.0 wt % also produced near-monodisperse latexes, suggesting that these PSPMA macromonomers are highly effective stabilizers. Alcoholic dispersion polymerization of styrene conducted in various ethanol/water mixtures with 10 wt % PSPMA(50) macromonomer produced relatively large near-monodisperse latexes. Increasing the water content in such formulations led to smaller latexes, as expected. Control experiments conducted with 10 wt % PSPMA(50) homopolymer produced relatively large polydisperse latexes via emulsion polymerization and only macroscopic precipitates via alcoholic dispersion polymerization. Thus the terminal styrene group on the macromonomer chains is essential for the formation of well-defined latexes. FT-IR spectroscopy indicated that these latexes contained PSPMA macromonomer, whereas (1)H NMR spectroscopy studies of dissolved latexes allowed stabilizer contents to be determined. Aqueous electrophoresis and X-ray photoelectron spectroscopy studies confirmed that the PSPMA macromonomer chains were located at the latex surface, as expected. Finally, these polyacid-stabilized polystyrene latexes exhibited excellent freeze-thaw stability and remained colloidally stable in the presence of electrolyte.

An overview of inverted colloidal crystal systems for tissue engineering.

PubMed

João, Carlos Filipe C; Vasconcelos, Joana Marta; Silva, Jorge Carvalho; Borges, João Paulo

2014-10-01

Scaffolding is at the heart of tissue engineering but the number of techniques available for turning biomaterials into scaffolds displaying the features required for a tissue engineering application is somewhat limited. Inverted colloidal crystals (ICCs) are inverse replicas of an ordered array of monodisperse colloidal particles, which organize themselves in packed long-range crystals. The literature on ICC systems has grown enormously in the past 20 years, driven by the need to find organized macroporous structures. Although replicating the structure of packed colloidal crystals (CCs) into solid structures has produced a wide range of advanced materials (e.g., photonic crystals, catalysts, and membranes) only in recent years have ICCs been evaluated as devices for medical/pharmaceutical and tissue engineering applications. The geometry, size, pore density, and interconnectivity are features of the scaffold that strongly affect the cell environment with consequences on cell adhesion, proliferation, and differentiation. ICC scaffolds are highly geometrically ordered structures with increased porosity and connectivity, which enhances oxygen and nutrient diffusion, providing optimum cellular development. In comparison to other types of scaffolds, ICCs have three major unique features: the isotropic three-dimensional environment, comprising highly uniform and size-controllable pores, and the presence of windows connecting adjacent pores. Thus far, this is the only technique that guarantees these features with a long-range order, between a few nanometers and thousands of micrometers. In this review, we present the current development status of ICC scaffolds for tissue engineering applications.

Reversible ratchet effects for vortices in conformal pinning arrays

DOE PAGES

Reichhardt, Charles; Ray, Dipanjan; Reichhardt, Cynthia Jane Olson

2015-05-04

A conformal transformation of a uniform triangular pinning array produces a structure called a conformal crystal which preserves the sixfold ordering of the original lattice but contains a gradient in the pinning density. Here we use numerical simulations to show that vortices in type-II superconductors driven with an ac drive over gradient pinning arrays produce the most pronounced ratchet effect over a wide range of parameters for a conformal array, while square gradient or random gradient arrays with equivalent pinning densities give reduced ratchet effects. In the conformal array, the larger spacing of the pinning sites in the direction transversemore » to the ac drive permits easy funneling of interstitial vortices for one driving direction, producing the enhanced ratchet effect. In the square array, the transverse spacing between pinning sites is uniform, giving no asymmetry in the funneling of the vortices as the driving direction switches, while in the random array, there are numerous easy-flow channels present for either direction of drive. We find multiple ratchet reversals in the conformal arrays as a function of vortex density and ac amplitude, and correlate the features with a reversal in the vortex ordering, which is greater for motion in the ratchet direction. In conclusion, the enhanced conformal pinning ratchet effect can also be realized for colloidal particles moving over a conformal array, indicating the general usefulness of conformal structures for controlling the motion of particles.« less

UV-VIS extinction spectra of gold particle coated by oligonucleotide shell

NASA Astrophysics Data System (ADS)

Bogatyrev, Vladimir A.; Vrublevsky, Stanislav A.; Trachuk, Lyubov A.; Khlebtsov, Nikolai G.

2005-06-01

We describe synthesis process of an oligonucleotide-functionalized colloidal gold marker CG-l5-T28, its optical properties and interaction with poly(A) in solution and on a solid-phase substrate. The marker is a complex of 15 nm diameter colloidal gold nanoparticles with covalently attached 5'-thiolated 28-base oligothymidine macromolecules. A positive hybridization reaction of the marker with poly(A) is observed by solid-phase analysis on hanging a spot color (from red to blue ) or on appearance of a red dye in dot-blot test as compared to control experiments with poly(U) target. The principles of spectrophotometric monitoring all stages of the marker preparation and application of spectrophotometry to detection of the polynucleotide hybridization in vitro are described. Experimental data were compared with theoretical calculations based on Mie theory for 2-layer model of gold core in polymeric shell with imaginary part of refractive index that typical for the real absorption spectra of NA. To explain the aggregation of CG-15-T28 caused by interaction with poly(A) in solution, we suggest a new model differing from a standard model of cross-linker binding.

Size and Structure of Clusters Formed by Shear Induced Coagulation: Modeling by Discrete Element Method.

PubMed

Kroupa, Martin; Vonka, Michal; Soos, Miroslav; Kosek, Juraj

2015-07-21

The coagulation process has a dramatic impact on the properties of dispersions of colloidal particles including the change of optical, rheological, as well as texture properties. We model the behavior of a colloidal dispersion with moderate particle volume fraction, that is, 5 wt %, subjected to high shear rates employing the time-dependent Discrete Element Method (DEM) in three spatial dimensions. The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was used to model noncontact interparticle interactions, while contact mechanics was described by the Johnson-Kendall-Roberts (JKR) theory of adhesion. The obtained results demonstrate that the steady-state size of the produced clusters is a strong function of the applied shear rate, primary particle size, and the surface energy of the particles. Furthermore, it was found that the cluster size is determined by the maximum adhesion force between the primary particles and not the adhesion energy. This observation is in agreement with several simulation studies and is valid for the case when the particle-particle contact is elastic and no plastic deformation occurs. These results are of major importance, especially for the emulsion polymerization process, during which the fouling of reactors and piping causes significant financial losses.

Poly(2-aminothiazole)-silica nanocomposite particles: Synthesis and morphology control

NASA Astrophysics Data System (ADS)

Zou, Hua; Wu, Di; Sun, Hao; Chen, Suwu; Wang, Xia

2018-04-01

Synthesis of conducting polymer-silica colloidal nanocomposites has been recognized as an effective method to overcome the poor processability of heterocyclic conducting polymers prepared by chemical oxidative method. However, the morphology control of such conducting polymer-silica nanocomposites was seldomly reported in the literature. Novel poly(2-aminothiazole)(PAT)-silica nanocomposite particles can be conveniently prepared by chemical oxidative polymerization of 2-aminothiazole using CuCl2 oxidant in the presence of ∼20 nm silica nanoparticles. The effects of varying the oxidant/monomer ratio and silica sol concentration on the morphology and size of the resulting PAT-silica nanocmposites have been studied. Optimization of the oxidant/monomer molar ratio and initial silica sol concentration allows relatively round spherical particles of 150-350 nm in diameter to be achieved. The nanocomposite particles have a well-defined raspberry-like morphology with a silica-rich surface, but a significant fraction of PAT component still exists on the surface and, which is beneficial for its applications. Furthermore, the surface compositions of the colloidal nanocomposites could be regulated to some extent. Based on the above results, a possible formation mechanism of the spherical nanocomposite particles is proposed.

Functionalization of magnetic nanocrystals by oligo (ethylene oxide) chains carrying diazonium and iniferter end groups.

PubMed

Ahmad, Randa; Griffete, Nébéwia; Lamouri, Aazdine; Mangeney, Claire

2013-10-01

The water stability of iron oxide nanoparticles (NPs) is a major issue for biomedical and biological applications. This paper presents a versatile approach for preparing water-soluble iron oxide nanoparticles coated by bifunctional oligo(ethylene oxide) (OEO) chains, carrying on the one side a diazonium end group for covalent grafting at the NP surface and on the other side an iniferter group (diethyl dithiocarbamate) for initiating the growing of poly(methacrylic acid). The nanoparticles were synthesized by coprecipitation in basic media and functionalized in situ by adding the diazonium salt directly in the synthesis medium. Oligo(ethylene oxide) with various chain lengths (from one to three monomer units) was grafted at the NP surface using this approach. The length of the OEO spacer between the NP surface and the iniferter end group was found to be a critical parameter for controlling the colloidal stability of the hybrid NPs. The polymerization time was also shown to strongly influence their colloidal stability, emphasizing the interest to control the interfacial properties of the hybrids for obtaining stable dispersions in water. Copyright © 2013 Elsevier Inc. All rights reserved.

Auto-production of biosurfactants reverses the coffee ring effect in a bacterial system

NASA Astrophysics Data System (ADS)

Sempels, Wouter; de Dier, Raf; Mizuno, Hideaki; Hofkens, Johan; Vermant, Jan

2013-04-01

The deposition of material at the edge of evaporating droplets, known as the ‘coffee ring effect’, is caused by a radially outward capillary flow. This phenomenon is common to a wide array of systems including colloidal and bacterial systems. The role of surfactants in counteracting these coffee ring depositions is related to the occurrence of local vortices known as Marangoni eddies. Here we show that these swirling flows are universal, and not only lead to a uniform deposition of colloids but also occur in living bacterial systems. Experiments on Pseudomonas aeruginosa suggest that the auto-production of biosurfactants has an essential role in creating a homogeneous deposition of the bacteria upon drying. Moreover, at biologically relevant conditions, intricate time-dependent flows are observed in addition to the vortex regime, which are also effective in reversing the coffee ring effect at even lower surfactant concentrations.

Perfect mixing of immiscible macromolecules at fluid interfaces

NASA Astrophysics Data System (ADS)

Sheiko, Sergei S.; Zhou, Jing; Arnold, Jamie; Neugebauer, Dorota; Matyjaszewski, Krzysztof; Tsitsilianis, Constantinos; Tsukruk, Vladimir V.; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.; Rubinstein, Michael

2013-08-01

The difficulty of mixing chemically incompatible substances—in particular macromolecules and colloidal particles—is a canonical problem limiting advances in fields ranging from health care to materials engineering. Although the self-assembly of chemically different moieties has been demonstrated in coordination complexes, supramolecular structures, and colloidal lattices among other systems, the mechanisms of mixing largely rely on specific interfacing of chemically, physically or geometrically complementary objects. Here, by taking advantage of the steric repulsion between brush-like polymers tethered to surface-active species, we obtained long-range arrays of perfectly mixed macromolecules with a variety of polymer architectures and a wide range of chemistries without the need of encoding specific complementarity. The net repulsion arises from the significant increase in the conformational entropy of the brush-like polymers with increasing distance between adjacent macromolecules at fluid interfaces. This entropic-templating assembly strategy enables long-range patterning of thin films on sub-100 nm length scales.

Liquid crystalline tactoids: ordered structure, defective coalescence and evolution in confined geometries

NASA Astrophysics Data System (ADS)

Wang, Pei-Xi; MacLachlan, Mark J.

2017-12-01

Tactoids are liquid crystalline microdroplets that spontaneously nucleate from isotropic dispersions, and transform into macroscopic anisotropic phases. These intermediate structures have been found in a range of molecular, polymeric and colloidal liquid crystals. Typically only studied by polarized optical microscopy, these ordered but easily deformable microdroplets are now emerging as interesting components for structural investigations and developing new materials. In this review, we highlight the structure, property and transformation of tactoids in different compositions, but especially cellulose nanocrystals. We have selected references that illustrate the diversity and most exciting developments in tactoid research, while capturing the historical development of this field. This article is part of a discussion meeting issue `New horizons for cellulose nanotechnology'.

Multifunctional Fluorescent-Magnetic Polymeric Colloidal Particles: Preparations and Bioanalytical Applications.

PubMed

Kaewsaneha, Chariya; Tangboriboonrat, Pramuan; Polpanich, Duangporn; Elaissari, Abdelhamid

2015-10-28

Fluorescent-magnetic particles (FMPs) play important roles in modern materials, especially as nanoscale devices in the biomedical field. The interesting features of FMPs are attributed to their dual detection ability, i.e., fluorescent and magnetic modes. Functionalization of FMPs can be performed using several types of polymers, allowing their use in various applications. The synergistic potentials for unique multifunctional, multilevel targeting nanoscale devices as well as combination therapies make them particularly attractive for biomedical applications. However, the synthesis of FMPs is challenging and must be further developed. In this review article, we summarized the most recent representative works on polymer-based FMP systems that have been applied particularly in the bioanalytical field.

Surface interaction forces of cellulose nanocrystals grafted with thermoresponsive polymer brushes.

PubMed

Zoppe, Justin O; Osterberg, Monika; Venditti, Richard A; Laine, Janne; Rojas, Orlando J

2011-07-11

The colloidal stability and thermoresponsive behavior of poly(N-isopropylacrylamide) brushes grafted from cellulose nanocrystals (CNCs) of varying graft densities and molecular weights was investigated. Indication of the grafted polymer brushes was obtained after AFM imaging of CNCs adsorbed on silica. Also, aggregation of the nanoparticles carrying grafts of high degree of polymerization was observed. The responsiveness of grafted CNCs in aqueous dispersions and as an ultrathin film was evaluated by using light scattering, viscosimetry, and colloidal probe microscopy (CPM). Light transmittance measurements showed temperature-dependent aggregation originating from the different graft densities and molecular weights. The lower critical solution temperature (LCST) of grafted poly(NiPAAm) brushes was found to decrease with the ionic strength, as is the case for free poly(NiPAAm) in aqueous solution. Thermal responsive behavior of grafted CNCs in aqueous dispersions was observed by a sharp increase in dispersion viscosity as the temperature approached the LCST. CPM in liquid media for asymmetric systems consisting of ultrathin films of CNCs and a colloidal silica probe showed the distinctive effects of the grafted polymer brushes on interaction and adhesive forces. The origin of such forces was found to be mainly electrostatic and steric in the case of bare and grafted CNCs, respectively. A decrease in the onset of attractive and adhesion forces of grafted CNCs films were observed with the ionic strength of the aqueous solution. The decreased mobility of polymer brushes upon partial collapse and decreased availability of hydrogen bonding sites with higher electrolyte concentration were hypothesized as the main reasons for the less prominent polymer bridging between interacting surfaces.

Electron transport within transparent assemblies of tin-doped indium oxide colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Grisolia, J.; Decorde, N.; Gauvin, M.; Sangeetha, N. M.; Viallet, B.; Ressier, L.

2015-08-01

Stripe-like compact assemblies of tin-doped indium oxide (ITO) colloidal nanocrystals (NCs) are fabricated by stop-and-go convective self-assembly (CSA). Systematic evaluation of the electron transport mechanisms in these systems is carried out by varying the length of carboxylate ligands protecting the NCs: butanoate (C4), octanoate (C8) and oleate (C18). The interparticle edge-to-edge distance L0, along with a number of carbon atoms in the alkyl chain of the coating ligand, are deduced from small-angle x-ray scattering (SAXS) measurements and exhibit a linear relationship with a slope of 0.11 nm per carbon pair unit. Temperature-dependent resistance characteristics are analyzed using several electron transport models: Efros-Shklovskii variable range hopping (ES-VRH), inelastic cotunneling (IC), regular island array and percolation. The analysis indicated that the first two models (ES-VRH and IC) fail to explain the observed behavior, and that only simple activated transport takes place in these systems under the experimental conditions studied (T = 300 K to 77 K). Related transport parameters were then extracted using the regular island array and percolation models. The effective tunneling decay constant βeff of the ligands and the Coulomb charging energy EC are found to be around 5.5 nm-1 and 25 meV, respectively, irrespective of ligand lengths. The theoretical tunneling decay constant β calculated using the percolation model is in the range 9 nm-1. Electromechanical tests on the ITO nanoparticle assemblies indicate that their sensitivities are as high as ˜30 and remain the same regardless of ligand lengths, which is in agreement with the constant effective βeff extracted from regular island array and percolation models.

Facile fabrication of highly ordered poly(vinylidene fluoride-trifluoroethylene) nanodot arrays for organic ferroelectric memory

NASA Astrophysics Data System (ADS)

Fang, Huajing; Yan, Qingfeng; Geng, Chong; Chan, Ngai Yui; Au, Kit; Yao, Jianjun; Ng, Sheung Mei; Leung, Chi Wah; Li, Qiang; Guo, Dong; Wa Chan, Helen Lai; Dai, Jiyan

2016-01-01

Nano-patterned ferroelectric materials have attracted significant attention as the presence of two or more thermodynamically equivalent switchable polarization states can be employed in many applications such as non-volatile memory. In this work, a simple and effective approach for fabrication of highly ordered poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) nanodot arrays is demonstrated. By using a soft polydimethylsiloxane mold, we successfully transferred the 2D array pattern from the initial monolayer of colloidal polystyrene nanospheres to the imprinted P(VDF-TrFE) films via nanoimprinting. The existence of a preferred orientation of the copolymer chain after nanoimprinting was confirmed by Fourier transform infrared spectra. Local polarization switching behavior was measured by piezoresponse force microscopy, and each nanodot showed well-formed hysteresis curve and butterfly loop with a coercive field of ˜62.5 MV/m. To illustrate the potential application of these ordered P(VDF-TrFE) nanodot arrays, the writing and reading process as non-volatile memory was demonstrated at a relatively low voltage. As such, our results offer a facile and promising route to produce arrays of ferroelectric polymer nanodots with improved piezoelectric functionality.

Electropolymerization of Uniform Polyaniline Nanorod Arrays on Conducting Oxides as Counter Electrodes in Dye-Sensitized Solar Cells.

PubMed

He, Ziming; Liu, Jing; Khoo, Si Yun; Tan, Timothy Thatt Yang

2016-01-01

Conventional techniques for the synthesis of oriented polyaniline (PANI) nanostructures are often complex or time consuming. Through an innovative reduced graphene oxide (rGO) modified FTO and a low-potential electropolymerization strategy, the rapid and template-free growth of a highly ordered PANI nanorod array on the FTO substrate is realized. The highly ordered nanostructure of the PANI array leads to a high electrocatalytic activity and chemical stability. The importance of the polymerization potential and rGO surface modification to achieve this nanostructure is revealed. Compared to platinum, the PANI nanorod array exhibits an enhanced performance and stability as counter electrodes in dye-sensitized solar cells, with a 17.6 % enhancement in power conversion efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graded nanowell arrays: a fine plasmonic "library" with an adjustable spectral range.

PubMed

Xue, Peihong; Ye, Shunsheng; Su, Hongyang; Wang, Shuli; Nan, Jingjie; Chen, Xingchi; Ruan, Weidong; Zhang, Junhu; Cui, Zhanchen; Yang, Bai

2017-05-25

We present an effective approach for fabricating graded plasmonic arrays based on ordered micro-/nanostructures with a geometric gradient. Ag nanowell arrays with graded geometric parameters were fabricated and systematically investigated. The order of the graded plasmonic arrays is generated by colloidal lithography, while the geometric gradient is the result of inclined reactive ion etching. The surface plasmon resonance (SPR) peaks were measured at different positions, which move gradually along the Ag nanowell arrays with a geometric gradient. Such micro-/nanostructure arrays with graded and integrated SPR peaks can work as a fine plasmonic "library" (FPL), and the spectral range can be controlled using a "coarse adjustment knob" (lattice constant) and a "fine adjustment knob" (pore diameter). Additionally, the spectral resolution of the FPL is high, which benefits from the high value of the full height/full width at half-maximum and the small step size of the wavelength shift (0.5 nm). Meanwhile, the FPL could be effectively applied as a well-defined model to verify the plasmonic enhancement in surface enhanced Raman scattering. As the FPL is an integrated optical material with graded individual SPR peaks, it can not only be a theoretical model for fundamental research, but also has great potential in high-throughput screening of optical materials, multiplex sensors, etc.

Nanoscale lateral displacement arrays for the separation of exosomes and colloids down to 20 nm

NASA Astrophysics Data System (ADS)

Austin, Robert; Wunsch, Benjamin; Smith, Joshua; Gifford, Stacey; Wang, Chao; Brink, Markus; Bruce, Robert; Stolovitzky, Gustavo; Astier, Yann

Deterministic lateral displacement (DLD) pillar arrays are an efficient technology to sort, separate and enrich micrometre-scale particles, which include parasites1, bacteria2, blood cells3 and circulating tumour cells in blood4. However, this technology has not been translated to the true nanoscale, where it could function on biocolloids, such as exosomes. Exosomes, a key target of liquid biopsies, are secreted by cells and contain nucleic acid and protein information about their originating tissue5. One challenge in the study of exosome biology is to sort exosomes by size and surface markers6, 7. We use manufacturable silicon processes to produce nanoscale DLD (nano-DLD) arrays of uniform gap sizes ranging from 25 to 235 nm. We show that at low Péclet (Pe) numbers, at which diffusion and deterministic displacement compete, nano-DLD arrays separate particles between 20 to 110 nm based on size with sharp resolution. Further, we demonstrate the size-based displacement of exosomes, and so open up the potential for on-chip sorting and quantification of these important biocolloids.

Nanoscale lateral displacement arrays for the separation of exosomes and colloids down to 20 nm

NASA Astrophysics Data System (ADS)

Wunsch, Benjamin H.; Smith, Joshua T.; Gifford, Stacey M.; Wang, Chao; Brink, Markus; Bruce, Robert L.; Austin, Robert H.; Stolovitzky, Gustavo; Astier, Yann

2016-11-01

Deterministic lateral displacement (DLD) pillar arrays are an efficient technology to sort, separate and enrich micrometre-scale particles, which include parasites, bacteria, blood cells and circulating tumour cells in blood. However, this technology has not been translated to the true nanoscale, where it could function on biocolloids, such as exosomes. Exosomes, a key target of 'liquid biopsies', are secreted by cells and contain nucleic acid and protein information about their originating tissue. One challenge in the study of exosome biology is to sort exosomes by size and surface markers. We use manufacturable silicon processes to produce nanoscale DLD (nano-DLD) arrays of uniform gap sizes ranging from 25 to 235 nm. We show that at low Péclet (Pe) numbers, at which diffusion and deterministic displacement compete, nano-DLD arrays separate particles between 20 to 110 nm based on size with sharp resolution. Further, we demonstrate the size-based displacement of exosomes, and so open up the potential for on-chip sorting and quantification of these important biocolloids.

High-Throughput Fabrication of Ultradense Annular Nanogap Arrays for Plasmon-Enhanced Spectroscopy.

PubMed

Cai, Hongbing; Meng, Qiushi; Zhao, Hui; Li, Mingling; Dai, Yanmeng; Lin, Yue; Ding, Huaiyi; Pan, Nan; Tian, Yangchao; Luo, Yi; Wang, Xiaoping

2018-06-13

The confinement of light into nanometer-sized metallic nanogaps can lead to an extremely high field enhancement, resulting in dramatically enhanced absorption, emission, and surface-enhanced Raman scattering (SERS) of molecules embedded in nanogaps. However, low-cost, high-throughput, and reliable fabrication of ultra-high-dense nanogap arrays with precise control of the gap size still remains a challenge. Here, by combining colloidal lithography and atomic layer deposition technique, a reproducible method for fabricating ultra-high-dense arrays of hexagonal close-packed annular nanogaps over large areas is demonstrated. The annular nanogap arrays with a minimum diameter smaller than 100 nm and sub-1 nm gap width have been produced, showing excellent SERS performance with a typical enhancement factor up to 3.1 × 10 6 and a detection limit of 10 -11 M. Moreover, it can also work as a high-quality field enhancement substrate for studying two-dimensional materials, such as MoSe 2 . Our method provides an attractive approach to produce controllable nanogaps for enhanced light-matter interaction at the nanoscale.

Face-specific Replacement of Calcite by Amorphous Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Liesegang, M.; Milke, R.; Neusser, G.; Mizaikoff, B.

2016-12-01

Amorphous silica, composed of nanoscale spheres, is an important biomineral, alteration product of silicate rocks on the Earth's surface, and precursor material for stable silicate minerals. Despite constant progress in silica sphere synthesis, fundamental knowledge of natural silica particle interaction and ordering processes leading to colloidal crystals is absent so far. To understand the formation pathways of silica spheres in a geologic environment, we investigated silicified Cretaceous mollusk shell pseudomorphs from Coober Pedy (South Australia) using focused ion beam (FIB)-SEM tomography, petrographic microscopy, µ-XRD, and EMPA. The shells consist of replaced calcite crystals (<2 mm) composed of ordered arrays of uniform, close-packed silica spheres 300 ± 10 nm in size. Concentric layered spheres composed of 40 nm-sized subparticles provide evidence that, at least in the final stage, particle aggregation was the major sphere growth mechanism. Silica sphere arrays in periodically changing orientations perfectly replicate polysynthetic twinning planes of calcite. FIB-SEM tomography shows that cubic closed-packed sphere arrangements preserve the twin lamellae, while the twin plane consists of a submicrometer layer of randomly ordered spheres and vacancies. To transfer crystallographic information from parent to product, the advancement of synchronized dissolution and precipitation fronts along lattice planes is essential. We assume that the volume-preserving replacement process proceeds via a face-specific dissolution-precipitation mechanism with intermediate subparticle aggregation and subsequent layer-by-layer deposition of spheres along a planar surface. Porosity created during the replacement reaction allows permanent fluid access to the propagating reaction interface. Fluid pH and ionic strength remain constant throughout the replacement process, permitting continuous silica nanoparticle formation and diffusion-limited colloid aggregation. Our study provides a natural example of the transformation of an atomic crystal to an amorphous, mesoscale ordered material; thus, links the research fields of natural colloidal crystal formation, carbonate-silica replacement, and crystallization by oriented particle aggregation (CPA).

Contact CMOS imaging of gaseous oxygen sensor array

PubMed Central

Daivasagaya, Daisy S.; Yao, Lei; Yi Yung, Ka; Hajj-Hassan, Mohamad; Cheung, Maurice C.; Chodavarapu, Vamsy P.; Bright, Frank V.

2014-01-01

We describe a compact luminescent gaseous oxygen (O2) sensor microsystem based on the direct integration of sensor elements with a polymeric optical filter and placed on a low power complementary metal-oxide semiconductor (CMOS) imager integrated circuit (IC). The sensor operates on the measurement of excited-state emission intensity of O2-sensitive luminophore molecules tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) ([Ru(dpp)3]2+) encapsulated within sol–gel derived xerogel thin films. The polymeric optical filter is made with polydimethylsiloxane (PDMS) that is mixed with a dye (Sudan-II). The PDMS membrane surface is molded to incorporate arrays of trapezoidal microstructures that serve to focus the optical sensor signals on to the imager pixels. The molded PDMS membrane is then attached with the PDMS color filter. The xerogel sensor arrays are contact printed on top of the PDMS trapezoidal lens-like microstructures. The CMOS imager uses a 32 × 32 (1024 elements) array of active pixel sensors and each pixel includes a high-gain phototransistor to convert the detected optical signals into electrical currents. Correlated double sampling circuit, pixel address, digital control and signal integration circuits are also implemented on-chip. The CMOS imager data is read out as a serial coded signal. The CMOS imager consumes a static power of 320 µW and an average dynamic power of 625 µW when operating at 100 Hz sampling frequency and 1.8 V DC. This CMOS sensor system provides a useful platform for the development of miniaturized optical chemical gas sensors. PMID:24493909

Contact CMOS imaging of gaseous oxygen sensor array.

PubMed

Daivasagaya, Daisy S; Yao, Lei; Yi Yung, Ka; Hajj-Hassan, Mohamad; Cheung, Maurice C; Chodavarapu, Vamsy P; Bright, Frank V

2011-10-01

We describe a compact luminescent gaseous oxygen (O 2 ) sensor microsystem based on the direct integration of sensor elements with a polymeric optical filter and placed on a low power complementary metal-oxide semiconductor (CMOS) imager integrated circuit (IC). The sensor operates on the measurement of excited-state emission intensity of O 2 -sensitive luminophore molecules tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) ([Ru(dpp) 3 ] 2+ ) encapsulated within sol-gel derived xerogel thin films. The polymeric optical filter is made with polydimethylsiloxane (PDMS) that is mixed with a dye (Sudan-II). The PDMS membrane surface is molded to incorporate arrays of trapezoidal microstructures that serve to focus the optical sensor signals on to the imager pixels. The molded PDMS membrane is then attached with the PDMS color filter. The xerogel sensor arrays are contact printed on top of the PDMS trapezoidal lens-like microstructures. The CMOS imager uses a 32 × 32 (1024 elements) array of active pixel sensors and each pixel includes a high-gain phototransistor to convert the detected optical signals into electrical currents. Correlated double sampling circuit, pixel address, digital control and signal integration circuits are also implemented on-chip. The CMOS imager data is read out as a serial coded signal. The CMOS imager consumes a static power of 320 µW and an average dynamic power of 625 µW when operating at 100 Hz sampling frequency and 1.8 V DC. This CMOS sensor system provides a useful platform for the development of miniaturized optical chemical gas sensors.

