Birth, Death and Transfiguration; The Synthesis of Preceramic Polymers, Their Pyrolysis and Their Conversion to Ceramics (Preprint)

DTIC Science & Technology

1989-05-31

have been able to prepare preceramic polymers whose pyrolysis gives -99% SiC , -99.5% Si 3N 4 , or any mixture of the two by appropriate manipulation of...SYNTHESIS OF PRECERAMIC POLYMERS , THEIR PYROLYSIS AND THEIR CONVERSION TO CERAMICS by Dietmar Seyferth ELCTE D MAY 1 9 989 EEl To be published MAY U...CLASSIFICATION OF THIS PAGE All other editions are obsolete. BIRTH, DEATH AND TRANSFIGURATION: THE SYNTHESIS OF PRECERAMIC POLYMERS , THEIR PYROLYSIS

Silicon-based Porous Ceramics via Freeze Casting of Preceramic Polymers

NASA Astrophysics Data System (ADS)

Naviroj, Maninpat

Freeze casting is a technique for processing porous materials that has drawn significant attention for its effectiveness in producing a variety of tailorable pore structures for ceramics, metals, and polymers. With freeze casting, pores are generated based on a solidification process where ice crystals act as a sacrificial template which can eventually be sublimated to create pores. While the majority of freeze-casting studies have been performed using conventional ceramic suspensions, this work explores an alternative processing route by freeze casting with preceramic polymer solutions. Significant differences exist between freeze casting of a particulate suspension and a polymeric solution. These changes affect the processing method, solidification behavior, and pore structure, thereby introducing new challenges and possibilities for the freeze-casting technique. The first part of this study explored the processing requirements involved with freeze casting of preceramic polymers, along with methods to control the resulting pore structure. Solvent choice, freezing front velocity, and polymer concentration were used as processing variables to manipulate the pore structures. A total of seven organic solvents were freeze cast with a polymethylsiloxane preceramic polymer to produce ceramics with isotropic, dendritic, prismatic, and lamellar pore morphologies. Changes in freezing front velocity and polymer concentration were shown to influence pore size, shape, and connectivity. Differences between suspension- and solution-based samples freeze cast under equivalent conditions were also investigated. Certain solidification microstructures were strongly affected by the presence of suspended particles, creating differences between pore structures generated from the same solvents. Additionally, processing of solution-based samples were found to be the more facile technique. Compressive strength and water permeability of dendritic and lamellar structures were analyzed to determine functional differences between the pore structures. Results show that dendritic structures were up to 30 times stronger, while lamellar structures provided higher permeability constants. A change in freezing front velocity was shown to significantly affect permeability but not compressive strength. Finally, improved pore alignment along the freezing direction was achieved by controlling the nucleation and growth of solvent crystals through the use of a grain-selection template. Dendritic samples freeze cast with a template showed substantial increase in pore alignment, as determined by image analysis and permeability tests, with the permeability constant increasing by up to 6-fold when compared to a control sample.

Silicon Nitride Ceramic Fibers from Preceramic Polymers.

DTIC Science & Technology

1987-06-01

the preceramic fibers into high strength Si3 N and silicon carbide nitride (SiCN) fibers. In the past year, we have learned to prepare polysilazanes...INTHELOY, Given the Empirical Formula for a Material, It Should be Possible to Prepare a Chemical Analog CERAMC CHMIAL MONOMERIC UNIT MONOMERIC UNIT SI3 N4...e a d e nf u ible B y. POLYSILAZANE PRECURSORS TO Si3 Nj IN PRACTICE: It Is Difficult to Synthesize Even Simple, High Molecular Weight Preceramic

Methylhydridopolysilazane and its Pyrolytic Conversion to Si3N4/SiC Ceramics

DTIC Science & Technology

1993-04-20

development of inorganic and organometallic polymers as preceramic materials for the synthesis of silicon carbide ( SiC ) and silicon nitride (Si 3N 4...disproportionation in the pyrolysis of preceramic polymers . The lack of a -50 ppm resonance in the CP-MAS NMR spectra of the MHPS systems is 12...1992); Chem. Abstr. 1992, 116, 220226g. 6. (a) Semen, J.; Loop, J.G., "A Preceramic Polymer Route to Molded SiC Ceramic Parts," Ceram. Eng. Sci. Proc

A Study of the Critical Factors Controlling the Synthesis of Ceramic Matrix Composites from Preceramic Polymers

DTIC Science & Technology

1990-12-15

THE SYNTHESIS OF CERAMIC MATRIX COMPOSITES PE - 61102F FROM PRECERAMIC POLYMERS PR -9999 6. AUTHOR(S) TA - 99 J. R. Strife(l), J. P. Wesson(1 ), and H...stability at temperatures up to 15000 C. 14. SUBJECT TERMS 15. NUMBER OF PAGES 49 C- SiC composites vinylmethylsilane 16. PRICE CODE polymer precursor...vapor infiltration of fibrous preforms. More recently, the conversion of preceramic polymers as a matrix synthesis process is being considered. This

Ceramic impregnated superabrasives

DOEpatents

Radtke, Robert P.; Sherman, Andrew

2009-02-10

A superabrasive fracture resistant compact is formed by depositing successive layers of ceramic throughout the network of open pores in a thermally stable self-bonded polycrystalline diamond or cubic boron nitride preform. The void volume in the preform is from approximately 2 to 10 percent of the volume of the preform, and the average pore size is below approximately 3000 nanometers. The preform is evacuated and infiltrated under at least about 1500 pounds per square inch pressure with a liquid pre-ceramic polymerizable precursor. The precursor is infiltrated into the preform at or below the boiling point of the precursor. The precursor is polymerized into a solid phase material. The excess is removed from the outside of the preform, and the polymer is pyrolized to form a ceramic. The process is repeated at least once more so as to achieve upwards of 90 percent filling of the original void volume. When the remaining void volume drops below about 1 percent the physical properties of the compact, such as fracture resistance, improve substantially. Multiple infiltration cycles result in the deposition of sufficient ceramic to reduce the void volume to below 0.5 percent. The fracture resistance of the compacts in which the pores are lined with formed in situ ceramic is generally at least one and one-half times that of the starting preforms.

Ceramic electrical insulation for electrical coils, transformers, and magnets

DOEpatents

Rice, John A.; Hazelton, Craig S.; Fabian, Paul E.

2002-01-01

A high temperature electrical insulation is described, which is suitable for electrical windings for any number of applications. The inventive insulation comprises a cured preceramic polymer resin, which is preferably a polysiloxane resin. A method for insulating electrical windings, which are intended for use in high temperature environments, such as superconductors and the like, advantageously comprises the steps of, first, applying a preceramic polymer layer to a conductor core, to function as an insulation layer, and second, curing the preceramic polymer layer. The conductor core preferably comprises a metallic wire, which may be wound into a coil. In the preferred method, the applying step comprises a step of wrapping the conductor core with a sleeve or tape of glass or ceramic fabric which has been impregnated by a preceramic polymer resin. The inventive insulation system allows conducting coils and magnets to be fabricated using existing processing equipment, and maximizes the mechanical and thermal performance at both elevated and cryogenic temperatures. It also permits co-processing of the wire and the insulation to increase production efficiencies and reduce overall costs, while still remarkably enhancing performance.

Production of continuous mullite fiber via sol-gel processing

NASA Technical Reports Server (NTRS)

Tucker, Dennis S.; Sparks, J. Scott; Esker, David C.

1990-01-01

The development of a continuous ceramic fiber which could be used in rocket engine and rocket boosters applications was investigated at the Marshall Space Flight Center. Methods of ceramic fiber production such as melt spinning, chemical vapor deposition, and precursor polymeric fiber decomposition are discussed and compared with sol-gel processing. The production of ceramics via the sol-gel method consists of two steps, hydrolysis and polycondensation, to form the preceramic, followed by consolidation into the glass or ceramic structure. The advantages of the sol-gel method include better homogeneity and purity, lower preparation temperature, and the ability to form unique compositions. The disadvantages are the high cost of raw materials, large shrinkage during drying and firing which can lead to cracks, and long processing times. Preparation procedures for aluminosilicate sol-gel and for continuous mullite fibers are described.

Repair of oxidation protection coatings on carbon-carbon using preceramic polymers

NASA Technical Reports Server (NTRS)

Schwab, Stuart T.; Graef, Renee C.

1991-01-01

The paper describes a field-applicable technique for the repair of damage to SiC protective coatings on carbon/carbon composites, using commercial preceramic polymers, such as perhydropolysilazane developed by the Southwest Research Institute and several commercial polymers (NICALON, PS110, PS116, PS117, NCP-200, and PHPS were tested). After being applied on the damaged panel and oxidized at 1400 C, these polymers form either SiC or Si3N4 (or a mixture of both). It was found that impact damaged carbon/carbon specimens repaired with perhydropolysilazane exhibit substantial oxidation resistance. Many of the other tested preceramic polymer were found to be unsuitable for the purpose of repair due to either low ceramic yield, foaming, or intumescence.

Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom

DOEpatents

Kanatzidis, Mercouri G; Katsoulidis, Alexandros

2015-03-10

Porous polymeric networks and composite materials comprising metal nanoparticles distributed in the polymeric networks are provided. Also provided are methods for using the polymeric networks and the composite materials in liquid- and vapor-phase waste remediation applications. The porous polymeric networks, are highly porous, three-dimensional structures characterized by high surface areas. The polymeric networks comprise polymers polymerized from aldehydes and phenolic molecules.

Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom

DOEpatents

Kanatzidis, Mercouri G.; Katsoulidis, Alexandros

2016-10-18

Porous polymeric networks and composite materials comprising metal nanoparticles distributed in the polymeric networks are provided. Also provided are methods for using the polymeric networks and the composite materials in liquid- and vapor-phase waste remediation applications. The porous polymeric networks, are highly porous, three-dimensional structures characterized by high surface areas. The polymeric networks comprise polymers polymerized from aldehydes and phenolic molecules.

Curing preceramic polymers by exposure to nitrogen dioxide

NASA Technical Reports Server (NTRS)

Rabe, James A. (Inventor); Lipowitz, Jonathan (Inventor); Lu, Paul P. (Inventor)

1991-01-01

A rapid method of infusibilizing (curing) preceramic polymers comprising treatment said polymers with gaseous nitrogen dioxide. The infusibilized polymers may be pyrolyzed to temperatures in excess of about 800.degree. C. to yield ceramic materials with low oxygen content and, thus, good thermal stability. The methods are especially useful for the production of ceramic fibers and, more specifically, to the on-line production of ceramic fibers.

Innovative Processing of Composites for Ultra-High Temperature Applications. Book 3

DTIC Science & Technology

1993-11-01

SiC Samples Prepared with Four Preceramic Polymer Infiltration / Pyrolysis (at 15750C) Cycles Figure 21 Scanning Electron...Micrograph of Large Pores near the Surface of Siliconized SIC Sample with Four Preceramic Polymer Infiltration / Pyrolysis (at 1575*C) Cycles II...In order to achieve dense, bulk composites with maximum SiC /Si ratio, two infiltration / pyrolysis cycles were used. S (4) After siliconization,

Laboratory for the Processing and Evaluation of Inorganic Matrix Composites

DTIC Science & Technology

1989-06-01

preceramic polymers .’ Ceramic data (yield and elemental composition ) for the pyrolysis ... polymer matrix composites can feature apparent fracture energies as high as those of unreinforced metals (Ashby and Jones 1980). I I Fig. 1 SiC VLS...materials has pyrolysis of shaped bodies of such " preceramic " polymers . received much attention in recent years.’ This procedure The issues that are

Re-evaluating the resource potential of lomas fog oasis environments for Preceramic hunter-gatherers under past ENSO modes on the south coast of Peru

NASA Astrophysics Data System (ADS)

Beresford-Jones, David; Pullen, Alexander G.; Whaley, Oliver Q.; Moat, Justin; Chauca, George; Cadwallader, Lauren; Arce, Susana; Orellana, Alfonso; Alarcón, Carmela; Gorriti, Manuel; Maita, Patricia K.; Sturt, Fraser; Dupeyron, Agathe; Huaman, Oliver; Lane, Kevin J.; French, Charles

2015-12-01

Lomas - ephemeral seasonal oases sustained by ocean fogs - were critical to ancient human ecology on the desert Pacific coast of Peru: one of humanity's few independent hearths of agriculture and "pristine" civilisation. The role of climate change since the Late Pleistocene in determining productivity and extent of past lomas ecosystems has been much debated. Here we reassess the resource potential of the poorly studied lomas of the south coast of Peru during the long Middle Pre-ceramic period (c. 8000-4500 BP): a period critical in the transition to agriculture, the onset of modern El Niño Southern Oscillation ('ENSO') conditions, and eustatic sea-level rise and stabilisation and beach progradation. Our method combines vegetation survey and herbarium collection with archaeological survey and excavation to make inferences about both Preceramic hunter-gatherer ecology and the changed palaeoenvironments in which it took place. Our analysis of newly discovered archaeological sites - and their resource context - show how lomas formations defined human ecology until the end of the Middle Preceramic Period, thereby corroborating recent reconstructions of ENSO history based on other data. Together, these suggest that a five millennia period of significantly colder seas on the south coast induced conditions of abundance and seasonal predictability in lomas and maritime ecosystems, that enabled Middle Preceramic hunter-gatherers to reduce mobility by settling in strategic locations at the confluence of multiple eco-zones at the river estuaries. Here the foundations of agriculture lay in a Broad Spectrum Revolution that unfolded, not through population pressure in deteriorating environments, but rather as an outcome of resource abundance.

Optimization and Characterization of Preceramic Inks for Direct Ink Writing of Ceramic Matrix Composite Structures

PubMed Central

Maden, Halide Selin; Wahl, Larissa; Baliello, Andrea

2018-01-01

In a previous work, an ink based on a preceramic polymer, SiC fillers, and chopped carbon fibers was proposed for the production of Ceramic Matrix Composite (CMC) structures by Direct Ink Writing (DIW) and subsequent pyrolysis. Thanks to the shear stresses generated at the nozzle tip during extrusion, carbon fibers can be aligned along the printing direction. Fumed silica was added to the ink in order to enhance its rheological properties; however, the printed structures still showed some deformation in the Z direction. In this work, a second ink was successfully developed to limit deformation and at the same time avoid the addition of fumed silica, which limited the potential temperature of application of the composites. Instead, the positive role of the preceramic polymer on the ink rheology was exploited by increasing its concentration in the ink. Rheological characterization carried out on both inks confirmed that they possessed Bingham shear thinning behavior and fast viscosity recovery. Single filaments with different diameters (~310 µm and ~460 µm) were produced with the latter ink by DIW and subsequent pyrolysis. Tested under a four-point flexural test, the filaments showed a mean flexural strength above 30 MPa, graceful failure, and fiber pull-out. The results of this work suggest that CMC components can effectively be fabricated via DIW of a preceramic ink with embedded short fibers; the preceramic polymer is able to provide the desired rheology for the process and to develop a dense matrix capable of incorporating both fibers and ceramic particles, whereas the fibers addition contributes to an increase of the fracture toughness of the material and to the development of a graceful failure mode. PMID:29597310

Optimization and Characterization of Preceramic Inks for Direct Ink Writing of Ceramic Matrix Composite Structures.

PubMed

Franchin, Giorgia; Maden, Halide Selin; Wahl, Larissa; Baliello, Andrea; Pasetto, Marco; Colombo, Paolo

2018-03-28

In a previous work, an ink based on a preceramic polymer, SiC fillers, and chopped carbon fibers was proposed for the production of Ceramic Matrix Composite (CMC) structures by Direct Ink Writing (DIW) and subsequent pyrolysis. Thanks to the shear stresses generated at the nozzle tip during extrusion, carbon fibers can be aligned along the printing direction. Fumed silica was added to the ink in order to enhance its rheological properties; however, the printed structures still showed some deformation in the Z direction. In this work, a second ink was successfully developed to limit deformation and at the same time avoid the addition of fumed silica, which limited the potential temperature of application of the composites. Instead, the positive role of the preceramic polymer on the ink rheology was exploited by increasing its concentration in the ink. Rheological characterization carried out on both inks confirmed that they possessed Bingham shear thinning behavior and fast viscosity recovery. Single filaments with different diameters (~310 µm and ~460 µm) were produced with the latter ink by DIW and subsequent pyrolysis. Tested under a four-point flexural test, the filaments showed a mean flexural strength above 30 MPa, graceful failure, and fiber pull-out. The results of this work suggest that CMC components can effectively be fabricated via DIW of a preceramic ink with embedded short fibers; the preceramic polymer is able to provide the desired rheology for the process and to develop a dense matrix capable of incorporating both fibers and ceramic particles, whereas the fibers addition contributes to an increase of the fracture toughness of the material and to the development of a graceful failure mode.

Organosilicon Polymers as Precursors for Silicon-Containing Ceramics.

DTIC Science & Technology

1987-02-23

preceramic polymer , shrinkage on pyrolysis could be considerable. Ceramic fibers of diverse chemical compositions are sought for...In the design of preceramic polymers , achievement of the desired elemental composition in the ceramic obtained from them ( SiC and Si3N4 in the...approximately one, pyrolysis of the product polymer gave a black ceramic solid in 84% yield which analysis showed to have a composition (1 SiC + 0.22

Morphologies, Processing and Properties of Ceramic Foams from Pre-Ceramic Foams from Pre-Ceramic Polymer Routes

NASA Technical Reports Server (NTRS)

Stackpoole, Mairead; Simoes, Conan R.; Venkatapathy, Ethiras (Technical Monitor)

2002-01-01

The current research is focused on processing ceramic foams that have potential as a thermal protection material. Ceramic foams with different architectures were formed from the pyrolysis of pre-ceramic polymers at 1200 C in different atmospheres. In some systems a sacrificial polyurethane was used as the blowing agent. We have also processed foams using sacrificial fillers to introduce controlled cell sizes. Each sacrificial filler or blowing agent leads to a unique morphology. The effect of different fillers on foam morphologies will be presented. The presentation will also focus on characterization of these foams in terms of mechanical and thermal properties. Foams processed using these approaches having bulk densities ranging from 0.15 to 0.9 g per cubic centimeter and a cell sizes from 5 to 500 micrometers. Compression strengths ranged from 2 to 7 MPa for these materials.

Using graphene networks to build bioinspired self-monitoring ceramics

PubMed Central

Picot, Olivier T.; Rocha, Victoria G.; Ferraro, Claudio; Ni, Na; D'Elia, Eleonora; Meille, Sylvain; Chevalier, Jerome; Saunders, Theo; Peijs, Ton; Reece, Mike J.; Saiz, Eduardo

2017-01-01

The properties of graphene open new opportunities for the fabrication of composites exhibiting unique structural and functional capabilities. However, to achieve this goal we should build materials with carefully designed architectures. Here, we describe the fabrication of ceramic-graphene composites by combining graphene foams with pre-ceramic polymers and spark plasma sintering. The result is a material containing an interconnected, microscopic network of very thin (20–30 nm), electrically conductive, carbon interfaces. This network generates electrical conductivities up to two orders of magnitude higher than those of other ceramics with similar graphene or carbon nanotube contents and can be used to monitor ‘in situ' structural integrity. In addition, it directs crack propagation, promoting stable crack growth and increasing the fracture resistance by an order of magnitude. These results demonstrate that the rational integration of nanomaterials could be a fruitful path towards building composites combining unique mechanical and functional performances. PMID:28181518

Dating Caral, a preceramic site in the Supe Valley on the central coast of Peru.

PubMed

Solis, R S; Haas, J; Creamer, W

2001-04-27

Radiocarbon dates from the site of Caral in the Supe Valley of Peru indicate that monumental corporate architecture, urban settlement, and irrigation agriculture began in the Americas by 4090 years before the present (2627 calibrated years B.C.) to 3640 years before the present (1977 calibrated years B.C.). Caral is located 23 kilometers inland from the Pacific coast and contains a central zone of monumental, residential, and nonresidential architecture covering an area of 65 hectares. Caral is one of 18 large preceramic sites in the Supe Valley.

Gourd and squash artifacts yield starch grains of feasting foods from preceramic Peru

PubMed Central

Duncan, Neil A.; Pearsall, Deborah M.; Benfer, Robert A.

2009-01-01

In a study of residues from gourd and squash artifacts, we recovered starch grains from manioc (Manihot esculenta), potato (Solanum sp.), chili pepper (Capsicum spp.), arrowroot (Maranta arundinacea), and algarrobo (Prosopis sp.) from feasting contexts at the Buena Vista site, a central Peruvian preceramic site dating to ≈2200 calendar years B.C. This study has implications for the study of plant food use wherever gourds or squashes are preserved, documents the earliest evidence for the consumption of algarrobo and arrowroot in Peru, and provides insights into foods consumed at feasts. PMID:19633184

Boron Nitride Obtained from Molecular Precursors: Aminoboranes Used as a BN Source for Coatings, Matrix, and Si 3N 4-BN Composite Ceramic Preparation

NASA Astrophysics Data System (ADS)

Thévenot, F.; Doche, C.; Mongeot, H.; Guilhon, F.; Miele, P.; Cornu, D.; Bonnetot, B.

1997-10-01

Aminoboranes, pure or partially converted into aminoborazines using thermal or aminolysis polymerization, have been used as boron nitride precursors. An amorphous BN preceramic is obtained when pyrolysed up to 1000°C that can be stabilized using further annealing up to 1400°C or crystallized into h-BN above 1700°C. These molecular precursors have been used to prepare carbon fiber/BN matrix microcomposites to get an efficient BN coating on graphite and as a BN source in Si3N4/BN composite ceramic. The properties of these new types of samples have been compared with those obtained by classical processes. The boron nitride obtained from these precursors is a good sintering agent during the hot-pressing of the samples. However, the crystallinity of BN, even sintered up to 1800°C, remains poor. In fact, most of the mechanical properties of the composite ceramic (density, porosity, hardness) are clearly improved and the aminoboranes can be considered as convenient boron nitride sources and helpful sintering agents in hot-pressing technology.

Autocatalytic polymerization generates persistent random walk of crawling cells.

PubMed

Sambeth, R; Baumgaertner, A

2001-05-28

The autocatalytic polymerization kinetics of the cytoskeletal actin network provides the basic mechanism for a persistent random walk of a crawling cell. It is shown that network remodeling by branching processes near the cell membrane is essential for the bimodal spatial stability of the network which induces a spontaneous breaking of isotropic cell motion. Details of the phenomena are analyzed using a simple polymerization model studied by analytical and simulation methods.

Polymeric Ionic Networks with High Charge Density: Solid-like Electrolytes in Lithium Metal Batteries

DOE PAGES

Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; ...

2015-11-02

Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10 -3 S cm -1 at 22 °C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.

SOM neural network fault diagnosis method of polymerization kettle equipment optimized by improved PSO algorithm.

PubMed

Wang, Jie-sheng; Li, Shu-xia; Gao, Jie

2014-01-01

For meeting the real-time fault diagnosis and the optimization monitoring requirements of the polymerization kettle in the polyvinyl chloride resin (PVC) production process, a fault diagnosis strategy based on the self-organizing map (SOM) neural network is proposed. Firstly, a mapping between the polymerization process data and the fault pattern is established by analyzing the production technology of polymerization kettle equipment. The particle swarm optimization (PSO) algorithm with a new dynamical adjustment method of inertial weights is adopted to optimize the structural parameters of SOM neural network. The fault pattern classification of the polymerization kettle equipment is to realize the nonlinear mapping from symptom set to fault set according to the given symptom set. Finally, the simulation experiments of fault diagnosis are conducted by combining with the industrial on-site historical data of the polymerization kettle and the simulation results show that the proposed PSO-SOM fault diagnosis strategy is effective.

Ceramic fibers for matrix composites in high-temperature engine applications

PubMed

Baldus; Jansen; Sporn

1999-07-30

High-temperature engine applications have been limited by the performance of metal alloys and carbide fiber composites at elevated temperatures. Random inorganic networks composed of silicon, boron, nitrogen, and carbon represent a novel class of ceramics with outstanding durability at elevated temperatures. SiBN(3)C was synthesized by pyrolysis of a preceramic N-methylpolyborosilazane made from the single-source precursor Cl(3)Si-NH-BCl(2). The polymer can be processed to a green fiber by melt-spinning, which then undergoes an intermediate curing step and successive pyrolysis. The ceramic fibers, which are presently produced on a semitechnical scale, combine several desired properties relevant for an application in fiber-reinforced ceramic composites: thermal stability, mechanical strength, high-temperature creep resistivity, low density, and stability against oxidation or molten silicon.

Bioactive Wollastonite-Diopside Foams from Preceramic Polymers and Reactive Oxide Fillers

PubMed Central

Fiocco, Laura; Elsayed, Hamada; Ferroni, Letizia; Gardin, Chiara; Zavan, Barbara; Bernardo, Enrico

2015-01-01

Wollastonite (CaSiO3) and diopside (CaMgSi2O6) silicate ceramics have been widely investigated as highly bioactive materials, suitable for bone tissue engineering applications. In the present paper, highly porous glass-ceramic foams, with both wollastonite and diopside as crystal phases, were developed from the thermal treatment of silicone polymers filled with CaO and MgO precursors, in the form of micro-sized particles. The foaming was due to water release, at low temperature, in the polymeric matrix before ceramic conversion, mainly operated by hydrated sodium phosphate, used as a secondary filler. This additive proved to be “multifunctional”, since it additionally favored the phase development, by the formation of a liquid phase upon firing, in turn promoting the ionic interdiffusion. The liquid phase was promoted also by the incorporation of powders of a glass crystallizing itself in wollastonite and diopside, with significant improvements in both structural integrity and crushing strength. The biological characterization of polymer-derived wollastonite-diopside foams, to assess the bioactivity of the samples, was performed by means of a cell culture test. The MTT assay and LDH activity tests gave positive results in terms of cell viability.

Reactive processing and mechanical properties of polymer derived silicon nitride matrix composites and their use in coating and joining ceramics and ceramic matrix composites

NASA Astrophysics Data System (ADS)

Stackpoole, Margaret Mary

Use of preceramic polymers offers many advantages over conventional ceramic processing routes. Advantages include being able to plastically form the part, form a pyrolized ceramic material at lower temperatures and form high purity microstructures which are tailorable depending on property requirements. To date preceramic polymers are mostly utilized in the production of low dimensional products such as fibers since loss of volatiles during pyrolysis leads to porosity and large shrinkage (in excess of 30%). These problems have been partially solved by use of active fillers (e.g. Ti, Cr, B). The reactive filler converts to a ceramic material with a volume expansion and this increases the density and reduces shrinkage and porosity. The expansion of the reactive filler thus compensates for the polymer shrinkage if the appropriate volume fraction of filler is present in a reactive atmosphere (e.g. N2 or NH3). This approach has resulted in structural composites with limited success. The present research investigates the possibility of using filled preceramic polymers to form net shaped ceramic composite materials and to investigate the use of these unique composite materials to join and coat ceramics and ceramic composites. The initial research focused on phase and microstructural development of bulk composites from the filled polymer/ceramic systems. A processing technique was developed to insure consistency between different samples and the most promising filler/polymer choices for this application have been determined. The processing temperatures and atmospheres have also been optimized. The work covers processing and characterization of bulk composites, joints and coatings. With careful control of processing near net shape bulk composites were fabricated. Both ambient and high temperature strength and fracture toughness was obtained for these composite systems. The potential of using reactively filled preceramic polymers to process joints and coatings was also investigated. A critical thickness below which crack free joints/coatings could be processed was determined. Finally, mechanical properties of the joints and coatings at ambient and elevated temperatures (including oxidation studies) have been evaluated. The interfacial fracture behavior of the joints and coatings was also evaluated.

Covalently bonded networks through surface-confined polymerization

NASA Astrophysics Data System (ADS)

El Garah, Mohamed; MacLeod, Jennifer M.; Rosei, Federico

2013-07-01

The prospect of synthesizing ordered, covalently bonded structures directly on a surface has recently attracted considerable attention due to its fundamental interest and for potential applications in electronics and photonics. This prospective article focuses on efforts to synthesize and characterize epitaxial one- and two-dimensional (1D and 2D, respectively) polymeric networks on single crystal surfaces. Recent studies, mostly performed using scanning tunneling microscopy (STM), demonstrate the ability to induce polymerization based on Ullmann coupling, thermal dehalogenation and dehydration reactions. The 2D polymer networks synthesized to date have exhibited structural limitations and have been shown to form only small domains on the surface. We discuss different approaches to control 1D and 2D polymerization, with particular emphasis on the surface phenomena that are critical to the formation of larger ordered domains.

New polymeric precursors to SiNCB, BN, and La(3)Ni(2)B(2)N(3) materials

NASA Astrophysics Data System (ADS)

Wideman, Thomas W.

Boron-containing non-oxide ceramics demonstrate a number of important structural, electronic and physical properties. However, the lack of general synthetic routes to generate these materials with controlled composition, under moderate conditions, and in processed forms, has hampered both scientific studies and practical applications. The goal of the work described in this dissertation was to develop efficient new polymeric precursor routes to boron-containing materials including SiNCB ceramics composites, boron nitride fibers, and quaternary metal boro-nitride superconductors. Two types of polyborosilazane precursors to SiNCB ceramics were developed. Borazine-co-silazane copolymers were prepared through the thermal copolymerization of borazine with two silazanes, tris(trimethylsilylamino)silane, and 1,1,3,3,5,5 -hexamethylcyclotrisilazane. Polyborosilazanes with pendent boron-containing species were obtained by the modification of preformed hydridopolysilazane polymers with three monofunctional boranes: pinacolborane, 2,4-diethylborazine and 1,3-dimethyl-1,3-diaza-2-boracyclopentane. Pyrolyses of both types of polyborosilazanes produced SiNCB ceramics with controllable boron contents, enhanced thermal stabilities, and reduced crystallinity. Processible polymeric precursors to BN were also achieved by the chemical modification of polyborazylene, (Bsb3Nsb3Hsb{˜ 4}rbrack sb{x}, with diethylamine, dipentylamine, and hexamethyldisilazane. The modified polymers, unlike the parent polyborazylene, do not crosslink at low temperatures, and therefore proved to be ideal melt-spinnable precursors to BN ceramic fibers. A new polymeric precursor route to the recently discovered Lasb3Nisb2Bsb2Nsb3 superconductor (Tc = 12K) was developed by reacting lanthanum and nickel powders dispersed in the polyborazylene, to produce the intermetallic in excellent yields. The use of the polymer as a "reagent" provided a controllable, solid state source of nitrogen, and allows for the large scale syntheses of Lasb3Nisb2Bsb2Nsb3 and other quaternary metal boro-nitrides. Two new preparations of borazine, Bsb3Nsb3Hsb6, a key molecular unit in many of the polymers described above, have also been developed. Chemical investigations and practical applications of borazine-based preceramic polymers have been limited by the inefficient syntheses and high cost of borazine, which may now be prepared in 55-65% yields by the convenient, inexpensive the reaction of ammonium and borohydride salts, and the decomposition of ammonia borane, in high-boiling ether solutions.