Trehalose-Based Block Copolycations Promote Polyplex Stabilization for Lyophilization and in Vivo pDNA Delivery

PubMed Central

2015-01-01

The development and thorough characterization of nonviral delivery agents for nucleic acid and genome editing therapies are of high interest to the field of nanomedicine. Indeed, this vehicle class offers the ability to tune chemical architecture/biological activity and readily package nucleic acids of various sizes and morphologies for a variety of applications. Herein, we present the synthesis and characterization of a class of trehalose-based block copolycations designed to stabilize polyplex formulations for lyophilization and in vivo administration. A 6-methacrylamido-6-deoxy trehalose (MAT) monomer was synthesized from trehalose and polymerized via reversible addition–fragmentation chain transfer (RAFT) polymerization to yield pMAT43. The pMAT43 macro-chain transfer agent was then chain-extended with aminoethylmethacrylamide (AEMA) to yield three different pMAT-b-AEMA cationic-block copolymers, pMAT-b-AEMA-1 (21 AEMA repeats), -2 (44 AEMA repeats), and -3 (57 AEMA repeats). These polymers along with a series of controls were used to form polyplexes with plasmids encoding firefly luciferase behind a strong ubiquitous promoter. The trehalose-coated polyplexes were characterized in detail and found to be resistant to colloidal aggregation in culture media containing salt and serum. The trehalose-polyplexes also retained colloidal stability and promoted high gene expression following lyophilization and reconstitution. Cytotoxicity, cellular uptake, and transfection ability were assessed in vitro using both human glioblastoma (U87) and human liver carcinoma (HepG2) cell lines wherein pMAT-b-AEMA-2 was found to have the optimal combination of high gene expression and low toxicity. pMAT-b-AEMA-2 polyplexes were evaluated in mice via slow tail vein infusion. The vehicle displayed minimal toxicity and discouraged nonspecific internalization in the liver, kidney, spleen, and lungs as determined by quantitative polymerase chain reaction (qPCR) and fluorescence imaging experiments. Hydrodynamic infusion of the polyplexes, however, led to very specific localization of the polyplexes to the mouse liver and promoted excellent gene expression in vivo. PMID:26807438

Colloidal Dispersions in Polymeric Media: Interparticle Forces, Microstructure and Rheology

NASA Astrophysics Data System (ADS)

Ndong, Rose Seynabou

To enhance properties of the ultimate materials, melt processed polymers are commonly filled with colloidal particles, such as inorganic oxides. Dispersing such particles in a melt is generally difficult due to the strong van der Waals attractions. These attractive forces can be modulated through surface modifications such as polymer adsorption and grafting. Indeed, the relative viscosity of 430 nm Al2O3particles stabilized by end-tethered poly(dimethylsiloxane) (PDMS) in PDMS melts decreases with increasing graft density and molecular weight as expected, but also with increasing molecular weight of the melt, contrary to well established theories. The relative steady shear viscosity exhibits neither a low shear limit nor a yield stress, but follows a power law characterized by relative high shear viscosity (eta infinity/mu) and a structural relaxation time (tau). The measured structural time can be correlated reasonably well with a characteristic relaxation time, tauo, estimated by equating the viscous resistance with the maximum attractive force. We further explored the significance of this power law with TiO2 nanoparticles in PDMS melts with a reduction in size and an increase in Hamaker constant. Bare, octadecyl-coated, and 9k-PDMS grafted TiO2 particles dispersed in neat and binary PDMS melts revealed behavior similar to that of the large alumina particles, as the increased strength of van der Waals forces offset the reduction in size. To complete the study ZrO2 nanoparticles were dispersed in solution of associative polymers and characterized by small amplitude oscillatory shear. The data exhibits two relaxation modes: Maxwellian behavior at high frequency imparted by the associating polymers and a power law spectrum at low frequency from the particles. The timescales and volume fraction dependence reflect the attractions between particles with adsorbed polymer layers dispersed in a percolated network of associative polymers. Together these studies demonstrate the range and origin of the rheology possible with particles dispersed in polymeric media.

Fabrication of bioinspired nanostructured materials via colloidal self-assembly

NASA Astrophysics Data System (ADS)

Huang, Wei-Han

Through millions of years of evolution, nature creates unique structures and materials that exhibit remarkable performance on mechanicals, opticals, and physical properties. For instance, nacre (mother of pearl), bone and tooth show excellent combination of strong minerals and elastic proteins as reinforced materials. Structured butterfly's wing and moth's eye can selectively reflect light or absorb light without dyes. Lotus leaf and cicada's wing are superhydrophobic to prevent water accumulation. The principles of particular biological capabilities, attributed to the highly sophisticated structures with complex hierarchical designs, have been extensively studied. Recently, a large variety of novel materials have been enabled by natural-inspired designs and nanotechnologies. These advanced materials will have huge impact on practical applications. We have utilized bottom-up approaches to fabricate nacre-like nanocomposites with "brick and mortar" structures. First, we used self-assembly processes, including convective self-assembly, dip-coating, and electrophoretic deposition to form well oriented layer structure of synthesized gibbsite (aluminum hydroxide) nanoplatelets. Low viscous monomer was permeated into layered nanoplatelets and followed by photo-curing. Gibbsite-polymer composite displays 2 times higher tensile strength and 3 times higher modulus when compared with pure polymer. More improvement occurred when surface-modified gibbsite platelets were cross-linked with the polymer matrix. We observed ˜4 times higher strength and nearly 1 order of magnitude higher modulus than pure polymer. To further improve the mechanical strength and toughness of inorganicorganic nanocomposites, we exploited ultrastrong graphene oxide (GO), a single atom thick hexagonal carbon sheet with pendant oxidation groups. GO nanocomposite is made by co-filtrating GO/polyvinyl alcohol suspension on 0.2 im pore-sized membrane. It shows ˜2 times higher strength and ˜15 times higher ultimate strains than nacre and pure GO paper (also synthesized by filtration). Specifically, it exhibits ˜30 times higher fracture energy than filtrated graphene paper and nacre, ˜100 times tougher than filtrated GO paper. Besides reinforced nanocomposites, we further explored the self-assembly of spherical colloids and the templating nanofabrication of moth-eye-inspired broadband antireflection coatings. Binary crystalline structures can be easily accomplished by spin-coating double-layer nonclose-packed colloidal crystals as templates, followed by colloidal templating. The polymer matrix between self-assembled colloidal crystal has been used as a sacrificial template to define the resulting periodic binary nanostructures, including intercalated arrays of silica spheres and polymer posts, gold nanohole arrays with binary sizes, and dimple-nipple antireflection coatings. The binary-structured antireflection coatings exhibit better antireflective properties than unitary coatings. Natural optical structures and nanocomposites teach us a great deal on how to create high performance artificial materials. The bottom-up technologies developed in this thesis are scalable and compatible with standard industrial processes, promising for manufacturing high-performance materials for the benefits of human beings.

Fabrication of Aligned Polyaniline Nanofiber Array via a Facile Wet Chemical Process.

PubMed

Sun, Qunhui; Bi, Wu; Fuller, Thomas F; Ding, Yong; Deng, Yulin

2009-06-17

In this work, we demonstrate for the first time a template free approach to synthesize aligned polyaniline nanofiber (PN) array on a passivated gold (Au) substrate via a facile wet chemical process. The Au surface was first modified using 4-aminothiophenol (4-ATP) to afford the surface functionality, followed subsequently by an oxidation polymerization of aniline (AN) monomer in an aqueous medium using ammonium persulfate as the oxidant and tartaric acid as the doping agent. The results show that a vertically aligned PANI nanofiber array with individual fiber diameters of ca. 100 nm, heights of ca. 600 nm and a packing density of ca. 40 pieces·µm(-2) , was synthesized. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nano-porous electrode systems by colloidal lithography for sensitive electrochemical detection: fabrication technology and properties

NASA Astrophysics Data System (ADS)

Lohmüller, Theobald; Müller, Ulrich; Breisch, Stefanie; Nisch, Wilfried; Rudorf, Ralf; Schuhmann, Wolfgang; Neugebauer, Sebastian; Kaczor, Markus; Linke, Stephan; Lechner, Sebastian; Spatz, Joachim; Stelzle, Martin

2008-11-01

A porous metal-insulator-metal sensor system was developed with the ultimate goal of enhancing the sensitivity of electrochemical sensors by taking advantage of redox cycling of electro active molecules between closely spaced electrodes. The novel fabrication technology is based on thin film deposition in combination with colloidal self-assembly and reactive ion etching to create micro- or nanopores. This cost effective approach is advantageous compared to common interdigitated electrode arrays (IDA) since it does not require high definition lithography technology. Spin-coating and random particle deposition, combined with a new sublimation process are discussed as competing strategies to generate monolayers of colloidal spheres. Metal-insulator-metal layer systems with low leakage currents < 10 pA and an insulator thickness as low as 100 nm were obtained at high yield (typically > 90%). We also discuss possible causes of sensor failure with respect to critical fabrication processes. Short circuits which could occur during or as a result of the pore etching process were investigated in detail. Infrared microscopy in combination with focused ion beam etching/SEM were used to reveal a defect mechanism creating interconnects and increased leakage current between the top and bottom electrodes. Redox cycling provides for amplification factors of >100. A general applicability for electrochemical diagnostic assays is therefore anticipated.

Multifunctional polymeric micelles loaded with doxorubicin and poly(dithienyl-diketopyrrolopyrrole) for near-infrared light-controlled chemo-phototherapy of cancer cells.

PubMed

Liu, Hui; Wang, Kai; Yang, Cangjie; Huang, Shuo; Wang, Mingfeng

2017-09-01

Polymeric micelles loaded with multiple therapeutic modalities are important to overcome challenges such as drug resistance and improve the therapeutic efficacy. Here we report a new polymer micellar drug carrier that integrates chemotherapy and photothermal therapy in a single platform. Specifically, a narrow bandgap poly(dithienyl-diketopyrrolopyrrole) (PDPP) polymer was encapsulated together with a model anticancer drug doxorubicin (DOX) in the hydrophobic cores of polymeric micelles formed by Pluronic F127, an amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer. The PDPP polymer served as an organic photothermal agent that absorbs near-infrared light (700-1000nm) and transforms into heat efficiently. The dual functional micelles co-loaded with PDPP and DOX in the hydrophobic compartment showed good colloidal stability after being stored at 4°C at least over two months, and remained visibly stable after 808-nm laser irradiation. The loaded DOX had negligible effect on the size and photothermal property of the micelles. The release of DOX from the micelles could be enhanced by the "breathing" effect of shrinking/swelling of the micelles induced by the temperature change, owing to the thermosensitive nature of the F127 polymers. Importantly, the ternary F127/PDPP/DOX micelles under 808-nm laser irradiation showed enhanced cytotoxicity against cancer cells such as HeLa cells, compared to F127 micelles containing single modality of either PDPP or DOX only. Copyright © 2017 Elsevier B.V. All rights reserved.

Star-shaped polymers of bio-inspired algae core and poly(acrylamide) and poly(acrylic acid) as arms in dissolution of silica/silicate.

PubMed

Chauhan, Kalpana; Patiyal, Priyanka; Chauhan, Ghanshyam S; Sharma, Praveen

2014-06-01

Silica, in natural waters (due to weathering of rocks) decreases system performance in water processing industry due to scaling. In view of that, the present work involves the synthesis of novel green star shaped additives of algae core (a bio-inspired material as diatom maintains silicic acid equilibrium in sea water) as silica polymerization inhibitors. Star shaped materials with bio-inspired core and poly(acrylamide) [poly(AAm)] and poly(acrylic acid) [poly(AAc)] arms were synthesized by economical green approach. The proficiency was evaluated in 'mini lab' scale for the synthesized APAAm (Algae-g-poly(AAm)) and APAAc (Algae-g-poly(AAc)) dendrimers (star shaped) in colloidal silica mitigation/inhibition at 35 °C and 55 °C. Synthesized dendrimers were equally proficient in silica inhibition at 12 h and maintains ≥450 ppm soluble silica. However, APAAm dendrimers of generation 0 confirmed better results (≈300 ppm) in contrast to APAAc dendrimers in silica inhibition at 55 °C. Additionally, dendrimers also worked as a nucleator for heterogeneous polymerization to inhibit silica homo-polymerization. APAAm dendrimer test set showed no silica deposit for more than 10 days of inhibition. EDX characterization results support nucleator mechanism with Si content of 6.97%-10.98% by weight in silica deposits (SiO2-APAAm dendrimer composites). Copyright © 2014 Elsevier Ltd. All rights reserved.

Nanopatterned submicron pores as a shield for nonspecific binding in surface plasmon resonance-based sensing.

PubMed

Raz, Sabina Rebe; Marchesini, Gerardo R; Bremer, Maria G E G; Colpo, Pascal; Garcia, Cesar Pascual; Guidetti, Guido; Norde, Willem; Rossi, Francois

2012-11-21

We present a novel approach to tackle the most common drawback of using surface plasmon resonance for analyte screening in complex biological matrices--the nonspecific binding to the sensor chip surface. By using a perforated membrane supported by a polymeric gel structure at the evanescent wave penetration depth, we have fabricated a non-fouling sieve above the sensing region. The sieve shields the evanescent wave from nonspecific interactions which interfere with SPR sensing by minimizing the fouled area of the polymeric gel and preventing the translocation of large particles, e.g. micelles or aggregates. The nanopatterned macropores were fabricated by means of colloidal lithography and plasma enhanced chemical vapor deposition of a polyethylene oxide-like film on top of a polymeric gel matrix commonly used in surface plasmon resonance analysis. The sieve was characterized using surface plasmon resonance imaging, contact angle, atomic force microscopy and scanning electron microscopy. The performance of the sieve was studied using an immunoassay for detection of antibiotic residues in full fat milk and porcine serum. The non-fouling membrane presented pores in the 92-138 nm range organized in a hexagonal crystal lattice with a clearance of about 5% of the total surface. Functionally, the membrane with the nanopatterned macropores showed significant improvements in immunoassay robustness and sensitivity in untreated complex samples. The utilization of the sensor built-in sieve for measurements in complex matrices offers reduction in pre-analytical sample preparation steps and thus shortens the total analysis time.

Cellulose Nanomaterials — A Path Towards Commercialization Workshop Report

Treesearch

Fred Hansen; Victoria Brun; Emily Keller; World Nieh; Theodore Wegner; Michael Meador; Lisa Friedersdorf

2014-01-01

Cellulose nanomaterials are primarily isolated from trees and other organisms; are naturally occurring polymeric materials that have demonstrated great promise for commercial applications across an array of industrial sectors; are renewable and environmentally sustainable; and have the potential to be produced in large volumes (i.e., millions of tons per year). The...

Modulation of cultured neural networks using neurotrophin release from hydrogel-coated microelectrode arrays

NASA Astrophysics Data System (ADS)

Jun, Sang Beom; Hynd, Matthew R.; Dowell-Mesfin, Natalie M.; Al-Kofahi, Yousef; Roysam, Badrinath; Shain, William; Kim, Sung June

2008-06-01

Polyacrylamide and poly(ethylene glycol) diacrylate hydrogels were synthesized and characterized for use as drug release and substrates for neuron cell culture. Protein release kinetics was determined by incorporating bovine serum albumin (BSA) into hydrogels during polymerization. To determine if hydrogel incorporation and release affect bioactivity, alkaline phosphatase was incorporated into hydrogels and a released enzyme activity determined using the fluorescence-based ELF-97 assay. Hydrogels were then used to deliver a brain-derived neurotrophic factor (BDNF) from hydrogels polymerized over planar microelectrode arrays (MEAs). Primary hippocampal neurons were cultured on both control and neurotrophin-containing hydrogel-coated MEAs. The effect of released BDNF on neurite length and process arborization was investigated using automated image analysis. An increased spontaneous activity as a response to the released BDNF was recorded from the neurons cultured on the top of hydrogel layers. These results demonstrate that proteins of biological interest can be incorporated into hydrogels to modulate development and function of cultured neural networks. These results also set the stage for development of hydrogel-coated neural prosthetic devices for local delivery of various biologically active molecules.

Corneal delivery of besifloxacin using rapidly dissolving polymeric microneedles.

PubMed

Bhatnagar, Shubhmita; Saju, Amala; Cheerla, Krishna Deepthi; Gade, Sudeep Kumar; Garg, Prashant; Venuganti, Venkata Vamsi Krishna

2018-06-01

Penetration of antibiotics into and through the cornea is a major limiting factor in the treatment of ocular infections. Several strategies are in vogue to overcome this limitation such as use of fortified drops, gels, and subconjunctival injections. Here, we present the fabrication of rapidly dissolving polymeric microneedle array to effectively deliver besifloxacin through the cornea. Microneedles were prepared using polyvinyl alcohol and polyvinyl pyrrolidone by the micromolding technique. The model fluoroquinolone antibiotic, besifloxacin, was loaded in 36 microneedles arranged in a 6 × 6 array format within a 1 cm 2 area. The average height and base width of microneedles was 961 ± 27 and 366 ± 16 μm, respectively. Each microneedle array contained 103.4 ± 8.5 μg of besifloxacin. Cryosectioning and confocal microscopy of excised human cornea revealed that microneedles penetrated to a depth of up to 200 μm. Microneedles were found to completely dissolve in the cornea within 5 min. Application of microneedles for 5 min significantly (p < 0.05) improved the besifloxacin deposition and permeation through the cornea compared with free besifloxacin solution. Similarly, besifloxacin-loaded microneedles showed greater antibacterial activity in Staphylococcus aureus-infected cornea in comparison to free besifloxacin solution. Taken together, rapidly dissolving microneedles can be developed to effectively deliver besifloxacin to treat bacterial infections in the cornea and eye.

Laser-assisted simultaneous transfer and patterning of vertically aligned carbon nanotube arrays on polymer substrates for flexible devices.

PubMed

In, Jung Bin; Lee, Daeho; Fornasiero, Francesco; Noy, Aleksandr; Grigoropoulos, Costas P

2012-09-25

We demonstrate a laser-assisted dry transfer technique for assembling patterns of vertically aligned carbon nanotube arrays on a flexible polymeric substrate. A laser beam is applied to the interface of a nanotube array and a polycarbonate sheet in contact with one another. The absorbed laser heat promotes nanotube adhesion to the polymer in the irradiated regions and enables selective pattern transfer. A combination of the thermal transfer mechanism with rapid direct writing capability of focused laser beam irradiation allows us to achieve simultaneous material transfer and direct micropatterning in a single processing step. Furthermore, we demonstrate that malleability of the nanotube arrays transferred onto a flexible substrate enables post-transfer tailoring of electric conductance by collapsing the aligned nanotubes in different directions. This work suggests that the laser-assisted transfer technique provides an efficient route to using vertically aligned nanotubes as conductive elements in flexible device applications.

Conductive polymer sensor arrays for smart orthopaedic implants

NASA Astrophysics Data System (ADS)

Micolini, Carolina; Holness, F. B.; Johnson, James A.; Price, Aaron D.

2017-04-01

This study proposes and demonstrates the design, implementation, and characterization of a 3D-printed smartpolymer sensor array using conductive polyaniline (PANI) structures embedded in a polymeric substrate. The piezoresistive characteristics of PANI were studied to evaluate the efficacy of the manufacturing of an embedded pressure sensor. PANI's stability throughout loading and unloading cycles together with the response to incremental loading cycles was investigated. It is demonstrated that this specially developed multi-material additive manufacturing process for polyaniline is a good candidate for the manufacture of implant components with smart-polymer sensors embedded for the analysis of joint loads in orthopaedic implants.

Epitaxially Grown Colloidal Crystals of Silica Microspheres on Patterned Substrate of Triangular Arrays

DTIC Science & Technology

2008-07-16

min after addition of binary mixture. Other images are taken (d) after supernatant removal, (e) after ammonia exposure, ( f ) after air-drying and dye...12] J.P. Hoogenboom , D. Derks, P. Vergeer, A. van Blaaderen, J. Chem. Phys. 117 (2002) 11320. [13] A. van Blaaderen, R. Ruel, P. Wiltzius, Nature...Axe, Y. Fujii, Phys. Rev. Lett. 62 (1989) 1524. [19] F . El Azhar, M. Baus, J.P. Ryekaert, E.J. Meijer, J. Chem. Phys. 112 (2000) 5121. [20] M.S

Focusing light through dynamical samples using fast continuous wavefront optimization.

PubMed

Blochet, B; Bourdieu, L; Gigan, S

2017-12-01

We describe a fast continuous optimization wavefront shaping system able to focus light through dynamic scattering media. A micro-electro-mechanical system-based spatial light modulator, a fast photodetector, and field programmable gate array electronics are combined to implement a continuous optimization of a wavefront with a single-mode optimization rate of 4.1 kHz. The system performances are demonstrated by focusing light through colloidal solutions of TiO 2 particles in glycerol with tunable temporal stability.

Light-assisted, templated self-assembly using a photonic-crystal slab.

PubMed

Jaquay, Eric; Martínez, Luis Javier; Mejia, Camilo A; Povinelli, Michelle L

2013-05-08

We experimentally demonstrate the technique of light-assisted, templated self-assembly (LATS). We excite a guided-resonance mode of a photonic-crystal slab with 1.55 μm laser light to create an array of optical traps. We demonstrate assembly of a square lattice of 520 nm diameter polystyrene particles spaced by 860 nm. Our results demonstrate how LATS can be used to fabricate reconfigurable structures with symmetries different from traditional colloidal self-assembly, which is limited by free energetic constraints.

Formation of Ordered and Disordered Dielectric/metal Nanowire Arrays and their Plasmonic Behavior

DTIC Science & Technology

2007-01-01

sheath geometry. 2. EXPERIMENTAL PROCEDURES Several different nanowire systems have been grown, including random Ga2O3 nanowires, InAs...nanowires, ZnO nanowires, as well as Au lines produced by e-beam lithography. The growth of the Ga2O3 nanowires was achieved by the controlled oxidation...CLOSELY-SPACED PARALLEL ZnO NANOWIRES AND CROSSED Ga2O3 NANOWIRES. As discussed above, due to the far separation of the gold colloid catalyst in the

Dissolving polymeric microneedle arrays for electrically assisted transdermal drug delivery.

PubMed

Garland, Martin J; Caffarel-Salvador, Ester; Migalska, Katarzyna; Woolfson, A David; Donnelly, Ryan F

2012-04-10

It has recently been proposed that the combination of skin barrier impairment using microneedles (MNs) coupled with iontophoresis (ITP) may broaden the range of drugs suitable for transdermal delivery, as well as enabling the rate of delivery to be achieved with precise electronic control. However, no reports exist on the combination of ITP with in situ drug loaded polymeric MN delivery systems. Furthermore, although a number of studies have highlighted the importance of MN design for transdermal drug delivery enhancement, to date, there has been no systematic investigation of the influence of MN geometry on the performance of polymeric MN arrays which are designed to remain in contact with the skin during the period of drug delivery. As such, for the first time, this study reports on the effect of MN heigth and MN density upon the transdermal delivery of small hydrophilic compounds (theophylline, methylene blue, and fluorescein sodium) across neonatal porcine skin in vitro, with the optimised MN array design evaluated for its potential in the electrically faciliatated delivery of peptide (bovine insulin) and protein (fluorescein isothiocyanate-labelled bovine serum albumin (FTIC-BSA)) macromolecules. The results of the in vitro drug release investigations revealed that the extent of transdermal delivery was dependent upon the design of the MN array employed, whereby an increase in MN height and an increase in MN density led to an increase in the extent of transdermal drug delivery achieved 6h after MN application. Overall, the in vitro permeation studies revealed that the MN design containing 361 MNs/cm(2) of 600 μm height resulted in the greatest extent of transdermal drug delivery. As such, this design was evaluated for its potential in the MN mediated iontophoretic transdermal delivery. Whilst the combination of MN and ITP did not further enhance the extent of small molecular weight solute delivery, the extent of peptide/protein release was significantly enhanced when ITP was used in combination of the soluble PMVE/MA MN arrays. For example, the cumulative amount of insulin permeated across neonatal porcine skin at 6h was found to be approximately 150 μg (3.25%), 227 μg (4.85%) and 462 μg (9.87%) for ITP, MN, and MN/ITP delivery strategies, respectively. Similarly, the cumulative amount of FTIC-BSA delivered across neonatal porcine skin after a 6h period was found to be approximately 110 μg (4.53%) for MN alone and 326 μg (13.40%) for MN in combination with anodal ITP (p<0.001). As such, drug loaded soluble PMVE/MA MN arrays show promise for the electrically controlled transdermal delivery of biomacromolecules in a simple, one-step approach. Copyright © 2012 Elsevier B.V. All rights reserved.

Self-assembly and electrostriction of arrays and chains of hopfion particles in chiral liquid crystals

PubMed Central

Ackerman, Paul J.; van de Lagemaat, Jao; Smalyukh, Ivan I.

2015-01-01

Some of the most exotic condensed matter phases, such as twist grain boundary and blue phases in liquid crystals and Abrikosov phases in superconductors, contain arrays of topological defects in their ground state. Comprised of a triangular lattice of double-twist tubes of magnetization, the so-called ‘A-phase’ in chiral magnets is an example of a thermodynamically stable phase with topologically nontrivial solitonic field configurations referred to as two-dimensional skyrmions, or baby-skyrmions. Here we report that three-dimensional skyrmions in the form of double-twist tori called ‘hopfions’, or ‘torons’ when accompanied by additional self-compensating defects, self-assemble into periodic arrays and linear chains that exhibit electrostriction. In confined chiral nematic liquid crystals, this self-assembly is similar to that of liquid crystal colloids and originates from long-range elastic interactions between particle-like skyrmionic torus knots of molecular alignment field, which can be tuned from isotropic repulsive to weakly or highly anisotropic attractive by low-voltage electric fields. PMID:25607778

Innovative polymeric system (IPS) for solvent-free lipophilic drug transdermal delivery via dissolving microneedles.

PubMed

Dangol, Manita; Yang, Huisuk; Li, Cheng Guo; Lahiji, Shayan Fakhraei; Kim, Suyong; Ma, Yonghao; Jung, Hyungil

2016-02-10

Lipophilic drugs are potential drug candidates during drug development. However, due to the need for hazardous organic solvents for their solubilization, these drugs often fail to reach the pharmaceutical market, and in doing so highlight the importance of solvent free systems. Although transdermal drug delivery systems (TDDSs) are considered prospective safe drug delivery routes, a system involving lipophilic drugs in solvent free or powder form has not yet been described. Here, we report, for the first time, a novel approach for the delivery of every kind of lipophilic drug in powder form based on an innovative polymeric system (IPS). The phase transition of powder form of lipophilic drugs due to interior chemical bonds between drugs and biodegradable polymers and formation of nano-sized colloidal structures allowed the fabrication of dissolving microneedles (DMNs) to generate a powerful TDDS. We showed that IPS based DMN with powder capsaicin enhances the therapeutic effect for treatment of the rheumatic arthritis in a DBA/1 mouse model compared to a solvent-based system, indicating the promising potential of this new solvent-free platform for lipophilic drug delivery. Copyright © 2016 Elsevier B.V. All rights reserved.

Preparation of silica-coated poly(styrene-co-4-vinylpyridine) particles and hollow particles.

PubMed

Zou, Hua; Wu, Shishan; Shen, Jian

2008-09-16

This paper presents a novel method for preparation of polymer-silica colloidal nanocomposites based on emulsion polymerization and subsequent sol-gel nanocoating process. The polystyrene latex particles bearing basic groups on their surfaces were successfully synthesized through emulsion polymerization using 4-vinylpyridine (4VP) as a functional comonomer and polyvinylpyrrolidone (PVP) as a surfactant. A series of poly(styrene-co-4-vinylpyridine)/SiO2 nanocomposite particles with smooth or rough core-shell morphology were obtained through the coating process. The poly(styrene-co-4-vinylpyridine) particles could be dissolved subsequently or simultaneously during the sol-gel coating process to form hollow particles. The effects of the amount of 4VP, PVP, NH(4)OH, and tetraethoxysilane (TEOS) on both the nanocomposite particles and hollow particles were investigated. Transmission electron microscopy showed that the morphology of the nanocomposite particles and hollow particles was strongly influenced by the initial feed of the comonomer 4VP and the coupling agent PVP. The conditions to obtain all hollow particles were also studied. Thermogravimetric analysis and energy dispersive X-ray spectroscopy analyses indicated that the interiors of hollow particles were not really "hollow".

Strong thin membrane structure for use as solar sail comprising substrate with reflective coating on one surface and an infra red emissivity increasing coating on the other surface

NASA Technical Reports Server (NTRS)

Frazer, Robert E. (Inventor)

1982-01-01

Production of strong lightweight membrane structure by applying a thin reflective coating such as aluminum to a rotating cylinder, applying a mesh material such as nylon over the aluminum coating, coating the mesh overlying the aluminum with a polymerizing material such as a para-xylylene monomer gas to polymerize as a film bound to the mesh and the aluminum, and applying an emissivity increasing material such as chromium and silicon monoxide to the polymer film to disperse such material colloidally into the growing polymer film, or applying such material to the final polymer film, and removing the resulting membrane structure from the cylinder. Alternatively, such membrane structure can be formed by etching a substrate in the form of an organic film such as a polyimide, or a metal foil, to remove material from the substrate and reduce its thickness, applying a thin reflective coating such as aluminum on one side of the substrate and applying an emissivity increasing coating such as chromium and silicon monoxide on the reverse side of the substrate.

Template-based preparation of free-standing semiconducting polymeric nanorod arrays on conductive substrates.

PubMed

Haberkorn, Niko; Weber, Stefan A L; Berger, Rüdiger; Theato, Patrick

2010-06-01

We describe the synthesis and characterization of a cross-linkable siloxane-derivatized tetraphenylbenzidine (DTMS-TPD), which was used for the fabrication of semiconducting highly ordered nanorod arrays on conductive indium tin oxide or Pt-coated substrates. The stepwise process allow fabricating of macroscopic areas of well-ordered free-standing nanorod arrays, which feature a high resistance against organic solvents, semiconducting properties and a good adhesion to the substrate. Thin films of the TPD derivate with good hole-conducting properties could be prepared by cross-linking and covalently attaching to hydroxylated substrates utilizing an initiator-free thermal curing at 160 degrees C. The nanorod arrays composed of cross-linked DTMS-TPD were fabricated by an anodic aluminum oxide (AAO) template approach. Furthermore, the nanorod arrays were investigated by a recently introduced method allowing to probe local conductivity on fragile structures. It revealed that more than 98% of the nanorods exhibit electrical conductance and consequently feature a good electrical contact to the substrate. The prepared nanorod arrays have the potential to find application in the fabrication of multilayered device architectures for building well-ordered bulk-heterojunction solar cells.

Development of Fabrication Methods of Filler/Polymer Nanocomposites: With Focus on Simple Melt-Compounding-Based Approach without Surface Modification of Nanofillers

PubMed Central

Tanahashi, Mitsuru

2010-01-01

Many attempts have been made to fabricate various types of inorganic nanoparticle-filled polymers (filler/polymer nanocomposites) by a mechanical or chemical approach. However, these approaches require modification of the nanofiller surfaces and/or complicated polymerization reactions, making them unsuitable for industrial-scale production of the nanocomposites. The author and coworkers have proposed a simple melt-compounding method for the fabrication of silica/polymer nanocomposites, wherein silica nanoparticles without surface modification were dispersed through the breakdown of loose agglomerates of colloidal nano-silica spheres in a kneaded polymer melt. This review aims to discuss experimental techniques of the proposed method and its advantages over other developed methods.

Supramolecular Engineering of Hierarchically Self-Assembled, Bioinspired, Cholesteric Nanocomposites Formed by Cellulose Nanocrystals and Polymers.

PubMed

Zhu, Baolei; Merindol, Remi; Benitez, Alejandro J; Wang, Baochun; Walther, Andreas

2016-05-04

Natural composites are hierarchically structured by combination of ordered colloidal and molecular length scales. They inspire future, biomimetic, and lightweight nanocomposites, in which extraordinary mechanical properties are in reach by understanding and mastering hierarchical structure formation as tools to engineer multiscale deformation mechanisms. Here we describe a hierarchically self-assembled, cholesteric nanocomposite with well-defined colloid-based helical structure and supramolecular hydrogen bonds engineered on the molecular level in the polymer matrix. We use reversible addition-fragmentation transfer polymerization to synthesize well-defined hydrophilic, nonionic polymers with a varying functionalization density of 4-fold hydrogen-bonding ureidopyrimidinone (UPy) motifs. We show that these copolymers can be coassembled with cellulose nanocrystals (CNC), a sustainable, stiff, rod-like reinforcement, to give ordered cholesteric phases with characteristic photonic stop bands. The dimensions of the helical pitch are controlled by the ratio of polymer/CNC, confirming a smooth integration into the colloidal structure. With respect to the effect of the supramolecular motifs, we demonstrate that those regulate the swelling when exposing the biomimetic hybrids to water, and they allow engineering the photonic response. Moreover, the amount of hydrogen bonds and the polymer fraction are decisive in defining the mechanical properties. An Ashby plot comparing previous ordered CNC-based nanocomposites with our new hierarchical ones reveals that molecular engineering allows us to span an unprecedented mechanical property range from highest inelastic deformation (strain up to ∼13%) to highest stiffness (E ∼ 15 GPa) and combinations of both. We envisage that further rational design of the molecular interactions will provide efficient tools for enhancing the multifunctional property profiles of such bioinspired nanocomposites.

Preparation of surfactant-free nanoparticles of methacrylic acid copolymers used for film coating.

PubMed

Nguyen, Cung An; Konan-Kouakou, Yvette Niamien; Allémann, Eric; Doelker, Eric; Quintanar-Guerrero, David; Fessi, Hatem; Gurny, Robert

2006-07-28

The aim of the present study was to prepare surfactant-free pseudolatexes of various methacrylic acid copolymers. These aqueous colloidal dispersions of polymeric materials for oral administration are intended for film coating of solid dosage forms or for direct manufacturing of nanoparticles. Nanoparticulate dispersions were produced by an emulsification-diffusion method involving the use of partially water-miscible solvents and the mutual saturation of the aqueous and organic phases prior to the emulsification in order to reduce the initial thermodynamic instability of the emulsion. Because of the self-emulsifying properties of the methacrylic acid copolymers, it was possible to prepare aqueous dispersions of colloidal size containing up to 30% wt/vol of Eudragit RL, RS, and E using 2-butanone or methyl acetate as partially water-miscible solvents, but without any surfactant. However, in the case of the cationic Eudragit E, protonation of the tertiary amine groups by acidification of the aqueous phase was necessary to improve the emulsion stability in the absence of surfactant and subsequently to prevent droplet coalescence during evaporation. In addition, a pseudolatex of Eudragit E was used to validate the coating properties of the formulation for solid dosage forms. Film-coated tablets of quinidine sulfate showed a transparent glossy continuous film that was firmly attached to the tablet. The dissolution profile of quinidine sulfate from the tablets coated with the Eudragit E pseudolatex was comparable to that of tablets coated with an acetonic solution of Eudragit E. Furthermore, both types of coating ensured similar taste masking. The emulsification-evaporation method used was shown to be appropriate for the preparation of surfactant-free colloidal dispersions of the 3 types of preformed methacrylic acid copolymers; the dispersions can subsequently be used for film coating of solid dosage forms.

Nanofabricated particles for engineered drug therapies: a preliminary biodistribution study of PRINT nanoparticles.

PubMed

Gratton, Stephanie E A; Pohlhaus, Patrick D; Lee, Jin; Guo, Ji; Cho, Moo J; Desimone, Joseph M

2007-08-16

A novel method for the fabrication of polymeric particles on the order of tens of nanometers to several microns is described. This imprint lithographic technique called PRINT (Particle Replication In Non-wetting Templates), takes advantage of the unique properties of elastomeric molds comprised of a low surface energy perfluoropolyether network, allowing the production of monodisperse, shape-specific nanoparticles from an extensive array of organic precursors. This engineered nature of particle production has a number of advantages over the construction of traditional nanoparticles such as liposomes, dendrimers, and colloidal precipitates. The gentle "top down" approach of PRINT enables the simultaneous and independent control over particle size and shape, composition, and surface functionality, and permits the loading of delicate cargos such as small organic therapeutics and biological macromolecules. Thus, this single tool serves as a comprehensive platform for the rational design and investigation of new nanocarriers in medicine, having applications ranging from therapeutics to advanced diagnostics. Preliminary in vitro and in vivo studies were conducted, demonstrating the future utility of PRINT particles as delivery vectors in nanomedicine. Monodisperse 200 nm poly(ethylene glycol)-based (PEG) particles were fabricated using PRINT methodology and characterized via scanning electron microscopy and dynamic light scattering. Incubation with HeLa cells showed very little cytotoxicity, even at high concentrations. The biodistribution and pharmacokinetics of [(125)I]-labeled particles were studied in healthy mice following bolus tail vein administration. The particles were distributed mainly to the liver and the spleen with an apparent distribution t(1/2) of approximately 17 min followed by slow redistribution with a t(1/2) of 3.3 h. The volume of distribution for the central and peripheral compartments was found to be approximately 3 mL and 5 mL, respectively.

Photodeposition Method For Fabricating A Three-Dimensional, Patterned Polymer Microstructure

DOEpatents

Walt, David R.; Healey, Brian G.

2001-03-13

The present invention is a photodeposition methodology for fabricating a three-dimensional patterned polymer microstructure. A variety of polymeric structures can be fabricated on solid substrates using unitary fiber optic arrays for light delivery. The methodology allows micrometer-scale photopatterning for the fabricated structures using masks substantially larger than the desired dimensions of the microstructure.

Investigating critical effects of variegated lubricants, glidants and hydrophilic additives on lag time of press coated ethylcellulose tablets.

PubMed

Patadia, Riddhish; Vora, Chintan; Mittal, Karan; Mashru, Rajashree

2016-01-01

The research envisaged focuses on vital impacts of variegated lubricants, glidants and hydrophilic additives on lag time of press coated ethylcellulose (EC) tablets using prednisone as a model drug. Several lubricants and glidants such as magnesium stearate, colloidal SiO2, sodium stearyl fumarate, talc, stearic acid, polyethylene glycol (6000) and glyceryl behenate were investigated to understand their effects on lag time by changing their concentrations in outer coat. Further, the effects of hydrophilic additives on lag time were examined for hydroxypropylmethylcellulose (E5), hydroxypropylcellulose (EF and SSL), povidone (K30), copovidone, polyethylene glycol (4000), lactose and mannitol. In vitro drug release testing revealed that each selected lubricant/glidant, if present even at concentration of 0.25% w/w, significantly reduced the lag time of press coated tablets. Specifically, colloidal SiO2 and/or magnesium stearate were detrimental while other lubricants/glidants were relatively less injurious. Among hydrophilic additives, freely water soluble fillers had utmost influence in lag time, whereas, comparatively less impact was observed with polymeric binders. Concisely, glidant and lubricant should be chosen to have minimal impact on lag time and further judicious selection of hydrophilic additives should be exercised for modulating lag time of pulsatile release formulations.

Hierarchical templating in deposition of semi-covalently imprinted inverse opal polythiophene film for femtomolar determination of human serum albumin.

PubMed

Dabrowski, Marcin; Cieplak, Maciej; Sharma, Piyush Sindhu; Borowicz, Pawel; Noworyta, Krzysztof; Lisowski, Wojciech; D'Souza, Francis; Kuhn, Alexander; Kutner, Wlodzimierz

2017-08-15

Nanostructured artificial receptor materials with unprecedented hierarchical structure for determination of human serum albumin (HSA) are designed and fabricated. For that purpose a new hierarchical template is prepared. This template allowed for simultaneous structural control of the deposited molecularly imprinted polymer (MIP) film on three length scales. A colloidal crystal templating with optimized electrochemical polymerization of 2,3'-bithiophene enables deposition of an MIP film in the form of an inverse opal. Thickness of the deposited polymer film is precisely controlled with the number of current oscillations during potentiostatic deposition of the imprinted poly(2,3'-bithiophene) film. Prior immobilization of HSA on the colloidal crystal allows formation of molecularly imprinted cavities exclusively on the internal surface of the pores. Furthermore, all binding sites are located on the surface of the imprinted cavities at locations corresponding to positions of functional groups present on the surface of HSA molecules due to prior derivatization of HSA molecules with appropriate functional monomers. This synergistic strategy results in a material with superior recognition performance. Integration of the MIP film as a recognition unit with a sensitive extended-gate field-effect transistor (EG-FET) transducer leads to highly selective HSA determination in the femtomolar concentration range. Copyright © 2017 Elsevier B.V. All rights reserved.

Biomimetic synthesis of raspberry-like hybrid polymer-silica core-shell nanoparticles by templating colloidal particles with hairy polyamine shell.

PubMed

Pi, Mengwei; Yang, Tingting; Yuan, Jianjun; Fujii, Syuji; Kakigi, Yuichi; Nakamura, Yoshinobu; Cheng, Shiyuan

2010-07-01

The nanoparticles composed of polystyrene core and poly[2-(diethylamino)ethyl methacrylate] (PDEA) hairy shell were used as colloidal templates for in situ silica mineralization, allowing the well-controlled synthesis of hybrid silica core-shell nanoparticles with raspberry-like morphology and hollow silica nanoparticles by subsequent calcination. Silica deposition was performed by simply stirring a mixture of the polymeric core-shell particles in isopropanol, tetramethyl orthosilicate (TMOS) and water at 25 degrees C for 2.5h. No experimental evidence was found for nontemplated silica formation, which indicated that silica deposition occurred exclusively in the PDEA shell and formed PDEA-silica hybrid shell. The resulting hybrid silica core-shell particles were characterized by transmission electron microscopy (TEM), thermogravimetry, aqueous electrophoresis, and X-ray photoelectron spectroscopy. TEM studies indicated that the hybrid particles have well-defined core-shell structure with raspberry morphology after silica deposition. We found that the surface nanostructure of hybrid nanoparticles and the composition distribution of PDEA-silica hybrid shell could be well controlled by adjusting the silicification conditions. These new hybrid core-shell nanoparticles and hollow silica nanoparticles would have potential applications for high-performance coatings, encapsulation and delivery of active organic molecules. 2010 Elsevier B.V. All rights reserved.

Cell motility regulation on a stepped micro pillar array device (SMPAD) with a discrete stiffness gradient.

PubMed

Lee, Sujin; Hong, Juhee; Lee, Junghoon

2016-02-28

Our tissues consist of individual cells that respond to the elasticity of their environment, which varies between and within tissues. To better understand mechanically driven cell migration, it is necessary to manipulate the stiffness gradient across a substrate. Here, we have demonstrated a new variant of the microfabricated polymeric pillar array platform that can decouple the stiffness gradient from the ECM protein area. This goal is achieved via a "stepped" micro pillar array device (SMPAD) in which the contact area with the cell was kept constant while the diameter of the pillar bodies was altered to attain the proper mechanical stiffness. Using double-step SU-8 mold fabrication, the diameter of the top of every pillar was kept uniform, whereas that of the bottom was changed, to achieve the desired substrate rigidity. Fibronectin was immobilized on the pillar tops, providing a focal adhesion site for cells. C2C12, HeLa and NIH3T3 cells were cultured on the SMPAD, and the motion of the cells was observed by time-lapse microscopy. Using this simple platform, which produces a purely physical stimulus, we observed that various types of cell behavior are affected by the mechanical stimulus of the environment. We also demonstrated directed cell migration guided by a discrete rigidity gradient by varying stiffness. Interestingly, cell velocity was highest at the highest stiffness. Our approach enables the regulation of the mechanical properties of the polymeric pillar array device and eliminates the effects of the size of the contact area. This technique is a unique tool for studying cellular motion and behavior relative to various stiffness gradients in the environment.

Stepwise molding, etching, and imprinting to form libraries of nanopatterned substrates.

PubMed

Zhao, Zhi; Cai, Yangjun; Liao, Wei-Ssu; Cremer, Paul S

2013-06-04

Herein, we describe a novel colloidal lithographic strategy for the stepwise patterning of planar substrates with numerous complex and unique designs. In conjunction with colloidal self-assembly, imprint molding, and capillary force lithography, reactive ion etching was used to create complex libraries of nanoscale features. This combinatorial strategy affords the ability to develop an exponentially increasing number of two-dimensional nanoscale patterns with each sequential step in the process. Specifically, dots, triangles, circles, and lines could be assembled on the surface separately and in combination with each other. Numerous architectures are obtained for the first time with high uniformity and reproducibility. These hexagonal arrays were made from polystyrene and gold features, whereby each surface element could be tuned from the micrometer size scale down to line widths of ~35 nm. The patterned area could be 1 cm(2) or even larger. The techniques described herein can be combined with further steps to make even larger libraries. Moreover, these polymer and metal features may prove useful in optical, sensing, and electronic applications.

Spherical silicon-shell photonic band gap structures fabricated by laser-assisted chemical vapor deposition

NASA Astrophysics Data System (ADS)

Wang, H.; Yang, Z. Y.; Lu, Y. F.

2007-02-01

Laser-assisted chemical vapor deposition was applied in fabricating three-dimensional (3D) spherical-shell photonic band gap (PBG) structures by depositing silicon shells covering silica particles, which had been self-assembled into 3D colloidal crystals. The colloidal crystals of self-assembled silica particles were formed on silicon substrates using the isothermal heating evaporation approach. A continuous wave Nd:YAG laser (1064nm wavelength) was used to deposit silicon shells by thermally decomposing disilane gas. Periodic silicon-shell/silica-particle PBG structures were obtained. By removing the silica particles enclosed in the silicon shells using hydrofluoric acid, hollow spherical silicon-shell arrays were produced. This technique is capable of fabricating structures with complete photonic band gaps, which is predicted by simulations with the plane wave method. The techniques developed in this study have the potential to flexibly engineer the positions of the PBGs by varying both the silica particle size and the silicon-shell thickness. Ellipsometry was used to investigate the specific photonic band gaps for both structures.

Bio-inspired, sub-wavelength surface structures for ultra-broadband, omni-directional anti-reflection in the mid and far IR.

PubMed

Gonzalez, Federico Lora; Gordon, Michael J

2014-06-02

Quasi-ordered moth-eye arrays were fabricated in Si using a colloidal lithography method to achieve highly efficient, omni-directional transmission of mid and far infrared (IR) radiation. The effect of structure height and aspect ratio on transmittance and scattering was explored experimentally and modeled quantitatively using effective medium theory. The highest aspect ratio structures (AR = 9.4) achieved peak transmittance of 98%, with >85% transmission for λ = 7-30 μm. A detailed photon balance was constructed by measuring transmission, forward scattering, specular reflection and diffuse reflection to quantify optical losses due to near-field effects. In addition, angle-dependent transmission measurements showed that moth-eye structures provide superior anti-reflective properties compared to unstructured interfaces over a wide angular range (0-60° incidence). The colloidal lithography method presented here is scalable and substrate-independent, providing a general approach to realize moth-eye structures and anti-reflection in many IR-compatible material systems.

Tip-localized actin polymerization and remodeling, reflected by the localization of ADF, profilin and villin, are fundamental for gravity-sensing and polar growth in characean rhizoids.

PubMed

Braun, Markus; Hauslage, Jens; Czogalla, Aleksander; Limbach, Christoph

2004-07-01

Polar organization and gravity-oriented, polarized growth of characean rhizoids are dependent on the actin cytoskeleton. In this report, we demonstrate that the prominent center of the Spitzenkörper serves as the apical actin polymerization site in the extending tip. After cytochalasin D-induced disruption of the actin cytoskeleton, the regeneration of actin microfilaments (MFs) starts with the reappearance of a flat, brightly fluorescing actin array in the outermost tip. The actin array rounds up, produces actin MFs that radiate in all directions and is then relocated into its original central position in the center of the Spitzenkörper. The emerging actin MFs rearrange and cross-link to form the delicate, subapical meshwork, which then controls the statolith positioning, re-establishes the tip-high calcium gradient and mediates the reorganization of the Spitzenkörper with its central ER aggregate and the accumulation of secretory vesicles. Tip growth and gravitropic sensing, which includes control of statolith positioning and gravity-induced sedimentation, are not resumed until the original polar actin organization is completely restored. Immunolocalization of the actin-binding proteins, actin-depolymerizing factor (ADF) and profilin, which both accumulate in the center of the Spitzenkörper, indicates high actin turnover and gives additional support for the actin-polymerizing function of this central, apical area. Association of villin immunofluorescence with two populations of thick undulating actin cables with uniform polarity underlying rotational cytoplasmic streaming in the basal region suggests that villin is the major actin-bundling protein in rhizoids. Our results provide evidence that the precise coordination of apical actin polymerization and dynamic remodeling of actin MFs by actin-binding proteins play a fundamental role in cell polarization, gravity sensing and gravity-oriented polarized growth of characean rhizoids.

Surface patterning of polymeric separation membranes and its influence on the filtration performance

NASA Astrophysics Data System (ADS)

Maruf, Sajjad

Polymeric membrane based separation technologies are crucial for addressing the global issues such as water purification. However, continuous operations of these processes are often hindered by fouling which increases mass transport resistance of the membrane to permeation and thus the energy cost, and eventually replacement of the membrane in the system. In comparison to other anti-fouling strategies, the use of controlled surface topography to mitigate fouling has not been realized mainly due to the lack of methods to create targeted topography on the porous membrane surface. This thesis aims to develop a new methodology to create surface-patterned polymeric separation membrane to improve their anti-fouling characteristics during filtration. First, successful fabrication of sub-micron surface patterns directly on a commercial ultrafiltration (UF) membrane surface using nanoimprint lithographic (NIL) technique was demonstrated. Comprehensive filtration studies revealed that the presence of these sub-micron surface patterns mitigates not only the onset of colloidal particle deposition, but also lowers the rate of growth of cake layer after initial deposition, in comparison with un-patterned membranes. The anti-fouling effects were also observed for model protein solutions. Staged filtration experiments, with backwash cleaning, revealed that the permeate flux of the patterned membrane after protein fouling was considerably higher than that of the pristine or un-patterned membrane. In addition to the surface-patterning of UF membranes, successful fabrication of a surface-patterned thin film composite (TFC) membrane was shown for the first time. A two-step fabrication process was carried out by (1) nanoimprinting a polyethersulfone (PES) support using NIL, and (2) forming a thin dense film atop the PES support via interfacial polymerization (IP). Fouling experiments suggest that the surface patterns alter the hydrodynamics at the membrane-feed interface, which is effective in decreasing fouling in dead end filtration system. In summary, this thesis represents the first ever fabrication of functional patterned polymeric separation membrane and systematic investigation of the influence of submicron surface patterns on pressure-driven liquid membrane separations. The results presented here will enable an effective non-chemical surface modification anti-fouling strategy, which can be directly added onto current commercial separation membrane manufacturing route.

Tidal and seasonal effects on the short-term temporal patterns of bacteria, microphytobenthos and exopolymers in natural intertidal biofilms (Brouage, France)

NASA Astrophysics Data System (ADS)

Orvain, Francis; De Crignis, Margot; Guizien, Katell; Lefebvre, Sébastien; Mallet, Clarisse; Takahashi, Eri; Dupuy, Christine

2014-09-01

Relationships between bacteria, microphytobenthos and extracellular polymeric substances (EPS) that make up microbial biofilms over bare mudflats were investigated at an hourly frequency during two 14-day spring-neap cycles in winter and summer 2008. Bacterial abundance and total chl a concentration were lower in summer (0.78 × 108 ± SD 0.39 × 108 cell.m- 2 and 59.0 ± SD 10.42 mgchla.m- 2) than in winter (3.7 × 108 ± SD 1.9 × 108 cell.m- 2 and 106.64 ± SD 11.29 mgchla.m- 2), coinciding with a high abundance of the gastropod Peringia ulvae in summer, which subsequently impacted 1st-cm chl a concentration by intense grazing. Bound and colloidal EPS carbohydrate temporal patterns were similar in winter (5.71 ± SD 3.95 and 4.67 ± SD 3.45 μg.g- 1, respectively) but were different in summer (14.9 ± SD 4.05 and 5.60 ± SD 4.50 μg.g- 1, respectively). Carbohydrate colloidal EPS appeared to be related to light and salinity, while 1st-mm chl a concentration was negatively affected by strong salinities and predation pressure by P. ulvae. The fluctuations of colloidal carbohydrates were remarkably similar in the two seasons with peaks just after spring tides when the highest irradiance was received by microphytobenthic cells. Apparently, colloidal EPS carbohydrates can protect cells against the high salinity values ranging from 32.3 to 50.4 PSU. The presence of bound EPS carbohydrates may be linked to sediment colonization and resistance of biofilm activity. Proteins in EPS were absent in winter and represented a small proportion in summer (10%), but they appeared to be a good indicator of potential synergistic effects between MPB and bacteria in summer. Conversely, bound EPS carbohydrates reached high levels in winter, while the number of bacteria decreased simultaneously, suggesting a negative effect on bacterial growth in the absence of proteins in EPS. There was a lower proportion (31%) of low molecular weight EPS in summer than in winter (83%), possibly in relation to desiccation.

Synthesis of Well-defined Amphiphilic Block Copolymers by Organotellurium-Mediated Living Radical Polymerization (TERP).

PubMed

Kumar, Santosh; Changez, Mohammad; Murthy, C N; Yamago, Shigeru; Lee, Jae-Suk

2011-10-04

Low-molecular weight amphiphilic diblock copolymers, polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), and (P2VP-b-PS) with different block ratios were synthesized for the first time via organotellurium-mediated living radical polymerization (TERP). For both the homo- and block copolymerizations, good agreement between the theoretical, and experimental molecular weights was found with nearly 100% yield in every case. The molecular weight distribution for all the samples ranged between 1.10 and 1.24, which is well below the theoretical lower limit of 1.50 for a conventional free radical polymerization. Furthermore, a very simple approach to producing highly dense arrays of titania nanoparticles (TiO2 ) is presented using a site-selective reaction of titanium tetraisopropoxide within the P2VP domains of micellar film of P2VP-b-PS in toluene through the sol-gel method. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Syringyl Methacrylate, a Hardwood Lignin-Based Monomer for High-Tg Polymeric Materials.

PubMed

Holmberg, Angela L; Reno, Kaleigh H; Nguyen, Ngoc A; Wool, Richard P; Epps, Thomas H

2016-05-17

As viable precursors to a diverse array of macromolecules, biomass-derived compounds must impart wide-ranging and precisely controllable properties to polymers. Herein, we report the synthesis and subsequent reversible addition-fragmentation chain-transfer polymerization of a new monomer, syringyl methacrylate (SM, 2,6-dimethoxyphenyl methacrylate), that can facilitate widespread property manipulations in macromolecules. Homopolymers and heteropolymers synthesized from SM and related monomers have broadly tunable and highly controllable glass transition temperatures ranging from 114 to 205 °C and zero-shear viscosities ranging from ∼0.2 kPa·s to ∼17,000 kPa·s at 220 °C, with consistent thermal stabilities. The tailorability of these properties is facilitated by the controlled polymerization kinetics of SM and the fact that one vs two o -methoxy groups negligibly affect monomer reactivity. Moreover, syringol, the precursor to SM, is an abundant component of depolymerized hardwood (e.g., oak) and graminaceous (e.g., switchgrass) lignins, making SM a potentially sustainable and low-cost candidate for tailoring macromolecular properties.

Cationic polymer brush-modified cellulose nanocrystals for high-affinity virus binding

NASA Astrophysics Data System (ADS)

Rosilo, Henna; McKee, Jason R.; Kontturi, Eero; Koho, Tiia; Hytönen, Vesa P.; Ikkala, Olli; Kostiainen, Mauri A.

2014-09-01

Surfaces capable of high-affinity binding of biomolecules are required in several biotechnological applications, such as purification, transfection, and sensing. Therein, the rod-shaped, colloidal cellulose nanocrystals (CNCs) are appealing due to their large surface area available for functionalization. In order to exploit electrostatic binding, their intrinsically anionic surfaces have to be cationized as biological supramolecules are predominantly anionic. Here we present a facile way to prepare cationic CNCs by surface-initiated atom-transfer radical polymerization of poly(N,N-dimethylaminoethyl methacrylate) and subsequent quaternization of the polymer pendant amino groups. The cationic polymer brush-modified CNCs maintained excellent dispersibility and colloidal stability in water and showed a ζ-potential of +38 mV. Dynamic light scattering and electron microscopy showed that the modified CNCs electrostatically bind cowpea chlorotic mottle virus and norovirus-like particles with high affinity. Addition of only a few weight percent of the modified CNCs in water dispersions sufficed to fully bind the virus capsids to form micrometer-sized assemblies. This enabled the concentration and extraction of the virus particles from solution by low-speed centrifugation. These results show the feasibility of the modified CNCs in virus binding and concentrating, and pave the way for their use as transduction enhancers for viral delivery applications.Surfaces capable of high-affinity binding of biomolecules are required in several biotechnological applications, such as purification, transfection, and sensing. Therein, the rod-shaped, colloidal cellulose nanocrystals (CNCs) are appealing due to their large surface area available for functionalization. In order to exploit electrostatic binding, their intrinsically anionic surfaces have to be cationized as biological supramolecules are predominantly anionic. Here we present a facile way to prepare cationic CNCs by surface-initiated atom-transfer radical polymerization of poly(N,N-dimethylaminoethyl methacrylate) and subsequent quaternization of the polymer pendant amino groups. The cationic polymer brush-modified CNCs maintained excellent dispersibility and colloidal stability in water and showed a ζ-potential of +38 mV. Dynamic light scattering and electron microscopy showed that the modified CNCs electrostatically bind cowpea chlorotic mottle virus and norovirus-like particles with high affinity. Addition of only a few weight percent of the modified CNCs in water dispersions sufficed to fully bind the virus capsids to form micrometer-sized assemblies. This enabled the concentration and extraction of the virus particles from solution by low-speed centrifugation. These results show the feasibility of the modified CNCs in virus binding and concentrating, and pave the way for their use as transduction enhancers for viral delivery applications. Electronic supplementary information (ESI) available: CNC surface chain fraction and degree of substitution after BriBBr modification, NMR spectra of the SI-ATRP reaction mixture at 0 and 120 min, conversion of the DMAEMA monomer during SI-ATRP, DLS size distribution profiles of CNCs and CNC-g-P(QDMAEMA), TEM images of NoV-VLPs and their complexes with CNC-g-P(QDMAEMA) at 0 mM NaCl. See DOI: 10.1039/c4nr03584d

High reduction of interfacial charge recombination in colloidal quantum dot solar cells by metal oxide surface passivation.