Preceramic maize from Paredones and Huaca Prieta, Peru

PubMed Central

Grobman, Alexander; Bonavia, Duccio; Dillehay, Tom D.; Piperno, Dolores R.; Iriarte, José; Holst, Irene

2012-01-01

Maize (Zea mays ssp. mays) is among the world's most important and ancient domesticated crops. Although the chronology of its domestication and initial dispersals out of Mexico into Central and South America has become more clear due to molecular and multiproxy archaeobotanical research, important problems remain. Among them is the paucity of information on maize's early morphological evolution and racial diversification brought about in part by the poor preservation of macrofossils dating to the pre-5000 calibrated years before the present period from obligate dispersal routes located in the tropical forest. We report newly discovered macrobotanical and microbotanical remains of maize that shed significant light on the chronology, land race evolution, and cultural contexts associated with the crop's early movements into South America and adaptation to new environments. The evidence comes from the coastal Peruvian sites of Paredones and Huaca Prieta, Peru; dates from the middle and late preceramic and early ceramic periods (between ca. 6700 and 3000 calibrated years before the present); and constitutes some of the earliest known cobs, husks, stalks, and tassels. The macrobotanical record indicates that a diversity of racial complexes characteristic of the Andean region emerged during the preceramic era. In addition, accelerator mass spectrometry radiocarbon determinations carried out directly on different structures of preserved maize plants strongly suggest that assays on burned cobs are more reliable than those on unburned cobs. Our findings contribute to knowledge of the early diffusion of maize and agriculture and have broader implications for understanding the development of early preindustrial human societies. PMID:22307642

Preceramic maize from Paredones and Huaca Prieta, Peru.

PubMed

Grobman, Alexander; Bonavia, Duccio; Dillehay, Tom D; Piperno, Dolores R; Iriarte, José; Holst, Irene

2012-01-31

Maize (Zea mays ssp. mays) is among the world's most important and ancient domesticated crops. Although the chronology of its domestication and initial dispersals out of Mexico into Central and South America has become more clear due to molecular and multiproxy archaeobotanical research, important problems remain. Among them is the paucity of information on maize's early morphological evolution and racial diversification brought about in part by the poor preservation of macrofossils dating to the pre-5000 calibrated years before the present period from obligate dispersal routes located in the tropical forest. We report newly discovered macrobotanical and microbotanical remains of maize that shed significant light on the chronology, land race evolution, and cultural contexts associated with the crop's early movements into South America and adaptation to new environments. The evidence comes from the coastal Peruvian sites of Paredones and Huaca Prieta, Peru; dates from the middle and late preceramic and early ceramic periods (between ca. 6700 and 3000 calibrated years before the present); and constitutes some of the earliest known cobs, husks, stalks, and tassels. The macrobotanical record indicates that a diversity of racial complexes characteristic of the Andean region emerged during the preceramic era. In addition, accelerator mass spectrometry radiocarbon determinations carried out directly on different structures of preserved maize plants strongly suggest that assays on burned cobs are more reliable than those on unburned cobs. Our findings contribute to knowledge of the early diffusion of maize and agriculture and have broader implications for understanding the development of early preindustrial human societies.

Tailored synthesis of monodispersed nano/submicron porous silicon oxycarbide (SiOC) spheres with improved Li-storage performance as an anode material for Li-ion batteries

NASA Astrophysics Data System (ADS)

Shi, Huimin; Yuan, Anbao; Xu, Jiaqiang

2017-10-01

A spherical silicon oxycarbide (SiOC) material (monodispersed nano/submicron porous SiOC spheres) is successfully synthesized via a specially designed synthetic strategy involving pyrolysis of phenyltriethoxysilane derived pre-ceramic polymer spheres at 900 °C. In order to prevent sintering of the pre-ceramic polymer spheres upon heating, a given amount of hollow porous SiO2 nanobelts which are separately prepared from tetraethyl orthosilicate with CuO nanobelts as templates are introduced into the pre-ceramic polymer spheres before pyrolysis. This material is investigated as an anode for lithium-ion batteries in comparison with the large-size bulk SiOC material synthesized under the similar conditions but without hollow SiO2 nanobelts. The maximum reversible specific capacity of ca. 900 mAh g-1 is delivered at the current density of 100 mA g-1 and ca. 98% of the initial capacity is remained after 100 cycles at 100 mA g-1 for the SiOC spheres material, which are much superior to the bulk SiOC material. The improved lithium storage performance in terms of specific capacity and cyclability is attributed to its particular morphology of monodisperse nano/submicron porous spheres as well as its modified composition and microstructure. This SiOC material has higher Li-storage activity and better stability against volume expansion during repeated lithiation and delithiation cycling.

Stress reduction in phase-separated, cross-linked networks: influence of phase structure and kinetics of reaction

PubMed Central

Szczepanski, Caroline R.; Stansbury, Jeffrey W.

2014-01-01

A mechanism for polymerization shrinkage and stress reduction was developed for heterogeneous networks formed via ambient, photo-initiated polymerization-induced phase separation (PIPS). The material system used consists of a bulk homopolymer matrix of triethylene glycol dimethacrylate (TEGDMA) modified with one of three non-reactive, linear prepolymers (poly-methyl, ethyl and butyl methacrylate). At higher prepolymer loading levels (10–20 wt%) an enhanced reduction in both shrinkage and polymerization stress is observed. The onset of gelation in these materials is delayed to a higher degree of methacrylate conversion (~15–25%), providing more time for phase structure evolution by thermodynamically driven monomer diffusion between immiscible phases prior to network macro-gelation. The resulting phase structure was probed by introducing a fluorescently tagged prepolymer into the matrix. The phase structure evolves from a dispersion of prepolymer at low loading levels to a fully co-continuous heterogeneous network at higher loadings. The bulk modulus in phase separated networks is equivalent or greater than that of poly(TEGDMA), despite a reduced polymerization rate and cross-link density in the prepolymer-rich domains. PMID:25418999

Boron-carbon-silicon polymers and the ceramic thereof

NASA Technical Reports Server (NTRS)

Riccitiello, Salvatore R. (Inventor); Hsu, Ming-Ta S. (Inventor); Chen, Timothy S. (Inventor)

1991-01-01

The present invention relates to a process for the production of an organoborosilicon preceramic polymer. The prepolymer is pyrolyzed to produce a ceramic article useful in high temperature (e.g., aerospace) or extreme environmental applications.

Self-assembled tunable networks of sticky colloidal particles

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

Demortiere, Arnaud; Snezhko, Oleksiy Alexey; Sapozhnikov, Maksim

Self-assembled tunable networks of microscopic polymer fibers ranging from wavy colloidal "fur" to highly interconnected networks are created from polymer systems and an applied electric field. The networks emerge via dynamic self-assembly in an alternating (ac) electric field from a non-aqueous suspension of "sticky" polymeric colloidal particles with a controlled degree of polymerization. The resulting architectures are tuned by the frequency and amplitude of the electric field and surface properties of the particles.

Mechanisms of leading edge protrusion in interstitial migration

PubMed Central

Wilson, Kerry; Lewalle, Alexandre; Fritzsche, Marco; Thorogate, Richard; Duke, Tom; Charras, Guillaume

2013-01-01

While the molecular and biophysical mechanisms underlying cell protrusion on two-dimensional substrates are well understood, our knowledge of the actin structures driving protrusion in three-dimensional environments is poor, despite relevance to inflammation, development and cancer. Here we report that, during chemotactic migration through microchannels with 5 μm × 5 μm cross-sections, HL60 neutrophil-like cells assemble an actin-rich slab filling the whole channel cross-section at their front. This leading edge comprises two distinct F-actin networks: an adherent network that polymerizes perpendicular to cell-wall interfaces and a ‘free’ network that grows from the free membrane at the cell front. Each network is polymerized by a distinct nucleator and, due to their geometrical arrangement, the networks interact mechanically. On the basis of our experimental data, we propose that, during interstitial migration, medial growth of the adherent network compresses the free network preventing its retrograde movement and enabling new polymerization to be converted into forward protrusion. PMID:24305616

Ceramic Nanocomposites from Tailor-Made Preceramic Polymers

PubMed Central

Mera, Gabriela; Gallei, Markus; Bernard, Samuel; Ionescu, Emanuel

2015-01-01

The present Review addresses current developments related to polymer-derived ceramic nanocomposites (PDC-NCs). Different classes of preceramic polymers are briefly introduced and their conversion into ceramic materials with adjustable phase compositions and microstructures is presented. Emphasis is set on discussing the intimate relationship between the chemistry and structural architecture of the precursor and the structural features and properties of the resulting ceramic nanocomposites. Various structural and functional properties of silicon-containing ceramic nanocomposites as well as different preparative strategies to achieve nano-scaled PDC-NC-based ordered structures are highlighted, based on selected ceramic nanocomposite systems. Furthermore, prospective applications of the PDC-NCs such as high-temperature stable materials for thermal protection systems, membranes for hot gas separation purposes, materials for heterogeneous catalysis, nano-confinement materials for hydrogen storage applications as well as anode materials for secondary ion batteries are introduced and discussed in detail. PMID:28347023

Organic microchemical performance of solvent resistant polycarbosilane based microreactor.

PubMed

Yoon, Tae-Ho; Jung, Sang-Hee; Kim, Dong-Pyo

2011-05-01

We report the successful fabrication of preceramic polymer allylhydridopolycarbosilane (AHPCS) derived microchannels with excellent organic solvent resistance and optical transparency via economic imprinting process, followed by UV and post thermal curing process at 160 degrees C for 3 h. The microchemical performance of the fabricated microreactors was evaluated by choosing two model micro chemical reactions under organic solvent conditions; syntheses of 2-aminothiazole in DMF and dimethylpyrazole in THF, and compared with glass-based microreactor having identical dimensions and batch system with analogy. It is clear that AHPCS derived microreactor showed excellent solvent resistance and chemical stability compare with glass derived microreactor made by high cost of photolithography and thermal bonding process. The novel preceramic polymer derived microreactors showed reliable mechanical and chemical stability and conversion yields compare with that of glass derived microreactors, which is very promising for developing an integrated microfluidics by adopting available microstructuring techniques of the polymers.

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

Redline, Erica Marie; Bolintineanu, Dan S.; Lane, J. Matthew

The aim of this study was to alter polymerization chemistry to improve network homogeneity in free-radical crosslinked systems. It was hypothesized that a reduction in heterogeneity of the network would lead to improved mechanical performance. Experiments and simulations were carried out to investigate the connection between polymerization chemistry, network structure and mechanical properties. Experiments were conducted on two different monomer systems - the first is a single monomer system, urethane dimethacrylate (UDMA), and the second is a two-monomer system consisting of bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) in a ratio of 70/30 BisGMA/TEGDMA by weight. Themore » methacrylate systems were crosslinked using traditional radical polymeriza- tion (TRP) with azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) as an initiator; TRP systems were used as the control. The monomers were also cross-linked using activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) as a type of controlled radical polymerization (CRP). FTIR and DSC were used to monitor reac- tion kinetics of the systems. The networks were analyzed using NMR, DSC, X-ray diffraction (XRD), atomic force microscopy (AFM), and small angle X-ray scattering (SAXS). These techniques were employed in an attempt to quantify differences between the traditional and controlled radical polymerizations. While a quantitative methodology for characterizing net- work morphology was not established, SAXS and AFM have shown some promising initial results. Additionally, differences in mechanical behavior were observed between traditional and controlled radical polymerized thermosets in the BisGMA/TEGDMA system but not in the UDMA materials; this finding may be the result of network ductility variations between the two materials. Coarse-grained molecular dynamics simulations employing a novel model of the CRP reaction were carried out for the UDMA system, with parameters calibrated based on fully atomistic simulations of the UDMA monomer in the liquid state. Detailed metrics based on network graph theoretical approaches were implemented to quantify the bond network topology resulting from simulations. For a broad range of polymerization parameters, no discernible differences were seen between TRP and CRP UDMA simulations at equal conversions, although clear differences exist as a function of conversion. Both findings are consistent with experiments. Despite a number of shortcomings, these models have demonstrated the potential of molecular simulations for studying network topology in these systems.« less

Nano Particle Control of Void Formation and Expansion in Polymeric and Composite Systems

DTIC Science & Technology

2009-05-01

ES) 8. PERFORMING ORGANIZATION REPORT NUMBER Glocal Network Corporation 3131 Western Avenue Ste M-526 Seattle, WA 98121...Scientific Research Arlington, VA 22203-1954 Principal Investigator Dr. James C. Seferis Polymeric Composites Laboratory GloCal Network...F.R.E.E.D.O.M., with the flexibility of a profit research and development organization, GloCal Network Corporation, with both entities doing business as the

Refining the Maritime Foundations of Andean Civilization: How Plant Fiber Technology Drove Social Complexity During the Preceramic Period.

PubMed

Beresford-Jones, David; Pullen, Alexander; Chauca, George; Cadwallader, Lauren; García, Maria; Salvatierra, Isabel; Whaley, Oliver; Vásquez, Víctor; Arce, Susana; Lane, Kevin; French, Charles

2018-01-01

Moseley's (1975) Maritime Foundations of Andean Civilization hypothesis challenges, in one of humanity's few pristine hearths of civilization, the axiom that agriculture is necessary for the rise of complex societies. We revisit that hypothesis by setting new findings from La Yerba II (7571-6674 Cal bp) and III (6485-5893 Cal bp), Río Ica estuary, alongside the wider archaeological record for the end of the Middle Preceramic Period on the Peruvian coast. The La Yerba record evinces increasing population, sedentism, and "Broad Spectrum Revolution" features, including early horticulture of Phaseolus and Canavalia beans. Yet unlike further north, these changes failed to presage the florescence of monumental civilization during the subsequent Late Preceramic Period. Instead, the south coast saw a profound "archaeological silence." These contrasting trajectories had little to do with any relative differences in marine resources, but rather to restrictions on the terrestrial resources that determined a society's capacity to intensify exploitation of those marine resources. We explain this apparent miscarriage of the Maritime Foundations of Andean Civilization (MFAC) hypothesis on the south coast of Peru by proposing more explicit links than hitherto, between the detailed technological aspects of marine exploitation using plant fibers to make fishing nets and the emergence of social complexity on the coast of Peru. Rather than because of any significant advantages in quality , it was the potential for increased quantities of production, inherent in the shift from gathered wild Asclepias bast fibers to cultivated cotton, that inadvertently precipitated revolutionary social change. Thereby refined, the MFAC hypothesis duly emerges more persuasive than ever.

Ullmann-type coupling of brominated tetrathienoanthracene on copper and silver

NASA Astrophysics Data System (ADS)

Gutzler, Rico; Cardenas, Luis; Lipton-Duffin, Josh; El Garah, Mohamed; Dinca, Laurentiu E.; Szakacs, Csaba E.; Fu, Chaoying; Gallagher, Mark; Vondráček, Martin; Rybachuk, Maksym; Perepichka, Dmitrii F.; Rosei, Federico

2014-02-01

We report the synthesis of extended two-dimensional organic networks on Cu(111), Ag(111), Cu(110), and Ag(110) from thiophene-based molecules. A combination of scanning tunnelling microscopy and X-ray photoemission spectroscopy yields insight into the reaction pathways from single molecules towards the formation of two-dimensional organometallic and polymeric structures via Ullmann reaction dehalogenation and C-C coupling. The thermal stability of the molecular networks is probed by annealing at elevated temperatures of up to 500 °C. On Cu(111) only organometallic structures are formed, while on Ag(111) both organometallic and covalent polymeric networks were found to coexist. The ratio between organometallic and covalent bonds could be controlled by means of the annealing temperature. The thiophene moieties start degrading at 200 °C on the copper surface, whereas on silver the degradation process becomes significant only at 400 °C. Our work reveals how the interplay of a specific surface type and temperature steers the formation of organometallic and polymeric networks and describes how these factors influence the structural integrity of two-dimensional organic networks.We report the synthesis of extended two-dimensional organic networks on Cu(111), Ag(111), Cu(110), and Ag(110) from thiophene-based molecules. A combination of scanning tunnelling microscopy and X-ray photoemission spectroscopy yields insight into the reaction pathways from single molecules towards the formation of two-dimensional organometallic and polymeric structures via Ullmann reaction dehalogenation and C-C coupling. The thermal stability of the molecular networks is probed by annealing at elevated temperatures of up to 500 °C. On Cu(111) only organometallic structures are formed, while on Ag(111) both organometallic and covalent polymeric networks were found to coexist. The ratio between organometallic and covalent bonds could be controlled by means of the annealing temperature. The thiophene moieties start degrading at 200 °C on the copper surface, whereas on silver the degradation process becomes significant only at 400 °C. Our work reveals how the interplay of a specific surface type and temperature steers the formation of organometallic and polymeric networks and describes how these factors influence the structural integrity of two-dimensional organic networks. Electronic supplementary information (ESI) available: Additional STM data and DFT results. See DOI: 10.1039/c3nr05710k

Step-Growth Polymerization.

ERIC Educational Resources Information Center

Stille, J. K.

1981-01-01

Following a comparison of chain-growth and step-growth polymerization, focuses on the latter process by describing requirements for high molecular weight, step-growth polymerization kinetics, synthesis and molecular weight distribution of some linear step-growth polymers, and three-dimensional network step-growth polymers. (JN)

A theory for fracture of polymeric gels

NASA Astrophysics Data System (ADS)

Mao, Yunwei; Anand, Lallit

2018-06-01

A polymeric gel is a cross-linked polymer network swollen with a solvent. If the concentration of the solvent or the deformation is increased to substantial levels, especially in the presence of flaws, then the gel may rupture. Although various theoretical aspects of coupling of fluid permeation with large deformation of polymeric gels are reasonably well-understood and modeled in the literature, the understanding and modeling of the effects of fluid diffusion on the damage and fracture of polymeric gels is still in its infancy. In this paper we formulate a thermodynamically-consistent theory for fracture of polymeric gels - a theory which accounts for the coupled effects of fluid diffusion, large deformations, damage, and also the gradient effects of damage. The particular constitutive equations for fracture of a gel proposed in our paper, contain two essential new ingredients: (i) Our constitutive equation for the change in free energy of a polymer network accounts for not only changes in the entropy, but also changes in the internal energy due the stretching of the Kuhn segments of the polymer chains in the network. (ii) The damage and failure of the polymer network is taken to occur by chain-scission, a process which is driven by the changes in the internal energy of the stretched polymer chains in the network, and not directly by changes in the configurational entropy of the polymer chains. The theory developed in this paper is numerically implemented in an open-source finite element code MOOSE, by writing our own application. Using this simulation capability we report on our study of the fracture of a polymeric gel, and some interesting phenomena which show the importance of the diffusion of the fluid on fracture response of the gel are highlighted.

Progress report

NASA Technical Reports Server (NTRS)

Abhiraman, A.; Collard, D.; Cardelino, B.; Bhatia, S.; Desai, P.; Harruna, I.; Khan, I.; Mariam, Y.; Mensah, T.; Mitchell, M.

1992-01-01

The NASA funding allowed Clark Atlanta University (CAU) to establish a High Performance Polymers And Ceramics (HiPPAC) Research Center. The HiPPAC Center is consolidating and expanding the existing polymer and ceramic research capabilities at CAU through the development of interdepartmental and interinstitutional research in: (1) polymer synthesis; (2) polymer characterization and properties; (3) polymer processing; (4) polymer-based ceramic synthesis; and (5) ceramic characterization and properties. This Center has developed strong interactions between scientists and materials scientists of CAU and their counterparts from sister institutions in the Atlanta University Center (AUC) and the Georgia Institute of Technology. As a component of the center, we have started to develop strong collaborations with scientists from other universities and the HBCU's, national and federal agency laboratories, and the private sector during this first year. During this first year we have refined the focus of the research in the HiPPAC Center to three areas with seven working groups that will start programmatic activities on January 1, 1993, as follows: (1) nonlinear optical properties of chitosan derivatives; (2) polymeric electronic materials; (3) nondestructive characterization and prediction of polyimide performance; (4) solution processing of high-performance materials; (5) processable polyimides for composite applications; (6) sol-gel based ceramic materials processing; and (7) synthetic based processing of pre-ceramic polymers.

Process for impregnating a concrete or cement body with a polymeric material

DOEpatents

Mattus, A.J.; Spence, R.D.

1988-05-04

A process for impregnating cementitious solids with polymeric materials by blending polymeric materials in a grout, allowing the grout to cure, and contacting the resulting solidified grout containing the polymeric materials with an organic mixture containing a monomer, a cross-linking agent and a catalyst. The mixture dissolves the polymerized particles and forms a channel for distributing the monomer throughout the network formed by the polymeric particles. The organic components are then cured to form a substantially water-impermeable mass.

Process for impregnating a concrete or cement body with a polymeric material

DOEpatents

Mattus, Alfred J.; Spence, Roger D.

1989-01-01

A process for impregnating cementitious solids with polymeric materials by blending polymeric materials in a grout, allowing the grout to cure, and contacting the resulting solidified grout containing the polymeric materials with an organic mixture containing a monomer, a cross-linking agent and a catalyst. The mixture dissolves the polymerized particles and forms a channel for distributing the monomer throughout the network formed by the polymeric particles. The organic components are then cured to form a substantially water-impermeable mass.

A High-Performance Recycling Solution for Polystyrene Achieved by the Synthesis of Renewable Poly(thioether) Networks Derived from d-Limonene

PubMed Central

Nash, Landon D.; Rodriguez, Jennifer N.; Lonnecker, Alexander T.; Raymond, Jeffery E.; Wilson, Thomas S.; Wooley, Karen L.; Maitland, Duncan J.

2014-01-01

Nanocomposite polymers have been prepared using a new sustainable materials synthesis process in which d-Limonene functions simultaneously both as a solvent for recycling polystyrene (PS) waste and as a monomer that undergoes UV-catalyzed thiol-ene polymerization reactions with polythiol co-monomers to afford polymeric products comprised of precipitated PS phases dispersed throughout elastomeric poly(thioether) networks. These blended networks exhibit mechanical properties that greatly exceed those of either polystyrene or the poly(thioether) network homopolymers alone. PMID:24249666

A master equation approach to actin polymerization applied to endocytosis in yeast.

PubMed

Wang, Xinxin; Carlsson, Anders E

2017-12-01

We present a Master Equation approach to calculating polymerization dynamics and force generation by branched actin networks at membranes. The method treats the time evolution of the F-actin distribution in three dimensions, with branching included as a directional spreading term. It is validated by comparison with stochastic simulations of force generation by actin polymerization at obstacles coated with actin "nucleation promoting factors" (NPFs). The method is then used to treat the dynamics of actin polymerization and force generation during endocytosis in yeast, using a model in which NPFs form a ring around the endocytic site, centered by a spot of molecules attaching the actin network strongly to the membrane. We find that a spontaneous actin filament nucleation mechanism is required for adequate forces to drive the process, that partial inhibition of branching and polymerization lead to different characteristic responses, and that a limited range of polymerization-rate values provide effective invagination and obtain correct predictions for the effects of mutations in the active regions of the NPFs.

A master equation approach to actin polymerization applied to endocytosis in yeast

PubMed Central

Wang, Xinxin

2017-01-01

We present a Master Equation approach to calculating polymerization dynamics and force generation by branched actin networks at membranes. The method treats the time evolution of the F-actin distribution in three dimensions, with branching included as a directional spreading term. It is validated by comparison with stochastic simulations of force generation by actin polymerization at obstacles coated with actin “nucleation promoting factors” (NPFs). The method is then used to treat the dynamics of actin polymerization and force generation during endocytosis in yeast, using a model in which NPFs form a ring around the endocytic site, centered by a spot of molecules attaching the actin network strongly to the membrane. We find that a spontaneous actin filament nucleation mechanism is required for adequate forces to drive the process, that partial inhibition of branching and polymerization lead to different characteristic responses, and that a limited range of polymerization-rate values provide effective invagination and obtain correct predictions for the effects of mutations in the active regions of the NPFs. PMID:29240771

A new approach to network heterogeneity: Polymerization Induced Phase Separation in photo-initiated, free-radical methacrylic systems

PubMed Central

Szczepanski, Caroline R.; Pfeifer, Carmem S.; Stansbury, Jeffrey W.

2012-01-01

Non-reactive, thermoplastic prepolymers (poly- methyl, ethyl and butyl methacrylate) were added to a model homopolymer matrix composed of triethylene glycol dimethacrylate (TEGDMA) to form heterogeneous networks via polymerization induced phase separation (PIPS). PIPS creates networks with distinct phase structure that can partially compensate for volumetric shrinkage during polymerization through localized internal volume expansion. This investigation utilizes purely photo-initiated, free-radical systems, broadening the scope of applications for PIPS since these processing conditions have not been studied previously. The introduction of prepolymer into TEGDMA monomer resulted in stable, homogeneous monomer formulations, most of which underwent PIPS upon photo-irradiation, creating heterogeneous networks. During polymerization the presence of prepolymer enhanced autoacceleration, allowing for a more extensive ambient cure of the material. Phase separation, as characterized by dynamic changes in sample turbidity, was monitored simultaneously with monomer conversion and either preceded or was coincident with network gelation. Dynamic mechanical analysis shows a broadening of the tan delta peak and secondary peak formation, characteristic of phase-separated materials, indicating one phase rich in prepolymer and another depleted form upon phase separation. In certain cases, PIPS leads to an enhanced physical reduction of volumetric shrinkage, which is attractive for many applications including dental composite materials. PMID:23109733

Interpenetrating polymer network ion exchange membranes and method for preparing same

DOEpatents

Alexandratos, Spiro D.; Danesi, Pier R.; Horwitz, E. Philip

1989-01-01

Interpenetrating polymer network ion exchange membranes include a microporous polymeric support film interpenetrated by an ion exchange polymer and are produced by absorbing and polymerizing monomers within the support film. The ion exchange polymer provides ion exchange ligands at the surface of and throughout the support film which have sufficient ligand mobility to extract and transport ions across the membrane.

Heat resistant substrates and battery separators made therefrom

NASA Technical Reports Server (NTRS)

Langer, Alois (Inventor); Scala, Luciano C. (Inventor); Ruffing, Charles R. (Inventor)

1976-01-01

A flexible substrate having a caustic resistant support and at least one membrane comprising a solid polymeric matrix containing a network of interconnected pores and interdispersed inorganic filler particles with a ratio of filler: polymer in the polymeric matrix of between about 1:1 to 5:1, is made by coating at least one side of the support with a filler:coating formulation mixture of inorganic filler particles and a caustic resistant, water insoluble polymer dissolved in an organic solvent, and removing the solvent from the mixture to provide a porous network within the polymeric matrix.

Microscale Mechanics of Actin Networks During Dynamic Assembly and Dissociation

NASA Astrophysics Data System (ADS)

Gurmessa, Bekele; Robertson-Anderson, Rae; Ross, Jennifer; Nguyen, Dan; Saleh, Omar

Actin is one of the key components of the cytoskeleton, enabling cells to move and divide while maintaining shape by dynamic polymerization, dissociation and crosslinking. Actin polymerization and network formation is driven by ATP hydrolysis and varies depending on the concentrations of actin monomers and crosslinking proteins. The viscoelastic properties of steady-state actin networks have been well-characterized, yet the mechanical properties of these non-equilibrium systems during dynamic assembly and disassembly remain to be understood. We use semipermeable microfluidic devices to induce in situ dissolution and re-polymerization of entangled and crosslinked actin networks, by varying ATP concentrations in real-time, while measuring the mechanical properties during disassembly and re-assembly. We use optical tweezers to sinusoidally oscillate embedded microspheres and measure the resulting force at set time-intervals and in different regions of the network during cyclic assembly/disassembly. We determine the time-dependent viscoelastic properties of non-equilibrium network intermediates and the reproducibility and homogeneity of network formation and dissolution. Results inform the role that cytoskeleton reorganization plays in the dynamic multifunctional mechanics of cells. NSF CAREER Award (DMR-1255446) and a Scialog Collaborative Innovation Award funded by Research Corporation for Scientific Advancement (Grant No. 24192).

Modification of linear prepolymers to tailor heterogeneous network formation through photo-initiated Polymerization-Induced Phase Separation

PubMed Central

Szczepanski, Caroline R.; Stansbury, Jeffrey W.

2015-01-01

Polymerization-induced phase separation (PIPS) was studied in ambient photopolymerizations of triethylene glycol dimethacrylate (TEGDMA) modified by poly(methyl methacrylate) (PMMA). The molecular weight of PMMA and the rate of network formation (through incident UV-irradiation) were varied to influence both the promotion of phase separation through increases in overall free energy, as well as the extent to which phase development occurs during polymerization through diffusion prior to network gelation. The overall free energy of the polymerizing system increases with PMMA molecular weight, such that PIPS is promoted thermodynamically at low loading levels (5 wt%) of a higher molecular weight PMMA (120 kDa), while a higher loading level (20 wt%) is needed to induce PIPS with lower PMMA molecular weight (11 kDa), and phase separation was not promoted at any loading level tested of the lowest molecular weight PMMA (1 kDa). Due to these differences in overall free energy, systems modified by PMMA (11 kDa) underwent phase separation via Nucleation and Growth, and systems modified by PMMA (120 kDa), followed the Spinodal Decomposition mechanism. Despite differences in phase structure, all materials form a continuous phase rich in TEGDMA homopolymer. At high irradiation intensity (Io=20mW/cm2), the rate of network formation prohibited significant phase separation, even when thermodynamically preferred. A staged curing approach, which utilizes low intensity irradiation (Io=300µW/cm2) for the first ~50% of reaction to allow phase separation via diffusion, followed by a high intensity flood-cure to achieve a high degree of conversion, was employed to form phase-separated networks with reduced polymerization stress yet equivalent final conversion and modulus. PMID:26190865

Polymerization development of "low-shrink" resin composites: Reaction kinetics, polymerization stress and quality of network.