PubMed

Chang, Jin; Kuga, Yuki; Mora-Seró, Iván; Toyoda, Taro; Ogomi, Yuhei; Hayase, Shuzi; Bisquert, Juan; Shen, Qing

2015-03-12

Bulk heterojunction (BHJ) solar cells based on colloidal QDs and metal oxide nanowires (NWs) possess unique and outstanding advantages in enhancing light harvesting and charge collection in comparison to planar architectures. However, the high surface area of the NW structure often brings about a large amount of recombination (especially interfacial recombination) and limits the open-circuit voltage in BHJ solar cells. This problem is solved here by passivating the surface of the metal oxide component in PbS colloidal quantum dot solar cells (CQDSCs). By coating thin TiO2 layers onto ZnO-NW surfaces, the open-circuit voltage and power conversion efficiency have been improved by over 40% in PbS CQDSCs. Characterization by transient photovoltage decay and impedance spectroscopy indicated that the interfacial recombination was significantly reduced by the surface passivation strategy. An efficiency as high as 6.13% was achieved through the passivation approach and optimization for the length of the ZnO-NW arrays (device active area: 16 mm2). All solar cells were tested in air, and exhibited excellent air storage stability (without any performance decline over more than 130 days). This work highlights the significance of metal oxide passivation in achieving high performance BHJ solar cells. The charge recombination mechanism uncovered in this work could shed light on the further improvement of PbS CQDSCs and/or other types of solar cells.

Electron transport in gold colloidal nanoparticle-based strain gauges.

PubMed

Moreira, Helena; Grisolia, Jérémie; Sangeetha, Neralagatta M; Decorde, Nicolas; Farcau, Cosmin; Viallet, Benoit; Chen, Ke; Viau, Guillaume; Ressier, Laurence

2013-03-08

A systematic approach for understanding the electron transport mechanisms in resistive strain gauges based on assemblies of gold colloidal nanoparticles (NPs) protected by organic ligands is described. The strain gauges were fabricated from parallel micrometer wide wires made of 14 nm gold (Au) colloidal NPs on polyethylene terephthalate substrates, elaborated by convective self-assembly. Electron transport in such devices occurs by inter-particle electron tunneling through the tunnel barrier imposed by the organic ligands protecting the NPs. This tunnel barrier was varied by changing the nature of organic ligands coating the nanoparticles: citrate (CIT), phosphines (BSPP, TDSP) and thiols (MPA, MUDA). Electro-mechanical tests indicate that only the gold NPs protected by phosphine and thiol ligands yield high gauge sensitivity. Temperature-dependent resistance measurements are explained using the 'regular island array model' that extracts transport parameters, i.e., the tunneling decay constant β and the Coulomb charging energy E(C). This reveals that the Au@CIT nanoparticle assemblies exhibit a behavior characteristic of a strong-coupling regime, whereas those of Au@BSPP, Au@TDSP, Au@MPA and Au@MUDA nanoparticles manifest a weak-coupling regime. A comparison of the parameters extracted from the two methods indicates that the most sensitive gauges in the weak-coupling regime feature the highest β. Moreover, the E(C) values of these 14 nm NPs cannot be neglected in determining the β values.

Electron transport in gold colloidal nanoparticle-based strain gauges

NASA Astrophysics Data System (ADS)

Moreira, Helena; Grisolia, Jérémie; Sangeetha, Neralagatta M.; Decorde, Nicolas; Farcau, Cosmin; Viallet, Benoit; Chen, Ke; Viau, Guillaume; Ressier, Laurence

2013-03-01

A systematic approach for understanding the electron transport mechanisms in resistive strain gauges based on assemblies of gold colloidal nanoparticles (NPs) protected by organic ligands is described. The strain gauges were fabricated from parallel micrometer wide wires made of 14 nm gold (Au) colloidal NPs on polyethylene terephthalate substrates, elaborated by convective self-assembly. Electron transport in such devices occurs by inter-particle electron tunneling through the tunnel barrier imposed by the organic ligands protecting the NPs. This tunnel barrier was varied by changing the nature of organic ligands coating the nanoparticles: citrate (CIT), phosphines (BSPP, TDSP) and thiols (MPA, MUDA). Electro-mechanical tests indicate that only the gold NPs protected by phosphine and thiol ligands yield high gauge sensitivity. Temperature-dependent resistance measurements are explained using the ‘regular island array model’ that extracts transport parameters, i.e., the tunneling decay constant β and the Coulomb charging energy EC. This reveals that the Au@CIT nanoparticle assemblies exhibit a behavior characteristic of a strong-coupling regime, whereas those of Au@BSPP, Au@TDSP, Au@MPA and Au@MUDA nanoparticles manifest a weak-coupling regime. A comparison of the parameters extracted from the two methods indicates that the most sensitive gauges in the weak-coupling regime feature the highest β. Moreover, the EC values of these 14 nm NPs cannot be neglected in determining the β values.

Design and physicochemical characterisation of novel dissolving polymeric microneedle arrays for transdermal delivery of high dose, low molecular weight drugs

PubMed Central

McCrudden, Maelíosa T.C.; Alkilani, Ahlam Zaid; McCrudden, Cian M.; McAlister, Emma; McCarthy, Helen O.; Woolfson, A. David; Donnelly, Ryan F.

2014-01-01

We describe formulation and evaluation of novel dissolving polymeric microneedle (MN) arrays for the facilitated delivery of low molecular weight, high dose drugs. Ibuprofen sodium was used as the model here and was successfully formulated at approximately 50% w/w in the dry state using the copolymer poly(methylvinylether/maleic acid). These MNs were robust and effectively penetrated skin in vitro, dissolving rapidly to deliver the incorporated drug. The delivery of 1.5 mg ibuprofen sodium, the theoretical mass of ibuprofen sodium contained within the dry MN alone, was vastly exceeded, indicating extensive delivery of the drug loaded into the baseplates. Indeed in in vitro transdermal delivery studies, approximately 33 mg (90%) of the drug initially loaded into the arrays was delivered over 24 h. Iontophoresis produced no meaningful increase in delivery. Biocompatibility studies and in vivo rat skin tolerance experiments raised no concerns. The blood plasma ibuprofen sodium concentrations achieved in rats (263 μg ml− 1 at the 24 h time point) were approximately 20 times greater than the human therapeutic plasma level. By simplistic extrapolation of average weights from rats to humans, a MN patch design of no greater than 10 cm2 could cautiously be estimated to deliver therapeutically-relevant concentrations of ibuprofen sodium in humans. This work, therefore, represents a significant progression in exploitation of MN for successful transdermal delivery of a much wider range of drugs. PMID:24556420

Sensor-integrated polymer actuators for closed-loop drug delivery system

NASA Astrophysics Data System (ADS)

Xu, Han; Wang, Chunlei; Kulinsky, Lawrence; Zoval, Jim; Madou, Marc

2006-03-01

This work presents manufacturing and testing of a closed-loop drug delivery system where drug release is achieved by an electrochemical actuation of an array of polymeric valves on a set of drug reservoirs. The valves are based on bi-layer structures made of polypyrrole/gold in the shape of a flap that is hinged on one side of a valve seat. Drugs stored in the underlying chambers are released by bending the bi-layer flaps back with a small applied bias. These polymeric valves simultaneously function as both drug release components and biological/chemical sensors responding to a specific biological or environmental stimulus. The sensors may send signals to the control module to realize closed-loop control of the drug release. In this study a glucose sensor has been integrated with the polymeric actuators through immobilization of glucose oxidase(GOx) within polypyrrole(PPy) valves. Sensitivities per unit area of the integrated glucose sensor have been measured and compared before and after the actuation of the sensor/actuator PPy/DBS/GOx film. Other sensing parameters such as linear range and response time were discussed as well. Using an array of these sensor/actuator cells, the amount of released drug, e.g. insulin, can be precisely controlled according to the surrounding glucose concentration detected by the glucose sensor. Activation of these reservoirs can be triggered either by the signal from the sensor, or by the signal from the operator. This approach also serves as the initial step to use the proposed system as an implantable drug delivery platform in the future.

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

Nuzzo, Ralph G.; Rogers, John A.; Menard, Etienne

The invention provides methods and devices for fabricating printable semiconductor elements and assembling printable semiconductor elements onto substrate surfaces. Methods, devices and device components of the present invention are capable of generating a wide range of flexible electronic and optoelectronic devices and arrays of devices on substrates comprising polymeric materials. The present invention also provides stretchable semiconductor structures and stretchable electronic devices capable of good performance in stretched configurations.

Two-photon polymerization for fabrication of biomedical devices

NASA Astrophysics Data System (ADS)

Ovsianikov, Aleksandr; Doraiswamy, Anand; Narayan, R.; Chichkov, B. N.

2007-01-01

Two-photon polymerization (2PP) is a novel technology which allows the fabrication of complex three-dimensional (3D) microstructures and nanostructures. The number of applications of this technology is rapidly increasing; it includes the fabrication of 3D photonic crystals [1-4], medical devices, and tissue scaffolds [5-6]. In this contribution, we discuss current applications of 2PP for microstructuring of biomedical devices used in drug delivery. While in general this sector is still dominated by oral administration of drugs, precise dosing, safety, and convenience are being addressed by transdermal drug delivery systems. Currently, main limitations arise from low permeability of the skin. As a result, only few types of pharmacological substances can be delivered in this manner [7]. Application of microneedle arrays, whose function is to help overcome the barrier presented by the epidermis layer of the skin, provides a very promising solution. Using 2PP we have fabricated arrays of hollow microneedles with different geometries. The effect of microneedle geometry on skin penetration is examined. Our results indicate that microneedles created using 2PP technique are suitable for in vivo use, and for integration with the next generation of MEMS- and NEMS-based drug delivery devices.

Gradiently Polymerized Solid Electrolyte Meets with Micro/Nano-Structured Cathode Array.

PubMed

Dong, Wei; Zeng, Xian-Xiang; Zhang, Xu-Dong; Li, Jin-Yi; Shi, Ji-Lei; Xiao, Yao; Shi, Yang; Wen, Rui; Yin, Ya-Xia; Wang, Tai-Shan; Wang, Chun-Ru; Guo, Yu-Guo

2018-05-02

The poor contact between the solid-state electrolyte and cathode materials leads to high interfacial resistance, severely limiting the rate capability of solid Li metal batteries. Herein, an integrative battery design is introduced with a gradiently polymerized solid electrolyte (GPSE), a micro-channel current collector array and nano-sized cathode particles. In-situ formed GPSE encapsulates cathode nanoparticles in the micro-channel with ductile inclusions to lower interfacial impedance, and the stiff surface layer of GPSE toward anode suppresses Li dendrites growth. Li metal batteries based on GPSE and Li-free hydrogenated V2O5 (V2O5-H) cathode exhibit an outstanding high-rate response of up to 5 C (the capacity ratio of 5 C / 1 C is 90.3%) and an ultralow capacity fade rate of 0.07% per cycle over 300 cycles. Other Li-containing cathodes as LiFePO4 and LiNi0.5Mn0.3Co0.2O2 can also operate effectively at 5 C and 2 C rate, respectively. Such an ingenious design may provide new insights into other solid metal batteries through interfacial engineering manipulation at micro and nano level.

Morphology Control of Multicomponent Polymeric Surfactants Using Pressure

NASA Astrophysics Data System (ADS)

Cho, Junhan

The development of nanoscale morphologies for a molten polymeric surfactant under pressure is investigated by using a recently formulated self-consistent field theory. A linear ABC block copolymer is taken as our model system that allows a disparity in the propensities for curved interfaces and pressure responses of ij-pairs. The interplay of those features lead the copolymer to new morphologies at a moderate segregation level and at ambient condition such as networks and pillars of 2-dimensional array. It is shown that pressure is an effective means of morphology control and identification for those new structures. The role of volume fluctuations in the development of those structures is discussed. J.C. acknowledges the support from Center for Photofunctional Energy Materials through Gyeonggi Regional Research Program.

Heterogeneous NiCo2O4@polypyrrole core/sheath nanowire arrays on Ni foam for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Hu, Jing; Li, Minchan; Lv, Fucong; Yang, Mingyang; Tao, Pengpeng; Tang, Yougen; Liu, Hongtao; Lu, Zhouguang

2015-10-01

A novel heterogeneous NiCo2O4@PPy core/sheath nanowire arrays are directly grown on Ni foam involving three facile steps, hydrothermal synthesis and calcination of NiCo2O4 nanowire arrays and subsequent in-situ oxidative polymerization of polypyrrole (PPy). When investigated as binder- and conductive additive-free electrodes for supercapacitors (SCs) in 6 M KOH, the NiCo2O4@PPy core/sheath nanowire arrays exhibit high areal capacitance of 3.49 F cm-2 at a discharge current density of 5 mA cm-2, which is almost 1.5 times as much as the pristine NiCo2O4 (2.30 F cm-2). More importantly, it can remain 3.31 F cm-2 (94.8% retention) after 5000 cycles. The as-obtained electrode also displays excellent rate capability, whose areal capacitance can still remain 2.79 F cm-2 while the discharge current density is increased to 50 mA cm-2. The remarkable electrochemical performance is mainly attributed to the unique heterogeneous core/sheath nanowire-array architectures.

Low Earth orbit environmental effects on the space station photovoltaic power generation systems

NASA Technical Reports Server (NTRS)

Nahra, Henry K.

1987-01-01

A summary of the Low Earth Orbital Environment, its impact on the Photovoltaic Power systems of the space station and the solutions implemented to resolve the environmental concerns or issues are described. Low Earth Orbital Environment (LEO) presents several concerns to the Photovoltaic power systems of the space station. These concerns include atomic oxygen interaction with the polymeric substrate of the solar arrays, ionized environment effects on the array operating voltage, the effects of the meteoroids and debris impacts and penetration through the different layers of the solar cells and their circuits, and the high energy particle and radiation effects on the overall solar array performance. Potential solutions to some of the degrading environmental interactions that will provide the photovoltaic power system of the space station with the desired life are also summarized.

Production of solid lipid nanoparticles (SLN): scaling up feasibilities.

PubMed

Dingler, A; Gohla, S

2002-01-01

Solid lipid nanoparticles (SLN/Lipopearls) are widely discussed as a new colloidal drug carrier system. In contrast to polymeric systems, such as Polylactic copolyol microcapsules, these systems show with a good biocompatibility, if applied parenterally. The solid lipid matrices can be comprised of fats or waxes, and allow protection of incorporated active ingredients against chemical and physical degradation. The SLN can either be produced by 'hot homogenization' of melted lipids at elevated temperatures or by a 'cold homogenization' process. This paper deals with production technologies for SLN formulations, based on non-ethoxylated fat components for topical application and high pressure homogenization. Based on the chosen fat components, a novel and easy manufacturing and scaling-up method was developed to maintain chemical and physical integrity of the encapsulated active ingredients in the carrier.

Fractal bimetallic plasmonic structures obtained by laser deposition of colloidal nanoparticles

NASA Astrophysics Data System (ADS)

Bukharov, D. N.; Arakelyan, S. M.; Kutrovskaya, S. V.; Kucherik, A. O.; Osipov, A. V.; Istratov, A. V.; Vartanyan, T. A.; Itina, T. E.; Kavokin, A. V.

2017-09-01

We produce bimetallic Au:Ag thin films by laser irradiation of the mixed solutions. After several laser scans, granular nanometric films are found to grow with a well-controlled composition, thickness and morphology. By changing laser scanning parameters, the film morphology can be varied from island structures to quasi-periodic arrays. The optical properties of the deposited structures are found to depend on the film composition, thickness and spacing between the particles. The transmittance spectra of the deposited films are shown to be governed by their morphology.

3D plasmonic nanoarchitectures for extreme light concentration

NASA Astrophysics Data System (ADS)

Arnob, Md Masud Parvez; Zhao, Fusheng; Shih, Wei-Chuan

2017-08-01

Plasmonic nanomaterials are known to concentrate incident light to their surfaces by collective electron oscillation. Plasmonic hot-spot refers to locations where electromagnetic fields are particularly enhanced relative to the incident field. Traditional plasmonic nanomaterials are 1D (e.g., colloidal nanoparticles) or 2D (lithographically patterned nanostructure arrays) in nature, which typically result in sparse field concentration patterns. To improve efficiency and better utilization of hot-spots, we investigate 3D plasmonic nanoarchitecture where abundant hot-spots are formed in a 3D volumetric fashion, a feature drastically departing from traditional nanostructures.

A composite hydrogels-based photonic crystal multi-sensor

NASA Astrophysics Data System (ADS)

Chen, Cheng; Zhu, Zhigang; Zhu, Xiangrong; Yu, Wei; Liu, Mingju; Ge, Qiaoqiao; Shih, Wei-Heng

2015-04-01

A facile route to prepare stimuli-sensitive poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) gelated crystalline colloidal array photonic crystal material was developed. PVA was physically gelated by utilizing an ethanol-assisted method, the resulting hydrogel/crystal composite film was then functionalized with PAA to form an interpenetrating hydrogel film. This sensor film is able to efficiently diffract the visible light and rapidly respond to various environmental stimuli such as solvent, pH and strain, and the accompanying structural color shift can be repeatedly changed and easily distinguished by naked eye.

Quadrupole ion traps and trap arrays: geometry, material, scale, performance.

PubMed

Ouyang, Z; Gao, L; Fico, M; Chappell, W J; Noll, R J; Cooks, R G

2007-01-01

Quadrupole ion traps are reviewed, emphasizing recent developments, especially the investigation of new geometries, guided by multiple particle simulations such as the ITSIM program. These geometries include linear ion traps (LITs) and the simplified rectilinear ion trap (RIT). Various methods of fabrication are described, including the use of rapid prototyping apparatus (RPA), in which 3D objects are generated through point-by-point laser polymerization. Fabrication in silicon using multilayer semi-conductor fabrication techniques has been used to construct arrays of micro-traps. The performance of instruments containing individual traps as well as arrays of traps of various sizes and geometries is reviewed. Two types of array are differentiated. In the first type, trap arrays constitute fully multiplexed mass spectrometers in which multiple samples are examined using multiple sources, analyzers and detectors, to achieve high throughput analysis. In the second, an array of individual traps acts collectively as a composite trap to increase trapping capacity and performance for a single sample. Much progress has been made in building miniaturized mass spectrometers; a specific example is a 10 kg hand-held tandem mass spectrometer based on the RIT mass analyzer. The performance of this instrument in air and water analysis, using membrane sampling, is described.

Spontaneous Formation of Nanopillar Arrays in Ultrathin Viscous Films: Critical Role of Thermocapillary Stresses

NASA Astrophysics Data System (ADS)

Troian, Sandra; Dietzel, Mathias

2010-03-01

Nanoscale structures manifest exceedingly large surface to volume ratios and are therefore highly susceptible to control by surface stresses. Actuation techniques which can exploit this feature provide a key strategy for construction and self-organization of large area arrays. During the past decade, several groups have reported that molten polymer nanofilms subject to an ultra-large transverse thermal gradient undergo spontaneous formation of nanopillar arrays. The prevailing explanation is that coherent interfacial reflection of acoustic phonons causes periodic modulation of the radiation pressure leading to instability and pillar growth. We demonstrate instead that thermocapillary forces play a crucial if not dominant role in the formation process due to the strong modulation of surface tension with temperature. Any nanoscale viscous film is prone to such formations, not just polymeric films. Analysis of the governing interface equation reveals the mechanism controlling the growth, spacing and symmetry of these self-assembling arrays. We discuss how these findings are being used in our laboratory to construct nanoscale components for optical and photonic applications.

Hierarchical Assembly of Multifunctional Oxide-based Composite Nanostructures for Energy and Environmental Applications

PubMed Central

Gao, Pu-Xian; Shimpi, Paresh; Gao, Haiyong; Liu, Caihong; Guo, Yanbing; Cai, Wenjie; Liao, Kuo-Ting; Wrobel, Gregory; Zhang, Zhonghua; Ren, Zheng; Lin, Hui-Jan

2012-01-01

Composite nanoarchitectures represent a class of nanostructured entities that integrates various dissimilar nanoscale building blocks including nanoparticles, nanowires, and nanofilms toward realizing multifunctional characteristics. A broad array of composite nanoarchitectures can be designed and fabricated, involving generic materials such as metal, ceramics, and polymers in nanoscale form. In this review, we will highlight the latest progress on composite nanostructures in our research group, particularly on various metal oxides including binary semiconductors, ABO3-type perovskites, A2BO4 spinels and quaternary dielectric hydroxyl metal oxides (AB(OH)6) with diverse application potential. Through a generic template strategy in conjunction with various synthetic approaches— such as hydrothermal decomposition, colloidal deposition, physical sputtering, thermal decomposition and thermal oxidation, semiconductor oxide alloy nanowires, metal oxide/perovskite (spinel) composite nanowires, stannate based nanocompostes, as well as semiconductor heterojunction—arrays and networks have been self-assembled in large scale and are being developed as promising classes of composite nanoarchitectures, which may open a new array of advanced nanotechnologies in solid state lighting, solar absorption, photocatalysis and battery, auto-emission control, and chemical sensing. PMID:22837702

Controllable Fabrication of Non-Close-Packed Colloidal Nanoparticle Arrays by Ion Beam Etching

NASA Astrophysics Data System (ADS)

Yang, Jie; Zhang, Mingling; Lan, Xu; Weng, Xiaokang; Shu, Qijiang; Wang, Rongfei; Qiu, Feng; Wang, Chong; Yang, Yu

2018-06-01

Polystyrene (PS) nanoparticle films with non-close-packed arrays were prepared by using ion beam etching technology. The effects of etching time, beam current, and voltage on the size reduction of PS particles were well investigated. A slow etching rate, about 9.2 nm/min, is obtained for the nanospheres with the diameter of 100 nm. The rate does not maintain constant with increasing the etching time. This may result from the thermal energy accumulated gradually in a long-time bombardment of ion beam. The etching rate increases nonlinearly with the increase of beam current, while it increases firstly then reach its saturation with the increase of beam voltage. The diameter of PS nanoparticles can be controlled in the range from 34 to 88 nm. Based on the non-close-packed arrays of PS nanoparticles, the ordered silicon (Si) nanopillars with their average diameter of 54 nm are fabricated by employing metal-assisted chemical etching technique. Our results pave an effective way to fabricate the ordered nanostructures with the size less than 100 nm.

Resonant-enhanced full-color emission of quantum-dot-based micro LED display technology.

PubMed

Han, Hau-Vei; Lin, Huang-Yu; Lin, Chien-Chung; Chong, Wing-Cheung; Li, Jie-Ru; Chen, Kuo-Ju; Yu, Peichen; Chen, Teng-Ming; Chen, Huang-Ming; Lau, Kei-May; Kuo, Hao-Chung

2015-12-14

Colloidal quantum dots which can emit red, green, and blue colors are incorporated with a micro-LED array to demonstrate a feasible choice for future display technology. The pitch of the micro-LED array is 40 μm, which is sufficient for high-resolution screen applications. The method that was used to spray the quantum dots in such tight space is called Aerosol Jet technology which uses atomizer and gas flow control to obtain uniform and controlled narrow spots. The ultra-violet LEDs are used in the array to excite the red, green and blue quantum dots on the top surface. To increase the utilization of the UV photons, a layer of distributed Bragg reflector was laid down on the device to reflect most of the leaked UV photons back to the quantum dot layers. With this mechanism, the enhanced luminous flux is 194% (blue), 173% (green) and 183% (red) more than that of the samples without the reflector. The luminous efficacy of radiation (LER) was measured under various currents and a value of 165 lm/Watt was recorded.

Self-Assembly and Electrostriction of Arrays and Chains of Hopfion Particles in Chiral Liquid Crystals

DOE PAGES

Ackerman, P. J.; van de Lagemaat, J.; Smalyukh, I. I.

2015-01-21

Some of the most exotic condensed matter phases, such as twist grain boundary and blue phases in liquid crystals and Abrikosov phases in superconductors, contain arrays of topological defects in their ground state. Comprised of a triangular lattice of double-twist tubes of magnetization, the so-called ‘A-phase’ in chiral magnets is an example of a thermodynamically stable phase with topologically nontrivial solitonic field configurations referred to as two-dimensional skyrmions, or baby-skyrmions. Here we report that three-dimensional skyrmions in the form of double-twist tori called ‘hopfions’, or ‘torons’ when accompanied by additional self-compensating defects, self-assemble into periodic arrays and linear chains thatmore » exhibit electrostriction. In confined chiral nematic liquid crystals, this self-assembly is similar to that of liquid crystal colloids and originates from long-range elastic interactions between particle-like skyrmionic torus knots of molecular alignment field, which can be tuned from isotropic repulsive to weakly or highly anisotropic attractive by low-voltage electric fields.« less

Nano-network with dual temperature and pH responsiveness based on copolymers of 2-hydroxyethyl methacrylate with 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]-undecane

NASA Astrophysics Data System (ADS)

Chiriac, Aurica P.; Nita, Loredana E.; Nistor, Manuela T.

2011-12-01

This study refers to the synthesis of a nano-network with dual temperature and pH responsiveness based on the 2-hydroxyethyl methacrylate (HEMA) copolymers with a comonomer with spiroacetal moiety and crosslinking capacity, namely 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]-undecane (U). The copolymers were synthesized by radical emulsion polymerization, using 4,4'-azobis(cyanopentanoic acid) as initiator, in the presence of sodium lauryl sulfate as tensioactive agent and poly(vinyl alcohol) as protective colloid. Three copolymer variants were taken into study resulted from the different ratio between the comonomers (HEMA/U), which was about 98/2, 95/5, and 90/10, respectively. The copolymers were characterized by FTIR and thermal analysis. The copolymers sensitivity was evidenced by studying the evolution of the hydrodynamic radius and zeta potential of the polymeric particles as a function of pH. Thus, the particles size increases with the comonomer amount, from 193 nm in case of the homopolymer up to 253 nm for the copolymer with maximum content of the comonomer (10%). The increase of the particle hydrodynamic radius with the growth of temperature was also put into evidence.

Fluorescence-tagged amphiphilic brush copolymer encapsulated Gd2O3 core-shell nanostructures for enhanced T 1 contrast effect and fluorescent imaging

NASA Astrophysics Data System (ADS)

Wang, Fenghe; Peng, Erwin; Liu, Feng; Li, Pingjing; Fong Yau Li, Sam; Xue, Jun Min

2016-10-01

To obtain suitable T 1 contrast agents for magnetic resonance imaging (MRI) application, aqueous Gd2O3 nanoparticles (NPs) with high longitudinal relativity (r 1) are demanded. High quality Gd2O3 NPs are usually synthesized through a non-hydrolytic route which requires post-synthetic modification to render the NPs water soluble. The current challenge is to obtain aqueous Gd2O3 NPs with high colloidal stability and enhanced r 1 relaxivity. To overcome this challenge, fluorescence-tagged amphiphilic brush copolymer (AFCP) encapsulated Gd2O3 NPs were proposed as suitable T 1 contrast agents. Such a coating layer provided (i) superior aqueous stability, (ii) biocompatibility, as well as (iii) multi-modality (conjugation with fluorescence dye). The polymeric coating layer thickness was simply adjusted by varying the phase-transfer parameters. By reducing the coating thickness, i.e. the distance between the paramagnetic centre and surrounding water protons, the r 1 relaxivity could be enhanced. In contrast, a thicker polymeric layer coating prevents Gd3+ ions leakage, thus improving its biocompatibility. Therefore, it is important to strike a balance between the biocompatibility and the r 1 relaxivity behaviour. Lastly, by conjugating fluorescence moiety, an additional imaging modality was enabled, as demonstrated from the cell-labelling experiment.

Co-delivery of doxorubicin and AS1411 aptamer by poly(ethylene glycol)-poly( β-amino esters) polymeric micelles for targeted cancer therapy

NASA Astrophysics Data System (ADS)

Zhang, Ran; Wang, Shi-Bin; Wu, Wen-Guo; Kankala, Ranjith Kumar; Chen, Ai-Zheng; Liu, Yuan-Gang; Fan, Jing-Qian

2017-06-01

Recently, targeted drug delivery systems (TDDS) have offered a great potential and benefits towards the anti-tumor drug delivery. In this work, we designed the TDDS using a biocompatible poly(ethylene glycol)-poly( β-amino esters) amphiphilic block copolymer (PEG-PAEs) synthesized by Michael addition polymerization for combinatorial therapy. Further, the chemotherapeutic agents' doxorubicin (DOX) and AS1411 DNA aptamer (Apt) are encapsulated in the PEG-PAEs NPs (PDANs) for co-delivery therapeutics. PDANs have shown the monodisperse spherical shape, smooth surface with a net positive charge (average diameter—183.1 ± 27.2 nm, zeta potential—31.2 ± 6.3 mV), and good colloidal stability (critical micelle concentration of PEG-PAEs is about 6.3 μg/mL). The pH-sensitive PAEs endowed PDANs both pH-triggered drug release characteristics and enhanced endo/lysosomal escape ability, thus improving the localization and cytotoxicity of DOX. AS1411 Apt conjugated PDANs precisely targeted nucleolin and their uptake correlates to a significant activity enhancement only in tumor cells (MCF-7) but not in normal cells (MCF-10A). Thus, PDANs can be a very promising targeted drug delivery platform for effective breast cancer therapy.

Synthesis of highly monodisperse particles composed of a magnetic core and fluorescent shell.