PubMed

Yamasaki, Lilyan C; De Vito Moraes, André G; Barros, Mathew; Lewis, Steven; Francci, Carlos; Stansbury, Jeffrey W; Pfeifer, Carmem S

2013-09-01

To evaluate "low-shrink" composites in terms of polymerization kinetics, stress development and mechanical properties. "Low-shrink" materials (Kalore/KAL, N'Durance/NDUR, and Filtek P90/P90) and one control (Esthet X HD/EHD) were tested. Polymerization stress (PS) was measured using the Instron 5565 tensometer. Volumetric shrinkage (VS) was determined by the ACTA linometer. Elastic modulus (E) and flexural strength (FS) were obtained by a three-point bending test. Degree of conversion (DC) and polymerization rate (Rp) were determined by NIR spectroscopy (6165cm(-1) for dimethacrylates; 4156 and 4071cm(-1) for P90). Photopolymerization was performed at 740mW/cm(2)×27s. Glass transition temperature (Tg), degree of heterogeneity and crosslink density were obtained in a DMA for the fully cured specimens. Analysis of extracts was done by (1)H NMR. Data were analyzed with one-way ANOVA/Tukey's test (α=0.05). The control presented the highest shrinkage and Tg. P90 showed the highest modulus, and NDUR demonstrated the highest conversion. The polymerization rates were comparable for all materials. NDUR and KAL had the highest and the lowest network homogeneity, respectively. The multifunctional P90 had the highest crosslink density, with no difference between other composites. The control had the greatest stress development, similar to NDUR. Crosslinking density and polymer network homogeneity were influenced by degree of conversion and monomer structure. Not all "low-shrink" composites reduced polymerization stress. P90 and NDUR had no leachable monomers, which was also a function of high crosslinking (P90) and high conversion (NDUR). Copyright © 2013 Academy of Dental Materials. All rights reserved.

Conducting Polymeric Hydrogel Electrolyte Based on Carboxymethylcellulose and Polyacrylamide/Polyaniline for Supercapacitor Applications

NASA Astrophysics Data System (ADS)

Suganya, N.; Jaisankar, V.; Sivakumar, E. K. T.

Conducting polymer hydrogels represent a unique class of materials that possess enormous application in flexible electronic devices. In the present work, conducting carboxymethylcellulose (CMC)-co-polyacrylamide (PAAm)/polyaniline was synthesized by a two-step interpenetrating network solution polymerization technique. The synthesized CMC-co-PAAm/polyaniline with interpenetrating network structure was prepared by in situ polymerization of aniline to enhance conductivity. The molecular structure and morphology of the copolymer hydrogels were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The novel conducting polymer hydrogels show good electrical and electrochemical behavior, which makes them potentially useful in electronic devices such as supercapacitors, biosensors, bioelectronics, solar cells and memory devices.

Impact of mixing time and sodium stearoyl lactylate on gluten polymerization during baking of wheat flour dough.

PubMed

Van Steertegem, Bénédicte; Pareyt, Bram; Brijs, Kristof; Delcour, Jan A

2013-12-15

The impact of differences in dough transient gluten network on gluten cross-linking during baking is insufficiently understood. We varied dough mixing times and/or added sodium stearoyl lactylate (SSL; 1.0% on flour dry matter basis) to the recipe and studied the effect on subsequent gluten polymerization during heating. The level of proteins extractable in sodium dodecyl sulfate containing media was fitted using first order kinetics. The extent and rate of gluten polymerization were lower when mixing for 8 min than when mixing for 2 min. This effect was even more outspoken in the presence of SSL. The present observations were explained as resulting from less gliadin incorporation in the polymer gluten network and from interaction of SSL with the gluten proteins. Finally, a higher degree of gluten polymerization during baking increased the firmness of the baked products. Copyright © 2013 Elsevier Ltd. All rights reserved.

Stone-boiling maize with limestone: experimental results and implications for nutrition among SE Utah preceramic groups

USDA-ARS?s Scientific Manuscript database

The presence of limestone among midden scatters associated with Grand Gulch phase (A.D. 200 to 400) Basketmaker II period habitation sites (Matson et al. 1988) on Cedar Mesa, southeastern Utah has suggested that these fragments are remnants of stone boiling activities that may have altered nutrition...

Construction of monomer-free, highly crosslinked, water-compatible polymers.

PubMed

Dailing, E A; Lewis, S H; Barros, M D; Stansbury, J W

2014-12-01

Polymeric dental adhesives require the formation of densely crosslinked network structures to best ensure mechanical strength and durability in clinical service. Monomeric precursors to these materials typically consist of mixtures of hydrophilic and hydrophobic components that potentially undergo phase separation in the presence of low concentrations of water, which is detrimental to material performance and has motivated significant investigation into formulations that reduce this effect. We have investigated an approach to network formation based on nanogels that are dispersed in inert solvent and directly polymerized into crosslinked polymers. Monomers of various hydrophilic or hydrophobic characteristics were copolymerized into particulate nanogels bearing internal and external polymerizable functionality. Nanogel dispersions were stable at high concentrations in acetone or, with some exceptions, in water and produced networks with a wide range of mechanical properties. Networks formed rapidly upon light activation and reached high conversion with extremely low volumetric shrinkage. Prepolymerizing monomers into reactive nanostructures significantly changes how hydrophobic materials respond to water compared with networks obtained from polymerizations involving free monomer. The modulus of fully hydrated networks formed solely from nanogels was shown to equal or exceed the modulus in the dry state for networks based on nanogels containing a hydrophobic dimethacrylate and hydrophilic monomethacrylate, a result that was not observed in a hydroxyethyl methacrylate (HEMA) homopolymer or in networks formed from nanogels copolymerized with HEMA. These results highlight the unique approach to network development from nanoscale precursors and properties that have direct implications in functional dental materials. © International & American Associations for Dental Research.

Photo-triggered solvent-free metamorphosis of polymeric materials.

PubMed

Honda, Satoshi; Toyota, Taro

2017-09-11

Liquefaction and solidification of materials are the most fundamental changes observed during thermal phase transitions, yet the design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion remains challenging. Here, we demonstrate that solvent-free repeatable molecular architectural transformation between liquid-star and nonliquid-network polymers that relies on cleavage and reformation of a covalent bond in hexaarylbiimidazole. Liquid four-armed star-shaped poly(n-butyl acrylate) and poly(dimethyl siloxane) with 2,4,5-triphenylimidazole end groups were first synthesized. Subsequent oxidation of the 2,4,5-triphenylimidazoles into 2,4,5-triphenylimidazoryl radicals and their coupling with these liquid star polymers to form hexaarylbiimidazoles afforded the corresponding nonliquid network polymers. The resulting nonliquid network polymers liquefied upon UV irradiation and produced liquid star-shaped polymers with 2,4,5-triphenylimidazoryl radical end groups that reverted to nonliquid network polymers again by recoupling of the generated 2,4,5-triphenylimidazoryl radicals immediately after terminating UV irradiation.The design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion is challenging. Here, the authors show solvent-free repeatable molecular architectural transformation between liquid-star and non-liquid-network polymers by the cleavage and reformation of covalent bonds in the polymer chain.

Application of an Addition-Fragmentation-Chain Transfer Monomer in Di(meth)acrylate Network Formation to Reduce Polymerization Shrinkage Stress.

PubMed

Shah, Parag K; Stansbury, Jeffrey W; Bowman, Christopher N

2017-08-14

A new addition-fragmentation chain transfer (AFT) capable moiety was incorporated into a dimethacrylate monomer that participated readily in network formation by copolymerizing with multifunctional methacrylates or acrylates. The process of AFT occurred simultaneously with photopolymerization of the AFT monomer (AFM) and other (meth)acrylate monomers leading to polymer stress relaxation via network reconfiguration. At low loading levels of the AFM, a significant reduction in shrinkage stress, especially for acrylate monomers, was observed with nominal effects on conversion. At higher loading levels of the AFM, the photopolymerization reaction kinetics and final double bond conversion were significantly lowered along with a delay in the gel-point conversion. Electron paramagnetic resonance studies during polymerization revealed the presence of a distinct radical species that was present in proportional quantities to the AFM content in the system. The lifetime and the character of the persistent radicals were altered due to the presence of the distinctive radical, in turn affecting the polymerization kinetics. With polymerization conducted at higher irradiance, the differential conversion between the control resin and samples with moderate AFM content was minimal, especially for the methacrylate-based formulations.

Morphologies, Processing and Properties of Ceramic Foams and Their Potential as TPS Materials

NASA Technical Reports Server (NTRS)

Stackpoole, Mairead; Simoes, Conan R.; Johnson, Sylvia M.

2002-01-01

The current research is focused on processing ceramic foams with compositions that have potential as a thermal protection material. The use of pre-ceramic polymers with the addition of sacrificial blowing agents or sacrificial fillers offers a viable approach to form either open or closed cell insulation. Our work demonstrates that this is a feasible method to form refractory ceramic foams at relatively low processing temperatures. It is possible to foam complex shapes then pyrolize the system to form a ceramic while retaining the shape of the unfired foam. Initial work focused on identifying suitable pre-ceramic polymers with desired properties such as ceramic yield and chemical make up of the pyrolysis product after firing. We focused on making foams in the Si system (Sic, Si02, Si-0-C), which is in use in current acreage TPS systems. Ceramic foams with different architectures were formed from the pyrolysis of pre-ceramic polymers at 1200 C in different atmospheres. In some systems a sacrificial polyurethane was used as the blowing agent. We have also processed foams using sacrificial fillers to introduce controlled cell sizes. Each sacrificial filler or blowing agent leads to a unique morphology. The effect of different fillers on foam morphologies and the characterization of these foams in terms of mechanical and thermal properties are presented. We have conducted preliminary arc jet testing on selected foams with the materials being exposed to typical re-entry conditions for acreage TPS and these results will be discussed. Foams processed using these approaches have bulk densities ranging from 0.15 to 0.9 g/cm3 and cell sizes ranging from 5 to 500 pm. Compression strengths ranged from 2 to 7 MPa for these systems. Finally, preliminary oxidation studies have been conducted on selected systems and will be discussed.

Gel-sol transition of the cytoplasm and its regulation

NASA Astrophysics Data System (ADS)

Janmey, Paul A.

1991-05-01

The cytoplasm of motile cells contains a dynamic system of filamentous protein polymers that endow the cell with elasticity permitting it to maintain its shape in the presence of mechanical forces encountered in vivo. Part of this cytoskeleton is composed of filaments of polymerized actin. Remodeling of this network is required for cell motility and cytoplasmic restructuring, and the reversible polymerization of actin per se has been suggested to cause morphologic changes such as cell ruffling and pseudopd extension. Changes in the degree of polymerization of acting and in the association of actin filaments into supramolecular structures are often associated with cell activation. Such activation is initiated by extracellular signals that bind to receptors which are often coupled by G-proteins to the production of intracellular second messangers. Cytoplasmic gel-sol transitions therefore can occur by formation and dissolution of actin networks, mediated by a variety of actin-binding proteins which are regulated by intracellular signalling molecules such as Ca2+ and polyphosphoinositides. The effects of three actin binding proteins: profilin, gelsolin and ABP (Tilamin) on the polymerization of actin and the viscoelasticity of the resulting networks measured in vitro suggest possible roles of these proteins in vivo. In particular, gelsolin, which activated by Ca2+ to sever and cap actin filaments, and released from filament ends by PIP2, appears to be a likely candidate for regulation of gel-sol transitions in response to cell activation. Recent results demonstrate that the hydrolysis of ATP that occurs following actin polymerization also influences the structure of the resulting filament. In addition being regulated by acting-binding proteins, the viscoelasticity of actin networks is also affected by the presence of the other two classes of cytoplasmic protein polymers, microtubules and intermediate filaments.

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.

A Hydrogel of Ultrathin Pure Polyaniline Nanofibers: Oxidant-Templating Preparation and Supercapacitor Application.

PubMed

Zhou, Kun; He, Yuan; Xu, Qingchi; Zhang, Qin'e; Zhou, An'an; Lu, Zihao; Yang, Li-Kun; Jiang, Yuan; Ge, Dongtao; Liu, Xiang Yang; Bai, Hua

2018-05-15

Although challenging, fabrication of porous conducting polymeric materials with excellent electronic properties is crucial for many applications. We developed a fast in situ polymerization approach to pure polyaniline (PANI) hydrogels, with vanadium pentoxide hydrate nanowires as both the oxidant and sacrifice template. A network comprised of ultrathin PANI nanofibers was generated during the in situ polymerization, and the large aspect ratio of these PANI nanofibers allowed the formation of hydrogels at a low solid content of 1.03 wt %. Owing to the ultrathin fibril structure, PANI hydrogels functioning as a supercapacitor electrode display a high specific capacitance of 636 F g -1 , a rate capability, and good cycling stability (∼83% capacitance retention after 10,000 cycles). This method was also extended to the preparation of polypyrrole and poly(3,4-ethylenedioxythiophene) hydrogels. This template polymerization method represents a rational strategy for design of conducing polymer networks, which can be readily integrated in high-performance devices or a further platform for functional composites.

Gel-forming reagents and uses thereof for preparing microarrays

DOEpatents

Golova, Julia; Chernov, Boris; Perov, Alexander

2010-11-09

New gel-forming reagents including monomers and cross-linkers, which can be applied to gel-drop microarray manufacturing by using co-polymerization approaches are disclosed. Compositions for the preparation of co-polymerization mixtures with new gel-forming monomers and cross-linker reagents are described herein. New co-polymerization compositions and cross-linkers with variable length linker groups between unsaturated C.dbd.C bonds that participate in the formation of gel networks are disclosed.

Predictive model for the Dutch post-consumer plastic packaging recycling system and implications for the circular economy.

PubMed

Brouwer, Marieke T; Thoden van Velzen, Eggo U; Augustinus, Antje; Soethoudt, Han; De Meester, Steven; Ragaert, Kim

2018-01-01

The Dutch post-consumer plastic packaging recycling network has been described in detail (both on the level of packaging types and of materials) from the household potential to the polymeric composition of the recycled milled goods. The compositional analyses of 173 different samples of post-consumer plastic packaging from different locations in the network were combined to indicatively describe the complete network with material flow analysis, data reconciliation techniques and process technological parameters. The derived potential of post-consumer plastic packages in the Netherlands in 2014 amounted to 341 Gg net (or 20.2 kg net.cap -1 .a -1 ). The complete recycling network produced 75.2 Gg milled goods, 28.1 Gg side products and 16.7 Gg process waste. Hence the net recycling chain yield for post-consumer plastic packages equalled 30%. The end-of-life fates for 35 different plastic packaging types were resolved. Additionally, the polymeric compositions of the milled goods and the recovered masses were derived with this model. These compositions were compared with experimentally determined polymeric compositions of recycled milled goods, which confirmed that the model predicts these compositions reasonably well. Also the modelled recovered masses corresponded reasonably well with those measured experimentally. The model clarified the origin of polymeric contaminants in recycled plastics, either sorting faults or packaging components, which gives directions for future improvement measures. Copyright © 2017 Elsevier Ltd. All rights reserved.

Morphology effect on the light scattering and dynamic response of polymer network liquid crystal phase modulator.

PubMed

Xiangjie, Zhao; Cangli, Liu; Jiazhu, Duan; Jiancheng, Zeng; Dayong, Zhang; Yongquan, Luo

2014-06-16

Polymer network liquid crystal (PNLC) was one of the most potential liquid crystal for submillisecond response phase modulation, which was possible to be applied in submillisecond response phase only spatial light modulator. But until now the light scattering when liquid crystal director was reoriented by external electric field limited its phase modulation application. Dynamic response of phase change when high voltage was applied was also not elucidated. The mechanism that determines the light scattering was studied by analyzing the polymer network morphology by SEM method. Samples were prepared by varying the polymerization temperature, UV curing intensity and polymerization time. The morphology effect on the dynamic response of phase change was studied, in which high voltage was usually applied and electro-striction effect was often induced. The experimental results indicate that the polymer network morphology was mainly characterized by cross linked single fibrils, cross linked fibril bundles or even both. Although the formation of fibril bundle usually induced large light scattering, such a polymer network could endure higher voltage. In contrast, although the formation of cross linked single fibrils induced small light scattering, such a polymer network cannot endure higher voltage. There is a tradeoff between the light scattering and high voltage endurance. The electro-optical properties such as threshold voltage and response time were taken to verify our conclusion. For future application, the monomer molecular structure, the liquid crystal solvent and the polymerization conditions should be optimized to generate optimal polymer network morphology.

Noncovalent assembly. A rational strategy for the realization of chain-growth supramolecular polymerization.

PubMed

Kang, Jiheong; Miyajima, Daigo; Mori, Tadashi; Inoue, Yoshihisa; Itoh, Yoshimitsu; Aida, Takuzo

2015-02-06

Over the past decade, major progress in supramolecular polymerization has had a substantial effect on the design of functional soft materials. However, despite recent advances, most studies are still based on a preconceived notion that supramolecular polymerization follows a step-growth mechanism, which precludes control over chain length, sequence, and stereochemical structure. Here we report the realization of chain-growth polymerization by designing metastable monomers with a shape-promoted intramolecular hydrogen-bonding network. The monomers are conformationally restricted from spontaneous polymerization at ambient temperatures but begin to polymerize with characteristics typical of a living mechanism upon mixing with tailored initiators. The chain growth occurs stereoselectively and therefore enables optical resolution of a racemic monomer. Copyright © 2015, American Association for the Advancement of Science.

Boron-carbon-silicon polymers and ceramic and a process for the production thereof

NASA Technical Reports Server (NTRS)

Riccitiello, Salvatore (Inventor); Hsu, Ming-Ta (Inventor); Chen, Timothy S. (Inventor)

1992-01-01

The present invention relates to a process for the production of an organoborosilicon preceramic polymer. The polymer is prepared by the reaction of vinylsilane or vinlymethylsilanes (acetylene)silane or acetylene alkyl silanes and borane or borane derivatives. The prepolymer form is pyrolyzed to produce a ceramic article useful in high temperature (e.g., aerospace) or extreme environmental applications.

Advanced Ceramics from Preceramic Polymers Modified at the Nano-Scale: A Review.

PubMed

Bernardo, Enrico; Fiocco, Laura; Parcianello, Giulio; Storti, Enrico; Colombo, Paolo

2014-03-06

Preceramic polymers, i.e. , polymers that are converted into ceramics upon heat treatment, have been successfully used for almost 40 years to give advanced ceramics, especially belonging to the ternary SiCO and SiCN systems or to the quaternary SiBCN system. One of their main advantages is the possibility of combining the shaping and synthesis of ceramics: components can be shaped at the precursor stage by conventional plastic-forming techniques, such as spinning, blowing, injection molding, warm pressing and resin transfer molding, and then converted into ceramics by treatments typically above 800 °C. The extension of the approach to a wider range of ceramic compositions and applications, both structural and thermo-structural (refractory components, thermal barrier coatings) or functional (bioactive ceramics, luminescent materials), mainly relies on modifications of the polymers at the nano-scale, i.e. , on the introduction of nano-sized fillers and/or chemical additives, leading to nano-structured ceramic components upon thermal conversion. Fillers and additives may react with the main ceramic residue of the polymer, leading to ceramics of significant engineering interest (such as silicates and SiAlONs), or cause the formation of secondary phases, significantly affecting the functionalities of the polymer-derived matrix.

Polyurethane/polymeric N-halamine antimicrobial and biofilm controlling semi-interpenetrating polymer network

NASA Astrophysics Data System (ADS)

Xiu, Kemao

Bacterial infection and biofilm formation cause serious medical, industrial, and environmental problems. In biomedical applications, bacterial contamination of medical devices often leads to infectious diseases accompanied with pain, suffer, and even death. Polyurethane (PU) is widely in biomedical applications due to its good mechanical properties and biocompatibility. However, its vulnerability to bacterial biofilm formation seriously limits its wider uses. Prior studies have shown that N-halamines could be incorporated into PU to achieve antimicrobial and biofilm-controlling effects through grafting, blending, and/or coating. To broaden the selection of modification methods in the development antimicrobial PU, this study synthesized polyurethane/polymeric N-halamine semi-interpenetrating polymer networks (semi-IPN). Polymerizable monomeric N-halamines were swollen into PU with initiators and crosslink agents. Post polymerization of the monomers led to the formation of semi-IPN with linear PU and N-halamine polymer networks. The semi-IPNs showed excellent antimicrobial and biofilm controlling ability towards both gram-positive and gram-negative bacteria. The effects of hydrophilicity, surface grafted N-halamine and structural characteristics of N-halamine on the antimicrobial behavior of the resulting semi-IPNs were also investigated.

Redox agents and N-ethylmaleimide affect protein polymerization during laboratory scale dry pasta production and cooking.

PubMed

Bruneel, Charlotte; Buggenhout, Joke; Lagrain, Bert; Brijs, Kristof; Delcour, Jan A

2016-04-01

Durum wheat (Triticum durum Desf.) semolina gluten proteins consist of monomeric gliadin and polymeric glutenin and determine the quality of pasta products made therefrom. During pasta drying, glutenin starts polymerizing already below 60 °C (65% relative humidity (RH)), whereas gliadin only is incorporated in the protein network at temperatures exceeding 68 °C (68% RH) through thiol (SH)/disulfide (SS) exchange reactions. Removal of free SH groups in glutenin by adding 2.3 μmol KBrO3 or KIO3 per g dry matter semolina protein (g protein) or 13.8 μmol N-ethylmaleimide/g protein reduces gliadin-glutenin cross-linking during pasta drying and/or cooking and yields cooked pasta of high quality. Introducing free SH groups by adding 13.8 μmol glutathione/g protein increases gliadin-glutenin cross-linking during pasta processing, resulting in cooked pasta of lower quality. We hypothesize that too much gliadin incorporation in the glutenin network during pasta processing tightens the protein network and results in lower cooking quality. Copyright © 2015 Elsevier Ltd. All rights reserved.

Multi-physics optimization of three-dimensional microvascular polymeric components

NASA Astrophysics Data System (ADS)

Aragón, Alejandro M.; Saksena, Rajat; Kozola, Brian D.; Geubelle, Philippe H.; Christensen, Kenneth T.; White, Scott R.

2013-01-01

This work discusses the computational design of microvascular polymeric materials, which aim at mimicking the behavior found in some living organisms that contain a vascular system. The optimization of the topology of the embedded three-dimensional microvascular network is carried out by coupling a multi-objective constrained genetic algorithm with a finite-element based physics solver, the latter validated through experiments. The optimization is carried out on multiple conflicting objective functions, namely the void volume fraction left by the network, the energy required to drive the fluid through the network and the maximum temperature when the material is subjected to thermal loads. The methodology presented in this work results in a viable alternative for the multi-physics optimization of these materials for active-cooling applications.

Surface-induced polymerization of actin.

PubMed Central

Renault, A; Lenne, P F; Zakri, C; Aradian, A; Vénien-Bryan, C; Amblard, F

1999-01-01

Living cells contain a very large amount of membrane surface area, which potentially influences the direction, the kinetics, and the localization of biochemical reactions. This paper quantitatively evaluates the possibility that a lipid monolayer can adsorb actin from a nonpolymerizing solution, induce its polymerization, and form a 2D network of individual actin filaments, in conditions that forbid bulk polymerization. G- and F-actin solutions were studied beneath saturated Langmuir monolayers containing phosphatidylcholine (PC, neutral) and stearylamine (SA, a positively charged surfactant) at PC:SA = 3:1 molar ratio. Ellipsometry, tensiometry, shear elastic measurements, electron microscopy, and dark-field light microscopy were used to characterize the adsorption kinetics and the interfacial polymerization of actin. In all cases studied, actin follows a monoexponential reaction-limited adsorption with similar time constants (approximately 10(3) s). At a longer time scale the shear elasticity of the monomeric actin adsorbate increases only in the presence of lipids, to a 2D shear elastic modulus of mu approximately 30 mN/m, indicating the formation of a structure coupled to the monolayer. Electron microscopy shows the formation of a 2D network of actin filaments at the PC:SA surface, and several arguments strongly suggest that this network is indeed causing the observed elasticity. Adsorption of F-actin to PC:SA leads more quickly to a slightly more rigid interface with a modulus of mu approximately 50 mN/m. PMID:10049338

Ceramic Fiber Coatings Development and Demonstration

DTIC Science & Technology

1993-05-28

from polycar- bosilane polymer . The fiber is mostly amorphous with some microcrystalline beta- SiC . A typical elemental composition (wt %) is 57... preceramic polymers yielded improvements mainly for oxide coatings and proved particularly promising for low cost processing. A schematic for this...deposition. COMPOSITE FABRICATION AND EVALUATION Coated fiber tows were infiltrated with Si 3N4 matrix by chemical vapor deposition in order to study

Bismaleimide/Preceramic Polymer Blends for Hybrid Material Transition Regions. Part 1. Processing and Characterization (Postprint)

DTIC Science & Technology

2014-01-01

and placed in a bea- ker with a silicone oil bath at 150C for 10 min while slowly adding the component A of the Matrimid A/B pow- der. To prepare the... pyrolytic cera- mic conversion reaction that was essentially completed at 700C. The observed 62% char yield for RD-730 is reason- ably close to the 67

Spontaneous actin dynamics in contractile rings

NASA Astrophysics Data System (ADS)

Kruse, Karsten; Wollrab, Viktoria; Thiagarajan, Raghavan; Wald, Anne; Riveline, Daniel

Networks of polymerizing actin filaments are known to be capable to self-organize into a variety of structures. For example, spontaneous actin polymerization waves have been observed in living cells in a number of circumstances, notably, in crawling neutrophils and slime molds. During later stages of cell division, they can also spontaneously form a contractile ring that will eventually cleave the cell into two daughter cells. We present a framework for describing networks of polymerizing actin filaments, where assembly is regulated by various proteins. It can also include the effects of molecular motors. We show that the molecular processes driven by these proteins can generate various structures that have been observed in contractile rings of fission yeast and mammalian cells. We discuss a possible functional role of each of these patterns. The work was supported by Agence Nationale de la Recherche, France, (ANR-10-LABX-0030-INRT) and by Deutsche Forschungsgemeinschaft through SFB1027.

Fluxgate magnetorelaxometry for characterization of hydrogel polymerization kinetics and physical entrapment capacity.

PubMed

Heim, E; Harling, S; Ludwig, F; Menzel, H; Schilling, M

2008-05-21

Hydrogels have the potential for providing drug delivery systems with long release rates. The polymerization kinetics and the physical entrapment capacity of photo-cross-linked hydroxyethyl methacrylate hydroxyethylstarch hydrogels are investigated with a non-destructive method. For this purpose, superparamagnetic nanoparticles as replacements for biomolecules are used as probes. By analyzing their magnetic relaxation behavior, the amounts of physically entrapped and mobile nanoparticles can be determined. The hydrogels were loaded with five different concentrations of nanoparticles. Different methods of analysis of the relaxation curves and the influence of the microviscosity are discussed. This investigation allows one to optimize the UV light irradiation time and to determine the amount of physically entrapped nanoparticles in the hydrogel network. It was found that the polymerization kinetics is faster for decreasing nanoparticle concentration but not all nanoparticles can be physically entrapped in the network.

Room temperature synthesis of heptazine-based microporous polymer networks as photocatalysts for hydrogen evolution.

PubMed

Kailasam, Kamalakannan; Schmidt, Johannes; Bildirir, Hakan; Zhang, Guigang; Blechert, Siegfried; Wang, Xinchen; Thomas, Arne

2013-06-25

Two emerging material classes are combined in this work, namely polymeric carbon nitrides and microporous polymer networks. The former, polymeric carbon nitrides, are composed of amine-bridged heptazine moieties and showed interesting performance as a metal-free photocatalyst. These materials have, however, to be prepared at high temperatures, making control of their chemical structure difficult. The latter, microporous polymer networks have received increasing interest due to their high surface area, giving rise to interesting applications in gas storage or catalysis. Here, the central building block of carbon nitrides, a functionalized heptazine as monomer, and tecton are used to create microporous polymer networks. The resulting heptazine-based microporous polymers show high porosity, while their chemical structure resembles the ones of carbon nitrides. The polymers show activity for the photocatalytic production of hydrogen from water, even under visible light illumination. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Particle-filled microporous materials

DOEpatents

McAllister, Jerome W.; Kinzer, Kevin E.; Mrozinski, James S.; Johnson, Eric J.; Dyrud, James F.

1990-01-01

A microporous particulate-filled thermoplastic polymeric article is provided. The article can be in the form of a film, a fiber, or a tube. The article has a thermoplastic polymeric structure having a plurality of interconnected passageways to provide a network of communicating pores. The microporous structure contains discrete submicron or low micron-sized particulate filler, the particulate filler being substantially non-agglomerated.

Particle-filled microporous materials

DOEpatents

McAllister, Jerome W.; Kinzer, Kevin E.; Mrozinski, James S.; Johnson, Eric J.

1992-07-14

A microporous particulate-filled thermoplastic polymeric article is provided. The article can be in the form of a film, a fiber, or a tube. The article has a thermoplastic polymeric structure having a plurality of interconnected passageways to provide a network of communicating pores. The microporous structure contains discrete submicron or low micron-sized particulate filler, the particulate filler being substantially non-agglomerated.

Epoxy thermoset networks derived from vegetable oils and their blends

NASA Astrophysics Data System (ADS)

Ryu, Chang; Ravalli, Matthew

2015-03-01

Epoxidized vegetable oils (EVOs), such as epoxidized soybean oil and linseed oils were prepared by the partial oxidation of the unsaturated double bonds in vegetable oils and used as monomers for preparing epoxy thermoset materials based on the cationic polymerization. These EVOs have been used to prepare epoxy thermosets of different network densities by cationic polymerization using onium salt catalyst. The crosslinked epoxy thermosets provide an ideal platform to study the structure-property-relationships of networked polymers. In particular, rheological studies on the epoxidized vegetable oil thermosets have been performed to measure the molecular weights between crosslinks (Mx) in the epoxy thermosets and to ultimately elucidate the role of functionality of epoxy groups in EVO on the mechanical and thermophysical properties of the epoxy thermoset materials. NSF DMR POLYMERS 1308617.

Formation of nanoscale networks: selectively swelling amphiphilic block copolymers with CO2-expanded liquids

NASA Astrophysics Data System (ADS)

Gong, Jianliang; Zhang, Aijuan; Bai, Hua; Zhang, Qingkun; Du, Can; Li, Lei; Hong, Yanzhen; Li, Jun

2013-01-01

Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO2-expanded liquid (CXL), CO2-methanol. The phase behavior of the CO2-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO2, forming homogeneous CXL under the experimental conditions. When treated with the CO2-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a temperature range of 45-60 °C. The formation mechanism of the network, involving plasticization of PS and selective swelling of P4VP, was proposed. Because the diblock copolymer diffusion process is controlled by the activated hopping of individual block copolymer chains with the thermodynamic barrier for moving PVP segments from one to another, the formation of the network structures is achieved in a short time scale and shows ``thermodynamically restricted'' character. Furthermore, the resulting polymer networks were employed as templates, for the preparation of polypyrrole networks, by an electrochemical polymerization process. The prepared porous polypyrrole film was used to fabricate a chemoresistor-type gas sensor which showed high sensitivity towards ammonia.Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO2-expanded liquid (CXL), CO2-methanol. The phase behavior of the CO2-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO2, forming homogeneous CXL under the experimental conditions. When treated with the CO2-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a temperature range of 45-60 °C. The formation mechanism of the network, involving plasticization of PS and selective swelling of P4VP, was proposed. Because the diblock copolymer diffusion process is controlled by the activated hopping of individual block copolymer chains with the thermodynamic barrier for moving PVP segments from one to another, the formation of the network structures is achieved in a short time scale and shows ``thermodynamically restricted'' character. Furthermore, the resulting polymer networks were employed as templates, for the preparation of polypyrrole networks, by an electrochemical polymerization process. The prepared porous polypyrrole film was used to fabricate a chemoresistor-type gas sensor which showed high sensitivity towards ammonia. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr33188h

Reactions of Hydrogen Chloride and Boron Trichloride with Trimethylsilylamino Groups

DTIC Science & Technology

1989-04-04

SUPPLEMENTARY NOTATION 17, COSATI CODES 18. SUBJECT TERMS (Continue on reverse if necessary and kientify by block number) FIELD ,,GROUP SU8 -GROUP...nitride preceramic polymers . Due to the low yield multistage synthesis, alternate routes to isomeric compositions and intermediates needed to be...Organo- metallic Polymers , Zeldin, M., Wynne, K. J., Allcock, H. R.; Ed, ACS Symposium Series 360. (4) Ebsworth, E.A.V. Volatile Silicon Compounds

Advanced Ceramics from Preceramic Polymers Modified at the Nano-Scale: A Review

PubMed Central

Bernardo, Enrico; Fiocco, Laura; Parcianello, Giulio; Storti, Enrico; Colombo, Paolo

2014-01-01

Preceramic polymers, i.e., polymers that are converted into ceramics upon heat treatment, have been successfully used for almost 40 years to give advanced ceramics, especially belonging to the ternary SiCO and SiCN systems or to the quaternary SiBCN system. One of their main advantages is the possibility of combining the shaping and synthesis of ceramics: components can be shaped at the precursor stage by conventional plastic-forming techniques, such as spinning, blowing, injection molding, warm pressing and resin transfer molding, and then converted into ceramics by treatments typically above 800 °C. The extension of the approach to a wider range of ceramic compositions and applications, both structural and thermo-structural (refractory components, thermal barrier coatings) or functional (bioactive ceramics, luminescent materials), mainly relies on modifications of the polymers at the nano-scale, i.e., on the introduction of nano-sized fillers and/or chemical additives, leading to nano-structured ceramic components upon thermal conversion. Fillers and additives may react with the main ceramic residue of the polymer, leading to ceramics of significant engineering interest (such as silicates and SiAlONs), or cause the formation of secondary phases, significantly affecting the functionalities of the polymer-derived matrix. PMID:28788548

Recent Developments in Ultra High Temperature Ceramics at NASA Ames

NASA Technical Reports Server (NTRS)

Johnson, Sylvia M.; Gasch, Matt; Lawson, John W.; Gusman, Michael I.; Stackpole, Margaret M.

2009-01-01

NASA Ames is pursuing a variety of approaches to modify and control the microstructure of UHTCs with the goal of improving fracture toughness, oxidation resistance and controlling thermal conductivity. The overall goal is to produce materials that can perform reliably as sharp leading edges or nose tips in hypersonic reentry vehicles. Processing approaches include the use of preceramic polymers as the SiC source (as opposed to powder techniques), the addition of third phases to control grain growth and oxidation, and the use of processing techniques to produce high purity materials. Both hot pressing and field assisted sintering have been used to make UHTCs. Characterization of the mechanical and thermal properties of these materials is ongoing, as is arcjet testing to evaluate performance under simulated reentry conditions. The preceramic polymer approach has generated a microstructure in which elongated SiC grains grow in the form of an in-situ composite. This microstructure has the advantage of improving fracture toughness while potentially improving oxidation resistance by reducing the amount and interconnectivity of SiC in the material. Addition of third phases, such as Ir, results in a very fine-grained microstructure, even in hot-pressed samples. The results of processing and compositional changes on microstructure and properties are reported, along with selected arcjet results.

New oxalate-bridged CrIII-MnII polymeric network incorporating a spin-crossover [Co(terpy)2]2+ cation.

PubMed

Kou, Hui-Zhong; Sato, Osamu

2007-11-12

The reaction of Mn2+ with [Cr(ox)3]3- in the presence of the spin-crossover [Co(terpy)2]2+ cation gives rise to a 1D [Co(terpy)2][Mn(H2O)ClCr(ox)3].H2O.0.5MeOH (1) or a 2D [Co(terpy)2][Mn(H2O)Cr(ox)3]2.5H2O.0.5MeOH (2). The trimetallic complexes display dominant ferromagnetic behavior, and spin-crossover of [Co(terpy)2]2+ is suppressed by the chemical pressure of the polymeric oxalate-bridged network.

Particle-filled microporous materials

DOEpatents

McAllister, J.W.; Kinzer, K.E.; Mrozinski, J.S.; Johnson, E.J.; Dyrud, J.F.

1990-09-18

A microporous particulate-filled thermoplastic polymeric article is provided. The article can be in the form of a film, a fiber, or a tube. The article has a thermoplastic polymeric structure having a plurality of interconnected passageways to provide a network of communicating pores. The microporous structure contains discrete submicron or low micron-sized particulate filler, the particulate filler being substantially non-agglomerated. 3 figs.

Solvent-Free Polymerization of L-Aspartic Acid in the Presence of D-Sorbitol to Obtain Water Soluble or Network Copolymers

USDA-ARS?s Scientific Manuscript database

L-aspartic acid was thermally polymerized in the presence of D-sorbitol with the goal of synthesizing new, higher molecular weight water soluble and absorbent copolymers. No reaction occurred when aspartic acid alone was heated at 170 or 200 degrees C. In contrast, heating sorbitol and aspartic ac...

Artificial neural network based particle size prediction of polymeric nanoparticles.

PubMed

Youshia, John; Ali, Mohamed Ehab; Lamprecht, Alf

2017-10-01

Particle size of nanoparticles and the respective polydispersity are key factors influencing their biopharmaceutical behavior in a large variety of therapeutic applications. Predicting these attributes would skip many preliminary studies usually required to optimize formulations. The aim was to build a mathematical model capable of predicting the particle size of polymeric nanoparticles produced by a pharmaceutical polymer of choice. Polymer properties controlling the particle size were identified as molecular weight, hydrophobicity and surface activity, and were quantified by measuring polymer viscosity, contact angle and interfacial tension, respectively. A model was built using artificial neural network including these properties as input with particle size and polydispersity index as output. The established model successfully predicted particle size of nanoparticles covering a range of 70-400nm prepared from other polymers. The percentage bias for particle prediction was 2%, 4% and 6%, for the training, validation and testing data, respectively. Polymer surface activity was found to have the highest impact on the particle size followed by viscosity and finally hydrophobicity. Results of this study successfully highlighted polymer properties affecting particle size and confirmed the usefulness of artificial neural networks in predicting the particle size and polydispersity of polymeric nanoparticles. Copyright © 2017 Elsevier B.V. All rights reserved.

Characterization of photochemical-cured acrylates with calorimetric methods

NASA Astrophysics Data System (ADS)

Strehmel, Bernd; Anwand, Dirk; Wetzel, Henrik

1994-05-01

Radical polymerization kinetics of different kinds of diacrylates was investigated in linear polymers (binders) by using an isoperibolic calorimeter. For all experiments benzoin compounds were added as photoinitiator. The ester between acrylic acid and bisphenol-A-diglycidylether (DDGDA) and hexamethylenediacrylate were used as monomers. Both compounds have a high limiting conversion and a large polymerization rate in the binders investigated. Additionally, three kinds of termination reaction were observed: first order, second order, and primary radical termination. The last reaction was mainly found in the case of using the hexamethylenediacrylate monomer. The materials were investigated by DSC to determine the phase behavior. Both monomers form one phase with the binder (polymethylmethacrylate, PMMA). In contrast, a phase separation was observed between the crosslinked hexamethylenediacrylate and PMMA. Formations of semi- interpenetrating networks were found in the case of crosslinked DDGDA and PMMA. The glass transition temperatures were determined at different polymerization degrees also. The obtained results indicate that most of the network formation occurred in the glassy state. Fluorescence probe technique was applied to study changes in the mobility during network formation. The fluorescence probe crystal violet (CV) was used because this compound shows a strong free volume-dependent fluorescence. It was found that in the glassy state, where most of networks were formed, a large variation of the molecular mobility was observed during irradiation of the photopolymers. This result was in agreement with the observations during DSC experiments.

Research Opportunities for Materials with Ultrafine Microstructures

DTIC Science & Technology

1989-12-31

monodispersed particles and hydrothermal synthesis of composites. Of recent interest in polymeric materials has been the development of rigid-rod...network with uniformly large pores (see Figure 2). An acidic DCCA, such as oxalic acid, in contrast, results in a somewhat smaller-scale network

Design of multi-phase dynamic chemical networks

NASA Astrophysics Data System (ADS)

Chen, Chenrui; Tan, Junjun; Hsieh, Ming-Chien; Pan, Ting; Goodwin, Jay T.; Mehta, Anil K.; Grover, Martha A.; Lynn, David G.

2017-08-01

Template-directed polymerization reactions enable the accurate storage and processing of nature's biopolymer information. This mutualistic relationship of nucleic acids and proteins, a network known as life's central dogma, is now marvellously complex, and the progressive steps necessary for creating the initial sequence and chain-length-specific polymer templates are lost to time. Here we design and construct dynamic polymerization networks that exploit metastable prion cross-β phases. Mixed-phase environments have been used for constructing synthetic polymers, but these dynamic phases emerge naturally from the growing peptide oligomers and create environments suitable both to nucleate assembly and select for ordered templates. The resulting templates direct the amplification of a phase containing only chain-length-specific peptide-like oligomers. Such multi-phase biopolymer dynamics reveal pathways for the emergence, self-selection and amplification of chain-length- and possibly sequence-specific biopolymers.

Findings of the U.S. Department of Defense Technology Assessment Team on Japanese High-Temperature Composites February 1989 Visit

DTIC Science & Technology

1993-06-01

I-4 1. Polymer Matrix Composites ................................................... r -4 2. Continuous-Fiber-Reinforced MMCs...Manufacturing CASTEM Casting Analysis System (KOBELCO) C-C Carbon-Carbon ( Composite ) CERASEP SiC - SiC CMC Made by SEP CF Carbon Fiber CFRP Carbon-Fiber...curing operations are done in clean rooms). Most operations are highly automated, with minimal manpower required. Some preceramic polymers appear to have

Laminated Object Manufacturing-Based Design Ceramic Matrix Composites

DTIC Science & Technology

2001-04-01

components for DoD applications. Program goals included the development of (1) a new LOM based design methodology for CMC, (2) optimized preceramic polymer ...3.1.1-20 3.1.1-12 Detail of LOM Composites Forming System w/ glass fiber/ polymer laminate................ 3.1.1-21 3.1.1-13...such as polymer matrix composites have faced similar barriers to implementation. These barriers have been overcome through the development of suitable

Literature Review of Polymer Derived Ceramics

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

Peterson, Reuben James

2016-05-25

Polymer Derived Ceramics (PDCs), also known as preceramic polymers, are valuable coating agents that are used to produce surface barriers on substrates such as stainless steel. These barriers protect against a multitude of environmental threats, and have been used since their research and development in 19772. This paper seeks to review and demonstrate the remarkable properties and versatility that PDCs have to offer, while also giving a brief overview of the processing techniques used today.

Improved Oxidation Resistance of 3-D Carbon/Carbon Composites

DTIC Science & Technology

1994-01-14

extraction process (which might be the extraction of the flavoring agents from hops or decaffeination of coffee beans) to point out how the pressure dependent...SiC) were made by a process termed Supercritical Fluid Infiltration. A preceramic polymer, e.g., a polycarbosilane which can pyrolyze to form SiC, is...using supercritical propane (in a process termed increasing pressure profiling), and it was found that some of the low molecular weight fractions gave

Hybrid polymer networks as ultra low `k` dielectric layers

DOEpatents

Lewicki, James; Worsley, Marcus A.

2016-02-16

According to one embodiment, a polymeric material includes at least one polydimethylsiloxane (PDMS) polymer, and at least one polyhedral oligomericsilsequioxane (POSS) molecule. According to another embodiment, a method includes providing at least one polydimethylsiloxane (PDMS) polymer, providing at least one polyhedral oligomericsilsequioxane (POSS) molecule, and coupling the at least one PDSM polymer to the at least one POSS molecule to form a hybrid polymeric material.

Microscale force response and morphology of tunable co-polymerized cytoskeleton networks

NASA Astrophysics Data System (ADS)

Ricketts, Shea; Yadav, Vikrant; Ross, Jennifer L.; Robertson-Anderson, Rae M.

The cytoskeleton is largely comprised of actin and microtubules that entangle and crosslink to form complex networks and structures, giving rise to nonlinear multifunctional mechanics in cells. The relative concentrations of semiflexible actin filaments and rigid microtubules tune cytoskeleton function, allowing cells to move and divide while maintaining rigidity and resilience. To elucidate this complex tunability, we create in vitro composites of co-polymerized actin and microtubules with actin:microtubule molar ratios of 0:1-1:0. We use optical tweezers and confocal microscopy to characterize the nonlinear microscale force response and morphology of the composites. We optically drag a microsphere 30 μm through varying actin-microtubule networks at 10 μm/s and 20 μm/s, and measure the force the networks exerts to resist the strain and the force relaxation following strain. We use dual-color confocal microscopy to image distinctly-labeled filaments in the networks, and characterize the integration of actin and microtubules, network connectivity, and filament rigidity. We find that increasing the fraction of microtubules in networks non-monotonically increases elasticity and stiffness, and hinders force relaxation by suppressing network mobility and fluctuations. NSF CAREER Award (DMR-1255446), Scialog Collaborative Innovation Award funded by Research Corporation for Scientific Advancement (Grant No. 24192).

Cross-linked β-cyclodextrin and carboxymethyl cellulose hydrogels for controlled drug delivery of acyclovir

PubMed Central

Malik, Nadia Shamshad; Ahmad, Mahmood; Minhas, Muhammad Usman

2017-01-01

To explore the potential role of polymers in the development of drug-delivery systems, this study investigated the use of β-cyclodextrin (β-CD), carboxymethyl cellulose (CMC), acrylic acid (AA) and N’ N’-methylenebis-acrylamide (MBA) in the synthesis of hydrogels for controlled drug delivery of acyclovir (ACV). Different proportions of β-CD, CMC, AA and MBA were blended with each other to fabricate hydrogels via free radical polymerization technique. Fourier transform infrared spectroscopy (FTIR) revealed successful grafting of components into the polymeric network. Thermal and morphological characterization confirmed the formation of thermodynamically stable hydrogels having porous structure. The pH-responsive behaviour of hydrogels has been documented by swelling dynamics and drug release behaviour in simulated gastrointestinal fluids. Drug release kinetics revealed controlled release behaviour of the antiviral drug acyclovir in developed polymeric network. Cross-linked β-cyclodextrin and carboxymethyl cellulose hydrogels can be used as promising candidates for the design and development of controlled drug-delivery systems. PMID:28245257

Highly water-absorbing silk yarn with interpenetrating network via in situ polymerization.

PubMed

Lee, Ka I; Wang, Xiaowen; Guo, Xia; Yung, Ka-Fu; Fei, Bin

2017-02-01

Silk was modified via in situ polymerization of two monomers acrylamide and sodium acrylate by swelling in an effective LiBr dissolution system. Swelling of natural silks in LiBr solutions of low concentration was clearly observed under optical microscope, and their conformational changes were revealed by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Dissolution tests and FTIR spectra of these modified silks suggested the presence of interpenetrating network of polyacrylamide and poly(sodium acrylate) in the silk yarns. These modified silks exhibited superior water absorption to that of raw silk and greatly improved mechanical properties in both dry and wet states. These novel modified silks also showed low cytotoxicity towards skin keratinocytes, having potential applications in biomedical textiles. This modification method by in situ polymerization after swelling in LiBr provides a new route to highly enhance the properties and performance of silk for various applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Design of interpenetrated network MWCNT/poly(1,5-DAN) on interdigital electrode: toward NO2 gas sensing.

PubMed

Nguyen, Dzung Tuan; Nguyen, My Thanh; Ho, Giang Truong; Nguyen, Toan Ngoc; Reisberg, S; Piro, B; Pham, M C

2013-10-15

In this paper, poly(1,5-diaminonaphthalene) was interpenetrated into the network made of multiwalled carbon nanotubes (MWCNT) on platinum interdigital electrode (IDE) by electro-polymerization of 1,5-diaminonaphthalene (1,5-DAN). The electro-polymerization process of 1,5-DAN on MWCNT was controlled by scanning the cyclic voltage at 50 mV s(-1) scan rate between -0.1 V and +0.95 V vs. saturated calomel electrode (SCE). The results of voltammetric responses and Raman spectroscopy represented that the films MWCNT/poly(1,5-DAN) were successfully created by this polymerization process. The films MWCNT/poly(1,5-DAN) were investigated for gas-sensing to NO2 at low concentration level. The gas-sensing results showed that the response-recovery times were long and strongly affected by thickness of the film MWCNT/poly(1,5-DAN). Nevertheless, these films represented auspicious results for gas sensors operating at room temperature. Copyright © 2013 Elsevier B.V. All rights reserved.

Elasticity and photoelasticity relationships for polyethylene terephthalate fiber networks by molecular simulation

NASA Astrophysics Data System (ADS)

Nayak, Kapileswar; Das, Sushanta; Nanavati, Hemant

2008-01-01

We present a framework for the development of elasticity and photoelasticity relationships for polyethylene terephthalate fiber networks, incorporating aspects of the primary molecular structure. Semicrystalline polymeric fiber networks are modeled as sequentially arranged crystalline and amorphous regions. Rotational isomeric states-Monte Carlo simulations of amorphous chains of up to 360 bonds (degree of polymerization, DP =60), confined between and bridging infinite impenetrable crystalline walls, have been characterized by Ω, the probability density of the intercrystal separation h, and Δβ, the polarizability anisotropy. lnΩ and Δβ have been modeled as functions of h, yielding the chain deformation relationships. The development has been extended to the fiber network to yield the photoelasticity relationships. We execute our framework by fitting to experimental stress-elongation data and employing the single fitted parameter to directly predict the birefringence-elongation behavior, without any further fitting. Incorporating the effect of strain-induced crystallization into the framework makes it physically more meaningful and yields accurate predictions of the birefringence-elongation behavior.

Thermomechanical Formation–Structure–Property Relationships in Photopolymerized Copper-Catalyzed Azide–Alkyne (CuAAC) Networks

PubMed Central

Baranek, Austin; Song, Han Byul; McBride, Mathew; Finnegan, Patricia; Bowman, Christopher N.

2016-01-01

Bulk photopolymerization of a library of synthesized multifunctional azides and alkynes was carried out toward developing structure–property relationships for CuAAC-based polymer networks. Multifunctional azides and alkynes were formulated with a copper catalyst and a photoinitiator, cured, and analyzed for their mechanical properties. Material properties such as the glass transition temperatures (Tg) show a strong dependence on monomer structure with Tg values ranging from 41 to 90 °C for the series of CuAAC monomers synthesized in this study. Compared to the triazoles, analogous thioether-based polymer networks exhibit a 45–49 °C lower Tg whereas analogous monomers composed of ethers in place of carbamates exhibit a 40 °C lower Tg. Here, the formation of the triazole moiety during the polymerization represents a critical component in dictating the material properties of the ultimate polymer network where material properties such as the rubbery modulus, cross-link density, and Tg all exhibit strong dependence on polymerization conversion, monomer composition, and structure postgelation. PMID:27867223

Load Adaptation of Lamellipodial Actin Networks.

PubMed

Mueller, Jan; Szep, Gregory; Nemethova, Maria; de Vries, Ingrid; Lieber, Arnon D; Winkler, Christoph; Kruse, Karsten; Small, J Victor; Schmeiser, Christian; Keren, Kinneret; Hauschild, Robert; Sixt, Michael

2017-09-21

Actin filaments polymerizing against membranes power endocytosis, vesicular traffic, and cell motility. In vitro reconstitution studies suggest that the structure and the dynamics of actin networks respond to mechanical forces. We demonstrate that lamellipodial actin of migrating cells responds to mechanical load when membrane tension is modulated. In a steady state, migrating cell filaments assume the canonical dendritic geometry, defined by Arp2/3-generated 70° branch points. Increased tension triggers a dense network with a broadened range of angles, whereas decreased tension causes a shift to a sparse configuration dominated by filaments growing perpendicularly to the plasma membrane. We show that these responses emerge from the geometry of branched actin: when load per filament decreases, elongation speed increases and perpendicular filaments gradually outcompete others because they polymerize the shortest distance to the membrane, where they are protected from capping. This network-intrinsic geometrical adaptation mechanism tunes protrusive force in response to mechanical load. Copyright © 2017 Elsevier Inc. All rights reserved.

3D-Hydrogel Based Polymeric Nanoreactors for Silver Nano-Antimicrobial Composites Generation.

PubMed

Soto-Quintero, Albanelly; Romo-Uribe, Ángel; Bermúdez-Morales, Víctor H; Quijada-Garrido, Isabel; Guarrotxena, Nekane

2017-08-01

This study underscores the development of Ag hydrogel nanocomposites, as smart substrates for antibacterial uses, via innovative in situ reactive and reduction pathways. To this end, two different synthetic strategies were used. Firstly thiol-acrylate (PSA) based hydrogels were attained via thiol-ene and radical polymerization of polyethylene glycol (PEG) and polycaprolactone (PCL). As a second approach, polyurethane (PU) based hydrogels were achieved by condensation polymerization from diisocyanates and PCL and PEG diols. In fact, these syntheses rendered active three-dimensional (3D) hydrogel matrices which were used as nanoreactors for in situ reduction of AgNO₃ to silver nanoparticles. A redox chemistry of stannous catalyst in PU hydrogel yielded spherical AgNPs formation, even at 4 °C in the absence of external reductant; and an appropriate thiol-functionalized polymeric network promoted spherical AgNPs well dispersed through PSA hydrogel network, after heating up the swollen hydrogel at 103 °C in the presence of citrate-reductant. Optical and swelling behaviors of both series of hydrogel nanocomposites were investigated as key factors involved in their antimicrobial efficacy over time. Lastly, in vitro antibacterial activity of Ag loaded hydrogels exposed to Pseudomona aeruginosa and Escherichia coli strains indicated a noticeable sustained inhibitory effect, especially for Ag-PU hydrogel nanocomposites with bacterial inhibition growth capabilities up to 120 h cultivation.

The polymeric nanofilm of triazinedithiolsilane fabricated by self-assembled technique on copper surface. Part 2: Characterization of composition and morphology

NASA Astrophysics Data System (ADS)

Wang, Yabin; Liu, Zhong; Huang, Yudong; Qi, Yutai

2015-11-01

In the first part, a novel design route for metal protection against corrosion was proposed, and a class of triazinedithiolsilane compounds was conceived as protector for copper. The protective capability of the polymeric nanofilm, fabricated by self-assembling one representative (abbreviated as TESPA) of triazinedithiolsilane compounds onto copper surface, has been investigated and evaluated by electrochemical tests. The results show that the polymeric nanofilm significantly inhibits copper corrosion. This study, on the one hand, concentrates on the chemical composition of the TESPA polymeric nanofilm by means of X-ray photoelectron spectroscopy (XPS). The XPS results reveal that the chemical bonds between copper and TESPA monomers, three dimensional disulfide units and siloxane networks are responsible for the satisfactory protection of TESPA polymeric nanofilm against copper corrosion. On the other hand, scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS) are utilized to reveal the morphology and the uniformity of the TESPA polymeric nanofilm. The SEM-EDS results demonstrate that the copper surfaces are uniformly covered with TESPA self-assembled monolayer and the polymeric nanofilm. The TESPA-covered copper surfaces turn out to be smoother than that of the bare copper surface.

Potassium fulvate as co-interpenetrating agent during graft polymerization of acrylic acid from cellulose.

PubMed

Ghazy, Mohamed B M; El-Hai, Farag Abd; Mohamed, Magdy F; Essawy, Hisham A

2016-10-01

Grafting polymerization of acrylic acid onto cellulose in presence of potassium fulvate (KF) as a co-interpenetrating agent results enhanced water sorption compared to materials prepared similarly in its absence. The insertion of potassium fulvate (KF) did not affect the grafting process and is thought to proceed in parallel to the graft polymerization via intensive polycondensation reactions of its function groups (-COOH and OH) with COOH of the monomer and OH groups of cellulose. The combination of graft copolymerization and polycondensation reactions is assumed to produce interpenetrating network structure. Fourier transform infrared (FTIR) confirmed successful incorporation within the network structure which is an evidence for formation of interpenetrating network. The obtained structures showed homogeneous uniform surface as revealed by scanning electron microscopy (SEM). The obtained superabsorbent possessed high water absorbency 422 and 48.8g/g in distilled water and saline (0.9wt.% NaCl solution), respectively, and enhanced water retention even at elevated temperatures as revealed by thermogravimetric analysis (TGA). This could be explained by the high content of hydrophilic groups. The new superabsorbents proved to be efficient devices for controlled release of fertilizers which expands their use in agricultural applications. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Synthesis and properties of hemicelluloses-based semi-IPN hydrogels.

PubMed

Peng, Feng; Guan, Ying; Zhang, Bing; Bian, Jing; Ren, Jun-Li; Yao, Chun-Li; Sun, Run-Cang

2014-04-01

Hemicelluloses were extracted from holocellulose of bamboo by alkaline treatment. The phosphorylated poly(vinyl alcohol) (P-PVA) samples with various substitution degrees were prepared through the esterification of PVA and phosphoric acid. A series of hydrogels of semi-interpenetrating polymeric networks (semi-IPN) composed of hemicelluloses-g-poly(acrylic acid) (HM-g-PAA) and the phosphorylated poly(vinyl alcohol) (P-PVA) were prepared by radical polymerization using potassium persulphate (KPS) as initiator. The HM-g-PAA networks were crosslinked by N,N-methylenebisacrylamide (MBA) as a crosslinking agent in the presence of linear P-PVA. FT-IR results confirmed that the hydrogels comprised a porous crosslink structure of P-PVA and HM with side chains that carried carboxylate and phosphorylate groups. SEM observations indicated that the incorporation of P-PVA induced highly porous structure, and P-PVA was uniformly dispersed in the polymeric network. The interior network structures of the semi-IPN matrix became more porous with increasing P-PVA. The TGA results showed that the thermo-decomposing temperature and thermal stability were increased effectively for intruding the chain of P-PVA. The maximum equilibrium swelling ratio of hydrogels in distilled water and 0.9 wt% sodium chloride solutions was up to 1085 g g(-1) and 87 g g(-1), respectively. The compressive strength increased with increasing the MBA/HM and P-PVA/HM ratios, and decreased with the increment of AA/HM ratio. Copyright © 2014 Elsevier B.V. All rights reserved.

Oligo(ethylene glycol)-sidechain microgels prepared in absence of cross-linking agent: Polymerization, characterization and variation of particle deformability.

PubMed

Welsch, Nicole; Lyon, L Andrew

2017-01-01

We present a systematic study of self-cross-linked microgels formed by precipitation polymerization of oligo ethylene glycol methacrylates. The cross-linking density of these microgels and, thus, the network flexibility can be easily tuned through the modulation of the reaction temperature during polymerization. Microgels prepared in absence of any difunctional monomer, i.e. cross-linker, show enhanced deformability and particle spreading on solid surfaces as compared to microgels cross-linked with varying amounts of poly(ethylene glycol diacrylate) (PEG-DA) in addition to self-crosslinking. Particles prepared at low reaction temperatures exhibit the highest degree of spreading due to the lightly cross-linked and flexible polymer network. Moreover, AFM force spectroscopy studies suggest that cross-linker-free microgels constitute of a more homogeneous polymer network than PEG-DA cross-linked particles and have elastic moduli at the particle apex that are ~5 times smaller than the moduli of 5 mol-% PEG-DA cross-linked microgels. Resistive pulse sensing experiments demonstrate that microgels prepared at 75 and 80°C without PEG-DA are able to deform significantly to pass through nanopores that are smaller than the microgel size. Additionally, we found that polymer network flexibility of microgels is a useful tool to control the formation of particle dewetting patterns. This offers a promising new avenue for build-up of 2D self-assembled particle structures with patterned chemical and mechanical properties.