PubMed

Nagao, Daisuke; Yokoyama, Mikio; Yamauchi, Noriko; Matsumoto, Hideki; Kobayashi, Yoshio; Konno, Mikio

2008-09-02

Highly monodisperse particles composed of a magnetic silica core and fluorescent polymer shell were synthesized with a combined technique of heterocoagulation and soap-free emulsion polymerization. Prior to heterocoagulation, monodisperse, submicrometer-sized silica particles were prepared with the Stober method, and magnetic nanoparticles were prepared with a modified Massart method in which a cationic silane coupling agent of N-trimethoxysilylpropyl- N, N, N-trimethylammonium chloride was added just after coprecipitation of Fe (2+) and Fe (3+). The silica particles with negative surface potential were heterocoagulated with the magnetic nanoparticles with positive surface potential. The magnetic silica particles obtained with the heterocoagulation were treated with sodium silicate to modify their surfaces with silica. In the formation of a fluorescent polymer shell onto the silica-coated magnetic silica cores, an amphoteric initiator of 2,2'-azobis[ N-(2-carboxyethyl)-2-2-methylpropionamidine] (VA-057) was used to control the colloidal stability of the magnetic cores during the polymer coating. The polymerization of St in the presence of a hydrophobic fluorophore of pyrene could coat the cores with fluorescent polymer shells, resulting in monodisperse particles with a magnetic silica core and fluorescent polymer shell. Measurements of zeta potential for the composite particles in different pH values indicated that the composite particles had an amphoteric property originating from VA-057 initiator.

Surface plasmon resonance sensor for antibiotics detection based on photo-initiated polymerization molecularly imprinted array.

PubMed

Luo, Qiaohui; Yu, Neng; Shi, Chunfei; Wang, Xiaoping; Wu, Jianmin

2016-12-01

A surface plasmon resonance (SPR) sensor combined with nanoscale molecularly imprinted polymer (MIP) film as recognition element was developed for selective detection of the antibiotic ciprofloxacin (CIP). The MIP film on SPR sensor chip was prepared by in situ photo-initiated polymerization method which has the advantages of short polymerization time, controllable thickness and good uniformity. The surface wettability and thickness of MIP film on SPR sensor chip were characterized by static contact angle measurement and stylus profiler. The MIP-SPR sensor exhibited high selectivity, sensitivity and good stability for ciprofloxacin. The imprinting factors of the MIP-SPR sensor to ciprofloxacin and its structural analogue ofloxacin were 2.63 and 3.80, which is much higher than those to azithromycin, dopamine and penicillin. The SPR response had good linear relation with CIP concentration over the range 10 -11 -10 -7 molL -1 . The MIP-SPR sensor also showed good repeatability and stability during cyclic detections. On the basis of the photo-initiated polymerization method, a surface plasmon resonance imaging (SPRi) chip modified with three types of MIP sensing spots was fabricated. The MIPs-SPRi sensor shows different response patterns to ciprofloxacin and azithromycin, revealing the ability to recognize different antibiotic molecules. Copyright © 2016 Elsevier B.V. All rights reserved.

3D-Printed Biodegradable Polymeric Vascular Grafts.

PubMed

Melchiorri, A J; Hibino, N; Best, C A; Yi, T; Lee, Y U; Kraynak, C A; Kimerer, L K; Krieger, A; Kim, P; Breuer, C K; Fisher, J P

2016-02-04

Congenital heart defect interventions may benefit from the fabrication of patient-specific vascular grafts because of the wide array of anatomies present in children with cardiovascular defects. 3D printing is used to establish a platform for the production of custom vascular grafts, which are biodegradable, mechanically compatible with vascular tissues, and support neotissue formation and growth. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthetic Nanovaccines Against Respiratory Pathogens (SYNARP)

DTIC Science & Technology

2010-07-01

nanoscale delivery systems can provide versatile platforms for development of effective, safe, and cost-efficient vaccines. The materials used in these...polymers was estimated by calculating the degree of polymerization (DP) using the peak area normalized with the protons representing hydrolyzed and...structures can be prototyped very easily and rapidly using a simple mask. In this work, the desired 5x5 array of discrete wells was created using

Non-Cell-Adhesive Substrates for Printing of Arrayed Biomaterials

PubMed Central

Appel, Eric A.; Larson, Benjamin L.; Luly, Kathryn M.; Kim, Jinseong D.

2015-01-01

Cellular microarrays have become extremely useful in expediting the investigation of large libraries of (bio)materials for both in vitro and in vivo biomedical applications. We have developed an exceedingly simple strategy for the fabrication of non-cell-adhesive substrates supporting the immobilization of diverse (bio)material features, including both monomeric and polymeric adhesion molecules (e.g. RGD and polylysine), hydrogels, and polymers. PMID:25430948

Characterizing string-of-pearls colloidal silica by multidetector hydrodynamic chromatography and comparison to multidetector size-exclusion chromatography, off-line multiangle static light scattering, and transmission electron microscopy.

PubMed

Brewer, Amandaa K; Striegel, André M

2011-04-15

The string-of-pearls-type morphology is ubiquitous, manifesting itself variously in proteins, vesicles, bacteria, synthetic polymers, and biopolymers. Characterizing the size and shape of analytes with such morphology, however, presents a challenge, due chiefly to the ease with which the "strings" can be broken during chromatographic analysis or to the paucity of information obtained from the benchmark microscopy and off-line light scattering methods. Here, we address this challenge with multidetector hydrodynamic chromatography (HDC), which has the ability to determine, simultaneously, the size, shape, and compactness and their distributions of string-of-pearls samples. We present the quadruple-detector HDC analysis of colloidal string-of-pearls silica, employing static multiangle and quasielastic light scattering, differential viscometry, and differential refractometry as detection methods. The multidetector approach shows a sample that is broadly polydisperse in both molar mass and size, with strings ranging from two to five particles, but which also contains a high concentration of single, unattached "pearls". Synergistic combination of the various size parameters obtained from the multiplicity of detectors employed shows that the strings with higher degrees of polymerization have a shape similar to the theory-predicted shape of a Gaussian random coil chain of nonoverlapping beads, while the strings with lower degrees of polymerization have a prolate ellipsoidal shape. The HDC technique is contrasted experimentally with multidetector size-exclusion chromatography, where, even under extremely gentle conditions, the strings still degraded during analysis. Such degradation is shown to be absent in HDC, as evidenced by the fact that the molar mass and radius of gyration obtained by HDC with multiangle static light scattering detection (HDC/MALS) compare quite favorably to those determined by off-line MALS analysis under otherwise identical conditions. The multidetector HDC results were also comparable to those obtained by transmission electron microscopy (TEM). Unlike off-line MALS or TEM, however, multidetector HDC is able to provide complete particle analysis based on the molar mass, size, shape, and compactness and their distributions for the entire sample population in less than 20 min. © 2011 American Chemical Society

Self-assembled polymeric nanocarriers for the targeted delivery of retinoic acid to the hair follicle

NASA Astrophysics Data System (ADS)

Lapteva, Maria; Möller, Michael; Gurny, Robert; Kalia, Yogeshvar N.

2015-11-01

Acne vulgaris is a highly prevalent dermatological disease of the pilosebaceous unit (PSU). An inability to target drug delivery to the PSU results in poor treatment efficacy and the incidence of local side-effects. Cutaneous application of nanoparticulate systems is reported to induce preferential accumulation in appendageal structures. The aim of this work was to prepare stable polymeric micelles containing retinoic acid (RA) using a biodegradable and biocompatible diblock methoxy-poly(ethylene glycol)-poly(hexylsubstituted lactic acid) copolymer (MPEG-dihexPLA) and to evaluate their ability to deliver RA to skin. An innovative punch biopsy sample preparation method was developed to selectively quantify follicular delivery; the amounts of RA present were compared to those in bulk skin, (i.e. without PSU), which served as the control. RA was successfully incorporated into micelle nanocarriers and protected from photoisomerization by inclusion of Quinoline Yellow. Incorporation into the spherical, homogeneous and nanometer-scale micelles (dn < 20 nm) increased the aqueous solubility of RA by >400-fold. Drug delivery experiments in vitro showed that micelles were able to deliver RA to porcine and human skins more efficiently than Retin-A® Micro (0.04%), a marketed gel containing RA loaded microspheres, (7.1 +/- 1.1% vs. 0.4 +/- 0.1% and 7.5 +/- 0.8% vs. 0.8 +/- 0.1% of the applied dose, respectively). In contrast to a non-colloidal RA solution, Effederm® (0.05%), both the RA loaded MPEG-dihexPLA polymeric micelles (0.005%) and Retin-A® Micro (0.04%) displayed selectivity for delivery to the PSU with 2-fold higher delivery to PSU containing samples than to control samples. Moreover, the micelle formulation outperformed Retin-A® Micro in terms of delivery efficiency to PSU presenting human skin (10.4 +/- 3.2% vs. 0.6 +/- 0.2%, respectively). The results indicate that the polymeric micelle formulation enabled an increased and targeted delivery of RA to the PSU, potentially translating to a safer and more efficient clinical management of acne.Acne vulgaris is a highly prevalent dermatological disease of the pilosebaceous unit (PSU). An inability to target drug delivery to the PSU results in poor treatment efficacy and the incidence of local side-effects. Cutaneous application of nanoparticulate systems is reported to induce preferential accumulation in appendageal structures. The aim of this work was to prepare stable polymeric micelles containing retinoic acid (RA) using a biodegradable and biocompatible diblock methoxy-poly(ethylene glycol)-poly(hexylsubstituted lactic acid) copolymer (MPEG-dihexPLA) and to evaluate their ability to deliver RA to skin. An innovative punch biopsy sample preparation method was developed to selectively quantify follicular delivery; the amounts of RA present were compared to those in bulk skin, (i.e. without PSU), which served as the control. RA was successfully incorporated into micelle nanocarriers and protected from photoisomerization by inclusion of Quinoline Yellow. Incorporation into the spherical, homogeneous and nanometer-scale micelles (dn < 20 nm) increased the aqueous solubility of RA by >400-fold. Drug delivery experiments in vitro showed that micelles were able to deliver RA to porcine and human skins more efficiently than Retin-A® Micro (0.04%), a marketed gel containing RA loaded microspheres, (7.1 +/- 1.1% vs. 0.4 +/- 0.1% and 7.5 +/- 0.8% vs. 0.8 +/- 0.1% of the applied dose, respectively). In contrast to a non-colloidal RA solution, Effederm® (0.05%), both the RA loaded MPEG-dihexPLA polymeric micelles (0.005%) and Retin-A® Micro (0.04%) displayed selectivity for delivery to the PSU with 2-fold higher delivery to PSU containing samples than to control samples. Moreover, the micelle formulation outperformed Retin-A® Micro in terms of delivery efficiency to PSU presenting human skin (10.4 +/- 3.2% vs. 0.6 +/- 0.2%, respectively). The results indicate that the polymeric micelle formulation enabled an increased and targeted delivery of RA to the PSU, potentially translating to a safer and more efficient clinical management of acne. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04770f

Colloidal crystals with diamond symmetry at optical lengthscales

NASA Astrophysics Data System (ADS)

Wang, Yifan; Jenkins, Ian C.; McGinley, James T.; Sinno, Talid; Crocker, John C.

2017-02-01

Future optical materials promise to do for photonics what semiconductors did for electronics, but the challenge has long been in creating the structure they require--a regular, three-dimensional array of transparent microspheres arranged like the atoms in a diamond crystal. Here we demonstrate a simple approach for spontaneously growing double-diamond (or B32) crystals that contain a suitable diamond structure, using DNA to direct the self-assembly process. While diamond symmetry crystals have been grown from much smaller nanoparticles, none of those previous methods suffice for the larger particles needed for photonic applications, whose size must be comparable to the wavelength of visible light. Intriguingly, the crystals we observe do not readily form in previously validated simulations; nor have they been predicted theoretically. This finding suggests that other unexpected microstructures may be accessible using this approach and bodes well for future efforts to inexpensively mass-produce metamaterials for an array of photonic applications.

Preparation of SMART wound dressings based on colloidal microgels and textile fibres

NASA Astrophysics Data System (ADS)

Cornelius, Victoria J.; Majcen, Natasa; Snowden, Martin J.; Mitchell, John C.; Voncina, Bojana

2007-01-01

Wound dressings and other types of wound healing technologies are experiencing fast-paced development and rapid growth. As the population ages, demand will continue to rise for advanced dressings used to treat chronic wounds, such as pressure ulcers, venous stasis ulcers, and diabetic ulcers. Moist wound dressings, which facilitate natural wound healing in a cost-effective manner, will be increasingly important. In commercially available hydrogel / gauze wound dressings the gel swells to adsorb wound excreta and provide an efficient non adhesive particle barrier. An alternative to hydrogels are microgels. Essentially discrete colloidal gel particles, as a result of their very high surface area to volume ratio compared to bulk gels, they have a much faster response to external stimuli such as temperature or pH. In response to either an increase or decrease in solvent quality these porous networks shrink and swell reversibly. When swollen the interstitial regions within the polymer matrix are available for further chemistry; such as the incorporation of small molecules. The reversible shrinking and swelling as a function of external stimuli provides a novel drug release system. As the environmental conditions of a wound change over its lifetime, tending to increase in pH if there is an infection combining these discrete polymeric particles with a substrate such as cotton, results in a smart wound dressing.

A Molecular Dynamics Study of Single-Walled Carbon Nanotubes (SWCNTs) Dispersed in Bile Salt Surfactants

NASA Astrophysics Data System (ADS)

Phelan, Frederick, Jr.; Sun, Huai

2014-03-01

Single-walled carbon nanotubes (SWNCTs) are materials with structural, electronic and optical properties that make them attractive for a myriad of advanced technology applications. A practical barrier to their use is that SWCNT synthesis techniques produce heterogeneous mixtures of varying lengths and chirality, whereas applications generally require tubes with narrow size distributions and individual type. Most separation techniques currently in use to obtain monodisperse tube fractions rely on dispersion of these materials in aqueous solution using surfactants. The dispersion process results in a mixture of colloidal structures in which individual tubes are dispersed and contained in a surfactant shell. Understanding the structure and properties of the SWCNT-surfactant complex at the molecular level, and how this is affected by chirality, is key to understanding and improving separations processes. In this study, we use molecular dynamics (MD) simulations to study the structure and properties of SWCNT-surfactant colloidal complexes. We tested a number of methods and protocols in order to build an accurate model for simulating SWCNT systems for a variety of bile salt surfactants as well as anionic co-surfactants, components that are widely used and important in experimental separation studies at NIST. The custom force field parameters used here will be stored in WebFF, a Web-hosted smart force-field repository for polymeric and organic materials being developed at NIST for the Materials Genome Initiative.

Enzymatically and chemically oxidized lignin nanoparticles for biomaterial applications.

PubMed

Mattinen, Maija-Liisa; Valle-Delgado, Juan José; Leskinen, Timo; Anttila, Tuomas; Riviere, Guillaume; Sipponen, Mika; Paananen, Arja; Lintinen, Kalle; Kostiainen, Mauri; Österberg, Monika

2018-04-01

Cross-linked and decolorized lignin nanoparticles (LNPs) were prepared enzymatically and chemically from softwood Kraft lignin. Colloidal lignin particles (CLPs, ca. 200 nm) in a non-malodorous aqueous dispersion could be dried and redispersed in tetrahydrofuran (THF) or in water retaining their stability i.e. spherical shape and size. Two fungal laccases, Trametes hirsuta (ThL) and Melanocarpus albomyces (MaL) were used in the cross-linking reactions. Reactivity of ThL and MaL on Lignoboost™ lignin and LNPs was confirmed by high performance size exclusion chromatography (HPSEC) and oxygen consumption measurements with simultaneous detection of red-brown color due to the formation of quinones. Zeta potential measurements verified oxidation of LNPs via formation of surface-oriented carboxylic acid groups. Dynamic light scattering (DLS) revealed minor changes in the particle size distributions of LNPs after laccase catalyzed radicalization, indicating preferably covalent intraparticular cross-linking over polymerization. Changes in the surface morphology of laccase treated LNPs were imaged by atomic force (AFM) and transmission emission (TEM) microscopy. Furthermore, decolorization of LNPs without degradation was obtained using ultrasonication with H 2 O 2 in alkaline reaction conditions. The research results have high impact for the utilization of Kraft lignin as nanosized colloidal particles in advanced bionanomaterial applications in medicine, foods and cosmetics including different sectors from chemical industry. Copyright © 2018 The Author(s). Published by Elsevier Inc. All rights reserved.

Review of world experience and properties of materials for encapsulation of terrestrial photovoltaic arrays

NASA Technical Reports Server (NTRS)

Carmichael, D. C.; Gaines, G. B.; Sliemers, F. A.; Kistler, C. W.; Igou, R. D.

1976-01-01

Published and unpublished information relating to encapsulation systems and materials properties was collected by searching the literature and appropriate data bases (over 1,300 documents were selected and reviewed) and by personal contacts including site and company visits. A data tabulation summarizing world experience with terrestrial photovoltaic arrays (50 installations) is presented in the report. Based on criteria of properties, processability, availability, and cost, candidate materials were identified which have potential for use in encapsulation systems for arrays with a lifetime of over 20 years high reliability, an efficiency greater than 10 percent, a total price less than $500/kW, and a production capacity of 500,000 kW/yr. The recommended materials (all commercially available) include, depending upon the device design, various borosilicate and soda-lime glasses and numerous polymerics suitable for specific encapsulation system functions.

High performance flexible pH sensor based on polyaniline nanopillar array electrode.

PubMed

Yoon, Jo Hee; Hong, Seok Bok; Yun, Seok-Oh; Lee, Seok Jae; Lee, Tae Jae; Lee, Kyoung G; Choi, Bong Gill

2017-03-15

Flexible pH sensor technologies have attracted a great deal of attention in many applications, such as, wearable health care devices and monitors for chemical and biological processes. Here, we fabricated flexible and thin pH sensors using a two electrode configuration comprised of a polyaniline nanopillar (PAN) array working electrode and an Ag/AgCl reference electrode. In order to provide nanostructure, soft lithography using a polymeric blend was employed to create a flexible nanopillar backbone film. Polyaniline-sensing materials were deposited on a patterned-nanopillar array by electrochemical deposition. The pH sensors produced exhibited a near-Nernstian response (∼60.3mV/pH), which was maintained in a bent state. In addition, pH sensors showed other excellent sensor performances in terms of response time, reversibility, repeatability, selectivity, and stability. Copyright © 2016 Elsevier Inc. All rights reserved.

Considerations in the sterile manufacture of polymeric microneedle arrays.

PubMed

McCrudden, Maelíosa T C; Alkilani, Ahlam Zaid; Courtenay, Aaron J; McCrudden, Cian M; McCloskey, Bronagh; Walker, Christine; Alshraiedeh, Nida; Lutton, Rebecca E M; Gilmore, Brendan F; Woolfson, A David; Donnelly, Ryan F

2015-02-01

We describe, for the first time, considerations in the sterile manufacture of polymeric microneedle arrays. Microneedles (MN) made from dissolving polymeric matrices and loaded with the model drugs ovalbumin (OVA) and ibuprofen sodium and hydrogel-forming MN composed of "super-swelling" polymers and their corresponding lyophilised wafer drug reservoirs loaded with OVA and ibuprofen sodium were prepared aseptically or sterilised using commonly employed sterilisation techniques. Moist and dry heat sterilisation, understandably, damaged all devices, leaving aseptic production and gamma sterilisation as the only viable options. No measureable bioburden was detected in any of the prepared devices, and endotoxin levels were always below the US Food & Drug Administration limits (20 endotoxin units/device). Hydrogel-forming MN were unaffected by gamma irradiation (25 kGy) in terms of their physical properties or capabilities in delivering OVA and ibuprofen sodium across excised neonatal porcine skin in vitro. However, OVA content in dissolving MN (down from approximately 101.1 % recovery to approximately 58.3 % recovery) and lyophilised wafer-type drug reservoirs (down from approximately 99.7 % recovery to approximately 60.1 % recovery) was significantly reduced by gamma irradiation, while the skin permeation profile of ibuprofen sodium from gamma-irradiated dissolving MN was markedly different from their non-irradiated counterparts. It is clear that MN poses a very low risk to human health when used appropriately, as evidenced here by low endotoxin levels and absence of microbial contamination. However, if guarantees of absolute sterility of MN products are ultimately required by regulatory authorities, it will be necessary to investigate the effect of lower gamma doses on dissolving MN loaded with active pharmaceutical ingredients and lyophilised wafers loaded with biomolecules in order to avoid the expense and inconvenience of aseptic processing.

Dysprosium sorption by polymeric composite bead: robust parametric optimization using Taguchi method.

PubMed

Yadav, Kartikey K; Dasgupta, Kinshuk; Singh, Dhruva K; Varshney, Lalit; Singh, Harvinderpal

2015-03-06

Polyethersulfone-based beads encapsulating di-2-ethylhexyl phosphoric acid have been synthesized and evaluated for the recovery of rare earth values from the aqueous media. Percentage recovery and the sorption behavior of Dy(III) have been investigated under wide range of experimental parameters using these beads. Taguchi method utilizing L-18 orthogonal array has been adopted to identify the most influential process parameters responsible for higher degree of recovery with enhanced sorption of Dy(III) from chloride medium. Analysis of variance indicated that the feed concentration of Dy(III) is the most influential factor for equilibrium sorption capacity, whereas aqueous phase acidity influences the percentage recovery most. The presence of polyvinyl alcohol and multiwalled carbon nanotube modified the internal structure of the composite beads and resulted in uniform distribution of organic extractant inside polymeric matrix. The experiment performed under optimum process conditions as predicted by Taguchi method resulted in enhanced Dy(III) recovery and sorption capacity by polymeric beads with minimum standard deviation. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecular Rotors for Universal Quantitation of Nanoscale Hydrophobic Interfaces in Microplate Format.

PubMed

Bisso, Paul W; Tai, Michelle; Katepalli, Hari; Bertrand, Nicolas; Blankschtein, Daniel; Langer, Robert

2018-01-10

Hydrophobic self-assembly pairs diverse chemical precursors and simple formulation processes to access a vast array of functional colloids. Exploration of this design space, however, is stymied by lack of broadly general, high-throughput colloid characterization tools. Here, we show that a narrow structural subset of fluorescent, zwitterionic molecular rotors, dialkylaminostilbazolium sulfonates [DASS] with intermediate-length alkyl tails, fills this major analytical void by quantitatively sensing hydrophobic interfaces in microplate format. DASS dyes supersede existing interfacial probes by avoiding off-target fluorogenic interactions and dye aggregation while preserving hydrophobic partitioning strength. To illustrate the generality of this approach, we demonstrate (i) a microplate-based technique for measuring mass concentration of small (20-200 nm), dilute (submicrogram sensitivity) drug delivery nanoparticles; (ii) elimination of particle size, surfactant chemistry, and throughput constraints on quantifying the complex surfactant/metal oxide adsorption isotherms critical for environmental remediation and enhanced oil recovery; and (iii) more reliable self-assembly onset quantitation for chemically and structurally distinct amphiphiles. These methods could streamline the development of nanotechnologies for a broad range of applications.

Anti-infiltration for fabrication of a suspended nanoparticle layer on porous close-packed colloidal arrays.

PubMed

Teh, Lay K; Yan, Qingfeng; Wong, Chee C

2009-04-01

We develop a new method to fabricate suspended sheets of nanocrystals (NCs) on porous surfaces. The method relies on the resistance of an aqueous suspension droplet to infiltrate a porous network; hence, the method is named anti-infiltration. The process works by combining fluid dynamics of a liquid droplet during impact/absorption onto a porous surface with the convective self-assembly of NCs. The immobilization of the liquid droplet edge due to the self-assembly of NCs at the meniscus is harnessed to halt the lateral spreading of the droplet and, consequently, the capillary penetration of the liquid immediately after droplet impact. Further capillary penetration of the liquid is drastically reduced because of the competition between capillary forces and convective losses as well as the rapid occlusion of the pores as soon as a continuous NC film has formed upon evaporation of the suspension. This method holds promise for a wide variety of optoelectronic, sensing, and separation membrane applications. As an example, we demonstrate that these suspended NC layers are suitable candidates as planar defects embedded within a colloidal photonic crystal.

Microcapsules fabricated from liquid marbles stabilized with latex particles.

PubMed

Ueno, Kazuyuki; Hamasaki, Sho; Wanless, Erica J; Nakamura, Yoshinobu; Fujii, Syuji

2014-03-25

Millimeter- and centimeter-sized "liquid marbles" were readily prepared by rolling water droplets on a powder bed of dried submicrometer-sized polystyrene latex particles carrying poly[2-(diethylamino)ethyl methacrylate] hairs (PDEA-PS). Scanning electron microscopy studies indicated that flocs of the PDEA-PS particles were adsorbed at the surface of these water droplets, leading to stable spherical liquid marbles. The liquid marbles were deformed as a result of water evaporation to adopt a deflated spherical geometry, and the rate of water evaporation decreased with increasing atmospheric relative humidity. Conversely, liquid marbles formed using saturated aqueous LiCl solution led to atmospheric water absorption by the liquid marbles and a consequent mass increase. The liquid marbles can be transformed into polymeric capsules containing water by exposure to solvent vapor: the PDEA-PS particles were plasticized with the solvent vapor to form a polymer film at the air-water interface of the liquid marbles. The polymeric capsules with aqueous volumes of 250 μL or less kept their oblate ellipsoid/near spherical shape even after complete water evaporation, which confirmed that a rigid polymeric capsule was successfully formed. Both the rate of water evaporation from the pure water liquid marbles and the rate of water adsorption into the aqueous LiCl liquid marbles were reduced with an increase of solvent vapor treatment time. This suggests that the number and size of pores within the polymer particles/flocs on the liquid marble surface decreased due to film formation during exposure to organic solvent vapor. In addition, organic-inorganic composite capsules and colloidal crystal capsules were fabricated from liquid marbles containing aqueous SiO2 dispersions.

Biophysical Properties and Oxygenation Potential of High-Molecular-Weight Glutaraldehyde-Polymerized Human Hemoglobins Maintained in the Tense and Relaxed Quaternary States

PubMed Central

Zhang, Ning; Jia, Yiping; Chen, Guo; Cabrales, Pedro

2011-01-01

Recent clinical evaluation of commercial glutaraldehyde-polymerized hemoglobins (PolyHbs) as transfusion solutions has demonstrated several adverse side effects. Chief among these is the hypertensive effect. Fortunately, previous studies have shown that the hypertensive effect can be attenuated by removing free hemoglobin (Hb) and low-molecular-weight (low-MW) PolyHbs from the PolyHb mixture. In this work, polymerized human Hb (PolyhHb) solutions were synthesized in two distinct quaternary states with high MW and subjected to extensive diafiltration to remove free Hb and low-MW PolyhHb components (<500 kDa). The resultant PolyhHb solutions possessed high MW, distinct quaternary state, distinct reactivities with O2 and CO, similar NO deoxygenating rate constants, distinct autoxidation rate constants, high viscosity, and low colloid osmotic pressure. To preliminarily assess the ability of PolyhHb solutions to oxygenate surrounding tissues fed by a blood vessel, we evaluated the ability of PolyhHbs to transport O2 to cultured hepatocytes in a mathematical model of a hollow fiber bioreactor. The structure of individual hollow fibers in the bioreactor is similar to that of a blood vessel and provides an easy way to assess the oxygenation potential of PolyhHbs without the need for expensive and time-consuming animal studies. It was observed that PolyhHbs with low O2 affinities were more effective in oxygenating cultured hepatocytes inside the bioreactor than high O2 affinity PolyhHbs. Taken together, our results show that it is possible to synthesize high-MW PolyhHbs with no free Hb and low-MW PolyhHb components that are capable of transporting O2 to cultured cells/tissues. PMID:20979534

Amphiphilic Ferrocene-Containing PEG Block Copolymers as Micellar Nanocarriers and Smart Surfactants.

PubMed

Alkan, Arda; Wald, Sarah; Louage, Benoit; De Geest, Bruno G; Landfester, Katharina; Wurm, Frederik R

2017-01-10

An important and usually the only function of most surfactants in heterophase systems is stabilizing one phase in another, for example, droplets or particles in water. Surfactants with additional chemical or physical handles are promising in controlling the colloidal properties by external stimuli. The redox stimulus is an attractive feature; however, to date only a few ionic redox-responsive surfactants have been reported. Herein, the first nonionic and noncytotoxic ferrocene-containing block copolymers are prepared, carrying a hydrophilic poly(ethylene glycol) (PEG) chain and multiple ferrocenes in the hydrophobic segment. These amphiphiles were studied as redox-sensitive surfactants that destabilize particles as obtained in miniemulsion polymerization. Because of the nonionic nature of such PEG-based copolymers, they can stabilize nanoparticles even after the addition of ions, whereas particles stabilized with ionic surfactants would be destabilized by the addition of salt. The redox-active surfactants were prepared by the anionic ring-opening polymerization of ferrocenyl glycidyl ether, with PEG monomethyl ether as the macroinitiator. The resultant block copolymers with molecular weights (M n ) between 3600 and 8600 g mol -1 and narrow molecular weight distributions (M w /M n = 1.04-1.10) were investigated via 1 H nuclear magnetic resonance and diffusion ordered spectroscopy, size exclusion chromatography, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Furthermore, the block copolymers were used as building blocks for redox-responsive micelles and as redox-responsive surfactants in radical polymerization in miniemulsion to stabilize model polystyrene nanoparticles. Oxidation of iron to the ferrocenium species converted the amphiphilic block copolymers into double hydrophilic macromolecules, which led to the destabilization of the nanoparticles. This destabilization of nanoparticle dispersions may be useful for the formation of coatings and the recovery of surfactants.

Scaling up feasibility of the production of solid lipid nanoparticles (SLN).

PubMed

Gohla, S H; Dingler, A

2001-01-01

Solid lipid nanoparticles (SLN/Lipopearls) are widely discussed as colloidal drug carrier system. In contrast to polymeric systems, such as polylactic copolyol capsules, these systems show up with a good biocompatibility, if applied parenterally. The solid lipid matrices can be comprised of fats or waxes and allow protection of incorporated active ingredients against chemical and physical degradation. The SLN can either be produced by "hot homogenisation" of melted lipids at elevated temperatures or a "cold homogenization" process. This paper deals with production technologies for SLN formulations, based on non-ethoxylated fat components for topical application and high pressure homogenization (APV Deutschland GmbH, D-Lübeck). Based on the chosen fat components, a novel and easy manufacturing and scaling up method was developed to maintain chemical and physical integrity of encapsulated active and carrier.