Oligo(ethylene glycol)-sidechain microgels prepared in absence of cross-linking agent: Polymerization, characterization and variation of particle deformability

PubMed Central

Lyon, L. Andrew

2017-01-01

We present a systematic study of self-cross-linked microgels formed by precipitation polymerization of oligo ethylene glycol methacrylates. The cross-linking density of these microgels and, thus, the network flexibility can be easily tuned through the modulation of the reaction temperature during polymerization. Microgels prepared in absence of any difunctional monomer, i.e. cross-linker, show enhanced deformability and particle spreading on solid surfaces as compared to microgels cross-linked with varying amounts of poly(ethylene glycol diacrylate) (PEG-DA) in addition to self-crosslinking. Particles prepared at low reaction temperatures exhibit the highest degree of spreading due to the lightly cross-linked and flexible polymer network. Moreover, AFM force spectroscopy studies suggest that cross-linker-free microgels constitute of a more homogeneous polymer network than PEG-DA cross-linked particles and have elastic moduli at the particle apex that are ~5 times smaller than the moduli of 5 mol-% PEG-DA cross-linked microgels. Resistive pulse sensing experiments demonstrate that microgels prepared at 75 and 80°C without PEG-DA are able to deform significantly to pass through nanopores that are smaller than the microgel size. Additionally, we found that polymer network flexibility of microgels is a useful tool to control the formation of particle dewetting patterns. This offers a promising new avenue for build-up of 2D self-assembled particle structures with patterned chemical and mechanical properties. PMID:28719648

Low Temperature Reactivities of Ultra-High Temperature Ceramics (Hf-X System)

DTIC Science & Technology

2006-03-01

as interacting fillers with the preceramic polymer formulations. In situ formation of the SiC phase was also evaluated as a practical approach in...silicon (reaction-bonded SiC ), which was introduced either as a powder mixed in the original composite formulation or as a subsequent infiltrant that...and their aerospace and turbine applications has led to a renewal of activities to fabricate MB 2/ SiC composites as the materials of choice, because

Additive Manufacturing of SiC Based Ceramics and Ceramic Matrix Composites

NASA Technical Reports Server (NTRS)

Halbig, Michael Charles; Singh, Mrityunjay

2015-01-01

Silicon carbide (SiC) ceramics and SiC fiber reinforcedSiC ceramic matrix composites (SiCSiC CMCs) offer high payoff as replacements for metals in turbine engine applications due to their lighter weight, higher temperature capability, and lower cooling requirements. Additive manufacturing approaches can offer game changing technologies for the quick and low cost fabrication of parts with much greater design freedom and geometric complexity. Four approaches for developing these materials are presented. The first two utilize low cost 3D printers. The first uses pre-ceramic pastes developed as feed materials which are converted to SiC after firing. The second uses wood containing filament to print a carbonaceous preform which is infiltrated with a pre-ceramic polymer and converted to SiC. The other two approaches pursue the AM of CMCs. The first is binder jet SiC powder processing in collaboration with rp+m (Rapid Prototyping+Manufacturing). Processing optimization was pursued through SiC powder blending, infiltration with and without SiC nano powder loading, and integration of nanofibers into the powder bed. The second approach was laminated object manufacturing (LOM) in which fiber prepregs and laminates are cut to shape by a laser and stacked to form the desired part. Scanning electron microscopy was conducted on materials from all approaches with select approaches also characterized with XRD, TGA, and bend testing.

Starch grain evidence for the preceramic dispersals of maize and root crops into tropical dry and humid forests of Panama.

PubMed

Dickau, Ruth; Ranere, Anthony J; Cooke, Richard G

2007-02-27

The Central American isthmus was a major dispersal route for plant taxa originally brought under cultivation in the domestication centers of southern Mexico and northern South America. Recently developed methodologies in the archaeological and biological sciences are providing increasing amounts of data regarding the timing and nature of these dispersals and the associated transition to food production in various regions. One of these methodologies, starch grain analysis, recovers identifiable microfossils of economic plants directly off the stone tools used to process them. We report on new starch grain evidence from Panama demonstrating the early spread of three important New World cultigens: maize (Zea mays), manioc (Manihot esculenta), and arrowroot (Maranta arundinacea). Maize starch recovered from stone tools at a site located in the Pacific lowlands of central Panama confirms previous archaeobotanical evidence for the use of maize there by 7800-7000 cal BP. Starch evidence from preceramic sites in the less seasonal, humid premontane forests of Chiriquí province, western Panama, shows that maize and root crops were present by 7400-5600 cal BP, several millennia earlier than previously documented. Several local starchy resources, including Zamia and Dioscorea spp., were also used. The data from both regions suggest that crop dispersals took place via diffusion or exchange of plant germplasm rather than movement of human populations practicing agriculture.

Starch grain evidence for the preceramic dispersals of maize and root crops into tropical dry and humid forests of Panama

PubMed Central

Dickau, Ruth; Ranere, Anthony J.; Cooke, Richard G.

2007-01-01

The Central American isthmus was a major dispersal route for plant taxa originally brought under cultivation in the domestication centers of southern Mexico and northern South America. Recently developed methodologies in the archaeological and biological sciences are providing increasing amounts of data regarding the timing and nature of these dispersals and the associated transition to food production in various regions. One of these methodologies, starch grain analysis, recovers identifiable microfossils of economic plants directly off the stone tools used to process them. We report on new starch grain evidence from Panama demonstrating the early spread of three important New World cultigens: maize (Zea mays), manioc (Manihot esculenta), and arrowroot (Maranta arundinacea). Maize starch recovered from stone tools at a site located in the Pacific lowlands of central Panama confirms previous archaeobotanical evidence for the use of maize there by 7800–7000 cal BP. Starch evidence from preceramic sites in the less seasonal, humid premontane forests of Chiriquí province, western Panama, shows that maize and root crops were present by 7400–5600 cal BP, several millennia earlier than previously documented. Several local starchy resources, including Zamia and Dioscorea spp., were also used. The data from both regions suggest that crop dispersals took place via diffusion or exchange of plant germplasm rather than movement of human populations practicing agriculture. PMID:17360697

Biphasic interactions between a cationic dendrimer and actin.

PubMed

Ruenraroengsak, Pakatip; Florence, Alexander T

2010-12-01

Gene delivery systems face the problem not only of the route toward the cell and tissues in question, but also of the molecularly crowded environment of both the cytoplasm and the nucleus itself. One of the physical barriers in the cytoplasm for diffusing nanoparticles is an actin network. Here, we describe the finding that a self-fluorescent sixth generation cationic dendrimer (6 nm in diameter) interacts reversibly and possibly electrostatically with actin filaments in vitro. Not only does this interaction slow the diffusion of the dendrimer but it also affects actin polymerization in a biphasic manner. At low concentrations the dendrimer behaves like a G-binding actin protein, retarding actin polymerization, whereas at high concentrations the dendrimer acts as a nucleating protein accelerating the polymerization. Thus in vivo the diffusion of a dendrimer carrier such as this has both physical and chemical elements: by decreasing polymerization it might accelerate its own transport, and by enhancing actin polymerization retard it. This finding suggests that such a dendrimer may have a role as an anticancer agent through its inhibitory effect on actin polymerization.

Tailoring physical properties of transglutaminase-modified gelatin films by varying drying temperature

USDA-ARS?s Scientific Manuscript database

Gelatin films prepared with or without transglutaminase (TGase) and dried at 15, 25 and 35 °C were analyzed for polymeric network structure, chemical composition and physical properties. Differences in protein network structure were observed by optical microscopy analysis in freeze-dried film-formin...

Dielectric loss property of strong acids doped polyaniline (PANi)

NASA Astrophysics Data System (ADS)

Amalia, Rianti; Hafizah, Mas Ayu Elita; Andreas, Manaf, Azwar

2018-04-01

In this study, strong acid doped polyaniline (PANi) has been successfully fabricated through the chemical oxidative polymerization process with various polymerization times. Nonconducting PANi resulting from the polymerization process at various polymerization times were then doped by a strong acid HClO4 to generate dielectric properties. Ammonium Persulfate (APS) as an initiator was used during Polymerization process to develop dark green precipitates which then called Emeraldine Base Polyaniline (PANi-EB). The PANi-EB was successively doped by strong acid HClO4 with dopant and PANi ratio 10:1 to enhance the electrical conductivity. The conductivity of doped PANi was evaluated by Four Point Probe. Results of evaluation showed that the conductivity values of HClO4 doped PANi were in the range 337-363 mS/cm. The dielectric properties of doped PANi were evaluated by Vector Network Analyzer (VNA) which suggested that an increase in the permittivity value in the conducting PANi. It is concluded that PANi could be a potential candidate for electromagnetic waves absorbing materials.

A novel chiral separation material: polymerized organogel formed by chiral gelators for the separation of D- and L-phenylalanine.

PubMed

Fu, Xinjian; Yang, Yang; Wang, Ningxia; Wang, Hong; Yang, Yajiang

2007-01-01

N-Stearine-N'-stearyl-L-phenylalanine, a chiral compound, was synthesized and used as a gelator for the gelation of polymerizable solvents, such as ss-hydroxyethyl methacrylate (HEMA), styrene, etc. The scanning electron microscope (SEM) images of the gelator aggregates show fibril-like helices, typical chiral aggregates with diameters of 100-200 nm. The solvent molecules were immobilized by capillary forces in the three-dimensional network structures of the organogels. The HEMA organogels containing crosslinker polyethylene glycol dimethacrylates (PEG200DMA) were subsequently polymerized by in situ UV irradiation. A porous polymerized organogels were obtained after removal of gelator aggregates through ethanol extraction. The chiral separation of D- and L-phenylalanine was carried out by the adsorption of the polymerized organogels. The adsorption efficiency of L-phenylalanine on the polymerized organogels was found to be dependent on the concentration of the gelator and crosslinker. (c) 2007 John Wiley & Sons, Ltd.

Effects of HMW-GS Ax1 or Dx2 absence on the glutenin polymerization and gluten micro structure of wheat (Triticum aestivum L.).

PubMed

Gao, Xin; Liu, Tianhong; Ding, Mengyun; Wang, Jun; Li, Chunlian; Wang, Zhonghua; Li, Xuejun

2018-02-01

Wheat (Triticum aestivum L.) dough strength and extensibility are mainly determined by the polymerization of glutenin. The number of high-molecular-weight glutenin subunits (HMW-GS) differs in various wheat varieties due to the silencing of some genes. The effects of Ax1 or Dx2 subunit absence on glutenin polymerization, dough mixing properties and gluten micro structure were investigated with two groups of near-isogenic lines. The results showed that Ax1 or Dx2 absence decreased the accumulation rate of glutenin polymers and thus delayed the rapid increase period for glutenin polymerization by at least ten days, which led to lower percentage of polymeric protein in mature grain. Ax1 or Dx2 absence significantly decreased the dough development time and dough stability, but increased the uniformity of micro structure. Lacunarity, derived from quantitative analysis of gluten network, is suggested as a new indicator for wheat quality. Copyright © 2017 Elsevier Ltd. All rights reserved.

Some experiments to study diffusive transport through a semi interpenetrating polymeric network in the absence and presence of aqueous electrolytes

NASA Astrophysics Data System (ADS)

Biswas, Pritha; Das, Atreyee; Yasmin, Tanvee; Kanjilal, Baishali; Chakrabarti, Haimanti

2018-05-01

The study of ion transport in biological system has become a topic of great current interest. This work presents the diffusive transport properties through a typical semi interpenetrating polymeric network (SIPN) which mimics many characteristic features of the walls of human food pipes. The SIPN matrix has been synthesised from Polyvinyl alcohol, Acrylamide monomer, Glutaraldehyde and Ammonium Per sulphate in our laboratory is utilised to study the diffusive transport in the absence and presence of aqueous electrolyte (KCl) at varying concentrations. The diffusivity of the SIPN polymer hydrogel was estimated by the `Theory of Elastomer' to get an insight into process of Potassium and Chlorine ion transport through the SIPN.

Design and Synthesis of Network-Forming Triblock Copolymers Using Tapered Block Interfaces

PubMed Central

Kuan, Wei-Fan; Roy, Raghunath; Rong, Lixia; Hsiao, Benjamin S.; Epps, Thomas H.

2012-01-01

We report a strategy for generating novel dual-tapered poly(isoprene-b-isoprene/styrene-b-styrene-b-styrene/methyl methacrylate-b-methyl methacrylate) [P(I-IS-S-SM-M)] triblock copolymers that combines anionic polymerization, atom transfer radical polymerization (ATRP), and Huisgen 1,3-dipolar cycloaddition click chemistry. The tapered interfaces between blocks were synthesized via a semi-batch feed using programmable syringe pumps. This strategy allows us to manipulate the transition region between copolymer blocks in triblock copolymers providing control over the interfacial interactions in our nanoscale phase-separated materials independent of molecular weight and block constituents. Additionally, we show the ability to retain a desirous and complex multiply-continuous network structure (alternating gyroid) in our dual-tapered triblock material. PMID:23066522

Low-Temperature Reactivities of Ultra-High Temperature Ceramics (Hf-X System)

DTIC Science & Technology

2005-12-01

as interacting fillers with the preceramic polymer formulations. In situ formation of the SiC phase was also evaluated as a practical approach in...led to a renewal of activities to fabricate MB2/ SiC composites as the materials of choice, because of their high thermal and oxidation resistance...HfB2/ SiC composite microstructures (and also HfC, ZrB2, and ZrC composites ) under pressureless conditions. These can be employed in reactive and

Innovative Processing of Composites for Ultra-High Temperature Applications. Book 1

DTIC Science & Technology

1993-11-01

pyrolysis step (in which the polymer is converted at higher temperatures to a SiC -rich ceramic). However, curing in air also leads to the high oxygen...The fac’ that the ceramic the vinylic SiC precursor, i.e., a compound or polymer resulting from pyrolysis of the vinylic precursor re- having vinylic...12 %herein said atmosphere 1. A method of preparing preceramic SiC fibers hay- 65 utilized for pyrolysis ik a reactime atmosphere contain- ing a very

Hydridosiloxanes as precursors to ceramic products

DOEpatents

Blum, Yigal D.; Johnson, Sylvia M.; Gusman, Michael I.

1997-01-01

A method is provided for preparing ceramic precursors from hydridosiloxane starting materials and then pyrolyzing these precursors to give rise to silicious ceramic materials. Si--H bonds present in the hydridosiloxane starting materials are catalytically activated, and the activated hydrogen atoms may then be replaced with nonhydrogen substituents. These preceramic materials are pyrolyzed in a selected atmosphere to give the desired ceramic product. Ceramic products which may be prepared by this technique include silica, silicon oxynitride, silicon carbide, metal silicates, and mullite.

Hydridosiloxanes as precursors to ceramic products

DOEpatents

Blum, Y.D.; Johnson, S.M.; Gusman, M.I.

1997-06-03

A method is provided for preparing ceramic precursors from hydridosiloxane starting materials and then pyrolyzing these precursors to give rise to silicious ceramic materials. Si-H bonds present in the hydridosiloxane starting materials are catalytically activated, and the activated hydrogen atoms may then be replaced with nonhydrogen substituents. These preceramic materials are pyrolyzed in a selected atmosphere to give the desired ceramic product. Ceramic products which may be prepared by this technique include silica, silicon oxynitride, silicon carbide, metal silicates, and mullite.

Releasing the brakes while hanging on: Cortactin effects on actin-driven motility.

PubMed

Gov, Nir S; Bernheim-Groswasser, Anne

2012-01-01

Actin polymerization plays a major role in many cellular processes, including cell motility, vesicle trafficking, and pathogen propulsion. The transformation of the (protrusive) polymerization forces into directed motion requires that the growing filaments are positioned next to the surface. This is achieved by localization of surface actin nucleators (WASP), which then activate Arp2/3 complex to form new actin branches. Yet, the same surface-bound WASP molecule which initiates the nucleation of new actin branches, also inherently prevents the translation of the polymerization forces into motion, essentially because the WASP molecule has to be in contact with the network during the formation of the new branch. In our recent paper we show that cortactin relaxes this internal inhibition by enhancing the release of WASP-VCA molecule from the new branching site after nucleation is initiated. We show that this enhanced release has two major effects; it increases the turnover rate of branching per WASP molecule, and it decreases the friction-like force caused by the binding of the moving surface with respect to the growing actin network.

Covalent Incorporation of Ionic Liquid into Ion-Conductive Networks via Thiol-Ene Photopolymerization.

PubMed

Tibbits, Andrew C; Yan, Yushan S; Kloxin, Christopher J

2017-07-01

Ene-functionalized ionic liquids with a range of different cationic groups and counteranions react stoichiometrically within a tetrathiol-divinyl ether formulation within 20 minutes to form thiol-ene polymers with measurable ionic conductivities via a photoinitiated polymerization and crosslinking reaction. Dynamic mechanical analysis indicates that these networks are more spatially heterogeneous and possess higher glass transition temperatures (T g ) compared with thiol-ene formulations without charge. While tuning the molar content of ionic liquid monomer is one method for adjusting the crosslink and charge densities of the thiol-ene polymeric ionic liquid networks, the presence of cation-anion interactions also plays a critical role in dictating the thermomechanical and conductive properties. Particularly, while cationic structure effects are not significant on the polymer properties, the use of a weakly coordinating hydrophobic anion (bistriflimide) instead of bromide-based networks results in an apparent decrease in hydrated ion conductivity (7.4 to 1.5 mS cm -1 ) and T g (-9.6 to -17.8 °C). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metastable Polymeric Nitrogen: The Ultimate Green High-Energy-Density Material

NASA Astrophysics Data System (ADS)

Ciezak, Jennifer

2007-06-01

High-energy-high-density materials offering increased stability, vulnerability, and environmental safety are being aggressively pursued to meet the requirements of the DoD Joint Visions and Future Force. Nearly two decades ago, it was proposed that polymeric nitrogen would exceed all of these requirements and possess nearly five times the energy of any conventional energetic material in use today. The present study details an investigation into nitrogen polymerization using a novel high-pressure approach utilizing sodium azide as the starting material. Due to the weaker bonding structure of the anionic azide chains in comparison to a N-N triple bond, one expects that the azide chains will create single-covalently bonded polymeric networks more easily than diatomic nitrogen. A polymeric form of sodium azide was synthesized at high pressures, but the material was not metastable at ambient conditions, which precluded performance testing. Quantum chemical calculations have indicated stabilization of the polymeric structure at ambient conditions may be possible with the addition of hydrogen. Vibrational spectroscopic characterization suggests that a meta-stable polymeric form of nitrogen has been synthesized under high-pressure using sodium azide/hydrogen as the starting materials. This material remains stable at ambient conditions upwards of two weeks depending on the storage conditions.

Proton conducting membranes for high temperature fuel cells with solid state water free membranes

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R. (Inventor); Yen, Shiao-Pin S. (Inventor)

2006-01-01

A water free, proton conducting membrane for use in a fuel cell is fabricated as a highly conducting sheet of converted solid state organic amine salt, such as converted acid salt of triethylenediamine with two quaternized tertiary nitrogen atoms, combined with a nanoparticulate oxide and a stable binder combined with the converted solid state organic amine salt to form a polymeric electrolyte membrane. In one embodiment the membrane is derived from triethylenediamine sulfate, hydrogen phosphate or trifiate, an oxoanion with at least one ionizable hydrogen, organic tertiary amine bisulfate, polymeric quaternized amine bisulfate or phosphate, or polymeric organic compounds with quaternizable nitrogen combined with Nafion to form an intimate network with ionic interactions.

Effect of hydrogen peroxide on the three-dimensional polymer network in composites.

PubMed

Durner, Jürgen; Stojanovic, Marija; Urcan, Ebru; Spahl, Werner; Haertel, Ursula; Hickel, Reinhard; Reichl, Franx-Xaver

2011-06-01

Less data are available about the effects of hydrogen peroxide on the three-dimensional polymer network of polymerized composites. Therefore the study was performed to test the effects of hydrogen peroxide on the three-dimensional polymer network in composites. Polymerized specimens from Tetric Flow®, Tetric Ceram® and Filtek™ Supreme XT were bleached with Opalescence® PF 15% for 5h or PF 35% for 0.5h, respectively, and then stored in methanol for 1d and 7d. Controls were unbleached specimens. The eluates were analyzed by gas chromatography/mass spectrometry. More methacrylic acid (MAA), bisphenol-A (BPA), ethoxylated bisphenol-A-dimethacrylate (BisEMA), hydroquinone monomethyl ether (HQME), 1,10-decanediol dimethacrylate (DDDMA) and/or triethylene glycol dimethacrylate (TEGDMA) were eluted from bleached specimens compared with non bleached controls (1d). The highest DDDMA amount of 419.8 μmol/l was found in the eluates after 7d in Tetric Flow® specimens treated with PF 15. The highest HQME amount of 159.6 μmol/l was found in eluates from Tetric Ceram® specimens treated with PF after 7d. The highest TEGDMA amount of 178.7 μmol/l was found in eluates from Filtek™ Supreme XT specimens treated with PF 35 after 7d. Bleaching with hydrogen peroxide has an effect on the three-dimensional polymer network in polymerized composites leading to an increase in the release of unpolymerized monomers, additives and unspecific oxidative products. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Iodopropyl-branched polysiloxane gel electrolytes with improved ionic conductivity upon cross-linking.

PubMed

De Gregorio, G L; Giannuzzi, R; Cipolla, M P; Agosta, R; Grisorio, R; Capodilupo, A; Suranna, G P; Gigli, G; Manca, M

2014-11-21

We here report the implementation of poly[(3-N-methylimidazoliumpropyl)methylsiloxane-co-dimethylsiloxane]iodides as suitable polymeric hosts for a novel class of in situ cross-linkable iodine/iodide-based gel-electrolytes for dye-sensitized solar cells. The polymers are first partially quaternized and then subjected to a thermal cross-linking which allows the formation of a 3D polymeric network which is accompanied by a dramatic enhancement of the ionic conductivity.

3D-Hydrogel Based Polymeric Nanoreactors for Silver Nano-Antimicrobial Composites Generation

PubMed Central

Soto-Quintero, Albanelly; Romo-Uribe, Ángel; Bermúdez-Morales, Víctor H.; Quijada-Garrido, Isabel

2017-01-01

This study underscores the development of Ag hydrogel nanocomposites, as smart substrates for antibacterial uses, via innovative in situ reactive and reduction pathways. To this end, two different synthetic strategies were used. Firstly thiol-acrylate (PSA) based hydrogels were attained via thiol-ene and radical polymerization of polyethylene glycol (PEG) and polycaprolactone (PCL). As a second approach, polyurethane (PU) based hydrogels were achieved by condensation polymerization from diisocyanates and PCL and PEG diols. In fact, these syntheses rendered active three-dimensional (3D) hydrogel matrices which were used as nanoreactors for in situ reduction of AgNO3 to silver nanoparticles. A redox chemistry of stannous catalyst in PU hydrogel yielded spherical AgNPs formation, even at 4 °C in the absence of external reductant; and an appropriate thiol-functionalized polymeric network promoted spherical AgNPs well dispersed through PSA hydrogel network, after heating up the swollen hydrogel at 103 °C in the presence of citrate-reductant. Optical and swelling behaviors of both series of hydrogel nanocomposites were investigated as key factors involved in their antimicrobial efficacy over time. Lastly, in vitro antibacterial activity of Ag loaded hydrogels exposed to Pseudomona aeruginosa and Escherichia coli strains indicated a noticeable sustained inhibitory effect, especially for Ag–PU hydrogel nanocomposites with bacterial inhibition growth capabilities up to 120 h cultivation. PMID:28763050

A New Vertebral Body Replacement Strategy Using Expandable Polymeric Cages

PubMed Central

Liu, Xifeng; Paulsen, Alex; Giambini, Hugo; Guo, Ji; Miller, A. Lee; Lin, Po-Chun; Yaszemski, Michael J.

2017-01-01

We have developed a novel polymeric expandable cage that can be delivered via a posterior-only surgical approach for the treatment of noncontained vertebral defects. This approach is less invasive than an anterior-only or combined approach and much more cost-effective than currently used expandable metal cages. The polymeric expandable cage is composed of oligo poly(ethylene glycol) fumarate (OPF), a hydrogel that has been previously shown to have excellent nerve and bone tissue biocompatibility. OPF hydrogel cages can expand to twice their original diameter and length within a surgical time frame following hydration. Modulation of parameters such as polymeric network crosslink density or the introduction of charge to the network allowed for precise expansion kinetics. To meet specific requirements due to size variations in patient vertebral bodies, we fabricated a series of molds with varied diameters and explored the expansion kinetics of the OPF cages. Results showed a stable expansion ratio of approximately twofold to the original size within 20 min, regardless of the absolute value of the cage size. Following implantation of a dried OPF cage into a noncontained vertebral defect and its in situ expansion with normal saline, other augmentation biomaterials, such as poly(propylene fumarate) (PPF), can be injected to the lumen of the OPF cage and allowed to crosslink in situ. The OPF/PPF composite scaffold can provide the necessary rigidity and stability to the augmented spine. PMID:27835935

Preparation, Characterization and Utilization of Electrodes Coated with Polymeric Networks Formed by Gamma Radiation Crosslinking.

DTIC Science & Technology

1987-04-01

polymers such as poly[ diallyl dimethyl ammonium chloride] , poly [vinylbenzyl trimethyl ammonium chloride], poly[styrene sulfonic acid , sodium salt] and...poly[acrylic acid ], which would ordinarily dissolve from the electrode surface in aqueous solution unless crosslinked into a network, and several...Irradiation on a Water-Soluble Polymer: DDAC 8 E. Electrochemistry of DDAC Networks on Platinum and Graphite 10 F. Poly [acrylic acid ] Films on Graphite

Large strain deformation behavior of polymeric gels in shear- and cavitation rheology

NASA Astrophysics Data System (ADS)

Hashemnejad, Seyed Meysam; Kundu, Santanu

Polymeric gels are used in many applications including in biomedical and in food industries. Investigation of mechanical responses of swollen polymer gels and linking that to the polymer chain dynamics are of significant interest. Here, large strain deformation behavior of two different gel systems and with different network architecture will be presented. We consider biologically relevant polysaccharide hydrogels, formed through ionic and covalent crosslinking, and physically associating triblock copolymer gels in a midblock selective solvent. Gels with similar low-strain shear modulus display distinctly different non-linear rheological behavior in large strain shear deformation. Both these gels display strain-stiffening behavior in shear-deformation prior to macroscopic fracture of the network, however, only the alginate gels display negative normal stress. The cavitation rheology data show that the critical pressure for cavitation is higher for alginate gels than that observed for triblock gels. These distinctly different large-strain deformation behavior has been related to the gel network structure, as alginate chains are much stiffer than the triblock polymer chains.

Toward a versatile toolbox for cucurbit[n]uril-based supramolecular hydrogel networks through in situ polymerization.

PubMed

Liu, Ji; Soo Yun Tan, Cindy; Lan, Yang; Scherman, Oren A

2017-09-15

The success of exploiting cucurbit[ n ]uril (CB[ n ])-based molecular recognition in self-assembled systems has sparked a tremendous interest in polymer and materials chemistry. In this study, polymerization in the presence of host-guest complexes is applied as a modular synthetic approach toward a diverse set of CB[8]-based supramolecular hydrogels with desirable properties, such as mechanical strength, toughness, energy dissipation, self-healing, and shear-thinning. A range of vinyl monomers, including acrylamide-, acrylate-, and imidazolium-based hydrophilic monomers, could be easily incorporated as the polymer backbones, leading to a library of CB[8] hydrogel networks. This versatile strategy explores new horizons for the construction of supramolecular hydrogel networks and materials with emergent properties in wearable and self-healable electronic devices, sensors, and structural biomaterials. © 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3105-3109.

From microporous regular frameworks to mesoporous materials with ultrahigh surface area: dynamic reorganization of porous polymer networks.

PubMed

Kuhn, Pierre; Forget, Aurélien; Su, Dangsheng; Thomas, Arne; Antonietti, Markus

2008-10-08

High surface area organic materials featuring both micro- and mesopores were synthesized under ionothermal conditions via the formation of polyaryltriazine networks. While the polytrimerization of nitriles in zinc chloride at 400 degrees C produces microporous polymers, higher reaction temperatures induce the formation of additional spherical mesopores with a narrow dispersity. The nitrogen-rich carbonaceous polymer materials thus obtained present surface areas and porosities up to 3300 m(2) g(-1) and 2.4 cm(3) g(-1), respectively. The key point of this synthesis relies on the occurrence of several high temperature polymerization reactions, where irreversible carbonization reactions coupled with the reversible trimerization of nitriles allow the reorganization of the dynamic triazine network. The ZnCl2 molten salt fulfills the requirement of a high temperature solvent, but is also required as catalyst. Thus, this dynamic polymerization system provides not only highly micro- and mesoporous materials, but also allows controlling the pore structure in amorphous organic materials.

Pressure induced polymerization of acetylide anions in CaC2 and 107 fold enhancement of electrical conductivity.

PubMed

Zheng, Haiyan; Wang, Lijuan; Li, Kuo; Yang, Youyou; Wang, Yajie; Wu, Jiajia; Dong, Xiao; Wang, Chun-Hai; Tulk, Christopher A; Molaison, Jamie J; Ivanov, Ilia N; Feygenson, Mikhail; Yang, Wenge; Guthrie, Malcolm; Zhao, Yusheng; Mao, Ho-Kwang; Jin, Changqing

2017-01-01

Transformation between different types of carbon-carbon bonding in carbides often results in a dramatic change of physical and chemical properties. Under external pressure, unsaturated carbon atoms form new covalent bonds regardless of the electrostatic repulsion. It was predicted that calcium acetylide (also known as calcium carbide, CaC 2 ) polymerizes to form calcium polyacetylide, calcium polyacenide and calcium graphenide under high pressure. In this work, the phase transitions of CaC 2 under external pressure were systematically investigated, and the amorphous phase was studied in detail for the first time. Polycarbide anions like C 6 6- are identified with gas chromatography-mass spectrometry and several other techniques, which evidences the pressure induced polymerization of the acetylide anions and suggests the existence of the polyacenide fragment. Additionally, the process of polymerization is accompanied with a 10 7 fold enhancement of the electrical conductivity. The polymerization of acetylide anions demonstrates that high pressure compression is a viable route to synthesize novel metal polycarbides and materials with extended carbon networks, while shedding light on the synthesis of more complicated metal organics.

Measuring the regulation of keratin filament network dynamics

PubMed Central

Moch, Marcin; Herberich, Gerlind; Aach, Til; Leube, Rudolf E.; Windoffer, Reinhard

2013-01-01

The organization of the keratin intermediate filament cytoskeleton is closely linked to epithelial function. To study keratin network plasticity and its regulation at different levels, tools are needed to localize and measure local network dynamics. In this paper, we present image analysis methods designed to determine the speed and direction of keratin filament motion and to identify locations of keratin filament polymerization and depolymerization at subcellular resolution. Using these methods, we have analyzed time-lapse fluorescence recordings of fluorescent keratin 13 in human vulva carcinoma-derived A431 cells. The fluorescent keratins integrated into the endogenous keratin cytoskeleton, and thereby served as reliable markers of keratin dynamics. We found that increased times after seeding correlated with down-regulation of inward-directed keratin filament movement. Bulk flow analyses further revealed that keratin filament polymerization in the cell periphery and keratin depolymerization in the more central cytoplasm were both reduced. Treating these cells and other human keratinocyte-derived cells with EGF reversed all these processes within a few minutes, coinciding with increased keratin phosphorylation. These results highlight the value of the newly developed tools for identifying modulators of keratin filament network dynamics and characterizing their mode of action, which, in turn, contributes to understanding the close link between keratin filament network plasticity and epithelial physiology. PMID:23757496

Hydrophobic Coatings on Cotton Obtained by in Situ Plasma Polymerization of a Fluorinated Monomer in Ethanol Solutions.

PubMed

Molina, Ricardo; Teixidó, Josep Maria; Kan, Chi-Wai; Jovančić, Petar

2017-02-15

Plasma polymerization using hydrophobic monomers in the gas phase is a well-known technology to generate hydrophobic coatings. However, synthesis of functional hydrophobic coatings using plasma technology in liquids has not yet been accomplished. This work is consequently focused on polymerization of a liquid fluorinated monomer on cotton fabric initiated by atmospheric plasma in a dielectric barrier discharge configuration. Functional hydrophobic coatings on cotton were successfully achieved using in situ atmospheric plasma-initiated polymerization of fluorinated monomer dissolved in ethanol. Gravimetric measurements reveal that the amount of polymer deposited on cotton substrates can be modulated with the concentration of monomer in ethanol solution, and cross-linking reactions occur during plasma polymerization of a fluorinated monomer even without the presence of a cross-linking agent. FTIR and XPS analysis were used to study the chemical composition of hydrophobic coatings and to get insights into the physicochemical processes involved in plasma treatment. SEM analysis reveals that at high monomer concentration, coatings possess a three-dimensional pattern with a characteristic interconnected porous network structure. EDX analysis reveals that plasma polymerization of fluorinated monomers takes place preferentially at the surface of cotton fabric and negligible polymerization takes place inside the cotton fabric. Wetting time measurements confirm the hydrophobicity of cotton coatings obtained although equilibrium moisture content was slightly decreased. Additionally, the abrasion behavior and resistance to washing of plasma-coated cotton has been evaluated.

Computer Simulations of Bottlebrush Melts and Soft Networks

NASA Astrophysics Data System (ADS)

Cao, Zhen; Carrillo, Jan-Michael; Sheiko, Sergei; Dobrynin, Andrey

We have studied dense bottlebrush systems in a melt and network state using a combination of the molecular dynamics simulations and analytical calculations. Our simulations show that the bottlebrush macromolecules in a melt behave as ideal chains with the effective Kuhn length bK. The bottlebrush induced bending rigidity is due to redistribution of the side chains upon backbone bending. Kuhn length of the bottlebrushes increases with increasing the side-chain degree of polymerization nsc as bK ~nsc0 . 46 . This model of bottlebrush macromolecules is extended to describe mechanical properties of bottlebrush networks in linear and nonlinear deformation regimes. In the linear deformation regime, the network shear modulus scales with the degree of polymerization of the side chains as G0 ~nsc + 1 - 1 as long as the ratio of the Kuhn length to the size of the fully extended bottlebrush backbone between crosslinks, Rmax, is smaller than unity, bK /Rmax < < 1 . Bottlebrush networks with bK /Rmax ~ 1 demonstrate behavior similar to that of networks of semiflexible chains with G0 ~nsc- 0 . 5 . In the nonlinear deformation regime, the deformation dependent shear modulus is a universal function of the first strain invariant I1 and bottlebrush backbone deformation ratio β describing stretching ability of the bottlebrush backbone between crosslinks. Nsf DMR-1409710 DMR-1436201.

Thermal decomposition of cyanate ester resins

DOT National Transportation Integrated Search

2001-09-01

Polycyanurate networks were prepared by thermal polymerization of cyanate ester monomers containing two or more cyanate ester : (O-CN) functional groups. The thermal decomposition chemistry of nine different polycyanurates was studied by : ther...

Semi-Interpenetrating polymer network hydrogels based on aspen hemicellulose and chitosan: Effect of crosslinking sequence on hydrogel properties

Treesearch

Muzaffer Ahmet Karaaslan; Mandla A. Tshabalala; Gisela Buschle-Diller

2012-01-01

Semi-interpenetrating network hydrogel films were prepared using hemicellulose and chemically crosslinked chitosan. Hemicellulose was extracted from aspen by using a novel alkaline treatment and characterized by HPSEC, and consisted of a mixture of high and low molecular weight polymeric fractions. HPLC analysis of the acid hydrolysate of the hemicellulose showed that...

Dimethacrylate network formation and polymer property evolution as determined by the selection of monomers and curing conditions

PubMed Central

Stansbury, Jeffrey W.

2011-01-01

Objectives This overview is intended to highlight connections between monomer structure and the development of highly crosslinked photopolymer networks including the conversion dependent properties of shrinkage, modulus and stress. Methods A review is provided that combines the polymer science and dental materials literature along with examples of relevant experimental results, which include measurements of reaction kinetics, photorheology as well as polymerization shrinkage and stress. Results While new monomers are continually under development for dental materials applications, mixtures of dimethacrylate monomers persist as the most common form of dental resins used on composite restorative materials. Monomer viscosity and reaction potential is derived from molecular structure and by employing real-time near-infrared spectroscopic techniques, the development of macromolecular networks is linked to the evolution of polymerization shrinkage (measured by linometer), modulus (measured by photorheometer), and stress (measured by tensometer). Relationships between the respective polymer properties are examined. Significance Through a better understanding of the polymer network formation and property development processes using conventional dimethacrylate monomer formulations, the rational design of improved materials is facilitated with the ultimate goal of achieving dental polymers that deliver enhanced clinical outcomes. PMID:22192248

Chronology of guitarrero cave, peru.

PubMed

Lynch, T F; Gillespie, R; Gowlett, J A; Hedges, R E

1985-08-30

Dating by accelerator mass spectrometry of wooden artifacts, cord, and charcoal samples from Guitarrero Cave, Peru, supports the antiquity of South America's earliest textiles and other perishable remains. The new dates are consistent with those obtained from disintegration counters and leave little doubt about the integrity of the lower Preceramic layers and their early cultivars. Re-evaluation of the mode of deposition suggests that most of the remains resulted from short-term use of the cave in the eighth millennium B.C., with a possible brief human visit as early as 12,560 years ago.

The Preparation of Silicon-Containing Ceramics by Organosilicon Polymer Pyrolysis

DTIC Science & Technology

1988-06-25

polymer , of composition [(CH3SiHNH)a(CH3SiNb]m, gives a black solid, a mixture of SiC , Si3N4, and some free carbon, on pyrolysis ...nitride (eq. 1) [7] is a possibility. 5 Si3N 4(s) + C (s) , 3 SiC (s) +2 N2(g) (1) The study of the pyrolysis products of preceramic polymers is not...approximately one, pyrolysis of the product polymer gave a black ceramic solid in 84% yield which analysis showed to have a formal composition (1 SiC +

Advanced Zinc Phosphate Conversion and Pre-Ceramic Polymetallosiloxane Coatings for Corrosion Protection of Steel and Aluminum, and Characteristics of Polyphenyletheretherketone-Based Materials

DTIC Science & Technology

1992-09-24

which the trivalent ion is the principal oxidation state, preferentially reacts with hydroxylated organosilane to form the Al-O-Si linkage at a low... tig front the carboxylic acid, COOH, in the p(AA) [6j. The spectra for all of the cobalt- and nickel-incorporated Zn-Ph samples show a slight...to study bonding in chromium , manganese, iron, and cobalt compounds J Chem Phys 57 (1972) pp 973-982 1 1 Lindberg, B.J. et at. Molecular

Actin-mediated bacterial propulsion: comet profile, velocity pulsations.

PubMed

Benza, V G

2008-05-23

The propulsion of bacteria under the action of an actin gel network is examined in terms of gel concentration dynamics. The model includes the elasticity of the network, the gel-bacterium interaction, the bulk and interface polymerization. A formula for the cruise velocity is obtained where the contributions to bacterial motility arising from elasticity and polymerization are made explicit. Higher velocities correspond to lower concentration peaks and longer tails, in agreement with experimental results. The condition for the onset of motion is explicitly given. The behavior of the system is explored by varying the growth rates and the gel elasticity. At steady state two regimes are found, respectively, of constant and pulsating velocity; in the latter case, the velocity undergoes sudden accelerations and subsequent recoveries. The transition to the pulsating regime is obtained by increasing the elastic response of the gel.

New physical concepts for cell amoeboid motion.

PubMed Central

Evans, E

1993-01-01

Amoeboid motion of cells is an essential mechanism in the function of many biological organisms (e.g., the regiment of scavenger cells in the immune defense system of animals). This process involves rapid chemical polymerization (with numerous protein constituents) to create a musclelike contractile network that advances the cell over the surface. Significant progress has been made in the biology and biochemistry of motile cells, but the physical dynamics of cell spreading and contraction are not well understood. The reason is that general approaches are formulated from complex mass, momentum, and chemical reaction equations for multiphase-multicomponent flow with the nontrivial difficulty of moving boundaries. However, there are strong clues to the dynamics that allow bold steps to be taken in simplifying the physics of motion. First, amoeboid cells often exhibit exceptional kinematics, i.e., steady advance and retraction of local fixed-shape patterns. Second, recent evidence has shown that cell projections "grow" by polymerization along the advancing boundary of the cell. Together, these characteristics represent a local growth process pinned to the interfacial contour of a contractile network. As such, the moving boundary becomes tractable, but subtle features of the motion lead to specific requirements for the chemical nature of the boundary polymerization process. To demonstrate these features, simple examples for limiting conditions of substrate interaction (i.e., "strong" and "weak" adhesion) are compared with data from experimental studies of yeast particle engulfment by blood granulocytes and actin network dynamics in fishscale keratocytes. Images FIGURE 2 FIGURE 4 PMID:8494986

New physical concepts for cell amoeboid motion.

PubMed

Evans, E

1993-04-01

Amoeboid motion of cells is an essential mechanism in the function of many biological organisms (e.g., the regiment of scavenger cells in the immune defense system of animals). This process involves rapid chemical polymerization (with numerous protein constituents) to create a musclelike contractile network that advances the cell over the surface. Significant progress has been made in the biology and biochemistry of motile cells, but the physical dynamics of cell spreading and contraction are not well understood. The reason is that general approaches are formulated from complex mass, momentum, and chemical reaction equations for multiphase-multicomponent flow with the nontrivial difficulty of moving boundaries. However, there are strong clues to the dynamics that allow bold steps to be taken in simplifying the physics of motion. First, amoeboid cells often exhibit exceptional kinematics, i.e., steady advance and retraction of local fixed-shape patterns. Second, recent evidence has shown that cell projections "grow" by polymerization along the advancing boundary of the cell. Together, these characteristics represent a local growth process pinned to the interfacial contour of a contractile network. As such, the moving boundary becomes tractable, but subtle features of the motion lead to specific requirements for the chemical nature of the boundary polymerization process. To demonstrate these features, simple examples for limiting conditions of substrate interaction (i.e., "strong" and "weak" adhesion) are compared with data from experimental studies of yeast particle engulfment by blood granulocytes and actin network dynamics in fishscale keratocytes.

Pressure-Induced Polymerization of LiN(CN) 2

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

Keefer, Derek W.; Gou, Huiyang; Purdy, Andrew P.

The high-pressure behavior of lithium dicyanamide (LiN(CN) 2) was studied with in situ Raman and infrared (IR) spectroscopies, and synchrotron angle-dispersive powder X-ray diffraction (PXRD) in a diamond anvil cell (DAC) to 22 GPa. The fundamental vibrational modes associated with molecular units were assigned using a combination of experimental data and density functional perturbation theory. Some low-frequency modes were observed for the first time. On the basis of spectroscopic and diffraction data, we suggest a polymorphic phase transformation at ~8 GPa, wherein dicyanamide ions remain as discrete molecular species. Above ca. 18 GPa, dicyanamide units polymerize, forming a largely disorderedmore » network, and the extent of polymerization may be increased by annealing at elevated temperature. The polymerized product consists of tricyanomelaminate-like groups containing sp 2-hybidized carbon–nitrogen bonds and exhibits a visible absorption edge near 540 nm. The product is recoverable to ambient conditions but is not stable in air/moisture.« less

On-Surface Domino Reactions: Glaser Coupling and Dehydrogenative Coupling of a Biscarboxylic Acid To Form Polymeric Bisacylperoxides.

PubMed

Held, Philipp Alexander; Gao, Hong-Ying; Liu, Lacheng; Mück-Lichtenfeld, Christian; Timmer, Alexander; Mönig, Harry; Barton, Dennis; Neugebauer, Johannes; Fuchs, Harald; Studer, Armido

2016-08-08

Herein we report the on-surface oxidative homocoupling of 6,6'-(1,4-buta-1,3-diynyl)bis(2-naphthoic acid) (BDNA) via bisacylperoxide formation on different Au substrates. By using this unprecedented dehydrogenative polymerization of a biscarboxylic acid, linear poly-BDNA with a chain length of over 100 nm was prepared. It is shown that the monomer BDNA can be prepared in situ at the surface via on-surface Glaser coupling of 6-ethynyl-2-naphthoic acid (ENA). Under the Glaser coupling conditions, BDNA directly undergoes polymerization to give the polymeric peroxide (poly-BDNA) representing a first example of an on-surface domino reaction. It is shown that the reaction outcome varies as a function of surface topography (Au(111) or Au(100)) and also of the surface coverage, to give branched polymers, linear polymers, or 2D metal-organic networks. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Zheng, Haiyan; Wang, Lijuan; Li, Kuo

Transformation between different types of carbon–carbon bonding in carbides often results in a dramatic change of physical and chemical properties. Under external pressure, unsaturated carbon atoms form new covalent bonds regardless of the electrostatic repulsion. It was predicted that calcium acetylide (also known as calcium carbide, CaC2) polymerizes to form calcium polyacetylide, calcium polyacenide and calcium graphenide under high pressure. In this work, the phase transitions of CaC2 under external pressure were systematically investigated, and the amorphous phase was studied in detail for the first time. Polycarbide anions like C 6 6- are identified with gas chromatography-mass spectrometry and severalmore » other techniques, which evidences the pressure induced polymerization of the acetylide anions and suggests the existence of the polyacenide fragment. Additionally, the process of polymerization is accompanied with a 107 fold enhancement of the electrical conductivity. The polymerization of acetylide anions demonstrates that high pressure compression is a viable route to synthesize novel metal polycarbides and materials with extended carbon networks, while shedding light on the synthesis of more complicated metal organics.« less

Chemotaxis and Actin Oscillations

NASA Astrophysics Data System (ADS)

Bodenschatz, Eberhard; Hsu, Hsin-Fang; Negrete, Jose; Beta, Carsten; Pumir, Alain; Gholami, Azam; Tarantola, Marco; Westendorf, Christian; Zykov, Vladimir

Recently, self-oscillations of the cytoskeletal actin have been observed in Dictyostelium, a model system for studying chemotaxis. Here we report experimental results on the self-oscillation mechanism and the role of regulatory proteins and myosin II. We stimulate cells rapidly and periodically by using photo un-caging of the chemoattractant in a micro-fluidic device and measured the cellular responses. We found that the response amplitude grows with stimulation strength only in a very narrow region of stimulation, after which the response amplitude reaches a plateau. Moreover, the frequency-response is not constant but rather varies with the strength of external stimuli. To understand the underlying mechanism, we analyzed the polymerization and de-polymerization time in the single cell level. Despite of the large cell-to-cell variability, we found that the polymerization time is independent of external stimuli and the de-polymerization time is prolonged as the stimulation strength increases. Our conclusions will be summarized and the role of noise in the signaling network will be discussed. German Science Foundation CRC 937.

Force-velocity relation for actin-polymerization-driven motility from Brownian dynamics simulations.

PubMed

Lee, Kun-Chun; Liu, Andrea J

2009-09-02

We report numerical simulation results for the force-velocity relation for actin-polymerization-driven motility. We use Brownian dynamics to solve a physically consistent formulation of the dendritic nucleation model with semiflexible filaments that self-assemble and push a disk. We find that at small loads, the disk speed is independent of load, whereas at high loads, the speed decreases and vanishes at a characteristic stall pressure. Our results demonstrate that at small loads, the velocity is controlled by the reaction rates, whereas at high loads the stall pressure is determined by the mechanical properties of the branched actin network. The behavior is consistent with experiments and with our recently proposed self-diffusiophoretic mechanism for actin-polymerization-driven motility. New in vitro experiments to measure the force-velocity relation are proposed.

High performance, durable polymers including poly(phenylene)

DOEpatents

Fujimoto, Cy; Pratt, Harry; Anderson, Travis Mark

2017-02-28

The present invention relates to functionalized polymers including a poly(phenylene) structure. In some embodiments, the polymers and copolymers of the invention include a highly localized concentration of acidic moieties, which facilitate proton transport and conduction through networks formed from these polymers. In addition, the polymers can include functional moieties, such as electron-withdrawing moieties, to protect the polymeric backbone, thereby extending its durability. Such enhanced proton transport and durability can be beneficial for any high performance platform that employs proton exchange polymeric membranes, such as in fuel cells or flow batteries.

Processable high-carbon-yielding polymer for micro- and nanofabrication

NASA Astrophysics Data System (ADS)

Perpall, Mark W.; Zengin, Huseyin; Perera, K. Prasanna U.; Zhou, Wensheng; Shah, Hiren; Wu, Xinyu; Creager, Stephen E.; Smith, Dennis W., Jr.; Foulger, Stephen H.; Ballato, John M.

2003-01-01

Bis-ortho-Diynyl Arene (BODA) monomers polymerize to network polynapthalene by the thermally-driven Bergman cyclization and subsequent radical polymerization via oligomeric intermediates that can be melt or solution processed. Further heating of the network to 1000 °C affords a high-yield glassy carbon structure that retains the approximate size and dimensions of the polymer precursor. The higher carbon-yield for BODA networks (75- 80 % by mass) is significantly greater than that of traditional phenol-formaldehyde resins and other carbon precursor polymers leading to its greater dimensional stability. Phenyl terminated BODA derived polymers were fabricated using microprocessing such as the micromolding in capillaries (MIMIC) technique, direct microtransfer molding, and molding in quartz capillary tubes. Nano-scale fabrication using closed packed silica spheres as templates was demonstrated with an hydroxy-terminated monomer which exhibits greatly enhanced compatibility for silica surfaces. After pyrolysis to glassy carbon, the silica is chemically etched leaving an inverse carbon opal photonic crystal which is electrically conductive. The wavelength of light diffracted is a function of the average refractive index of the carbon/ filler composite, which can be modified for use as sensitive detector elements.

Effects of polymerization and nucleotide identity on the conformational dynamics of the bacterial actin homolog MreB

PubMed Central

Colavin, Alexandre; Hsin, Jen; Huang, Kerwyn Casey

2014-01-01

The assembly of protein filaments drives many cellular processes, from nucleoid segregation, growth, and division in single cells to muscle contraction in animals. In eukaryotes, shape and motility are regulated through cycles of polymerization and depolymerization of actin cytoskeletal networks. In bacteria, the actin homolog MreB forms filaments that coordinate the cell-wall synthesis machinery to regulate rod-shaped growth and contribute to cellular stiffness through unknown mechanisms. Like actin, MreB is an ATPase and requires ATP to polymerize, and polymerization promotes nucleotide hydrolysis. However, it is unclear whether other similarities exist between MreB and actin because the two proteins share low sequence identity and have distinct cellular roles. Here, we use all-atom molecular dynamics simulations to reveal surprising parallels between MreB and actin structural dynamics. We observe that MreB exhibits actin-like polymerization-dependent structural changes, wherein polymerization induces flattening of MreB subunits, which restructures the nucleotide-binding pocket to favor hydrolysis. MreB filaments exhibited nucleotide-dependent intersubunit bending, with hydrolyzed polymers favoring a straighter conformation. We use steered simulations to demonstrate a coupling between intersubunit bending and the degree of flattening of each subunit, suggesting cooperative bending along a filament. Taken together, our results provide molecular-scale insight into the diversity of structural states of MreB and the relationships among polymerization, hydrolysis, and filament properties, which may be applicable to other members of the broad actin family. PMID:24550504

Effects of polymerization and nucleotide identity on the conformational dynamics of the bacterial actin homolog MreB.

PubMed

Colavin, Alexandre; Hsin, Jen; Huang, Kerwyn Casey

2014-03-04

The assembly of protein filaments drives many cellular processes, from nucleoid segregation, growth, and division in single cells to muscle contraction in animals. In eukaryotes, shape and motility are regulated through cycles of polymerization and depolymerization of actin cytoskeletal networks. In bacteria, the actin homolog MreB forms filaments that coordinate the cell-wall synthesis machinery to regulate rod-shaped growth and contribute to cellular stiffness through unknown mechanisms. Like actin, MreB is an ATPase and requires ATP to polymerize, and polymerization promotes nucleotide hydrolysis. However, it is unclear whether other similarities exist between MreB and actin because the two proteins share low sequence identity and have distinct cellular roles. Here, we use all-atom molecular dynamics simulations to reveal surprising parallels between MreB and actin structural dynamics. We observe that MreB exhibits actin-like polymerization-dependent structural changes, wherein polymerization induces flattening of MreB subunits, which restructures the nucleotide-binding pocket to favor hydrolysis. MreB filaments exhibited nucleotide-dependent intersubunit bending, with hydrolyzed polymers favoring a straighter conformation. We use steered simulations to demonstrate a coupling between intersubunit bending and the degree of flattening of each subunit, suggesting cooperative bending along a filament. Taken together, our results provide molecular-scale insight into the diversity of structural states of MreB and the relationships among polymerization, hydrolysis, and filament properties, which may be applicable to other members of the broad actin family.

Pressure induced polymerization of acetylide anions in CaC 2 and 10 7 fold enhancement of electrical conductivity

DOE PAGES

Zheng, Haiyan; Wang, Lijuan; Li, Kuo; ...

2016-08-17

Transformation between different types of carbon–carbon bonding in carbides often results in a dramatic change of physical and chemical properties. Under external pressure, unsaturated carbon atoms form new covalent bonds regardless of the electrostatic repulsion. It was predicted that calcium acetylide (also known as calcium carbide, CaC 2) polymerizes to form calcium polyacetylide, calcium polyacenide and calcium graphenide under high pressure. In this work, the phase transitions of CaC 2 under external pressure were systematically investigated, and the amorphous phase was studied in detail for the first time. Polycarbide anions like C 6 6– are identified with gas chromatography-mass spectrometrymore » and several other techniques, which evidences the pressure induced polymerization of the acetylide anions and suggests the existence of the polyacenide fragment. Additionally, the process of polymerization is accompanied with a 10 7 fold enhancement of the electrical conductivity. As a result, the polymerization of acetylide anions demonstrates that high pressure compression is a viable route to synthesize novel metal polycarbides and materials with extended carbon networks, while shedding light on the synthesis of more complicated metal organics.« less

Real-time synchronous measurement of curing characteristics and polymerization stress in bone cements with a cantilever-beam based instrument

NASA Astrophysics Data System (ADS)

Palagummi, Sri Vikram; Landis, Forrest A.; Chiang, Martin Y. M.

2018-03-01

An instrumentation capable of simultaneously determining degree of conversion (DC), polymerization stress (PS), and polymerization exotherm (PE) in real time was introduced to self-curing bone cements. This comprises the combination of an in situ high-speed near-infrared spectrometer, a cantilever-beam instrument with compliance-variable feature, and a microprobe thermocouple. Two polymethylmethacrylate-based commercial bone cements, containing essentially the same raw materials but differ in their viscosity for orthopedic applications, were used to demonstrate the applicability of the instrumentation. The results show that for both the cements studied the final DC was marginally different, the final PS was different at the low compliance, the peak of the PE was similar, and their polymerization rates were significantly different. Systematic variation of instrumental compliance for testing reveals differences in the characteristics of PS profiles of both the cements. This emphasizes the importance of instrumental compliance in obtaining an accurate understanding of PS evaluation. Finally, the key advantage for the simultaneous measurements is that these polymerization properties can be correlated directly, thus providing higher measurement confidence and enables a more in-depth understanding of the network formation process.

Adhesive F-actin Waves: A Novel Integrin-Mediated Adhesion Complex Coupled to Ventral Actin Polymerization

PubMed Central

Case, Lindsay B.; Waterman, Clare M.

2011-01-01

At the leading lamellipodium of migrating cells, protrusion of an Arp2/3-nucleated actin network is coupled to formation of integrin-based adhesions, suggesting that Arp2/3-mediated actin polymerization and integrin-dependent adhesion may be mechanistically linked. Arp2/3 also mediates actin polymerization in structures distinct from the lamellipodium, in “ventral F-actin waves” that propagate as spots and wavefronts along the ventral plasma membrane. Here we show that integrins engage the extracellular matrix downstream of ventral F-actin waves in several mammalian cell lines as well as in primary mouse embryonic fibroblasts. These “adhesive F-actin waves” require a cycle of integrin engagement and disengagement to the extracellular matrix for their formation and propagation, and exhibit morphometry and a hierarchical assembly and disassembly mechanism distinct from other integrin-containing structures. After Arp2/3-mediated actin polymerization, zyxin and VASP are co-recruited to adhesive F-actin waves, followed by paxillin and vinculin, and finally talin and integrin. Adhesive F-actin waves thus represent a previously uncharacterized integrin-based adhesion complex associated with Arp2/3-mediated actin polymerization. PMID:22069459

CVD Polymers for Devices and Device Fabrication.

PubMed

Wang, Minghui; Wang, Xiaoxue; Moni, Priya; Liu, Andong; Kim, Do Han; Jo, Won Jun; Sojoudi, Hossein; Gleason, Karen K

2017-03-01

Chemical vapor deposition (CVD) polymerization directly synthesizes organic thin films on a substrate from vapor phase reactants. Dielectric, semiconducting, electrically conducting, and ionically conducting CVD polymers have all been readily integrated into devices. The absence of solvent in the CVD process enables the growth of high-purity layers and avoids the potential of dewetting phenomena, which lead to pinhole defects. By limiting contaminants and defects, ultrathin (<10 nm) CVD polymeric device layers have been fabricated in multiple laboratories. The CVD method is particularly suitable for synthesizing insoluble conductive polymers, layers with high densities of organic functional groups, and robust crosslinked networks. Additionally, CVD polymers are prized for the ability to conformally cover rough surfaces, like those of paper and textile substrates, as well as the complex geometries of micro- and nanostructured devices. By employing low processing temperatures, CVD polymerization avoids damaging substrates and underlying device layers. This report discusses the mechanisms of the major CVD polymerization techniques and the recent progress of their applications in devices and device fabrication, with emphasis on initiated CVD (iCVD) and oxidative CVD (oCVD) polymerization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mesoscopic model of actin-based propulsion.

PubMed

Zhu, Jie; Mogilner, Alex

2012-01-01

Two theoretical models dominate current understanding of actin-based propulsion: microscopic polymerization ratchet model predicts that growing and writhing actin filaments generate forces and movements, while macroscopic elastic propulsion model suggests that deformation and stress of growing actin gel are responsible for the propulsion. We examine both experimentally and computationally the 2D movement of ellipsoidal beads propelled by actin tails and show that neither of the two models can explain the observed bistability of the orientation of the beads. To explain the data, we develop a 2D hybrid mesoscopic model by reconciling these two models such that individual actin filaments undergoing nucleation, elongation, attachment, detachment and capping are embedded into the boundary of a node-spring viscoelastic network representing the macroscopic actin gel. Stochastic simulations of this 'in silico' actin network show that the combined effects of the macroscopic elastic deformation and microscopic ratchets can explain the observed bistable orientation of the actin-propelled ellipsoidal beads. To test the theory further, we analyze observed distribution of the curvatures of the trajectories and show that the hybrid model's predictions fit the data. Finally, we demonstrate that the model can explain both concave-up and concave-down force-velocity relations for growing actin networks depending on the characteristic time scale and network recoil. To summarize, we propose that both microscopic polymerization ratchets and macroscopic stresses of the deformable actin network are responsible for the force and movement generation.

DNA-nanoparticle assemblies go organic: macroscopic polymeric materials with nanosized features.

PubMed

Mentovich, Elad D; Livanov, Konstantin; Prusty, Deepak K; Sowwan, Mukules; Richter, Shachar

2012-05-30

One of the goals in the field of structural DNA nanotechnology is the use of DNA to build up 2- and 3-D nanostructures. The research in this field is motivated by the remarkable structural features of DNA as well as by its unique and reversible recognition properties. Nucleic acids can be used alone as the skeleton of a broad range of periodic nanopatterns and nanoobjects and in addition, DNA can serve as a linker or template to form DNA-hybrid structures with other materials. This approach can be used for the development of new detection strategies as well as nanoelectronic structures and devices. Here we present a new method for the generation of unprecedented all-organic conjugated-polymer nanoparticle networks guided by DNA, based on a hierarchical self-assembly process. First, microphase separation of amphiphilic block copolymers induced the formation of spherical nanoobjects. As a second ordering concept, DNA base pairing has been employed for the controlled spatial definition of the conjugated-polymer particles within the bulk material. These networks offer the flexibility and the diversity of soft polymeric materials. Thus, simple chemical methodologies could be applied in order to tune the network's electrical, optical and mechanical properties. One- two- and three-dimensional networks have been successfully formed. Common to all morphologies is the integrity of the micelles consisting of DNA block copolymer (DBC), which creates an all-organic engineered network.