SELECTED ABSTRACTS OF ATOMIC ENERGY PROJECT UNCLASSIFIED REPORT LITERATURE IN THE FIELD OF RADIATION CHEMISTRY AND BIBLIOGRAPHY OF THE PUBLISHED LITERATURE--5TH ANNUAL SUPPLEMENT (PAPERS NOTED UP TO DECEMBER 1960)

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

Clarke, R.W. comp.

1961-05-01

References (2538) are given to U. S. and foreign reports and published literature published from 1957 through 1961. The references contain information on theory, interpretations, water and aqueous inorganic systems, organic compounds (including polymerization reactions and organic coolants), gaseous systems (excluding organic compounds), solid systems (excluding organic compounds), biochemistry and radiobiology (excluding animal studies, including irradiation of foodstuffs, bacteria, and insects), and miscellaneous (including colloids, corrosion, industrial applications of radiation, irradiation equipment, and general reviews and reports). The report references are arranged alphabetically/serially by report reference number, and the open literature rcferences alphabetically by first named author. Separate author andmore » subject indexes are included. (P.C.H.)« less

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

PubMed

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

2012-07-13

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

Designing with non-linear viscoelastic fluids

NASA Astrophysics Data System (ADS)

Schuh, Jonathon; Lee, Yong Hoon; Allison, James; Ewoldt, Randy

2017-11-01

Material design is typically limited to hard materials or simple fluids; however, design with more complex materials can provide ways to enhance performance. Using the Criminale-Ericksen-Filbey (CEF) constitutive model in the thin film lubrication limit, we derive a modified Reynolds Equation (based on asymptotic analysis) that includes shear thinning, first normal stress, and terminal regime viscoelastic effects. This allows for designing non-linear viscoelastic fluids in thin-film creeping flow scenarios, i.e. optimizing the shape of rheological material properties to achieve different design objectives. We solve the modified Reynolds equation using the pseudo-spectral method, and describe a case study in full-film lubricated sliding where optimal fluid properties are identified. These material-agnostic property targets can then guide formulation of complex fluids which may use polymeric, colloidal, or other creative approaches to achieve the desired non-Newtonian properties.

Synthesis and chromatographic characterization of dextran-coated zirconia high-performance liquid chromatographic stationary phases.

PubMed

Dunlap, C J; Carr, P W

1996-10-11

Porous zirconia particles made by the oil emulsion (OE) method and the polymerization-induced colloid aggregation (PICA) method have been coated with a small, carboxymethylated (approximately 5%) dextran polymer and crosslinked in place. The parameters of the coating process (dextran concentration, adsorption time and crosslinker concentration) have all been examined and an optimum value for each determined. The coated and uncoated materials were characterized by nitrogen sorptometry and size-exclusion chromatography (SEC) using solutes (polystyrenes and dextrans) of well-defined molecular masses. Nitrogen sorptometry results show that the PICA material has a much lower pore volume and smaller pore diameter than do the OE materials. Despite this, the elution volumes of the SEC probes change very little upon polymer coating the PICA material while the OE material shows a very large change upon coating.

Solid Lipid Nanoparticles and Nanostructured Lipid Carriers: Structure, Preparation and Application

PubMed Central

Naseri, Neda; Valizadeh, Hadi; Zakeri-Milani, Parvin

2015-01-01

Lipid nanoparticles (LNPs) have attracted special interest during last few decades. Solid lipid nanoparticles (SLNs) and nanostructured lipid carriers (NLCs) are two major types of Lipid-based nanoparticles. SLNs were developed to overcome the limitations of other colloidal carriers, such as emulsions, liposomes and polymeric nanoparticles because they have advantages like good release profile and targeted drug delivery with excellent physical stability. In the next generation of the lipid nanoparticle, NLCs are modified SLNs which improve the stability and capacity loading. Three structural models of NLCs have been proposed. These LNPs have potential applications in drug delivery field, research, cosmetics, clinical medicine, etc. This article focuses on features, structure and innovation of LNPs and presents a wide discussion about preparation methods, advantages, disadvantages and applications of LNPs by focusing on SLNs and NLCs. PMID:26504751

Analyte species and concentration identification using differentially functionalized microcantilever arrays and artificial neural networks

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

Senesac, Larry R; Datskos, Panos G; Sepaniak, Michael J

2006-01-01

In the present work, we have performed analyte species and concentration identification using an array of ten differentially functionalized microcantilevers coupled with a back-propagation artificial neural network pattern recognition algorithm. The array consists of ten nanostructured silicon microcantilevers functionalized by polymeric and gas chromatography phases and macrocyclic receptors as spatially dense, differentially responding sensing layers for identification and quantitation of individual analyte(s) and their binary mixtures. The array response (i.e. cantilever bending) to analyte vapor was measured by an optical readout scheme and the responses were recorded for a selection of individual analytes as well as several binary mixtures. Anmore » artificial neural network (ANN) was designed and trained to recognize not only the individual analytes and binary mixtures, but also to determine the concentration of individual components in a mixture. To the best of our knowledge, ANNs have not been applied to microcantilever array responses previously to determine concentrations of individual analytes. The trained ANN correctly identified the eleven test analyte(s) as individual components, most with probabilities greater than 97%, whereas it did not misidentify an unknown (untrained) analyte. Demonstrated unique aspects of this work include an ability to measure binary mixtures and provide both qualitative (identification) and quantitative (concentration) information with array-ANN-based sensor methodologies.« less

Methods and devices for fabricating and assembling printable semiconductor elements

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

Nuzzo, Ralph G.; Rogers, John A.; Menard, Etienne

The invention provides methods and devices for fabricating printable semiconductor elements and assembling printable semiconductor elements onto substrate surfaces. Methods, devices and device components of the present invention are capable of generating a wide range of flexible electronic and optoelectronic devices and arrays of devices on substrates comprising polymeric materials. The present invention also provides stretchable semiconductor structures and stretchable electronic devices capable of good performance in stretched configurations.

Methods and devices for fabricating and assembling printable semiconductor elements

DOEpatents

Nuzzo, Ralph G; Rogers, John A; Menard, Etienne; Lee, Keon Jae; Khang, Dahl-Young; Sun, Yugang; Meitl, Matthew; Zhu, Zhengtao

2014-03-04

The invention provides methods and devices for fabricating printable semiconductor elements and assembling printable semiconductor elements onto substrate surfaces. Methods, devices and device components of the present invention are capable of generating a wide range of flexible electronic and optoelectronic devices and arrays of devices on substrates comprising polymeric materials. The present invention also provides stretchable semiconductor structures and stretchable electronic devices capable of good performance in stretched configurations.

Coatings Would Protect Polymers Against Atomic Oxygen

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Rutledge, Sharon K.

1995-01-01

Proposed interposition of layers of silver oxide tens to hundreds of angstroms thick between polymeric substrates and overlying films helps protect substrates against chemical attack by monatomic oxygen. In original application, polymer substrate would be, sheet of polyimide supporting array of solar photovoltaic cells on spacecraft in low orbit around Earth. Concept also applicable to protection of equipment in terrestrial laboratory and industrial vacuum and plasma chambers in which monatomic oxygen present.

Determination of benzimidazole anthelmintics in milk and honey by monolithic fiber-based solid-phase microextraction combined with high-performance liquid chromatography-diode array detection.

PubMed

Zhang, Yong; Huang, Xiaojia; Yuan, Dongxing

2015-01-01

A porous poly(methacrylic acid-co-ethylene dimethacrylate) monolithic fiber (MEMF) for solid-phase microextraction (SPME) of five benzimidazole anthelmintics was prepared by in-situ polymerization. The effect of polymerization conditions on SPME of the target analytes was studied thoroughly. The physicochemical properties of the monolith were characterized by infrared spectroscopy, elemental analysis, scanning electron microscopy, and mercury intrusion porosimetry. Several conditions affecting the extraction efficiency were investigated and, under the optimized conditions, a simple and sensitive method for the determination of trace benzimidazoles residues in milk and honey was established by coupling MEMF-SPME with high-performance liquid chromatography-diode array detection (MEMF-SPME-HPLC-DAD). Under the optimum experimental conditions, the limits of detection (S/N = 3) of the method were 0.11-0.30 μg L(-1) for milk and 0.086-0.28 μg L(-1) for honey. Evaluation of intra-day and inter-day precision showed reproducibility was satisfactory-relative standard deviations (RSD) for both were <10 %. Finally, the method was successfully used for determination of benzimidazole residues in milk and honey. Recoveries obtained for determination of benzimidazole anthelmintics in spiked samples ranged from 72.3 to 121 %, with RSD always <11 %.

A composite sensor array impedentiometric electronic tongue Part II. Discrimination of basic tastes.

PubMed

Pioggia, G; Di Francesco, F; Marchetti, A; Ferro, M; Leardi, R; Ahluwalia, A

2007-05-15

An impedentiometric electronic tongue based on the combination of a composite sensor array and chemometric techniques aimed at the discrimination of soluble compounds able to elicit different gustative perceptions is presented. A composite array consisting of chemo-sensitive layers based on carbon nanotubes or carbon black dispersed in polymeric matrices and doped polythiophenes was used. The electrical impedance of the sensor array was measured at a frequency of 150 Hz by means of an impedance meter. The experimental set-up was designed in order to allow the automatic selection of a test solution and dipping of the sensor array following a dedicated measurement protocol. Measurements were carried out on 15 different solutions eliciting 5 different tastes (sodium chloride, citric acid, glucose, glutamic acid and sodium dehydrocholate for salty, sour, sweet, umami and bitter, respectively) at 3 concentration levels comprising the human perceptive range. In order to avoid over-fitting, more than 100 repetitions for each sample were carried in a 4-month period. Principal component analysis (PCA) was used to detect and remove outliers. Classification was performed by linear discriminant analysis (LDA). A fairly good degree of discrimination was obtained.

Development of a poly(dimethylacrylamide) based matrix material for solid phase high density peptide array synthesis employing a laser based material transfer

NASA Astrophysics Data System (ADS)

Ridder, Barbara; Foertsch, Tobias C.; Welle, Alexander; Mattes, Daniela S.; von Bojnicic-Kninski, Clemens M.; Loeffler, Felix F.; Nesterov-Mueller, Alexander; Meier, Michael A. R.; Breitling, Frank

2016-12-01

Poly(dimethylacrylamide) (PDMA) based matrix materials were developed for laser-based in situ solid phase peptide synthesis to produce high density arrays. In this specific array synthesis approach, amino acid derivatives are embedded into a matrix material, serving as a ;solid; solvent material at room temperature. Then, a laser pulse transfers this mixture to the target position on a synthesis slide, where the peptide array is synthesized. Upon heating above the glass transition temperature of the matrix material, it softens, allowing diffusion of the amino acid derivatives to the synthesis surface and serving as a solvent for peptide bond formation. Here, we synthesized PDMA six-arm star polymers, offering the desired matrix material properties, using atom transfer radical polymerization. With the synthesized polymers as matrix material, we structured and synthesized arrays with combinatorial laser transfer. With densities of up to 20,000 peptide spots per cm2, the resolution could be increased compared to the commercially available standard matrix material. Time-of-Flight Secondary Ion Mass Spectrometry experiments revealed the penetration behavior of an amino acid derivative into the prepared acceptor synthesis surface and the effectiveness of the washing protocols.

Hyperbranched Polyglycerol as a Colloid in Cold Organ Preservation Solutions

PubMed Central

Gao, Sihai; Guan, Qiunong; Chafeeva, Irina; Brooks, Donald E.; Nguan, Christopher Y. C.; Kizhakkedathu, Jayachandran N.; Du, Caigan

2015-01-01

Hydroxyethyl starch (HES) is a common colloid in organ preservation solutions, such as in University of Wisconsin (UW) solution, for preventing graft interstitial edema and cell swelling during cold preservation of donor organs. However, HES has undesirable characteristics, such as high viscosity, causing kidney injury and aggregation of erythrocytes. Hyperbranched polyglycerol (HPG) is a branched compact polymer that has low intrinsic viscosity. This study investigated HPG (MW-0.5 to 119 kDa) as a potential alternative to HES for cold organ preservation. HPG was synthesized by ring-opening multibranching polymerization of glycidol. Both rat myocardiocytes and human endothelial cells were used as an in vitro model, and heart transplantation in mice as an in vivo model. Tissue damage or cell death was determined by both biochemical and histological analysis. HPG polymers were more compact with relatively low polydispersity index than HES in UW solution. Cold preservation of mouse hearts ex vivo in HPG solutions reduced organ damage in comparison to those in HES-based UW solution. Both size and concentration of HPGs contributed to the protection of the donor organs; 1 kDa HPG at 3 wt% solution was superior to HES-based UW solution and other HPGs. Heart transplants preserved with HPG solution (1 kDa, 3%) as compared with those with UW solution had a better functional recovery, less tissue injury and neutrophil infiltration in syngeneic recipients, and survived longer in allogeneic recipients. In cultured myocardiocytes or endothelial cells, significantly more cells survived after cold preservation with the HPG solution than those with the UW solution, which was positively correlated with the maintenance of intracellular adenosine triphosphate and cell membrane fluidity. In conclusion, HPG solution significantly enhanced the protection of hearts or cells during cold storage, suggesting that HPG is a promising colloid for the cold storage of donor organs and cells in transplantation. PMID:25706864

Comparison of Hb-200 and 6% hetastarch 450/0.7 during initial fluid resuscitation of 20 dogs with gastric dilatation-volvulus.

PubMed

Haak, Carol E; Rudloff, Elke; Kirby, Rebecca

2012-04-01

To compare the use of polymerized stroma-free bovine hemoglobin (Hb-200) and 6% hetastarch 450/0.7 (HES 450/0.7) in 0.9% saline during fluid resuscitation of dogs with gastric dilatation-volvulus (GDV). Prospective, randomized clinical case series. Private specialty and referral clinic. Twenty client-owned dogs presenting with GDV. Dogs presenting with GDV and abnormal perfusion parameters first received rapid IV infusion of a buffered isotonic replacement crystalloid (15 mL/kg) and IV opioids. Patients were then randomized to receive either Hb-200 (N = 10) or HES 450/0.7 (N = 10). Balanced isotonic replacement crystalloids (10-20 mL/kg IV) were rapidly infused along with either Hb-200 or HES in 5 mL/kg IV aliquots to meet resuscitation end points. Resuscitation was defined as meeting at least 2 of 3 criteria: (1) capillary refill time 1-2 seconds, pink mucous membrane color, strong femoral pulse quality; (2) heart rate (HR) ≤ 150/min; or (3) indirect arterial systolic blood pressure (SBP) > 90 mm Hg. HR, SBP, packed cell volume, hemoglobin, glucose, venous pH, bicarbonate, base excess, anion gap, and colloid osmotic pressure were compared at hospital entry and within 30 minutes post-resuscitation. Compared to the HES group, the Hb-200 group required significantly less colloid (4.2 versus 18.4 mL/kg) and crystalloid (31.3 versus 48.1 mL/kg) to reach resuscitation end points (P = 0.001). Time to resuscitation was significantly shorter in the Hb-200 group (12.5 versus 52.5 min). Dogs with GDV receiving Hb-200 during initial resuscitation required smaller volumes of both crystalloid and colloid fluids and reached resuscitation end points faster than dogs receiving HES 450/0.7 (P = 0.02). © Veterinary Emergency and Critical Care Society 2012.

Hyperbranched polyglycerol as a colloid in cold organ preservation solutions.

PubMed

Gao, Sihai; Guan, Qiunong; Chafeeva, Irina; Brooks, Donald E; Nguan, Christopher Y C; Kizhakkedathu, Jayachandran N; Du, Caigan

2015-01-01

Hydroxyethyl starch (HES) is a common colloid in organ preservation solutions, such as in University of Wisconsin (UW) solution, for preventing graft interstitial edema and cell swelling during cold preservation of donor organs. However, HES has undesirable characteristics, such as high viscosity, causing kidney injury and aggregation of erythrocytes. Hyperbranched polyglycerol (HPG) is a branched compact polymer that has low intrinsic viscosity. This study investigated HPG (MW-0.5 to 119 kDa) as a potential alternative to HES for cold organ preservation. HPG was synthesized by ring-opening multibranching polymerization of glycidol. Both rat myocardiocytes and human endothelial cells were used as an in vitro model, and heart transplantation in mice as an in vivo model. Tissue damage or cell death was determined by both biochemical and histological analysis. HPG polymers were more compact with relatively low polydispersity index than HES in UW solution. Cold preservation of mouse hearts ex vivo in HPG solutions reduced organ damage in comparison to those in HES-based UW solution. Both size and concentration of HPGs contributed to the protection of the donor organs; 1 kDa HPG at 3 wt% solution was superior to HES-based UW solution and other HPGs. Heart transplants preserved with HPG solution (1 kDa, 3%) as compared with those with UW solution had a better functional recovery, less tissue injury and neutrophil infiltration in syngeneic recipients, and survived longer in allogeneic recipients. In cultured myocardiocytes or endothelial cells, significantly more cells survived after cold preservation with the HPG solution than those with the UW solution, which was positively correlated with the maintenance of intracellular adenosine triphosphate and cell membrane fluidity. In conclusion, HPG solution significantly enhanced the protection of hearts or cells during cold storage, suggesting that HPG is a promising colloid for the cold storage of donor organs and cells in transplantation.

Fully optical backplane system using novel optical plug and slot

NASA Astrophysics Data System (ADS)

Cho, In-Kui; Ahn, Seung-Ho; Lee, Woo-Jin; Han, Sang-Pil; Kim, Jin-Tae; Choi, Chun-Ki; Shin, Kyung-Up; Yoon, Keun Byoung; Jeong, Myung-Yung; Park, Hyo Hoon

2005-10-01

A fully optical PCB with transmitter/receiver system boards and optical bakcplane was prepared, which is board-to-board interconnection by an optical slot. We report a 10 Gb/s PRBS NRZ data transmission between transmitter system board and optical backplane embedded multimode polymeric waveguide arrays. The basic concept of the optical PCB is as follows; 1) Metal optical bench is integrated with optoelectronic devices, driver and receiver circuits, polymeric waveguide and access line PCB module. 2) Multimode polymeric waveguide inside an optical backplane, which is embedded into PCB, 3) Optical slot and plug for high-density (channel pitch : 500 um) board-to-board interconnection. The polymeric waveguide technology can be used for transmission of data between transmitter/receiver processing boards and backplane boards. The main components are low-loss tapered polymeric waveguides and a novel optical plug and slot for board-to-board interconnections, respectively. The transmitter/receiver processing boards are designed as plug types, and can be easily plugged-in and -out at an optical backplane board. The optical backplane boards are prepared by employing the lamination processes for conventional electrical PCBs. A practical optical backplane system was implemented with two processing boards and an optical backplane. As connection components between the transmitter/receiver processing boards and backplane board, optical slots made of a 90°-bending structure-embedded optical plug was used. A 10 Gb/s data link was successfully demonstrated. The bit error rate (BER) was determined and is 5.6×10 -9(@10Gb/s) and the BER of 8 Gb/s is < 10 -12.

Thiol surface functionalization via continuous phase plasma polymerization of allyl mercaptan, with subsequent maleimide-linked conjugation of collagen.

PubMed

Stynes, Gil D; Gengenbach, Thomas R; Kiroff, George K; Morrison, Wayne A; Kirkland, Mark A

2017-07-01

Thiol groups can undergo a large variety of chemical reactions and are used in solution phase to conjugate many bioactive molecules. Previous research on solid substrates with continuous phase glow discharge polymerization of thiol-containing monomers may have been compromised by oxidation. Thiol surface functionalization via glow discharge polymerization has been reported as requiring pulsing. Herein, continuous phase glow discharge polymerization of allyl mercaptan (2-propene-1-thiol) was used to generate significant densities of thiol groups on a mixed macrodiol polyurethane and tantalum. Three general classes of chemistry are used to conjugate proteins to thiol groups, with maleimide linkers being used most commonly. Here the pH specificity of maleimide reactions was used effectively to conjugate surface-bound thiol groups to amine groups in collagen. XPS demonstrated surface-bound thiol groups without evidence of oxidation, along with the subsequent presence of maleimide and collagen. Glow discharge reactor parameters were optimized by testing the resistance of bound collagen to degradation by 8 M urea. The nature of the chemical bonding of collagen to surface thiol groups was effectively assessed by colorimetric assay (ELISA) of residual collagen after incubation in 8 M urea over 8 days and after incubation with keratinocytes over 15 days. The facile creation of useable solid-supported thiol groups via continuous phase glow discharge polymerization of allyl mercaptan opens a route for attaching a vast array of bioactive molecules. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1940-1948, 2017. © 2017 Wiley Periodicals, Inc.

Directing Stem Cell Differentiation via Electrochemical Reversible Switching between Nanotubes and Nanotips of Polypyrrole Array.

PubMed

Wei, Yan; Mo, Xiaoju; Zhang, Pengchao; Li, Yingying; Liao, Jingwen; Li, Yongjun; Zhang, Jinxing; Ning, Chengyun; Wang, Shutao; Deng, Xuliang; Jiang, Lei

2017-06-27

Control of stem cell behaviors at solid biointerfaces is critical for stem-cell-based regeneration and generally achieved by engineering chemical composition, topography, and stiffness. However, the influence of dynamic stimuli at the nanoscale from solid biointerfaces on stem cell fate remains unclear. Herein, we show that electrochemical switching of a polypyrrole (Ppy) array between nanotubes and nanotips can alter surface adhesion, which can strongly influence mechanotransduction activation and guide differentiation of mesenchymal stem cells (MSCs). The Ppy array, prepared via template-free electrochemical polymerization, can be reversibly switched between highly adhesive hydrophobic nanotubes and poorly adhesive hydrophilic nanotips through an electrochemical oxidation/reduction process, resulting in dynamic attachment and detachment to MSCs at the nanoscale. Multicyclic attachment/detachment of the Ppy array to MSCs can activate intracellular mechanotransduction and osteogenic differentiation independent of surface stiffness and chemical induction. This smart surface, permitting transduction of nanoscaled dynamic physical inputs into biological outputs, provides an alternative to classical cell culture substrates for regulating stem cell fate commitment. This study represents a general strategy to explore nanoscaled interactions between stem cells and stimuli-responsive surfaces.

Facile fabrication of CNT-based chemical sensor operating at room temperature

NASA Astrophysics Data System (ADS)

Sheng, Jiadong; Zeng, Xian; Zhu, Qi; Yang, Zhaohui; Zhang, Xiaohua

2017-12-01

This paper describes a simple, low cost and effective route to fabricate CNT-based chemical sensors, which operate at room temperature. Firstly, the incorporation of silk fibroin in vertically aligned CNT arrays (CNTA) obtained through a thermal chemical vapor deposition (CVD) method makes the direct removal of CNT arrays from substrates without any rigorous acid or sonication treatment feasible. Through a simple one-step in situ polymerization of anilines, the functionalization of CNT arrays with polyaniline (PANI) significantly improves the sensing performance of CNT-based chemical sensors in detecting ammonia (NH3) and hydrogen chloride (HCl) vapors. Chemically modified CNT arrays also show responses to organic vapors like menthol, ethyl acetate and acetone. Although the detection limits of chemically modified CNT-based chemical sensors are of the same orders of magnitudes reported in previous studies, these CNT-based chemical sensors show advantages of simplicity, low cost and energy efficiency in preparation and fabrication of devices. Additionally, a linear relationship between the relative sensitivity and concentration of analyte makes precise estimations on the concentrations of trace chemical vapors possible.

Atomic-resolution structure of the CAP-Gly domain of dynactin on polymeric microtubules determined by magic angle spinning NMR spectroscopy.

PubMed

Yan, Si; Guo, Changmiao; Hou, Guangjin; Zhang, Huilan; Lu, Xingyu; Williams, John Charles; Polenova, Tatyana

2015-11-24

Microtubules and their associated proteins perform a broad array of essential physiological functions, including mitosis, polarization and differentiation, cell migration, and vesicle and organelle transport. As such, they have been extensively studied at multiple levels of resolution (e.g., from structural biology to cell biology). Despite these efforts, there remain significant gaps in our knowledge concerning how microtubule-binding proteins bind to microtubules, how dynamics connect different conformational states, and how these interactions and dynamics affect cellular processes. Structures of microtubule-associated proteins assembled on polymeric microtubules are not known at atomic resolution. Here, we report a structure of the cytoskeleton-associated protein glycine-rich (CAP-Gly) domain of dynactin motor on polymeric microtubules, solved by magic angle spinning NMR spectroscopy. We present the intermolecular interface of CAP-Gly with microtubules, derived by recording direct dipolar contacts between CAP-Gly and tubulin using double rotational echo double resonance (dREDOR)-filtered experiments. Our results indicate that the structure adopted by CAP-Gly varies, particularly around its loop regions, permitting its interaction with multiple binding partners and with the microtubules. To our knowledge, this study reports the first atomic-resolution structure of a microtubule-associated protein on polymeric microtubules. Our approach lays the foundation for atomic-resolution structural analysis of other microtubule-associated motors.

Nanoconfinement: an effective way to enhance PVDF piezoelectric properties.

PubMed

Cauda, Valentina; Stassi, Stefano; Bejtka, Katarzyna; Canavese, Giancarlo

2013-07-10

The dimensional confinement and oriented crystallization are both key factors in determining the piezoelectric properties of a polymeric nanostructured material. Here we prepare arrays of one-dimensional polymeric nanowires showing piezoelectric features by template-wetting two distinct polymers into anodic porous alumina (APA) membranes. In particular, poly(vinylidene fluoride), PVDF, and its copolymer poly(vinylidene fluoride-trifluoroethylene), PVTF, are obtained in commercially available APA, showing a final diameter of about 200 nm and several micrometers in length, reflecting the templating matrix features. We show that the crystallization of both polymers into a ferroelectric phase is directed by the nanotemplate confinement. Interestingly, the PVDF nanowires mainly crystallize into the β-phase in the nanoporous matrix, whereas the reference thin film of PVDF crystallizes in the α nonpolar phase. In the case of the PVTF nanowires, needle-like crystals oriented perpendicularly to the APA channel walls are observed, giving insight on the molecular orientation of the polymer within the nanowire structure. A remarkable piezoelectric behavior of both 1-D polymeric nanowires is observed, upon recording ferroelectric polarization, hysteresis, and displacement loops. In particular, an outstanding piezoelectric effect is observed for the PVDF nanowires with respect to the polymeric thin film, considering that no poling was carried out. Current versus voltage (I-V) characteristics showed a consistent switching behavior of the ferroelectric polar domains, thus revealing the importance of the confined and oriented crystallization of the polymer in monodimensional nanoarchitectures.

Rigid spine reinforced polymer microelectrode array probe and method of fabrication

DOEpatents

Tabada, Phillipe; Pannu, Satinderpall S

2014-05-27

A rigid spine-reinforced microelectrode array probe and fabrication method. The probe includes a flexible elongated probe body with conductive lines enclosed within a polymeric material. The conductive lines connect microelectrodes found near an insertion end of the probe to respective leads at a connector end of the probe. The probe also includes a rigid spine, such as made from titanium, fixedly attached to the probe body to structurally reinforce the probe body and enable the typically flexible probe body to penetrate and be inserted into tissue, such as neural tissue. By attaching or otherwise fabricating the rigid spine to connect to only an insertion section of the probe body, an integrally connected cable section of the probe body may remain flexible.

Enhanced performance of core-shell structured polyaniline at helical carbon nanotube hybrids for ammonia gas sensor

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

Tian, Xin; Wang, Qiang; Chen, Xiangnan

2014-11-17

A core-shell structured hybrid of polyaniline at helical carbon nanotubes was synthesized using in situ polymerization, which the helical carbon nanotubes were uniformly surrounded by a layer of polyaniline nanorods array. More interestingly, repeatable responses were experimentally observed that the sensitivity to ammonia gas of the as-prepared helical shaped core-shell hybrid displays an enhancement of more than two times compared to those of only polyaniline or helical carbon nanotubes sensors because of the peculiar structures with high surface area. This kind of hybrid comprising nanorod arrays of conductive polymers covering carbon nanotubes and related structures provide a potential in sensorsmore » of trace gas detection for environmental monitoring and safety forecasting.« less

Enhanced interfacial contact between PbS and TiO2 layers in quantum dot solar cells using 2D-arrayed TiO2 hemisphere nanostructures

NASA Astrophysics Data System (ADS)

Lee, Wonseok; Ryu, Ilhwan; Lee, Haein; Yim, Sanggyu

2018-02-01

Two-dimensionally (2D) arrayed hemispherical nanostructures of TiO2 thin films were successfully fabricated using a simple procedure of spin-coating or dip-coating TiO2 nanoparticles onto 2D close-packed polystyrene (PS) nanospheres, followed by PS extraction. The nanostructured TiO2 film was then used as an n-type layer in a lead sulfide (PbS) colloidal quantum dot solar cell. The TiO2 nanostructure could provide significantly increased contacts with subsequently deposited PbS quantum dot layer. In addition, the periodically arrayed nanostructure could enhance optical absorption of the cell by redirecting the path of the incident light and increasing the path length passing though the active layer. As a result, the power conversion efficiency (PCE) reached 5.13%, which is approximately a 1.7-fold increase over that of the control cell without nanostructuring, 3.02%. This PCE enhancement can mainly be attributed to the increase of the short-circuit current density from 19.6 mA/cm2 to 30.6 mA/cm2, whereas the open-circuit voltage and fill factor values did not vary significantly.