Magnetic assembly of transparent and conducting graphene-based functional composites

NASA Astrophysics Data System (ADS)

Le Ferrand, Hortense; Bolisetty, Sreenath; Demirörs, Ahmet F.; Libanori, Rafael; Studart, André R.; Mezzenga, Raffaele

2016-06-01

Innovative methods producing transparent and flexible electrodes are highly sought in modern optoelectronic applications to replace metal oxides, but available solutions suffer from drawbacks such as brittleness, unaffordability and inadequate processability. Here we propose a general, simple strategy to produce hierarchical composites of functionalized graphene in polymeric matrices, exhibiting transparency and electron conductivity. These are obtained through protein-assisted functionalization of graphene with magnetic nanoparticles, followed by magnetic-directed assembly of the graphene within polymeric matrices undergoing sol-gel transitions. By applying rotating magnetic fields or magnetic moulds, both graphene orientation and distribution can be controlled within the composite. Importantly, by using magnetic virtual moulds of predefined meshes, graphene assembly is directed into double-percolating networks, reducing the percolation threshold and enabling combined optical transparency and electrical conductivity not accessible in single-network materials. The resulting composites open new possibilities on the quest of transparent electrodes for photovoltaics, organic light-emitting diodes and stretchable optoelectronic devices.

Silane–Acrylate Chemistry for Regulating Network Formation in Radical Photopolymerization

PubMed Central

2017-01-01

Photoinitiated silane–ene chemistry has the potential to pave the way toward spatially resolved organosilicon compounds, which might find application in biomedicine, microelectronics, and other advanced fields. Moreover, this approach could serve as a viable alternative to the popular photoinitiated thiol–ene chemistry, which gives access to defined and functional photopolymer networks. A difunctional bis(trimethylsilyl)silane with abstractable hydrogens (DSiH) was successfully synthesized in a simple one-pot procedure. The radical reactivity of DSiH with various homopolymerizable monomers (i.e., (meth)acrylate, vinyl ester, acrylamide) was assessed via 1H NMR spectroscopic studies. DSiH shows good reactivity with acrylates and vinyl esters. The most promising silane–acrylate system was further investigated in cross-linking formulations toward its reactivity (e.g., heat of polymerization, curing time, occurrence of gelation, double-bond conversion) and compared to state-of-the-art thiol–acrylate resins. The storage stability of prepared resin formulations is greatly improved for silane–acrylate systems vs thiol–ene resins. Double-bond conversion at the gel point (DBCgel) and overall DBC were increased, and polymerization-induced shrinkage stress has been significantly reduced with the introduction of silane–acrylate chemistry. Resulting photopolymer networks exhibit a homogeneous network architecture (indicated by a narrow glass transition) that can be tuned by varying silane concentration, and this confirms the postulated regulation of radical network formation. Similar to thiol–acrylate networks, this leads to more flexible photopolymer networks with increased elongation at break and improved impact resistance. Additionally, swelling tests indicate a high gel fraction for silane–acrylate photopolymers. PMID:29033466

Computer Simulations of Bottle Brushes: From Melts to Soft Networks

DOE PAGES

Cao, Zhen; Carrillo, Jan-Michael Y.; Sheiko, Sergei S.; ...

2015-07-13

We use a combination of Molecular dynamics simulations and analytical calculations, and study dens bottle-brush systems in a melt and network State. Analysis of our simulation results shows that bottle-brush macromolecules in melt behave as ideal chains with effective Kuhn length b K. Simulations show that the bottle-brush-induced bending rigidity is due to an entropy decrease caused by redistribution of the side chains upon backbone bending. The Kuhn length of the bottle:brushes increases with increasing the side-chain degree of polymerization n sc as b K proportional to n sc 0.46. Moreover, this model of bottle brush macromolecules is extended tomore » describe mechanical properties of bottle brush networks in linear and nonlinear deformation regimes. In the linear deformation regime, the network shear modulus scales with the degree of polymerization of the side chains as G 0 proportional to (n sc + 1) -1 as long as the ratio of the Kuhn length, b K, to the size of the fully extended bottle-brush backbone between cross-links, R-max, is smaller than unity, b K/R max << 1. Bottle-brush networks With b K/R max proportional to 1 demonstrate behavior similar to that of networks Of semiflexible chains with G 0 proportional to n sc -0.5. Finally, in the nonlinear network deformation regime, the deformation-dependent shear modulus is a universal function of the first strain invariant I 1 and bottle-brush backbone deformation ratio beta describing stretching ability of the bottle-brush backbone between cross-links.« less

Synthesis, characterization, and morphology study of poly(acrylamide-co-acrylic acid)-grafted-poly(styrene-co-methyl methacrylate) "raspberry"-shape like structure microgels by pre-emulsified semi-batch emulsion polymerization.

PubMed

Ramli, Ros Azlinawati; Hashim, Shahrir; Laftah, Waham Ashaier

2013-02-01

A novel microgels were polymerized using styrene (St), methyl methacrylate (MMA), acrylamide (AAm), and acrylic acid (AAc) monomers in the presence of N,N'-methylenebisacrylamide (MBA) cross-linker. Pre-emulsified monomer was first prepared followed by polymerizing monomers using semi-batch emulsion polymerization. Fourier Transform Infrared Spectroscopy (FTIR) and (1)H Nuclear Magnetic Resonance (NMR) were used to determine the chemical structure and to indentify the related functional group. Grafting and cross-linking of poly(acrylamide-co-acrilic acid)-grafted-poly(styrene-co-methyl methacrylate) [poly(AAm-co-AAc)-g-poly(St-co-MMA)] microgels are approved by the disappearance of band at 1300 cm(-1), 1200 cm(-1) and 1163 cm(-1) of FTIR spectrum and the appearance of CH peaks at 5.5-5.7 ppm in (1)H NMR spectrum. Scanning Electron Microscope (SEM) images indicated that poly(St-co-MMA) particle was lobed morphology coated by cross-linked poly(AAm-co-AAc) shell. Furthermore, SEM results revealed that poly(AAm-co-AAc)-g-poly(St-co-MMA) is composite particle that consist of "raspberry"-shape like structure core. Internal structures of the microgels showed homogeneous network of pores, an extensive interconnection among pores, thicker pore walls, and open network structures. Water absorbency test indicated that the sample with particle size 0.43 μm had lower equilibrium water content, % than the sample with particle size 7.39 μm. Copyright © 2012 Elsevier Inc. All rights reserved.

One-step synthesis and characterization of polyaniline nanofiber/silver nanoparticle composite networks as antibacterial agents.

PubMed

Poyraz, Selcuk; Cerkez, Idris; Huang, Tung Shi; Liu, Zhen; Kang, Litao; Luo, Jujie; Zhang, Xinyu

2014-11-26

Through a facile and effective seeding polymerization reaction via a one-step redox/complexation process, which took place in aqueous medium at ambient temperature, silver nanoparticles (Ag NPs) embedded polyaniline nanofiber (PANI NF) networks were synthesized as antibacterial agents. During the reaction, not only NF morphology formation of the resulting conducting polymers (CPs) but also amplification of the aqueous silver nitrate (AgNO3) solutions' oxidative potentials were managed by vanadium pentoxide (V2O5) sol-gel nanofibers, which acted as well-known nanofibrous seeding agents and the auxiliary oxidative agent at the same time. The PANI/Ag nanocomposites were proven to exhibit excellent antibacterial property against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. Antibacterial property performance and average life span of the nanocomposite network were optimized through the homogeneous distribution/embedment of Ag NPs within one-dimensional (1-D) PANI NF matrix. The antibacterial efficacy tests and nanocomposite material characterization results further indicated that the sole components of PANI/Ag have a synergistic effect to each other in terms of antibacterial property. Thus, this well-known catalytic seeding approach via a one-step oxidative polymerization reaction can be considered as a general methodology and a substantial fabrication tool to synthesize Ag NP decorated nanofibrillar PANI networks as advanced antibacterial agents.

Synthesis and photopolymerization of low shrinkage methacrylate monomers containing bulky substituent groups.

PubMed

Ge, Junhao; Trujillo, Marianela; Stansbury, Jeffrey

2005-12-01

This study was conducted to determine whether novel photopolymerizable formulations based on dimethacrylate monomers with bulky substituent groups could provide low polymerization shrinkage without sacrifice to degree of conversion, and mechanical properties of the polymers. Relatively high molecular weight dimethacrylate monomers were prepared from rigid bisphenol A core groups. Photopolymerization kinetics and shrinkage as well as flexural strength and glass transition temperatures were evaluated for various comonomer compositions. Copolymerization of the bulky monomers with TEGDMA show higher conversion but similar shrinkage compared with Bis-GMA/TEGDMA controls. The resulting polymers have suitable mechanical strength properties for potential dental restorative materials applications. When copolymerized with PEGDMA, the bulky monomers show lower shrinkage, comparable conversion, and more homogeneous polymeric network structures compared with Bis-EMA/PEGDMA systems. The novel dimethacrylate monomers with reduced reactive group densities can decrease the polymerization shrinkage as anticipated, but there is no significant evidence that the bulky substituent groups have any additional effect on reducing shrinkage based on the physical interactions as polymer side chains. The bulky groups improve the double bond conversion and help maintain the mechanical properties of the resulting polymer, which would otherwise decrease rapidly due to the reduced crosslinking density. Further, it was found that bulky monomers help produce more homogeneous copolymer networks.

The Role of Network Architecture in Collagen Mechanics.

PubMed

Jansen, Karin A; Licup, Albert J; Sharma, Abhinav; Rens, Robbie; MacKintosh, Fred C; Koenderink, Gijsje H

2018-06-05

Collagen forms fibrous networks that reinforce tissues and provide an extracellular matrix for cells. These networks exhibit remarkable strain-stiffening properties that tailor the mechanical functions of tissues and regulate cell behavior. Recent models explain this nonlinear behavior as an intrinsic feature of disordered networks of stiff fibers. Here, we experimentally validate this theoretical framework by measuring the elastic properties of collagen networks over a wide range of self-assembly conditions. We show that the model allows us to quantitatively relate both the linear and nonlinear elastic behavior of collagen networks to their underlying architecture. Specifically, we identify the local coordination number (or connectivity) 〈z〉 as a key architectural parameter that governs the elastic response of collagen. The network elastic response reveals that 〈z〉 decreases from 3.5 to 3 as the polymerization temperature is raised from 26 to 37°C while being weakly dependent on concentration. We furthermore infer a Young's modulus of 1.1 MPa for the collagen fibrils from the linear modulus. Scanning electron microscopy confirms that 〈z〉 is between three and four but is unable to detect the subtle changes in 〈z〉 with polymerization conditions that rheology is sensitive to. Finally, we show that, consistent with the model, the initial stress-stiffening response of collagen networks is controlled by the negative normal stress that builds up under shear. Our work provides a predictive framework to facilitate future studies of the regulatory effect of extracellular matrix molecules on collagen mechanics. Moreover, our findings can aid mechanobiological studies of wound healing, fibrosis, and cancer metastasis, which require collagen matrices with tunable mechanical properties. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Microwave Processing of Polymeric Materials

DTIC Science & Technology

1992-04-01

DECLASSIFICATION/DOWNGRADING SCHEDULE Approved for public release; distribution is unlimited 4 . PERFORMING ORGANIZATION REPORT NUMBER(S) 5. MONITORING ORGANIZATION... 4 2.1.1. Microwave Processing ................................................................. 4 2.1.1.1. Epoxy Resin Networks... 4 2.1.1.2. Epoxy Resin Composites

Biochemical separations by continuous-bed chromatography.

PubMed

Tisch, T L; Frost, R; Liao, J L; Lam, W K; Remy, A; Scheinpflug, E; Siebert, C; Song, H; Stapleton, A

1998-08-07

Innovations in column-packing media for biomolecule purification have progressed from large spherical, porous polysaccharide beads to advanced polymeric supports. Continuous-bed technology is a radical new technology for chromatography based on the polymerization of advanced monomers and ionomers directly in the chromatographic column. The polymer chains form aggregates which coalesce into a dense, homogeneous network of interconnected nodules consisting of microparticles with an average diameter of 3000 A. The voids or channels between the nodules are large enough to permit a high hydrodynamic flow. Due to the high cross-linking of the polymer matrix, the surface of each nodule is nonporous yet the polymeric microparticles provide a very large surface area for high binding capacity. This paper will demonstrate the properties and advantages of using a continuous bed support for high resolution biomolecule separations at high flow-rates without sacrificing capacity.

Method for rapidly producing microporous and mesoporous materials

DOEpatents

Coronado, Paul R.; Poco, John F.; Hrubesh, Lawrence W.; Hopper, Robert W.

1997-01-01

An improved, rapid process is provided for making microporous and mesoporous materials, including aerogels and pre-ceramics. A gel or gel precursor is confined in a sealed vessel to prevent structural expansion of the gel during the heating process. This confinement allows the gelation and drying processes to be greatly accelerated, and significantly reduces the time required to produce a dried aerogel compared to conventional methods. Drying may be performed either by subcritical drying with a pressurized fluid to expel the liquid from the gel pores or by supercritical drying. The rates of heating and decompression are significantly higher than for conventional methods.

In-situ Formation of Reinforcement Phases in Ultra High Temperature Ceramic Composites

NASA Technical Reports Server (NTRS)

Stackpoole, Margaret M (Inventor); Gasch, Matthew J (Inventor); Olson, Michael W (Inventor); Hamby, Ian W. (Inventor); Johnson, Sylvia M (Inventor)

2013-01-01

A tough ultra-high temperature ceramic (UHTC) composite comprises grains of UHTC matrix material, such as HfB.sub.2, ZrB.sub.2 or other metal boride, carbide, nitride, etc., surrounded by a uniform distribution of acicular high aspect ratio reinforcement ceramic rods or whiskers, such as of SiC, is formed from uniformly mixing a powder of the UHTC material and a pre-ceramic polymer selected to form the desired reinforcement species, then thermally consolidating the mixture by hot pressing. The acicular reinforcement rods may make up from 5 to 30 vol % of the resulting microstructure.

Nanoscale Reinforced, Polymer Derived Ceramic Matrix Coatings

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

Rajendra Bordia

The goal of this project was to explore and develop a novel class of nanoscale reinforced ceramic coatings for high temperature (600-1000 C) corrosion protection of metallic components in a coal-fired environment. It was focused on developing coatings that are easy to process and low cost. The approach was to use high-yield preceramic polymers loaded with nano-size fillers. The complex interplay of the particles in the polymer, their role in controlling shrinkage and phase evolution during thermal treatment, resulting densification and microstructural evolution, mechanical properties and effectiveness as corrosion protection coatings were investigated. Fe-and Ni-based alloys currently used in coal-firedmore » environments do not possess the requisite corrosion and oxidation resistance for next generation of advanced power systems. One example of this is the power plants that use ultra supercritical steam as the working fluid. The increase in thermal efficiency of the plant and decrease in pollutant emissions are only possible by changing the properties of steam from supercritical to ultra supercritical. However, the conditions, 650 C and 34.5 MPa, are too severe and result in higher rate of corrosion due to higher metal temperatures. Coating the metallic components with ceramics that are resistant to corrosion, oxidation and erosion, is an economical and immediate solution to this problem. Good high temperature corrosion protection ceramic coatings for metallic structures must have a set of properties that are difficult to achieve using established processing techniques. The required properties include ease of coating complex shapes, low processing temperatures, thermal expansion match with metallic structures and good mechanical and chemical properties. Nanoscale reinforced composite coatings in which the matrix is derived from preceramic polymers have the potential to meet these requirements. The research was focused on developing suitable material systems and processing techniques for these coatings. In addition, we investigated the effect of microstructure on the mechanical properties and oxidation protection ability of the coatings. Coatings were developed to provide oxidation protection to both ferritic and austentic alloys and Ni-based alloys. The coatings that we developed are based on low viscosity pre-ceramic polymers. Thus they can be easily applied to any shape by using a variety of techniques including dip-coating, spray-coating and painting. The polymers are loaded with a variety of nanoparticles. The nanoparticles have two primary roles: control of the final composition and phases (and hence the properties); and control of the shrinkage during thermal decomposition of the polymer. Thus the selection of the nanoparticles was the most critical aspect of this project. Based on the results of the processing studies, the performance of selected coatings in oxidizing conditions (both static and cyclic) was investigated.« less

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

Zheng, Haiyan; Wang, Lijuan; Li, Kuo

Transformation between different types of carbon–carbon bonding in carbides often results in a dramatic change of physical and chemical properties. Under external pressure, unsaturated carbon atoms form new covalent bonds regardless of the electrostatic repulsion. It was predicted that calcium acetylide (also known as calcium carbide, CaC 2) polymerizes to form calcium polyacetylide, calcium polyacenide and calcium graphenide under high pressure. In this work, the phase transitions of CaC 2 under external pressure were systematically investigated, and the amorphous phase was studied in detail for the first time. Polycarbide anions like C 6 6– are identified with gas chromatography-mass spectrometrymore » and several other techniques, which evidences the pressure induced polymerization of the acetylide anions and suggests the existence of the polyacenide fragment. Additionally, the process of polymerization is accompanied with a 10 7 fold enhancement of the electrical conductivity. As a result, the polymerization of acetylide anions demonstrates that high pressure compression is a viable route to synthesize novel metal polycarbides and materials with extended carbon networks, while shedding light on the synthesis of more complicated metal organics.« less

Design and Application of Nanogel-Based Polymer Networks

NASA Astrophysics Data System (ADS)

Dailing, Eric Alan

Crosslinked polymer networks have wide application in biomaterials, from soft hydrogel scaffolds for cell culture and tissue engineering to glassy, high modulus dental restoratives. Composite materials formed with nanogels as a means for tuning network structure on the nanoscale have been reported, but no investigation into nanogels as the primary network component has been explored to this point. This thesis was dedicated to studying network formation from the direct polymerization of nanogels and investigating applications for these unique materials. Covalently crosslinked polymer networks were synthesized from polymerizable nanogels without the use of reactive small monomers or oligomers. Network properties were controlled by the chemical and physical properties of the nanogel, allowing for materials to be designed from nanostructured macromolecular precursors. Nanogels were synthesized from a thermally initiated solution free radical polymerization of a monomethacrylate, a dimethacrylate, and a thiol-based chain transfer agent. Monomers with a range of hydrophilic and hydrophobic character were copolymerized, and polymerizable groups were introduced through an alcohol-isocyanate click reaction. Nanogels were dispersible in water up to 75 wt%, including nanogels that contained a relatively high fraction of a conventionally water-insoluble component. Nanogels with molecular weights that ranged from 10's to 100's of kDa and hydrodynamic radii between 4 and 10 nm were obtained. Macroscopic crosslinked polymer networks were synthesized from the photopolymerization of methacrylate-functionalized nanogels in inert solvent, which was typically water. The nanogel composition and internal branching density affected both covalent and non-covalent interparticle interactions, which dictated the final mechanical properties of the networks. Nanogels with progressively disparate hydrophilic and hydrophobic character were synthesized to explore the potential for creating densely crosslinked, small monomer free dental materials. Nanogel-based networks showed no decrease in flexural modulus between the dry and water-equilibrated states in contrast to nanogel-monomer composites that exhibited a decrease in modulus upon water infiltration. The nanogel networks also exhibited higher conversion and lower volumetric shrinkage compared to the composite networks. Adhesive nanogels were designed with amphiphilic character and specific hydrogen-bonding groups. These nanogels gelled within 10 s of low intensity UV light exposure and demonstrated the ability to bond strongly to both hydrophilic and hydrophobic substrates that were dry or under water. Nanogel-based coatings were explored as a means to create multistructured, multifunctional polymer networks. Shape memory polymers were coated with nanogels through a dip-coating and subsequent photocrosslinking method. The presence of the coating did not affect the shape recovery of the polymer, and coatings formed with dexamethasone-loaded nanogels were demonstrated to release a physiologically relevant amount of the anti-inflammatory drug. These materials have potential application as minimally invasive implantable devices. Coatings were also formed from interfacial redox polymerizations. Nanogels with varying crosslinking density were coated onto dexamethasone-loaded networks, which had the effect of changing the diffusion coefficient of dexamethasone as it was released from the core network. A fluorescein-loaded nanogel was coated onto a rhodamine-loaded network, which provided multidrug release from both the coating and the core material through two distinct release profiles.

Low temperature process for obtaining thin glass films

DOEpatents

Brinker, C. Jeffrey; Reed, Scott T.

1984-01-01

A method for coating a substrate with a glass-like film comprises, applying to the substrate an aqueous alcoholic solution containing a polymeric network of partially hydrolyzed metal alkoxide into which network there is incorporated finely powdered glass, whereby there is achieved on the substrate a coherent and adherent initial film; and heating said film to a temperature sufficient to melt said powdered glass component, thereby converting said initial film to a final densified film.

Low temperature process for obtaining thin glass films

DOEpatents

Brinker, C.J.; Reed, S.T.

A method for coating a substrate with a glass-like film comprises, applying to the substrate an aqueous alcoholic solution containing a polymeric network of partially hydrolyzed metal alkoxide into which network there is incorporated finely powdered glass, whereby there is achieved on the substrate a coherent and adherent initial film; and heating said film to a temperature sufficient to melt said powdered glass component, thereby converting said initial film to a final densified film.

Bioactive Polymeric Materials for Tissue Repair

PubMed Central

Bienek, Diane R.; Tutak, Wojtek; Skrtic, Drago

2017-01-01

Bioactive polymeric materials based on calcium phosphates have tremendous appeal for hard tissue repair because of their well-documented biocompatibility. Amorphous calcium phosphate (ACP)-based ones additionally protect against unwanted demineralization and actively support regeneration of hard tissue minerals. Our group has been investigating the structure/composition/property relationships of ACP polymeric composites for the last two decades. Here, we present ACP’s dispersion in a polymer matrix and the fine-tuning of the resin affects the physicochemical, mechanical, and biological properties of ACP polymeric composites. These studies illustrate how the filler/resin interface and monomer/polymer molecular structure affect the material’s critical properties, such as ion release and mechanical strength. We also present evidence of the remineralization efficacy of ACP composites when exposed to accelerated acidic challenges representative of oral environment conditions. The utility of ACP has recently been extended to include airbrushing as a platform technology for fabrication of nanofiber scaffolds. These studies, focused on assessing the feasibility of incorporating ACP into various polymer fibers, also included the release kinetics of bioactive calcium and phosphate ions from nanofibers and evaluate the biorelevance of the polymeric ACP fiber networks. We also discuss the potential for future integration of the existing ACP scaffolds into therapeutic delivery systems used in the precision medicine field. PMID:28134776

A multifunctional polymeric nanofilm with robust chemical performances for special wettability.

PubMed

Wang, Yabin; Lin, Feng; Dong, Yaping; Liu, Zhong; Li, Wu; Huang, Yudong

2016-03-07

A multifunctional polymeric nanofilm of a triazinedithiolsilane compound, which can protect metallic substrates and activate the corresponding surface simultaneously, is introduced onto a copper mesh surface via facile solution-immersion approaches. The resultant interface exhibits hydrophilic features due to the existence of silanol groups (SiOH) outward and has the potential to act as a superhydrophilic and underwater superoleophobic material. As the polymeric nanofilm atop the copper mesh is modified with long-chain octadecyltrichlorosilane (OTS), the functionalized surface becomes superhydrophobic and superoleophilic. The OTS-modified polymeric nanofilm shows outstanding chemical durability and stability that are seldom concurrently satisfied for a material with special wettability, owing to its inherent architecture. These textures generate high separation efficiency, durable separation capability and excellent thermal stability. The protective ability, originating from the textures of the underlying cross-linked disulfide units (-SS-) and siloxane networks (SiOSi) on the top of the nanofilm, prolongs the chemical durability. The activating capability stemming from the residual SiOH groups improves the chemical stability as a result of the chemical bonds developed by these sites. The significant point of this investigation lies in enlightening us on the fabrication of multifunctional polymeric nanofilms on different metal surfaces using various triazinedithiolsilane compounds, and on the construction of interfaces with controllable wettable performances in demanding research or industrial applications.

Plasma-initiated polymerization of chitosan-based CS-g-P(AM-DMDAAC) flocculant for the enhanced flocculation of low-algal-turbidity water.

PubMed

Sun, Yongjun; Zhu, Chengyu; Sun, Wenquan; Xu, Yanhua; Xiao, Xuefeng; Zheng, Huaili; Wu, Huifang; Liu, Cuiyun

2017-05-15

In this work, a highly efficient and environmentally friendly chitosan-based graft flocculant, namely, acrylamide- and dimethyl diallyl ammonium chloride-grafted chitosan [CS-g-P(AM-DMDAAC)], was prepared successfully through plasma initiation. FTIR results confirmed the successful polymerization of CS-g-P(AM-DMDAAC) and P(AM-DMDAAC). P(AM-DMDAAC) was the copolymer of acrylamide- and dimethyl diallyl ammonium chloride. SEM results revealed that a densely cross-linked network structure formed on the surface. XRD results verified that the ordered crystal structure of chitosan in CS-g-P(AM-DMDAAC) was changed into an amorphous structure after plasma-induced polymerization. The flocculation results of low-algal-turbidity water further showed the optimal flocculation efficiency of turbidity removal rate, COD removal rate, and Chl-a removal rate were 99.02%, 96.11%, and 92.20%, respectively. The flocculation efficiency of CS-g-P(AM-DMDAAC) were significantly higher than those obtained by cationic polyacrylamide (CPAM) and Polymeric aluminum and iron (PAFC). This work provided a valuable basis for the design of eco-friendly naturally modified polymeric flocculants to enhance the flocculation of low-algal-turbidity water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterization of dimethacrylate polymeric networks: a study of the crosslinked structure formed by monomers used in dental composites

PubMed Central

Shelton, Zachary R.; Braga, Roberto R.; Windmoller, Dario; Machado, José C.

2011-01-01

The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonomers, with final polymeric network structure defined by monomer type/reactivity and degree of conversion. This fundamental study evaluates how increasing concentrations of the flexible triethylene glycol dimethacrylate (TEGDMA) influences void formation in bisphenol A diglycidyl dimethacrylate (BisGMA) co-polymerizations and correlates this aspect of network structure with reaction kinetic parameters and macroscopic volumetric shrinkage. Photopolymerization kinetics was followed in real-time by a near-infrared (NIR) spectroscopic technique, viscosity was assessed with a viscometer, volumetric shrinkage was followed with a linometer, free volume formation was determined by positron annihilation lifetime spectroscopy (PALS) and the sol-gel composition was determined by extraction with dichloromethane followed by 1H-NMR analysis. Results show that, as expected, volumetric shrinkage increases with TEGDMA concentration and monomer conversion. Extraction/1H-NMR studies show increasing participation of the more flexible TEGDMA towards the limiting stages of conversion/crosslinking development. As the conversion progresses, either based on longer irradiation times or greater TEGDMA concentrations, the network becomes more dense, which is evidenced by the decrease in free volume and weight loss after extraction in these situations. For the same composition (BisGMA/TEGDMA 60–40 mol%) light-cured for increasing periods of time (from 10 to 600 s), free volume decreased and volumetric shrinkage increased, in a linear relationship with conversion. However, the correlation between free volume and macroscopic volumetric shrinkage was shown to be rather complex for variable compositions exposed for the same time (600 s). The addition of TEGDMA decreases free-volume up to 40 mol% (due to increased conversion), but above that concentration, in spite of the increase in conversion/crosslinking, free volume pore size increases due to the high concentration of the more flexible monomer. In those cases, the increase in volumetric shrinkage was due to higher functional group concentration, in spite of the greater free volume. Therefore, through the application of the PALS model, this study elucidates the network formation in dimethacrylates commonly used in dental materials. PMID:21499538

Characterization of dimethacrylate polymeric networks: a study of the crosslinked structure formed by monomers used in dental composites.

PubMed

Pfeifer, Carmem S; Shelton, Zachary R; Braga, Roberto R; Windmoller, Dario; Machado, José C; Stansbury, Jeffrey W

2011-02-01

The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonomers, with final polymeric network structure defined by monomer type/reactivity and degree of conversion. This fundamental study evaluates how increasing concentrations of the flexible triethylene glycol dimethacrylate (TEGDMA) influences void formation in bisphenol A diglycidyl dimethacrylate (BisGMA) co-polymerizations and correlates this aspect of network structure with reaction kinetic parameters and macroscopic volumetric shrinkage. Photopolymerization kinetics was followed in real-time by a near-infrared (NIR) spectroscopic technique, viscosity was assessed with a viscometer, volumetric shrinkage was followed with a linometer, free volume formation was determined by positron annihilation lifetime spectroscopy (PALS) and the sol-gel composition was determined by extraction with dichloromethane followed by (1)H-NMR analysis. Results show that, as expected, volumetric shrinkage increases with TEGDMA concentration and monomer conversion. Extraction/(1)H-NMR studies show increasing participation of the more flexible TEGDMA towards the limiting stages of conversion/crosslinking development. As the conversion progresses, either based on longer irradiation times or greater TEGDMA concentrations, the network becomes more dense, which is evidenced by the decrease in free volume and weight loss after extraction in these situations. For the same composition (BisGMA/TEGDMA 60-40 mol%) light-cured for increasing periods of time (from 10 to 600 s), free volume decreased and volumetric shrinkage increased, in a linear relationship with conversion. However, the correlation between free volume and macroscopic volumetric shrinkage was shown to be rather complex for variable compositions exposed for the same time (600 s). The addition of TEGDMA decreases free-volume up to 40 mol% (due to increased conversion), but above that concentration, in spite of the increase in conversion/crosslinking, free volume pore size increases due to the high concentration of the more flexible monomer. In those cases, the increase in volumetric shrinkage was due to higher functional group concentration, in spite of the greater free volume. Therefore, through the application of the PALS model, this study elucidates the network formation in dimethacrylates commonly used in dental materials.