In Situ Localized Growth of Ordered Metal Oxide Hollow Sphere Array on Microheater Platform for Sensitive, Ultra-Fast Gas Sensing.

PubMed

Rao, Ameya; Long, Hu; Harley-Trochimczyk, Anna; Pham, Thang; Zettl, Alex; Carraro, Carlo; Maboudian, Roya

2017-01-25

A simple and versatile strategy is presented for the localized on-chip synthesis of an ordered metal oxide hollow sphere array directly on a low power microheater platform to form a closely integrated miniaturized gas sensor. Selective microheater surface modification through fluorinated monolayer self-assembly and its subsequent microheater-induced thermal decomposition enables the position-controlled deposition of an ordered two-dimensional colloidal sphere array, which serves as a sacrificial template for metal oxide growth via homogeneous chemical precipitation; this strategy ensures control in both the morphology and placement of the sensing material on only the active heated area of the microheater platform, providing a major advantage over other methods of presynthesized nanomaterial integration via suspension coating or printing. A fabricated tin oxide hollow sphere-based sensor shows high sensitivity (6.5 ppb detection limit) and selectivity toward formaldehyde, and extremely fast response (1.8 s) and recovery (5.4 s) times. This flexible and scalable method can be used to fabricate high performance miniaturized gas sensors with a variety of hollow nanostructured metal oxides for a range of applications, including combining multiple metal oxides for superior sensitivity and tunable selectivity.

Near-infrared photoluminescence biosensing platform with gold nanorods-over-gallium arsenide nanohorn array.

PubMed

Zhang, Yiming; Jiang, Tao; Tang, Longhua

2017-11-15

The near-infrared (NIR) optical detection of biomolecules with high sensitivity and reliability have been expected, however, it is still a challenge. In this work, we present a gold nanorods (AuNRs)-over-gallium arsenide nanohorn-like array (GaAs NHA) system that can be used for the ultrasensitive and specific NIR photoluminescence (PL) detection of DNA and proteins. The fabrication of GaAs NHA involved the technique of colloidal lithography and inductively coupled plasma dry etching, yielding large-area and well-defined nanostructural array, and exhibiting an improved PL emission compared to the planar GaAs substrate. Importantly, we found that the DNA-bridged AuNRs attachment on NHA could further improve the PL intensity from GaAs, and thereby provide the basis for the NIR optical sensing of biological analytes. We demonstrated that DNA and thrombin could be sensitively and specifically detected, with the detection limit of 1 pM for target DNA and 10 pM for thrombin. Such ultrasensitive NIR optical platform can extend to the detection of other biomarkers and is promising for clinical diagnostics. Copyright © 2017 Elsevier B.V. All rights reserved.

Lassoing saddle splay and the geometrical control of topological defects

NASA Astrophysics Data System (ADS)

Tran, Lisa; Lavrentovich, Maxim O.; Beller, Daniel A.; Li, Ningwei; Stebe, Kathleen J.; Kamien, Randall D.

2016-06-01

Systems with holes, such as colloidal handlebodies and toroidal droplets, have been studied in the nematic liquid crystal (NLC) 4-cyano-4'-pentylbiphenyl (5CB): Both point and ring topological defects can occur within each hole and around the system while conserving the system's overall topological charge. However, what has not been fully appreciated is the ability to manipulate the hole geometry with homeotropic (perpendicular) anchoring conditions to induce complex, saddle-like deformations. We exploit this by creating an array of holes suspended in an NLC cell with oriented planar (parallel) anchoring at the cell boundaries. We study both 5CB and a binary mixture of bicyclohexane derivatives (CCN-47 and CCN-55). Through simulations and experiments, we study how the bulk saddle deformations of each hole interact to create defect structures, including an array of disclination lines, reminiscent of those found in liquid-crystal blue phases. The line locations are tunable via the NLC elastic constants, the cell geometry, and the size and spacing of holes in the array. This research lays the groundwork for the control of complex elastic deformations of varying length scales via geometrical cues in materials that are renowned in the display industry for their stability and easy manipulability.

Chemical transfers along slowly eroding catenas developed on granitic cratons in southern Africa

USGS Publications Warehouse

Khomo, Lesego; Bern, Carleton R.; Hartshorn, Anthony S.; Rogers, Kevin H.; Chadwick, Oliver A.

2013-01-01

A catena is a series of distinct but co-evolving soils arrayed along a slope. On low-slope, slowly eroding catenas the redistribution of mass occurs predominantly as plasma, the dissolved and suspended constituents in soil water. We applied mass balance methods to track how redistribution via plasma contributed to physical and geochemical differentiation of nine slowly eroding (~ 5 mm ky− 1) granitic catenas. The catenas were arrayed in a 3 × 3 climate by relief matrix and located in Kruger National Park, South Africa. Most of the catenas contained at least one illuviated soil profile that had undergone more volumetric expansion and less mass loss, and these soils were located in the lower halves of the slopes. By comparison, the majority of slope positions were eluviated. Soils from the wetter climates (550 and 730 mm precipitation yr− 1) generally had undergone greater collapse and lost more mass, while soils in the drier climate (470 mm yr− 1) had undergone expansion and lost less mass. Effects of differences in catena relief were less clear. Within each climate zone, soil horizon mass loss and strain were correlated, as were losses of most major elements, illustrating the predominant influence of primary mineral weathering. Nevertheless, mass loss and volumetric collapse did not become extreme because of the skeleton of resistant primary mineral grains inherited from the granite. Colloidal clay redistribution, as traced by the ratio of Ti to Zr in soil, suggested clay losses via suspension from catena eluvial zones. Thus illuviation of colloidal clays into downslope soils may be crucial to catena development by restricting subsurface flow there. Our analysis provides quantitative support for the conceptual understanding of catenas in cratonic landscapes and provides an endmember reference point in understanding the development of slowly eroding soil landscapes.

Experimental studies on a novel roll-to-roll powder hot embossing for large-area fabrication of micropyramid arrays on polymers

NASA Astrophysics Data System (ADS)

Yi, Peiyun; Deng, Yujun; Shu, Yunyi; Peng, Linfa

2018-08-01

Roll-to-roll (R2R) hot embossing is regarded as a cost-effective replication technology to fabricate microstructures on polymer films. However, the characteristics of continuous and fast forming for the R2R hot embossing process limits material flow during the filling stage and results in significant springback during the demolding stage. To resolve this issue, this study proposed a novel R2R powder hot embossing process, which combines the merits of the continuous fabrication of R2R hot embossing and near-net-shape forming of powder sintering and also decreases the whole cycle of the fabrication from films to microstructures. First, the relation between the molten layer thickness and processing parameters was discussed and an analytical model was established to predict the feed of the polymeric powder during R2R powder hot embossing. Then, with the use of a micro-pyramid array mold, the impact of the process parameters including mold temperature, feeding speed and applied force on the geometrical dimension of the patterned microstructures was discussed. Last, based on the response surface analysis, a process window, in terms of the mold temperature of 132 °C –145 °C, feeding speed of 0.1–1.4 m min‑1 and applied force of 15–50 kgf was determined for the continuous fabrication of completely-filled micropyramid arrays with the R2R powder hot embossing process. This research demonstrated the feasibility and superiority of the proposed R2R powder hot embossing process in continuously fabricating micropatterned structures on polymeric films.

Microbial mobilization of plutonium and other actinides from contaminated soil

DOE PAGES

Francis, A. J.; Dodge, C. J.

2015-12-01

Here we examined the dissolution of Pu, U, and Am in contaminated soil from the Nevada Test Site (NTS) due to indigenous microbial activity. Scanning transmission x-ray microscopy (STXM) analysis of the soil showed that Pu was present in its polymeric form and associated with Fe- and Mn- oxides and aluminosilicates. Uranium analysis by x-ray diffraction (μ-XRD) revealed discrete U-containing mineral phases, viz., schoepite, sharpite, and liebigite; synchrotron x-ray fluorescence (μ-XRF) mapping showed its association with Fe- and Ca-phases; and μ-x-ray absorption near edge structure (μ-XANES) confirmed U(IV) and U(VI) oxidation states. Addition of citric acid or glucose to themore » soil and incubated under aerobic or anaerobic conditions enhanced indigenous microbial activity and the dissolution of Pu. Detectable amount of Am and no U was observed in solution. In the citric acid-amended sample, Pu concentration increased with time and decreased to below detection levels when the citric acid was completely consumed. In contrast, with glucose amendment, Pu remained in solution. Pu speciation studies suggest that it exists in mixed oxidation states (III/IV) in a polymeric form as colloids. Although Pu(IV) is the most prevalent and generally considered to be more stable chemical form in the environment, our findings suggest that under the appropriate conditions, microbial activity could affect its solubility and long-term stability in contaminated environments.« less

Counterion-Release Entropy Governs the Inhibition of Serum Proteins by Polyelectrolyte Drugs.

PubMed

Xu, Xiao; Ran, Qidi; Dey, Pradip; Nikam, Rohit; Haag, Rainer; Ballauff, Matthias; Dzubiella, Joachim

2018-02-12

Dendritic polyelectrolytes constitute high potential drugs and carrier systems for biomedical purposes. Still, their biomolecular interaction modes, in particular those determining the binding affinity to proteins, have not been rationalized. We study the interaction of the drug candidate dendritic polyglycerol sulfate (dPGS) with serum proteins using isothermal titration calorimetry (ITC) interpreted and complemented with molecular computer simulations. Lysozyme is first studied as a well-defined model protein to verify theoretical concepts, which are then applied to the important cell adhesion protein family of selectins. We demonstrate that the driving force of the strong complexation, leading to a distinct protein corona, originates mainly from the release of only a few condensed counterions from the dPGS upon binding. The binding constant shows a surprisingly weak dependence on dPGS size (and bare charge) which can be understood by colloidal charge-renormalization effects and by the fact that the magnitude of the dominating counterion-release mechanism almost exclusively depends on the interfacial charge structure of the protein-specific binding patch. Our findings explain the high selectivity of P- and L-selectins over E-selectin for dPGS to act as a highly anti-inflammatory drug. The entire analysis demonstrates that the interaction of proteins with charged polymeric drugs can be predicted by simulations with unprecedented accuracy. Thus, our results open new perspectives for the rational design of charged polymeric drugs and carrier systems.

Microbial mobilization of plutonium and other actinides from contaminated soil

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

Francis, A. J.; Dodge, C. J.

Here we examined the dissolution of Pu, U, and Am in contaminated soil from the Nevada Test Site (NTS) due to indigenous microbial activity. Scanning transmission x-ray microscopy (STXM) analysis of the soil showed that Pu was present in its polymeric form and associated with Fe- and Mn- oxides and aluminosilicates. Uranium analysis by x-ray diffraction (μ-XRD) revealed discrete U-containing mineral phases, viz., schoepite, sharpite, and liebigite; synchrotron x-ray fluorescence (μ-XRF) mapping showed its association with Fe- and Ca-phases; and μ-x-ray absorption near edge structure (μ-XANES) confirmed U(IV) and U(VI) oxidation states. Addition of citric acid or glucose to themore » soil and incubated under aerobic or anaerobic conditions enhanced indigenous microbial activity and the dissolution of Pu. Detectable amount of Am and no U was observed in solution. In the citric acid-amended sample, Pu concentration increased with time and decreased to below detection levels when the citric acid was completely consumed. In contrast, with glucose amendment, Pu remained in solution. Pu speciation studies suggest that it exists in mixed oxidation states (III/IV) in a polymeric form as colloids. Although Pu(IV) is the most prevalent and generally considered to be more stable chemical form in the environment, our findings suggest that under the appropriate conditions, microbial activity could affect its solubility and long-term stability in contaminated environments.« less

Multifunctional reduction-responsive SPIO&DOX-loaded PEGylated polymeric lipid vesicles for magnetic resonance imaging-guided drug delivery

NASA Astrophysics Data System (ADS)

Wang, Sheng; Yang, Weitao; Du, Hongli; Guo, Fangfang; Wang, Hanjie; Chang, Jin; Gong, Xiaoqun; Zhang, Bingbo

2016-04-01

Multifunctional superparamagnetic iron-oxide (SPIO)-based nanoparticles have been emerging as candidate nanosystems for cancer diagnosis and therapy. Here, we report the use of reduction- responsive SPIO/doxorubicin (DOX)-loaded poly(ethylene glycol) monomethyl ether (PEG)ylated polymeric lipid vesicles (SPIO&DOX-PPLVs) as a novel theranostic system for tumor magnetic resonance imaging (MRI) diagnosis and controlled drug delivery. These SPIO&DOX-PPLVs are composed of SPIOs that function as MR contrast agents for tumor enhancement and PPLVs as polymer matrices for encapsulating SPIO and antitumor drugs. The in vitro characterizations show that the SPIO&DOX-PPLVs have nanosized structures (˜80 nm), excellent colloidal stability, good biocompatibility, as well as T 2-weighted MRI capability with a relatively high T 2 relaxivity (r 2 = 213.82 mM-1 s-1). In vitro drug release studies reveal that the release rate of DOX from the SPIO&DOX-PPLVs is accelerated in the reduction environment. An in vitro cellular uptake study and an antitumor study show that the SPIO&DOX-PPLVs have magnetic targeting properties and effective antitumor activity. In vivo studies show the SPIO&DOX-PPLVs have excellent T 2-weighted tumor targeted MRI capability, image-guided drug delivery capability, and high antitumor effects. These results suggest that the SPIO&DOX-PPLVs are promising nanocarriers for MRI diagnosis and cancer therapy applications.

Wastewater characterisation by combining size fractionation, chemical composition and biodegradability.

PubMed

Ravndal, Kristin T; Opsahl, Eystein; Bagi, Andrea; Kommedal, Roald

2017-12-18

The potential for resource recovery from wastewater can be evaluated based on a detailed characterisation of wastewater. In this paper, results from fractionation and characterisation of two distinct wastewaters are reported. Using tangential flow filtration, the wastewater was fractionated into 10 size fractions ranging from 1 kDa to 1 mm, wherein the chemical composition and biodegradability were determined. Carbohydrates were dominant in particulate size fractions larger than 100 μm, indicating a potential of cellulose recovery from these fractions. While the particulate size fractions between 0.65 and 100 μm show a potential as a source for biofuel production due to an abundance of saturated C16 and C18 lipids. Both wastewaters were dominated by particulate (>0.65 μm), and oligo- and monomeric (<1 kDa) COD. Polymeric (1-1000 kDa) and colloidal (1000 kDa-0.65 μm) fractions had a low COD content, expected due to degradation in the sewer system upstream of the wastewater treatment plant. Biodegradation rates of particulate fractions increase with decreasing size. However, this was not seen in polymeric fractions where degradation rate was governed by chemical composition. Analytical validation of molecular weight and particle size distribution showed below filter cut-off retention of particles and polymers close to nominal cut-off, shifting the actual size distribution. Copyright © 2017. Published by Elsevier Ltd.

Gold Nanoparticles Grafted with PLL-b-PNIPAM: Interplay on Thermal/pH Dual-Response and Optical Properties.

PubMed

Li, Hui-Juan; Li, Peng-Yun; Li, Li-Ying; Haleem, Abdul; He, Wei-Dong

2018-04-16

Narrowly distributed poly(l-lysine- b - N -isopropylacrylamide) (PLL- b -PNIPAM) was prepared through ring-opening polymerization of ε-benzyloxycarbonyl-l-lysine N -carboxy-α-amino anhydride and atom transfer radical polymerization of NIPAM, followed with the removal of ε-benzyloxycarbonyl group. Then gold nanoparticles (AuNPs) grafted with PLL- b -PNIPAM (PNIPAM-PLL-AuNPs) were obtained by the reduction of chloroauric acid with sodium citrate in the presence of PLL- b -PNIPAM. PNIPAM-PLL-AuNPs and its precursors were thoroughly characterized by proton magnetic resonance spectroscope, Fourier transform infrared spectroscope, UV-vis spectroscope, transmission electron microscopy, dynamic light scattering, thermogravimetric analysis, and circular dichroism. The obtained PNIPAM-PLL-AuNPs exhibited high colloid stability even at strong alkaline (pH = 12) and acidic (pH = 2) conditions. The thermal and pH dual-responsive behaviors of the grafting PLL- b -PNIPAM chains was observed to be affected by AuNPs, while not for the secondary structure of PLL chains. Correspondingly, the surface plasmon resonance (SPR) of AuNPs was found to be sensitive to both pH value and temperature. A blue shift in the SPR happened both with increasing pH value and increasing temperature. The stimuli-response was reversible in heating-cooling cycles. The gold nanoparticles with both pH and temperature response may have potential applications in biomedical areas and biosensors.

Application of ceramic membranes with pre-ozonation for treatment of secondary wastewater effluent.

PubMed

Lehman, S Geno; Liu, Li

2009-04-01

Membrane fouling is an inevitable problem when microfiltration (MF) and ultrafiltraion (UF) are used to treat wastewater treatment plant (WWTP) effluent. While historically the use of MF/UF for water and wastewater treatment has been almost exclusively focused on polymeric membranes, new generation ceramic membranes were recently introduced in the market and they possess unique advantages over currently available polymeric membranes. Ceramic membranes are mechanically superior and are more resistant to severe chemical and thermal environments. Due to the robustness of ceramic membranes, strong oxidants such as ozone can be used as pretreatment to reduce the membrane fouling. This paper presents results of a pilot study designed to investigate the application of new generation ceramic membranes for WWTP effluent treatment. Ozonation and coagulation pretreatment were evaluated to optimize the membrane operation. The ceramic membrane demonstrated stable performance at a filtration flux of 100 gfd (170LMH) at 20 degrees C with pretreatment using PACl (1mg/L as Al) and ozone (4 mg/L). To understand the effects of ozone and coagulation pretreatment on organic foulants, natural organic matter (NOM) in four waters - raw, ozone treated, coagulation treated, and ozone followed by coagulation treated wastewaters - were characterized using high performance size exclusion chromatography (HPSEC). The HPSEC analysis demonstrated that ozone treatment is effective at degrading colloidal NOMs which are likely responsible for the majority of membrane fouling.

DNA-programmable nanoparticle crystallization.

PubMed

Park, Sung Yong; Lytton-Jean, Abigail K R; Lee, Byeongdu; Weigand, Steven; Schatz, George C; Mirkin, Chad A

2008-01-31

It was first shown more than ten years ago that DNA oligonucleotides can be attached to gold nanoparticles rationally to direct the formation of larger assemblies. Since then, oligonucleotide-functionalized nanoparticles have been developed into powerful diagnostic tools for nucleic acids and proteins, and into intracellular probes and gene regulators. In contrast, the conceptually simple yet powerful idea that functionalized nanoparticles might serve as basic building blocks that can be rationally assembled through programmable base-pairing interactions into highly ordered macroscopic materials remains poorly developed. So far, the approach has mainly resulted in polymerization, with modest control over the placement of, the periodicity in, and the distance between particles within the assembled material. That is, most of the materials obtained thus far are best classified as amorphous polymers, although a few examples of colloidal crystal formation exist. Here, we demonstrate that DNA can be used to control the crystallization of nanoparticle-oligonucleotide conjugates to the extent that different DNA sequences guide the assembly of the same type of inorganic nanoparticle into different crystalline states. We show that the choice of DNA sequences attached to the nanoparticle building blocks, the DNA linking molecules and the absence or presence of a non-bonding single-base flexor can be adjusted so that gold nanoparticles assemble into micrometre-sized face-centred-cubic or body-centred-cubic crystal structures. Our findings thus clearly demonstrate that synthetically programmable colloidal crystallization is possible, and that a single-component system can be directed to form different structures.

Assessing the physical-chemical properties and stability of dapivirine-loaded polymeric nanoparticles.

PubMed

das Neves, José; Amiji, Mansoor; Bahia, Maria Fernanda; Sarmento, Bruno

2013-11-18

Nanocarriers may provide interesting delivery platforms for microbicide drugs and their characterization should be addressed early in development. Differently surface-engineered dapivirine-loaded, poly(epsilon-caprolactone) (PCL)-based nanoparticles (NPs) were obtained by nanoprecipitation using polyethylene oxide (PEO), sodium lauryl sulfate (SLS), or cetyltrimethylammonium bromide (CTAB) as surface modifiers. Physical-chemical properties of NP aqueous dispersions were evaluated upon storage at -20-40 °C for one year. NPs presented 170-200 nm in diameter, roundish-shape, low polydispersity index (≤0.18), and high drug association efficiency (≥97%) and loading (≥12.7%). NPs differed in zeta potential, depending on surface modifier (PEO: -27.9 mV; SLS: -54.7 mV; CTAB: +42.4 mV). No interactions among formulation components were detected by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR), except for SLS-PCL NPs. Colloidal properties of NPs were lost at -20 °C storage. Negatively charged NPs were stable up to one year at 5-40°C; as for CTAB-PCL NPs, particle aggregation was observed from 30 to 90 days of storage depending on temperature. Colloidal instability affected the in vitro drug release of CTAB-PCL NPs after 360 days. In any case, no degradation of dapivirine was apparent. Overall, PEO-PCL and SLS-PCL NPs presented suitable properties as nanocarriers for dapivirine. Conversely, CTAB-PCL NPs require additional strategies in order to increase stability. Copyright © 2013 Elsevier B.V. All rights reserved.

Stable environmentally sensitive cationic hydrogels for controlled delivery applications.

PubMed

Deo, Namita; Ruetsch, S; Ramaprasad, K R; Kamath, Y

2010-01-01

New thermosensitive, cationic hydrogels were synthesized by the dispersion copolymerization of N-isopropylacrylamide (NIPAM) and (3-acrylamidopropyl)trimethylammonium chloride (AAPTAC). In the polymerization protocol, an amide-based comonomer, (3-acrylamidopropyl)trimethylammonium chloride, was reacted as a new alternative monomer for introducing positive charges into the thermosensitive hydrogel. The hydrogels were synthesized without making any pH adjustment in the aqueous medium. These hydrogel particles exhibited colloidal stability in the pH range of 1.5 to 11.0, while similar cationic hydrogels were reported to be unstable at pHs higher than 6. The stronger cationic character of the selected comonomer provided higher colloidal stability to the poly(NIPAM-co-AAPTAC) hydrogels. Furthermore, these hydrogels displayed sensitivity towards temperature, pH, and salt concentration. Interestingly, the particle size of hydrogels was found to be decreased significantly with an increase in temperature and salt concentration. In addition, using pyrene fluorescence spectroscopy, it was established that the hydrophobicity/hydrophilicity of the hydrogel particles was largely controlled by both pH and temperature. The thermosensitive hydrogels reported in this paper may be suitable for delivering different actives for cosmetic and medical applications. Although direct application of these hydrogel particles in cosmetics has not been shown at this stage, the methodology of making them and controlling their absorption and release properties as a function of temperature and pH has been demonstrated. Furthermore, these hydrogels may also have applications in scavenging organic and inorganic toxics.

A theoretical study of colloidal forces near an amphiphilic polymer brush

NASA Astrophysics Data System (ADS)

Wu, Jianzhong

2011-03-01

Polymer-based ``non-stick'' coatings are promising as the next generation of effective, environmentally-friendly marine antifouling systems that minimize nonspecific adsorption of extracellular polymeric substances (EPS). However, design and development of such systems are impeded by the poor knowledge of polymer-mediated interactions of biomacromolecules with the protected substrate. In this work, a polymer density functional theory (DFT) is used to predict the potential of mean force between spherical biomacromolecules and amphiphilic copolymer brushes within a coarse-grained model that captures essential nonspecific interactions such as the molecular excluded volume effects and the hydrophobic energies. The relevance of theoretical results for practical control of the EPS adsorption is discussed in terms of the efficiency of different brush configurations to prevent biofouling. It is shown that the most effective antifouling surface may be accomplished by using amphiphilic brushes with a long hydrophilic backbone and a hydrophobic end at moderate grafting density.

Double-phase-functionalized magnetic Janus polymer microparticles containing TiO2 and Fe2O3 nanoparticles encapsulated in mussel-inspired amphiphilic polymers.

PubMed

Yabu, Hiroshi; Ohshima, Hiroyuki; Saito, Yuta

2014-10-22

Recently, anisotropic colloidal polymeric materials including Janus microparticles, which have two distinct aspects on their surfaces or interiors, have garnered much interest due to their anisotropic alignment and rotational orientation with respect to external electric or magnetic fields. Janus microparticles are also good candidates for pigments in "twisting ball type" electronic paper, which is considered promising for next-generation flexible display devices. We demonstrate here a universal strategy to encapsulate inorganic nanoparticles and to introduce different such inorganic nanoparticles into distinct polymer phases in Janus microparticles. TiO2 and Fe2O3 nanoparticles were separately encapsulated in two different mussel-inspired amphiphilic copolymers, and then organic-inorganic composite Janus microparticles were prepared by simple evaporation of solvent from the dispersion containing the polymer and nanoparticle. These Janus microparticles were observed to rotate quickly in response to applied magnetic fields.

Metastable Amyloid Phases and their Conversion to Mature Fibrils

NASA Astrophysics Data System (ADS)

Muschol, Martin; Miti, Tatiana; Mulaj, Mentor; Schmit, Jeremy

Self-assembly of proteins into amyloid fibrils plays a key role in both functional biological responses and pathogenic disorders which include Alzheimer's disease and type II diabetes. Amyloid fibril assembly frequently generates compact oligomeric and curvilinear polymeric intermediates which are implicated to be toxic to cells. Yet, the relation between these early-stage oligomeric aggregates and late-stage rigid fibrils, which are the hallmark structure of amyloid plaques, has remained unclear. Our measurements indicate that lysozyme amyloid oligomers and their curvilinear fibrils only form after crossing a salt and protein concentration dependent threshold. These oligomeric aggregates are structurally distinct from rigid fibrils and are metastable against nucleation and growth of rigid fibrils. Our experimental transition boundaries match well with colloidal model predictions accounting for salt-modulated charge repulsion. We also report our preliminary findings on the mechanism by which these metastable oligomeric phases are converted into stable amyloid fibrils.

Bronze-mean hexagonal quasicrystal

NASA Astrophysics Data System (ADS)

Dotera, Tomonari; Bekku, Shinichi; Ziherl, Primož

2017-10-01

The most striking feature of conventional quasicrystals is their non-traditional symmetry characterized by icosahedral, dodecagonal, decagonal or octagonal axes. The symmetry and the aperiodicity of these materials stem from an irrational ratio of two or more length scales controlling their structure, the best-known examples being the Penrose and the Ammann-Beenker tiling as two-dimensional models related to the golden and the silver mean, respectively. Surprisingly, no other metallic-mean tilings have been discovered so far. Here we propose a self-similar bronze-mean hexagonal pattern, which may be viewed as a projection of a higher-dimensional periodic lattice with a Koch-like snowflake projection window. We use numerical simulations to demonstrate that a disordered variant of this quasicrystal can be materialized in soft polymeric colloidal particles with a core-shell architecture. Moreover, by varying the geometry of the pattern we generate a continuous sequence of structures, which provide an alternative interpretation of quasicrystalline approximants observed in several metal-silicon alloys.

Electrostimulated Release of Neutral Drugs from Polythiophene Nanoparticles: Smart Regulation of Drug-Polymer Interactions.

PubMed

Puiggalí-Jou, Anna; Micheletti, Paolo; Estrany, Francesc; Del Valle, Luis J; Alemán, Carlos

2017-09-01

Poly(3,4-ethylenedioxythiophene) (PEDOT) nanoparticles are loaded with curcumin and piperine by in situ emulsion polymerization using dodecyl benzene sulfonic acid both as a stabilizer and a doping agent. The loaded drugs affect the morphology, size, and colloidal stability of the nanoparticles. Furthermore, kinetics studies of nonstimulated drug release have evidenced that polymer···drug interactions are stronger for curcumin than for piperine. This observation suggests that drug delivery systems based on combination of the former drug with PEDOT are much appropriated to show an externally tailored release profile. This is demonstrated by comparing the release profiles obtained in presence and absence of electrical stimulus. Results indicate that controlled and time-programmed release of curcumin is achieved in a physiological medium by applying a negative voltage of -1.25 V to loaded PEDOT nanoparticles. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymeric Micelles in Anticancer Therapy: Targeting, Imaging and Triggered Release

PubMed Central

Bult, Wouter; Bos, Mariska; Storm, Gert; Nijsen, J. Frank W.; Hennink, Wim E.

2010-01-01

ABSTRACT Micelles are colloidal particles with a size around 5–100 nm which are currently under investigation as carriers for hydrophobic drugs in anticancer therapy. Currently, five micellar formulations for anticancer therapy are under clinical evaluation, of which Genexol-PM has been FDA approved for use in patients with breast cancer. Micelle-based drug delivery, however, can be improved in different ways. Targeting ligands can be attached to the micelles which specifically recognize and bind to receptors overexpressed in tumor cells, and chelation or incorporation of imaging moieties enables tracking micelles in vivo for biodistribution studies. Moreover, pH-, thermo-, ultrasound-, or light-sensitive block copolymers allow for controlled micelle dissociation and triggered drug release. The combination of these approaches will further improve specificity and efficacy of micelle-based drug delivery and brings the development of a ‘magic bullet’ a major step forward. PMID:20725771

Investigation of the Bitumen Modification Process Regime Parameters Influence on Polymer-Bitumen Bonding Qualitative Indicators

NASA Astrophysics Data System (ADS)

Belyaev, P. S.; Mishchenko, S. V.; Belyaev, V. P.; Belousov, O. A.; Frolov, V. A.

2018-04-01

The objects of this study are petroleum road bitumen and polymeric bituminous binder for road surfaces obtained by polymer materials. The subject of the study is monitoring the polymer-bitumen binder quality changes as a result of varying the bitumen modification process. The purpose of the work is to identify the patterns of the modification process and build a mathematical model that provides the ability to calculate and select technological equipment. It is shown that the polymer-bitumen binder production with specified quality parameters can be ensured in apparatuses with agitators in turbulent mode without the colloidal mills use. Bitumen mix and modifying additives limiting indicators which can be used as restrictions in the form of mathematical model inequalities are defined. A mathematical model for the polymer-bitumen binder preparation has been developed and its adequacy has been confirmed.

Performance evaluation of startup for a yeast membrane bioreactor (MBRy) treating landfill leachate.

PubMed

Amaral, Míriam C S; Gomes, Rosimeire F; Brasil, Yara L; Oliveira, Sílvia M A; Moravia, Wagner G

2017-12-06

The startup process of a membrane bioreactor inoculated with yeast biomass (Saccharomyces cerevisiae) and used in the treatment of landfill leachate was evaluated. The yeast membrane bioreactor (MBRy) was inoculated with an exogenous inoculum, a granulated active dry commercial bakers' yeast. The MBRy was successfully started up with a progressive increase in the landfill leachate percentage in the MBRy feed and the use of Sabouraud Dextrose Broth. The membrane plays an important role in the startup phase because of its full biomass retention and removal of organic matter. MBRy is a suitable and promising process to treat recalcitrant landfill leachate. After the acclimation period, the COD and NH 3 removal efficiency reached values of 72 ± 3% and 39 ± 2% respectively. MBRy shows a low membrane-fouling potential. The membrane fouling was influenced by soluble microbial products, extracellular polymeric substances, sludge particle size, and colloidal dissolved organic carbon.

Monodisperse Block Copolymer Particles with Controllable Size, Shape, and Nanostructure

NASA Astrophysics Data System (ADS)

Shin, Jae Man; Kim, Yongjoo; Kim, Bumjoon; PNEL Team

Shape-anisotropic particles are important class of novel colloidal building block for their functionality is more strongly governed by their shape, size and nanostructure compared to conventional spherical particles. Recently, facile strategy for producing non-spherical polymeric particles by interfacial engineering received significant attention. However, achieving uniform size distribution of particles together with controlled shape and nanostructure has not been achieved. Here, we introduce versatile system for producing monodisperse BCP particles with controlled size, shape and morphology. Polystyrene-b-polybutadiene (PS-b-PB) self-assembled to either onion-like or striped ellipsoid particle, where final structure is governed by amount of adsorbed sodium dodecyl sulfate (SDS) surfactant at the particle/surrounding interface. Further control of molecular weight and particle size enabled fine-tuning of aspect ratio of ellipsoid particle. Underlying physics of free energy for morphology formation and entropic penalty associated with bending BCP chains strongly affects particle structure and specification.

A comparison of the physical, chemical, and biological properties of sludges from a complete-mix activated sludge reactor and a submerged membrane bioreactor.

PubMed

Merlo, Rion P; Trussell, R Shane; Hermanowicz, Slawomir W; Jenkins, David

2007-03-01

The properties of sludges from a pilot-scale submerged membrane bioreactor (SMBR) and two bench-scale complete-mix, activated sludge (CMAS) reactors treating municipal primary effluent were determined. Compared with the CMAS sludges, the SMBR sludge contained a higher amount of soluble microbial products (SMP) and colloidal material attributed to the use of a membrane for solid-liquid separation; a higher amount nocardioform bacteria, resulting from efficient foam trapping; and a lower amount of extracellular polymeric substances (EPS), possibly because there was no selective pressure for the sludge to settle. High aeration rates in both the CMAS and SMBR reactors produced sludges with higher numbers of smaller particles. Normalized capillary suction time values for the SMBR sludge were lower than for the CMAS sludges, possibly because of its lower EPS content.

Pharmaceutical applications of magnetic resonance imaging (MRI).

PubMed

Richardson, J Craig; Bowtell, Richard W; Mäder, Karsten; Melia, Colin D

2005-06-15

Magnetic resonance imaging (MRI) is a powerful imaging modality that provides internal images of materials and living organisms on a microscopic and macroscopic scale. It is non-invasive and non-destructive, and one of very few techniques that can observe internal events inside undisturbed specimens in situ. It is versatile, as a wide range of NMR modalities can be accessed, and 2D and 3D imaging can be undertaken. Despite widespread use and major advances in clinical MRI, it has seen limited application in the pharmaceutical sciences. In vitro studies have focussed on drug release mechanisms in polymeric delivery systems, but isolated studies of bioadhesion, tablet properties, and extrusion and mixing processes illustrate the wider potential. Perhaps the greatest potential however, lies in investigations of pharmaceuticals in vivo, where pilot human and animal studies have demonstrated we can obtain unique insights into the behaviour of gastrointestinal, topical, colloidal, and targeted drug delivery systems.

Colloidal chitin nanogels: A plethora of applications under one shell.

PubMed

Vishnu Priya, M; Sabitha, M; Jayakumar, R

2016-01-20

Chitin nanogels (CNGs) are a relatively new class of natural polymeric nanomaterials which have a large potential in the field of drug delivery and nanotherapeutics. These nanogels being very biocompatible are non-toxic when internalized by cells. In this review various properties, preparation techniques and applications of CNGs have been described. CNGs because of their nano-size possess certain unique properties which enable them to be used in a number of biomedical applications. CNGs are prepared by simple regeneration technique without using any cross-linkers. Various polymers, drugs and fluorescent dyes can be blended or incorporated or labelled with the chitin hydrogel network. Drugs and molecules encapsulated within CNGs can be used for targeted delivery, in vivo monitoring or even for therapeutic purposes. Here various applications of CNGs in the field of drug delivery, imaging, sensing and therapeutics have been discussed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Pathogenesis of thyroid nodules: histological classification?

PubMed

Salabè, G B

2001-02-01

Thyroid nodule genesis may be considered as an amplification of thyroid heterogeneity due to genetic and/or epigenetic mechanisms. We classified the thyroid nodules in five types with distinct histological features: hyperplastic, neoplastic, colloid, cystic and thyroiditic nodules. Hyperplastic: Thyrocyte proliferation is under the control of TSH but several other paracrine and autocrine factors are secreted by follicular cells, the stromal apparatus and the lymphocytes, which are implicated in initiation and perpetuation of thyroid hyperplasia. Growth occurs mainly through TSHR, cAMP and PKA. Constitutive cAMP overproduction has been shown to be due to point mutation of the TSHR or Gs protein, producing overgrowth and hyperfunction. Neoplastic: Several activated oncogenes have been identified in thyroid malignancies. Oncogenes relevant to the thyroid carcinogenesis are: mutated TSHR and gsp (constitutive activation of cAMP); TRK (receptor for NGF); RET/PTC (phosphorylation of tyrosine kinase receptor)--an isoform of this oncogene is induced by radiation: ras (it encodes Gs proteins transducing mitogenic signals); and c-MET (receptor for hepatocyte growth factor). The evolution of a differentiated thyroid cancer towards an undifferentiated cancer is due to a mutation of a family of proteins (i.e., p53), which acts as a brake, preventing the genomic instability of cancer. It is suggested that a tumor initiates by RET or ras and possibly progresses--as a result of additional mutations and by p53 mutation--to anaplastic carcinoma. Colloid: Flattening of the epithelium and dilatation of follicles containing viscous material--made up by a concentrated solution of thyroglobulin (hTg)--is the characteristic of the colloid nodule. A defect of intraluminal reabsorption of hTg has been suggested but not proven. Experimentally, a load of iodine is able to change thyroid hyperplasia to a colloid feature; however, a load of iodine is rarely found in the clinical history of patients. A new clue to the pathogenesis comes from the finding that a relevant part of the colloid (10-20%) is made up of insoluble globules, where hTg is compacted in a polymeric form. It is suggested that stocking hTg into globules is defective in colloid nodules, leading to enormous enlargement of the follicle. Cystic: It is estimated that between 15 and 40% of thyroid nodules are partly or entirely cystic. The 'true cyst' is rare; most of the so-called cystic nodules are 'pseudocysts', which follow necrosis and colliquation. Necrosis issues as an imbalance between growth and the precisely regulated process of angiogenesis. More recently, the VEGF/VPF has been found to be at the origin of recent and recurrent cysts. Immunotoxic and apoptotic mechanisms have also been suggested. Chemical analysis of cystic fluid showed a 'denatured' and 'serum-like' pattern suggesting different mechanisms in the pathogenesis of the pseudocystic thyroid nodules. Thyroiditic: Nodular lymphocytic thyroiditis (NLT) includes two different entities: 1) lymphocyte thyroiditis growing as a nodule in a hyperplastic or normal gland, and 2) lymphocyte thyroiditis associated in the same nodule with other nodular diseases of the thyroid: papillary thyroid carcinoma and lymphoma have been found to be associated to chronic lymphocytic thyroiditis.

A System for Multiplexed Direct Electrical Detection of DNA Synthesis.

PubMed

Anderson, Erik P; Daniels, Jonathan S; Yu, Heng; Karhanek, Miloslav; Lee, Thomas H; Davis, Ronald W; Pourmand, Nader

2008-01-29

An electronic system for the multiplexed detection of DNA polymerization is designed and characterized. DNA polymerization is detected by the measurement of small transient currents arising from ion diffusion during polymerization. A transimpedance amplifier is used to detect these small currents; we implemented a twenty-four channel recording system on a single printed circuit board. Various contributions to the input-referred current noise are analyzed and characterized, as it limits the minimum detectable current and thus the biological limit of detection. We obtained 8.5 pA RMS mean noise current (averaged over all 24 channels) over the recording bandwidth (DC to 2 kHz). With digital filtering, the input-referred current noise of the acquisition system is reduced to 2.4 pA, which is much lower than the biological noise. Electrical crosstalk between channels is measured, and a model for the crosstalk is presented. Minimizing the crosstalk is critical because it can lead to erroneous microarray data. With proper precautions, crosstalk is reduced to a negligible value (less than 1.4%). Using a micro-fabricated array of 24 gold electrodes, we demonstrated system functionality by detecting the presence of a target DNA oligonucleotide which hybridized onto its corresponding target.

Time-dependent areal mass density for disc-shaped substrates in a corona-activated flow stream at atmospheric pressure for argon/acetylene admixture

NASA Astrophysics Data System (ADS)

Xie, Shuzheng; Islam, Rokibul; Hussein, Bashir; Englund, Karl; Pedrow, Patrick

2015-09-01

In this research we use a 40-needle array energized with 60 Hz AC voltage in the range 5 to 15 kV RMS. Plasma processing takes place downstream from a grounded planar screen (the opposing electrode). The needle-to-screen gap is in the range 4 to 10 cm and its E-field generates weakly ionized plasma via streamers and back corona. Deposited material is plasma-polymerized acetylene. Substrates are potassium bromide, mica, wood, paper, and gold-covered solids. Substrate chemical species influence the efficiency with which the disc amasses plasma-polymerized material, at least until the substrate is fully covered with film. Early plasma-polymerization is accompanied by nucleation-site-dominated nodules but longer term deposition results in a film that fully covers the substrate. We will report on time-dependent areal mass density associated with run times in the range 5-60 minutes. Film thickness will be measured using instruments that include visible light microscopy, TEM, and SEM. Others in our research group are studying areal mass density for early times (1-5 minutes) when nodule growth (at nucleation sites) dominates the deposition process.

Fabrication of Micropatterned Dipeptide Hydrogels by Acoustic Trapping of Stimulus-Responsive Coacervate Droplets.

PubMed

Nichols, Madeleine K; Kumar, Ravinash Krishna; Bassindale, Philip G; Tian, Liangfei; Barnes, Adrian C; Drinkwater, Bruce W; Patil, Avinash J; Mann, Stephen

2018-06-01

Acoustic standing waves offer an excellent opportunity to trap and spatially manipulate colloidal objects. This noncontact technique is used for the in situ formation and patterning in aqueous solution of 1D or 2D arrays of pH-responsive coacervate microdroplets comprising poly(diallyldimethylammonium) chloride and the dipeptide N-fluorenyl-9-methoxy-carbonyl-D-alanine-D-alanine. Decreasing the pH of the preformed droplet arrays results in dipeptide nanofilament self-assembly and subsequent formation of a micropatterned supramolecular hydrogel that can be removed as a self-supporting monolith. Guest molecules such as molecular dyes, proteins, and oligonucleotides are sequestered specifically within the coacervate droplets during acoustic processing to produce micropatterned hydrogels containing spatially organized functional components. Using this strategy, the site-specific isolation of multiple enzymes to drive a catalytic cascade within the micropatterned hydrogel films is exploited. © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Ackerman, P. J.; van de Lagemaat, J.; Smalyukh, I. I.

Some of the most exotic condensed matter phases, such as twist grain boundary and blue phases in liquid crystals and Abrikosov phases in superconductors, contain arrays of topological defects in their ground state. Comprised of a triangular lattice of double-twist tubes of magnetization, the so-called ‘A-phase’ in chiral magnets is an example of a thermodynamically stable phase with topologically nontrivial solitonic field configurations referred to as two-dimensional skyrmions, or baby-skyrmions. Here we report that three-dimensional skyrmions in the form of double-twist tori called ‘hopfions’, or ‘torons’ when accompanied by additional self-compensating defects, self-assemble into periodic arrays and linear chains thatmore » exhibit electrostriction. In confined chiral nematic liquid crystals, this self-assembly is similar to that of liquid crystal colloids and originates from long-range elastic interactions between particle-like skyrmionic torus knots of molecular alignment field, which can be tuned from isotropic repulsive to weakly or highly anisotropic attractive by low-voltage electric fields.« less

Cicada-Wing-Inspired Self-Cleaning Antireflection Coatings on Polymer Substrates.

PubMed

Chen, Ying-Chu; Huang, Zhe-Sheng; Yang, Hongta

2015-11-18

The cicada has transparent wings with remarkable self-cleaning properties and high transmittance over the whole visible spectral range, which is derived from periodic conical structures covering the wing surface. Here we report a scalable self-assembly technique for fabricating multifunctional optical coatings that mimic cicada-wing structures. Spin-coated two-dimensional non-close-packed colloidal crystals are utilized as etching masks to pattern subwavelength-structured cone arrays directly on polymer substrates. The resulting gratings exhibit broadband antireflection performance and superhydrophobic properties after surface modification. The dependence of the cone shape and size on the antireflective and self-cleaning properties has also been investigated in this study.

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

Shaw, L. A.; Chizari, S.; Panas, R. M.

The aim of this research is to demonstrate a holographically driven photopolymerization process for joining colloidal particles to create planar microstructures fixed to a substrate, which can be monitored with real-time measurement. Holographic optical tweezers (HOT) have been used to arrange arrays of microparticles prior to this work; here we introduce a new photopolymerization process for rapidly joining simultaneously handled microspheres in a plane. Additionally, we demonstrate a new process control technique for efficiently identifying when particles have been successfully joined by measuring a sufficient reduction in the particles’ Brownian motion. Furthermore, this technique and our demonstrated joining approach enablemore » HOT technology to take critical steps toward automated additive fabrication of microstructures.« less

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.

The detection of organic solvent vapor by using polymer coated chemocapacitor sensor

NASA Astrophysics Data System (ADS)

Rusdiarna Indrapraja, Apik; Rivai, Muhammad; Arifin, Achmad; Purwanto, Djoko

2017-05-01

A chemocapacitor consists of planar interdigital electrodes (IDE) made by two comb electrodes on a substrate. A dielectric film was applied on the electrodes in which the absorbed vapor will modify its permittivity. This study has fabricated chemocapacitor with the IDE distance of 0.5 mm, while the dielectric film was a sensitive layer consisting of a polymeric material. The deposition of the polymeric film was accomplished by drop casting. A sensor array consisting of four chemocapacitors coated with different polymers namely PEG-1540, PEG-20M, PEG-6000, and PVP was used to obtain the pattern of shift in the capacitance. The integrated circuit AD7746 was used as the capacitance to-digital converter (CDC). The organic solvents of ethanol, benzene, and aceton were used as the vapor samples in this experiment. The results showed that the change in the capacitance value increases proportionally to the concentration of vapour where sensors coated with PEG-1540 and PVP have higher sensitivity, i.e. 0.0028pF/part per thousand and 0.0027pF/part per thousand, respectively. Based on the capacitance to digital conversion capabilities, the system provides there solution of 0.4084ppm. The sensor array could produce a different pattern for each of the vapor sample. The Neural Network pattern recognition system could identify the type of vapor automatically with the root mean square error of 10-5

Chemically stable Au nanorods as probes for sensitive surface enhanced scattering (SERS) analysis of blue BIC ballpoint pens

NASA Astrophysics Data System (ADS)

Alyami, Abeer; Saviello, Daniela; McAuliffe, Micheal A. P.; Cucciniello, Raffaele; Mirabile, Antonio; Proto, Antonio; Lewis, Liam; Iacopino, Daniela

2017-08-01

Au nanorods were used as an alternative to commonly used Ag nanoparticles as Surface Enhanced Raman Scattering (SERS) probes for identification of dye composition of blue BIC ballpoint pens. When used in combination with Thin Layer Chromatography (TLC), Au nanorod colloids allowed identification of the major dye components of the BIC pen ink, otherwise not identifiable by normal Raman spectroscopy. Thanks to their enhanced chemical stability compared to Ag colloids, Au nanorods provided stable and reproducible SERS signals and allowed easy identification of phthalocyanine and triarylene dyes in the pen ink mixture. These findings were supported by FTIR and MALDI analyses, also performed on the pen ink. Furthermore, the self-assembly of Au nanorods into large area ordered superstructures allowed identification of BIC pen traces. SERS spectra of good intensity and high reproducibility were obtained using Au nanorod vertical arrays, due to the high density of hot spots and morphological reproducibility of these superstructures. These results open the way to the employment of SERS for fast screening analysis and for quantitative analysis of pens and faded pens which are relevant for the fields of forensic and art conservation sciences.

Dynamics of colloidal particles in electrohydrodynamic convection of nematic liquid crystal.

PubMed

Takahashi, Kentaro; Kimura, Yasuyuki

2014-07-01

We have studied the dynamics of micrometer-sized colloidal particles in electrohydrodynamic convection of nematic liquid crystal. Above the onset voltage of electroconvection, the parallel array of convection rolls appears to be perpendicular to the nematic field at first. The particles are forced to rotate by convection flow and are trapped within a single roll in this voltage regime. A slow glide motion along the roll axis is also observed. The frequency of rotational motion and the glide velocity increase with the applied voltage. Under a much larger voltage where the roll axis temporally fluctuates, the particles occasionally hop to the neighbor rolls. In this voltage regime, the motion of the particles becomes two-dimensional. The motion perpendicular to the roll axis exhibits diffusion behavior at a long time period. The effective diffusion constant is 10(3)-10(4) times larger than the molecular one. The observed behavior is compared with the result obtained by a simple stochastic model for the transport of the particles in convection. The enhancement of diffusion can be quantitatively described well by the rotation frequency in a roll, the width of the roll, and the hopping probability to the neighbor rolls.

Acoustic actuation of in situ fabricated artificial cilia

NASA Astrophysics Data System (ADS)

Orbay, Sinem; Ozcelik, Adem; Bachman, Hunter; Huang, Tony Jun

2018-02-01

We present on-chip acoustic actuation of in situ fabricated artificial cilia. Arrays of cilia structures are UV polymerized inside a microfluidic channel using a photocurable polyethylene glycol (PEG) polymer solution and photomasks. During polymerization, cilia structures are attached to a silane treated glass surface inside the microchannel. Then, the cilia structures are actuated using acoustic vibrations at 4.6 kHz generated by piezo transducers. As a demonstration of a practical application, DI water and fluorescein dye solutions are mixed inside a microfluidic channel. Using pulses of acoustic excitations, and locally fabricated cilia structures within a certain region of the microchannel, a waveform of mixing behavior is obtained. This result illustrates one potential application wherein researchers can achieve spatiotemporal control of biological microenvironments in cell stimulation studies. These acoustically actuated, in situ fabricated, cilia structures can be used in many on-chip applications in biological, chemical and engineering studies.

Production development of organic nonflammable spacecraft potting, encapsulating and conformal coating compounds. Volume 1: Discussion, figures, and references

NASA Technical Reports Server (NTRS)

Lieberman, S. L.

1974-01-01

Based upon extensive contacts with vendors, a broad array of non-flammable polymeric specie, and additives generally noted to have flame retarding properties, were considered. The following polymeric matrices were examined: modified silicone and fluorosilicone RTV's polyesters, epoxies, urethanes, and epoxy-urethanes. Optimization of formulations to obtain a suitable balance between the various properties and flammability resistance led to the final selection of a silicone RTV/additive-loaded compound which meets almost all program requirements. The very low valued properties found are within a realistic level of design toleration. Complete formulation, processing, and test data is provided for this compound, EPOCAST 87517-A/B, and the other formulations prepared by the project. Details of those test methods are presented along with procedures utilized in the program. In addition, a description of the special flammability facility previously designed and then modified for this program is also presented.

Simple design for DNA nanotubes from a minimal set of unmodified strands: rapid, room-temperature assembly and readily tunable structure.

PubMed

Hamblin, Graham D; Hariri, Amani A; Carneiro, Karina M M; Lau, Kai L; Cosa, Gonzalo; Sleiman, Hanadi F

2013-04-23

DNA nanotubes have great potential as nanoscale scaffolds for the organization of materials and the templation of nanowires and as drug delivery vehicles. Current methods for making DNA nanotubes either rely on a tile-based step-growth polymerization mechanism or use a large number of component strands and long annealing times. Step-growth polymerization gives little control over length, is sensitive to stoichiometry, and is slow to generate long products. Here, we present a design strategy for DNA nanotubes that uses an alternative, more controlled growth mechanism, while using just five unmodified component strands and a long enzymatically produced backbone. These tubes form rapidly at room temperature and have numerous, orthogonal sites available for the programmable incorporation of arrays of cargo along their length. As a proof-of-concept, cyanine dyes were organized into two distinct patterns by inclusion into these DNA nanotubes.

Silicon crystallization in nanodot arrays organized by block copolymer lithography

NASA Astrophysics Data System (ADS)

Perego, Michele; Andreozzi, Andrea; Seguini, Gabriele; Schamm-Chardon, Sylvie; Castro, Celia; BenAssayag, Gerard

2014-12-01

Asymmetric polystyrene- b-polymethylmethacrylate (PS- b-PMMA) block copolymers are used to fabricate nanoporous PS templates with different pore diameter depending on the specific substrate neutralization protocol. The resulting polymeric templates are used as masks for the subsequent deposition of a thin ( h = 5 nm) amorphous Si layer by electron beam evaporation. After removal of the polymeric film and of the silicon excess, well-defined hexagonally packed amorphous Si nanodots are formed on the substrate. Their average diameter ( d < 20 nm), density (1.2 × 1011 cm-2), and lateral distribution closely mimic the original nanoporous template. Upon capping with SiO2 and high temperature annealing (1050 °C, N2), each amorphous Si nanodot rearranges in agglomerates of Si nanocrystals ( d < 4 nm). The average diameter and shape of these Si nanocrystals strongly depend on the size of the initial Si nanodot.

Interaction between a recombinant prion protein and organo-mineral complexes as evidenced by CPMAS 13C-NMR

NASA Astrophysics Data System (ADS)

Russo, F.; Scotti, R.; Gianfreda, L.; Conte, P.; Rao, M. A.

2009-04-01

Prion proteins (PrP) are the main responsible for Transmissible Spongiform Encephalopathies (TSE). The TSE etiological agent is a misfolded form of the normal cellular prion protein. The amyloidal aggregates accumulated in the brain of infected animals and mainly composed of PrPSc exhibit resistance to protease attack and many conventional inactivating procedures. The prion protein diseases cause an environmental issue because the environment and in particular the soil compartment can be contaminated and then become a potential reservoir and diffuser of TSEs infectivity as a consequence of (i) accidental dispersion from storage plants of meat and bone meal, (ii) incorporation of contaminated material in fertilizers, (iii) possible natural contamination of pasture soils by grazing herds, and (v) burial of carcasses. The environmental problem can be even more relevant because very low amounts of PrPSc are able to propagate the disease. Several studies evidenced that infectious prion protein remains active in soils for years. Contaminated soils result, thus, a possible critical route of TSE transmission in wild animals. Soil can also protect prion protein toward degradation processes due to the presence of humic substances and inorganic components such as clays. Mineral and organic colloids and the more common association between clay minerals and humic substances can contribute to the adsorption/entrapment of molecules and macromolecules. The polymerization of organic monomeric humic precursors occurring in soil in the presence of oxidative enzymes or manganese and iron oxides, is considered one of the most important processes contributing to the formation of humic substances. The process is very fast and produces a population of polymeric products of different molecular structures, sizes, shapes and complexity. Other molecules and possibly biomacromolecules such as proteins may be involved. The aim of the present work was to study by CPMAS 13C-NMR the interactions between a non pathogenic ovine recombinant prion protein and a model soil system represented by a manganese oxide in the form of birnessite (δ-MnO2), coated with a polymerized catechol. To better understand the effect of the polymerization process, PrP was added to the birnessite-cathecol system either before or after the polymerization processes. The NMR spectra of the prion protein interacting directly with birnessite revealed disappearance of the signals due to the paramagnetic nature of manganese oxide or abiotic degradation. Conversely, the signal pattern of the protein re-appeared as it is mixed to the soil-like system either during or after the catechol polymerization process. Results suggested that the possible interactions of the prion protein on soil systems can be mediated by natural organic matter. However, deeper studies on more complex real soil systems are needed to definitely confirm such hypothesis.

Polymeric Nanoelectrodes for Investigating Cellular Adhesion

NASA Astrophysics Data System (ADS)

Thapa, Prem; Paneru, Govind; Flanders, Bret

2011-03-01

Polyethylene dioxythiophene nano-filaments were grown on lithographic electrode arrays by the recently developed directed electrochemical nanowire assembly technique. These filaments are firmly attached to the electrode but are not attached to the glass substrate. Hence, they behave like cantilevered rods (with one free end). Individual cells of the slime mold Dictystolium discoideum initiate contact by extending pseudopods to the nanoelectrodes when cultured on the electrode arrays. Scanning electron micrographs of the interfaces show the contact area to be of the order of 0.1 μ m 2 . Confocal images reveal the focal adhesions in the cell-electrode contact region. Deflection of the nanoelectrode by an individual cell can be used to measure the force exerted by the cell. Recent results on this innovative force sensing approach will be discussed. NSF.

Printed freeform lens arrays on multi-core fibers for highly efficient coupling in astrophotonic systems.

PubMed

Dietrich, Philipp-Immanuel; Harris, Robert J; Blaicher, Matthias; Corrigan, Mark K; Morris, Tim M; Freude, Wolfgang; Quirrenbach, Andreas; Koos, Christian

2017-07-24

Coupling of light into multi-core fibers (MCF) for spatially resolved spectroscopy is of great importance to astronomical instrumentation. To achieve high coupling efficiencies along with fill-fractions close to unity, micro-optical elements are required to concentrate the incoming light to the individual cores of the MCF. In this paper we demonstrate facet-attached lens arrays (LA) fabricated by two-photon polymerization. The LA provide close to 100% fill-fraction along with efficiencies of up to 73% (down to 1.4 dB loss) for coupling of light from free space into an MCF core. We show the viability of the concept for astrophotonic applications by integrating an MCF-LA assembly in an adaptive-optics test bed and by assessing its performance as a tip/tilt sensor.

Wafer-Scale Integration of Inverted Nanopyramid Arrays for Advanced Light Trapping in Crystalline Silicon Thin Film Solar Cells.

PubMed

Zhou, Suqiong; Yang, Zhenhai; Gao, Pingqi; Li, Xiaofeng; Yang, Xi; Wang, Dan; He, Jian; Ying, Zhiqin; Ye, Jichun

2016-12-01

Crystalline silicon thin film (c-Si TF) solar cells with an active layer thickness of a few micrometers may provide a viable pathway for further sustainable development of photovoltaic technology, because of its potentials in cost reduction and high efficiency. However, the performance of such cells is largely constrained by the deteriorated light absorption of the ultrathin photoactive material. Here, we report an efficient light-trapping strategy in c-Si TFs (~20 μm in thickness) that utilizes two-dimensional (2D) arrays of inverted nanopyramid (INP) as surface texturing. Three types of INP arrays with typical periodicities of 300, 670, and 1400 nm, either on front, rear, or both surfaces of the c-Si TFs, are fabricated by scalable colloidal lithography and anisotropic wet etch technique. With the extra aid of antireflection coating, the sufficient optical absorption of 20-μm-thick c-Si with a double-sided 1400-nm INP arrays yields a photocurrent density of 39.86 mA/cm(2), which is about 76 % higher than the flat counterpart (22.63 mA/cm(2)) and is only 3 % lower than the value of Lambertian limit (41.10 mA/cm(2)). The novel surface texturing scheme with 2D INP arrays has the advantages of excellent antireflection and light-trapping capabilities, an inherent low parasitic surface area, a negligible surface damage, and a good compatibility for subsequent process steps, making it a good alternative for high-performance c-Si TF solar cells.