DNA-nanoparticle assemblies go organic: Macroscopic polymeric materials with nanosized features

PubMed Central

2012-01-01

Background One of the goals in the field of structural DNA nanotechnology is the use of DNA to build up 2- and 3-D nanostructures. The research in this field is motivated by the remarkable structural features of DNA as well as by its unique and reversible recognition properties. Nucleic acids can be used alone as the skeleton of a broad range of periodic nanopatterns and nanoobjects and in addition, DNA can serve as a linker or template to form DNA-hybrid structures with other materials. This approach can be used for the development of new detection strategies as well as nanoelectronic structures and devices. Method Here we present a new method for the generation of unprecedented all-organic conjugated-polymer nanoparticle networks guided by DNA, based on a hierarchical self-assembly process. First, microphase separation of amphiphilic block copolymers induced the formation of spherical nanoobjects. As a second ordering concept, DNA base pairing has been employed for the controlled spatial definition of the conjugated-polymer particles within the bulk material. These networks offer the flexibility and the diversity of soft polymeric materials. Thus, simple chemical methodologies could be applied in order to tune the network's electrical, optical and mechanical properties. Results and conclusions One- two- and three-dimensional networks have been successfully formed. Common to all morphologies is the integrity of the micelles consisting of DNA block copolymer (DBC), which creates an all-organic engineered network. PMID:22646980

The F-Actin Binding Protein Cortactin Regulates the Dynamics of the Exocytotic Fusion Pore through its SH3 Domain

PubMed Central

González-Jamett, Arlek M.; Guerra, María J.; Olivares, María J.; Haro-Acuña, Valentina; Baéz-Matus, Ximena; Vásquez-Navarrete, Jacqueline; Momboisse, Fanny; Martinez-Quiles, Narcisa; Cárdenas, Ana M.

2017-01-01

Upon cell stimulation, the network of cortical actin filaments is rearranged to facilitate the neurosecretory process. This actin rearrangement includes both disruption of the preexisting actin network and de novo actin polymerization. However, the mechanism by which a Ca2+ signal elicits the formation of new actin filaments remains uncertain. Cortactin, an actin-binding protein that promotes actin polymerization in synergy with the nucleation promoting factor N-WASP, could play a key role in this mechanism. We addressed this hypothesis by analyzing de novo actin polymerization and exocytosis in bovine adrenal chromaffin cells expressing different cortactin or N-WASP domains, or cortactin mutants that fail to interact with proline-rich domain (PRD)-containing proteins, including N-WASP, or to be phosphorylated by Ca2+-dependent kinases, such as ERK1/2 and Src. Our results show that the activation of nicotinic receptors in chromaffin cells promotes cortactin translocation to the cell cortex, where it colocalizes with actin filaments. We further found that, in association with PRD-containing proteins, cortactin contributes to the Ca2+-dependent formation of F-actin, and regulates fusion pore dynamics and the number of exocytotic events induced by activation of nicotinic receptors. However, whereas the actions of cortactin on the fusion pore dynamics seems to depend on the availability of monomeric actin and its phosphorylation by ERK1/2 and Src kinases, cortactin regulates the extent of exocytosis by a mechanism independent of actin polymerization. Together our findings point out a role for cortactin as a critical modulator of actin filament formation and exocytosis in neuroendocrine cells. PMID:28522963

Leiodermatolide, a novel marine natural product, has potent cytotoxic and anti-mitotic activity against cancer cells, appears to affect microtubule dynamics, and exhibits anti-tumor activity

PubMed Central

Guzmán, Esther A.; Xu, Qunli; Pitts, Tara P.; Mitsuhashi, Kaoru Ogawa; Baker, Cheryl; Linley, Patricia A.; Oestreicher, Judy; Tendyke, Karen; Winder, Priscilla L.; Suh, Edward M.; Wright, Amy E.

2016-01-01

Pancreatic cancer, the fourth leading cause of cancer death in the United States, has a negative prognosis because metastasis occurs before symptoms manifest. Leiodermatolide, a polyketide macrolide with antimitotic activity isolated from a deep water sponge of the genus Leiodermatium, exhibits potent and selective cytotoxicity towards the pancreatic cancer cell lines AsPC-1, PANC-1, BxPC-3, and MIA PaCa-2, and potent cytotoxicity against skin, breast and colon cancer cell lines. Induction of apoptosis by leiodermatolide was confirmed in the AsPC-1, BxPC-3 and MIA PaCa-2 cells. Leiodermatolide induces cell cycle arrest but has no effects on in vitro polymerization or depolymerization of tubulin alone, while it enhances polymerization of tubulin containing microtubule associated proteins (MAPs). Observations through confocal microscopy show that leiodermatolide, at low concentrations, causes minimal effects on polymerization or depolymerization of the microtubule network in interphase cells, but disruption of spindle formation in mitotic cells. At higher concentrations, depolymerization of the microtubule network is observed. Visualization of the growing microtubule in HeLa cells expressing GFP-tagged plus end binding protein EB-1 showed that leiodermatolide stopped the polymerization of tubulin. These results suggest that leiodermatolide may affect tubulin dynamics without directly interacting with tubulin and hint at a unique mechanism of action. In a mouse model of metastatic pancreatic cancer, leiodermatolide exhibited significant tumor reduction when compared to gemcitabine and controls. The anti-tumor activities of leiodermatolide, as well as the proven utility of anti-mitotic compounds against cancer, make leiodermatolide an interesting compound with potential chemotherapeutic effects that may merit further research. PMID:27376928

Visible-Light Initiated Free-Radical/Cationic Ring-Opening Hybrid Photopolymerization of Methacrylate/Epoxy: Polymerization Kinetics, Crosslinking Structure, and Dynamic Mechanical Properties.

PubMed

Ge, Xueping; Ye, Qiang; Song, Linyong; Misra, Anil; Spencer, Paulette

2015-04-01

The effects of polymerization kinetics and chemical miscibility on the crosslinking structure and mechanical properties of polymers cured by visible-light initiated free-radical/cationic ring-opening hybrid photopolymerization are determined. A three-component initiator system is used and the monomer system contains methacrylates and epoxides. The photopolymerization kinetics is monitored in situ by Fourier transform infrared-attenuated total reflectance. The crosslinking structure is studied by modulated differential scanning calorimetry and dynamic mechanical analysis. X-ray microcomputed tomography is used to evaluate microphase separation. The mechanical properties of polymers formed by hybrid formed by free-radical polymerization. These investigations mark the first time that the benefits of the chain transfer reaction between epoxy and hydroxyl groups of methacrylate, on the crosslinking network and microphase separation during hybrid visible-light initiated photopolymerization, have been determined.

Preparing high-density polymer brushes by mechanically assisted polymer assembly (MAPA)

NASA Astrophysics Data System (ADS)

Wu, Tao; Efimenko, Kirill; Genzer, Jan

2001-03-01

We introduce a novel method of modifying the surface properties of materials. This technique, called MAPA (="mechanically assisted polymer assembly"), is based on: 1) chemically attaching polymerization initiators to the surface of an elastomeric network that has been previously stretched by a certain length, Δx, and 2) growing end-anchored macromolecules using surface initiated ("grafting from") atom transfer living radical polymerization. After the polymerization, the strain is removed from the substrate, which returns to its original size causing the grafted macromolecules to stretch away from the substrate and form a dense polymer brush. We demonstrate the feasibility of the MAPA method by preparing high-density polymer brushes of poly(acryl amide), PAAm. We show that, as expected, the grafting density of the PAAm brushes can be increased by increasing Δx. We demonstrate that polymer brushes with extremely high grafting densities can be successfully prepared by MAPA.

Extravasation of polymeric nanomedicines across tumor vasculature.

PubMed

Danquah, Michael K; Zhang, Xin A; Mahato, Ram I

2011-07-18

Tumor microvasculature is fraught with numerous physiological barriers which hinder the efficacy of anticancer agents. These barriers include chaotic blood supply, poor tumor vasculature permeability, limited transport across the interstitium due to high interstitial pressure and absence of lymphatic network. Abnormal microvasculature also leads to hypoxia and acidosis which limits effectiveness of chemotherapy. These barriers restrict drug or drug carrier extravasation which hampers tumor regression. Targeting key features of the tumor microenvironment such as tumor microvessels, interstitial hypertension and tumor pH is a promising approach to improving the efficacy of anticancer drugs. This review highlights the current knowledge on the distinct tumor microenvironment generated barriers which limit extravasation of drugs and focuses on modalities for overcoming these barriers using multi-functional polymeric carriers. Special attention is given to utilizing polymeric nanomedicines to facilitate extravasation of anticancer drugs for future cancer therapy. Copyright © 2010 Elsevier B.V. All rights reserved.

Hsp90 binds microtubules and is involved in the reorganization of the microtubular network in angiosperms.

PubMed

Krtková, Jana; Zimmermann, Aleksandra; Schwarzerová, Kateřina; Nick, Peter

2012-09-15

Microtubules (MTs) are essential for many processes in plant cells. MT-associated proteins (MAPs) influence MT polymerization dynamics and enable them to perform their functions. The molecular chaperone Hsp90 has been shown to associate with MTs in animal and plant cells. However, the role of Hsp90-MT binding in plants has not yet been investigated. Here, we show that Hsp90 associates with cortical MTs in tobacco cells and decorates MTs in the phragmoplast. Further, we show that tobacco Hsp90_MT binds directly to polymerized MTs in vitro. The inhibition of Hsp90 by geldanamycin (GDA) severely impairs MT re-assembly after cold-induced de-polymerization. Our results indicate that the plant Hsp90 interaction with MTs plays a key role in cellular events, where MT re-organization is needed. Copyright © 2012 Elsevier GmbH. All rights reserved.

Processing of continuous fiber reinforced ceramic composites for ultra high temperature applications using organosilicon polymer precursors

NASA Astrophysics Data System (ADS)

Nicholas, James Robert

The current work is on the development of continuous fiber reinforced ceramic materials (CFCCs) for use in ultra high temperature applications. These applications subject materials to extremely high temperatures(> 2000°C). Monolithic ceramics are currently being used for these applications, but the tendency to fail catastrophically has driven the need for the next generation of material. Reinforcing with continuous fibers significantly improves the toughness of the monolithic materials; however, this is a manufacturing challenge. The development of commercial, low-viscosity preceramic polymers provides new opportunities to fabricate CFCCs. Preceramic polymers behave as polymers at low temperatures and are transformed into ceramics upon heating to high temperatures. The polymer precursors enable the adaptation of well-established polymer processing techniques to produce high quality materials at relatively low cost. In the present work, SMP-10 from Starfire Systems, and PURS from KiON Corp. were used to manufacture ZrB2-SiC/SiC CFCCs using low cost vacuum bagging process in conjunction with the polymer infiltration and pyrolysis process. The microstructure was investigated using scanning electron microscopy and it was determined that the initial greenbody cure produced porosity of both closed and open pores. The open pores were found to be more successfully re-infiltrated using neat resin compared to slurry reinfiltrate; however, the closed pores were found to be impenetrable during subsequent reinfiltrations. The mechanical performance of the manufactured samples was evaluated using flexure tests and found the fiber reinforcement prevented catastrophic failure behavior by increasing fracture toughness. Wedge sample were fabricated and evaluated to demonstrate the ability to produce CFCC of complex geometry.

Molecular interference of fibrin’s divalent polymerization mechanism enables modulation of multiscale material properties

PubMed Central

Brown, Ashley C.; Baker, Stephen; Douglas, Alison; Keating, Mark; Alvarez-Elizondo, Martha; Botvinick, Elliot; Guthold, Martin; Barker, Thomas H.

2015-01-01

Protein based polymers provide an exciting and complex landscape for tunable natural biomaterials through modulation of molecular level interactions. Here we demonstrate the ability to modify protein polymer structural and mechanical properties at multiple length scales by molecular ‘interference’ of fibrin’s native polymerization mechanism. We have previously reported that engagement of fibrin’s polymerization ‘hole b’, also known as ‘b-pockets’, through PEGylated complimentary ‘knob B’ mimics can increase fibrin network porosity but also, somewhat paradoxically, increase network stiffness. Here, we explore the possible mechanistic underpinning of this phenomenon through characterization of the effects of knob B-fibrin interaction at multiple length scales from molecular to bulk polymer. Despite its weak monovalent binding affinity for fibrin, addition of both knob B and PEGylated knob B at concentrations near the binding coefficient, Kd, increased fibrin network porosity, consistent with the reported role of knob B-hole b interactions in promoting lateral growth of fibrin fibers. Addition of PEGylated knob B decreases the extensibility of single fibrin fibers at concentrations near its Kd but increases extensibility of fibers at concentrations above its Kd. The data suggest this bimodal behavior is due to the individual contributions knob B, which decreases fiber extensibility, and PEG, which increase fiber extensibility. Taken together with laser trap-based microrheological and bulk rheological analyses of fibrin polymers, our data strongly suggests that hole b engagement increases in single fiber stiffness that translates to higher storage moduli of fibrin polymers despite their increased porosity. These data point to possible strategies for tuning fibrin polymer mechanical properties through modulation of single fiber mechanics. PMID:25725552

Curvature and torsion in growing actin networks

NASA Astrophysics Data System (ADS)

Shaevitz, Joshua W.; Fletcher, Daniel A.

2008-06-01

Intracellular pathogens such as Listeria monocytogenes and Rickettsia rickettsii move within a host cell by polymerizing a comet-tail of actin fibers that ultimately pushes the cell forward. This dense network of cross-linked actin polymers typically exhibits a striking curvature that causes bacteria to move in gently looping paths. Theoretically, tail curvature has been linked to details of motility by considering force and torque balances from a finite number of polymerizing filaments. Here we track beads coated with a prokaryotic activator of actin polymerization in three dimensions to directly quantify the curvature and torsion of bead motility paths. We find that bead paths are more likely to have low rather than high curvature at any given time. Furthermore, path curvature changes very slowly in time, with an autocorrelation decay time of 200 s. Paths with a small radius of curvature, therefore, remain so for an extended period resulting in loops when confined to two dimensions. When allowed to explore a three-dimensional (3D) space, path loops are less evident. Finally, we quantify the torsion in the bead paths and show that beads do not exhibit a significant left- or right-handed bias to their motion in 3D. These results suggest that paths of actin-propelled objects may be attributed to slow changes in curvature, possibly associated with filament debranching, rather than a fixed torque.

Magnetic assembly of transparent and conducting graphene-based functional composites

PubMed Central

Le Ferrand, Hortense; Bolisetty, Sreenath; Demirörs, Ahmet F.; Libanori, Rafael; Studart, André R.; Mezzenga, Raffaele

2016-01-01

Innovative methods producing transparent and flexible electrodes are highly sought in modern optoelectronic applications to replace metal oxides, but available solutions suffer from drawbacks such as brittleness, unaffordability and inadequate processability. Here we propose a general, simple strategy to produce hierarchical composites of functionalized graphene in polymeric matrices, exhibiting transparency and electron conductivity. These are obtained through protein-assisted functionalization of graphene with magnetic nanoparticles, followed by magnetic-directed assembly of the graphene within polymeric matrices undergoing sol–gel transitions. By applying rotating magnetic fields or magnetic moulds, both graphene orientation and distribution can be controlled within the composite. Importantly, by using magnetic virtual moulds of predefined meshes, graphene assembly is directed into double-percolating networks, reducing the percolation threshold and enabling combined optical transparency and electrical conductivity not accessible in single-network materials. The resulting composites open new possibilities on the quest of transparent electrodes for photovoltaics, organic light-emitting diodes and stretchable optoelectronic devices. PMID:27354243

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.

Porous polymer media

DOEpatents

Shepodd, Timothy J.

2002-01-01

Highly crosslinked monolithic porous polymer materials for chromatographic applications. By using solvent compositions that provide not only for polymerization of acrylate monomers in such a fashion that a porous polymer network is formed prior to phase separation but also for exchanging the polymerization solvent for a running buffer using electroosmotic flow, the need for high pressure purging is eliminated. The polymer materials have been shown to be an effective capillary electrochromatographic separations medium at lower field strengths than conventional polymer media. Further, because of their highly crosslinked nature these polymer materials are structurally stable in a wide range of organic and aqueous solvents and over a pH range of 2-12.

Advanced Materials by Atom Transfer Radical Polymerization.

PubMed

Matyjaszewski, Krzysztof

2018-06-01

Atom transfer radical polymerization (ATRP) has been successfully employed for the preparation of various advanced materials with controlled architecture. New catalysts with strongly enhanced activity permit more environmentally benign ATRP procedures using ppm levels of catalyst. Precise control over polymer composition, topology, and incorporation of site specific functionality enables synthesis of well-defined gradient, block, comb copolymers, polymers with (hyper)branched structures including stars, densely grafted molecular brushes or networks, as well as inorganic-organic hybrid materials and bioconjugates. Examples of specific applications of functional materials include thermoplastic elastomers, nanostructured carbons, surfactants, dispersants, functionalized surfaces, and biorelated materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic carbon aerogels from the sol-gel polymerization of phenolic-furfural mixtures

DOEpatents

Pekala, R.W.

1998-04-28

The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes {<=}1000 {angstrom}, and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050 C to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors. 8 figs.

Organic carbon aerogels from the sol-gel polymerization of phenolic-furfural mixtures

DOEpatents

Pekala, Richard W.

1998-04-28

The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes .ltoreq.1000 .ANG., and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050.degree. C. to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors.

Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures

DOEpatents

Pekala, Richard W.

1995-01-01

The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes.ltoreq.1000.ANG., and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050.degree. C. to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors.

Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures

DOEpatents

Pekala, R.W.

1995-12-19

The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes{<=}1000{angstrom}, and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050 C to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors. 8 figs.

Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures

DOEpatents

Pekala, Richard W.

1996-01-01

The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes .ltoreq.1000.ANG., and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050.degree. C. to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors.

Self-supported fibrin-polyvinyl alcohol interpenetrating polymer networks: an easily handled and rehydratable biomaterial.

PubMed

Bidault, Laurent; Deneufchatel, Marie; Vancaeyzeele, Cédric; Fichet, Odile; Larreta-Garde, Véronique

2013-11-11

A fibrin hydrogel at physiological concentration (5 mg/mL) was associated with polyvinyl alcohol (PVA) inside an interpenetrating polymer networks (IPN) architecture. Previously, PVA has been modified with methacrylate functions in order to cross-link it by free-radical polymerization. The fibrin network was synthesized by the enzymatic hydrolysis of fibrinogen by thrombin. The resulting self-supported materials simultaneously exhibit the properties of the fibrin hydrogel and those of the synthetic polymer network. Their storage modulus is 50-fold higher than that of the fibrin hydrogel and they are completely rehydratable. These materials are noncytotoxic toward human fibroblast and the fibrin present on the surface of PVAm-based IPNs favors cell development.

Molecular Level Coating of Metal Oxide Particles

NASA Technical Reports Server (NTRS)

McDaniel, Patricia R. (Inventor); St.Clair, Terry L. (Inventor)

2002-01-01

Polymer encapsulated metal oxide particles are prepared by combining a polyamide acid in a polar osmotic solvent with a metal alkoxide solution. The polymer was imidized and the metal oxide formed simultaneously in a refluxing organic solvent. The resulting polymer-metal oxide is an intimately mixed commingled blend, possessing, synergistic properties of both the polymer and preceramic metal oxide. The encapsulated metal oxide particles have multiple uses including, being useful in the production of skin lubricating creams, weather resistant paints, as a filler for paper. making ultraviolet light stable filled printing ink, being extruded into fibers or ribbons, and coatings for fibers used in the production of composite structural panels.

Molecular Level Coating for Metal Oxide Particles

NASA Technical Reports Server (NTRS)

McDaniel, Patricia R. (Inventor); Saint Clair, Terry L. (Inventor)

2000-01-01

Polymer encapsulated metal oxide particles are prepared by combining a polyamide acid in a polar aprotic solvent with a metal alkoxide solution. The polymer was imidized and the metal oxide formed simultaneously in a refluxing organic solvent. The resulting polymer-metal oxide is an intimately mixed commingled blend, possessing synergistic properties of both the polymer and preceramic metal oxide. The encapsulated metal oxide particles have multiple uses including, being useful in the production of skin lubricating creams, weather resistant paints, as a filler for paper, making ultraviolet light stable filled printing ink, being extruded into fibers or ribbons, and coatings for fibers used in the production of composite structural panels.

Method for rapidly producing microporous and mesoporous materials

DOEpatents

Coronado, P.R.; Poco, J.F.; Hrubesh, L.W.; Hopper, R.W.

1997-11-11

An improved, rapid process is provided for making microporous and mesoporous materials, including aerogels and pre-ceramics. A gel or gel precursor is confined in a sealed vessel to prevent structural expansion of the gel during the heating process. This confinement allows the gelation and drying processes to be greatly accelerated, and significantly reduces the time required to produce a dried aerogel compared to conventional methods. Drying may be performed either by subcritical drying with a pressurized fluid to expel the liquid from the gel pores or by supercritical drying. The rates of heating and decompression are significantly higher than for conventional methods. 3 figs.

Bottlebrush-Guided Polymer Crystallization Resulting in Supersoft and Reversibly Moldable Physical Networks

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

Daniel, William F. M.; Xie, Guojun; Vatankhah Varnoosfaderani, Mohammad

The goal of this study is to use ABA triblock copolymers with central bottlebrush B segments and crystalline linear chain A segments to demonstrate the effect of side chains on the formation and mechanical properties of physical networks cross-linked by crystallites. For this purpose, a series of bottlebrush copolymers was synthesized consisting of central amorphous bottlebrush polymer segments with a varying degree of polymerization (DP) of poly(n-butyl acrylate) (PnBA) side chains and linear tail blocks of crystallizable poly(octadecyl acrylate-stat-docosyl acrylate) (poly(ODA-stat-DA)). The materials were generated by sequential atom transfer radical polymerization (ATRP) steps starting with a series of bifunctional macroinitiatorsmore » followed by the growth of two ODA-stat-DA linear-chain tails and eventually growing poly(nBA) side chains with increasing DPs. Crystallization of the poly(ODA-stat-DA) tails resulted in a series of reversible physical networks with bottlebrush strands bridging crystalline cross-links. They displayed very low moduli of elasticity of the order of 10 3–10 4 Pa. These distinct properties are due to the bottlebrush architecture, wherein densely grafted side chains play a dual role by facilitating disentanglement of the network strands and confining crystallization of the linear-chain tails. This combination leads to physical cross-linking of supersoft networks without percolation of the crystalline phase. The cross-link density was effectively controlled by the DP of the side chains with respect to the DP of the linear tails (n A). Furthermore, shorter side chains allowed for crystallization of the linear tails of neighboring bottlebrushes, while steric repulsion between longer side chains hindered the phase separation and crystallization process and prevented network formation.« less

Bottlebrush-Guided Polymer Crystallization Resulting in Supersoft and Reversibly Moldable Physical Networks

DOE PAGES

Daniel, William F. M.; Xie, Guojun; Vatankhah Varnoosfaderani, Mohammad; ...

2017-02-24

The goal of this study is to use ABA triblock copolymers with central bottlebrush B segments and crystalline linear chain A segments to demonstrate the effect of side chains on the formation and mechanical properties of physical networks cross-linked by crystallites. For this purpose, a series of bottlebrush copolymers was synthesized consisting of central amorphous bottlebrush polymer segments with a varying degree of polymerization (DP) of poly(n-butyl acrylate) (PnBA) side chains and linear tail blocks of crystallizable poly(octadecyl acrylate-stat-docosyl acrylate) (poly(ODA-stat-DA)). The materials were generated by sequential atom transfer radical polymerization (ATRP) steps starting with a series of bifunctional macroinitiatorsmore » followed by the growth of two ODA-stat-DA linear-chain tails and eventually growing poly(nBA) side chains with increasing DPs. Crystallization of the poly(ODA-stat-DA) tails resulted in a series of reversible physical networks with bottlebrush strands bridging crystalline cross-links. They displayed very low moduli of elasticity of the order of 10 3–10 4 Pa. These distinct properties are due to the bottlebrush architecture, wherein densely grafted side chains play a dual role by facilitating disentanglement of the network strands and confining crystallization of the linear-chain tails. This combination leads to physical cross-linking of supersoft networks without percolation of the crystalline phase. The cross-link density was effectively controlled by the DP of the side chains with respect to the DP of the linear tails (n A). Furthermore, shorter side chains allowed for crystallization of the linear tails of neighboring bottlebrushes, while steric repulsion between longer side chains hindered the phase separation and crystallization process and prevented network formation.« less

Transient inter-cellular polymeric linker.

PubMed

Ong, Siew-Min; He, Lijuan; Thuy Linh, Nguyen Thi; Tee, Yee-Han; Arooz, Talha; Tang, Guping; Tan, Choon-Hong; Yu, Hanry

2007-09-01

Three-dimensional (3D) tissue-engineered constructs with bio-mimicry cell-cell and cell-matrix interactions are useful in regenerative medicine. In cell-dense and matrix-poor tissues of the internal organs, cells support one another via cell-cell interactions, supplemented by small amount of the extra-cellular matrices (ECM) secreted by the cells. Here we connect HepG2 cells directly but transiently with inter-cellular polymeric linker to facilitate cell-cell interaction and aggregation. The linker consists of a non-toxic low molecular-weight polyethyleneimine (PEI) backbone conjugated with multiple hydrazide groups that can aggregate cells within 30 min by reacting with the aldehyde handles on the chemically modified cell-surface glycoproteins. The cells in the cellular aggregates proliferated; and maintained the cortical actin distribution of the 3D cell morphology while non-aggregated cells died over 7 days of suspension culture. The aggregates lost distinguishable cell-cell boundaries within 3 days; and the ECM fibers became visible around cells from day 3 onwards while the inter-cellular polymeric linker disappeared from the cell surfaces over time. The transient inter-cellular polymeric linker can be useful for forming 3D cellular and tissue constructs without bulk biomaterials or extensive network of engineered ECM for various applications.

Tris(trimethylsilyl)silane as a co-initiator for dental adhesive: Photo-polymerization kinetics and dynamic mechanical property

PubMed Central

Song, Linyong; Ye, Qiang; Ge, Xueping; Misra, Anil; Spencer, Paulette

2017-01-01

Objectives The purpose of this study was to evaluate the polymerization behavior of a model dentin adhesive with tris(trimethylsilyl)silane (TTMSS) as a co-initiator, and to investigate the polymerization kinetics and mechanical properties of copolymers in dry and wet conditions. Methods A co-monomer mixture based on HEMA/BisGMA (45/55, w/w) was used as a model dentin adhesive. The photoinitiator system included camphorquinone (CQ) as the photosensitizer and the co-initiator was ethyl-4-(dimethylamino) benzoate (EDMAB) or TTMSS. Iodonium salt, diphenyliodonium hexafluorophosphate (DPIHP) serving as a catalyst, was selectively added into the adhesive formulations. The control and the experimental formulations were characterized with regard to the degree of conversion (DC) and dynamic mechanical properties under dry and wet conditions. Results In two-component photoinitiator system (CQ/TTMSS), with an increase of TTMSS concentration, the polymerization rate and DC of C═C double bond increased, and showed a dependence on the irradiation time and curing light intensity. The copolymers that contained the three-component photoinitiator system (CQ/TTMSS/DPIHP) showed similar dynamic mechanical properties, under both dry and wet conditions, to the EDMAB-containing system. Significance The DC of formulations using TTMSS as co-initiator showed a strong dependence on irradiation time. With the addition of TTMSS, the maximum polymerization rate can be adjusted and the network structure became more homogenous. The results indicated that the TTMSS could be used as a substitute for amine-type co-initiator in visible-light induced free radical polymerization of methacrylate-based dentin adhesives. PMID:26616688

Cell-micropatterning by micromolding in capillary technique based on UV polymerization

NASA Astrophysics Data System (ADS)

Park, Min J.; Choi, Won M.; Park, O. O.

2006-01-01

Although optical lithography or photolithography is one of the most well-established techniques for micro, nano-fabrication, its usage with proteins and cells is restricted by steps that must be carried out in harsh organic solvents. Here, we present simple methods for cell-micropatterning using poly(dimethylsiloxane) (PDMS) as a mold. Cell non-adhesive surface or nonfouling surface providing a physico-chemical barrier to cell attachment was introduced for biomaterial pattering, where cells fail to interact with the surface over desired periods of time determined by each application. Poly(ethylene glycol) (PEG) was selected as nonfouling material to inhibit protein adsorption from biological media. The fouling resistance of PEG polymer is often explained by a steric repulsion interaction, resulting from the compression of PEG chains as proteins approach the surface. We also chose fibronectin to direct cell attachment because it is an extracellular matrix protein that is involved in the adhesion and spreading of anchorage-dependent cells. In our experiment, we propose two methods by application of micromolding in capillary (MIMIC) method based on UV polymerization to obtain a surface of alternating PEG and fibronectin. First to fabricate PEG microstructure via MIMIC method, a pre-patterned PDMS mold is placed on a desired substrate, and then the relief structure in the mold forms a network of empty channels. A drop of ethylene glycol monomer solution containing initiator for UV polymerization is placed at the open ends of the network of channels, which is then polymerized by exposure to UV light at room temperature. Once PEG microstructure is fabricated, incubation of the patterned surface in a fibronectin-containing solution allows back-filling of only the bare regions with fibronectin via adsorption. In the alternative method, a substrate is first incubated in a fibronectin-containing solution, leading to the adsorption of fibronectin over the entire surface, and the fibronectin-adsorbed substrate is then micropatterned with the PEG by MIMIC based on UV polymerization. Both methods create reproducible alternating PEG and fibronectin patterns applicable to cell-surface interactions on the microscale.

Merging Bottom-Up with Top-Down: Continuous Lamellar Networks and Block Copolymer Lithography

NASA Astrophysics Data System (ADS)

Campbell, Ian Patrick

Block copolymer lithography is an emerging nanopatterning technology with capabilities that may complement and eventually replace those provided by existing optical lithography techniques. This bottom-up process relies on the parallel self-assembly of macromolecules composed of covalently linked, chemically distinct blocks to generate periodic nanostructures. Among the myriad potential morphologies, lamellar structures formed by diblock copolymers with symmetric volume fractions have attracted the most interest as a patterning tool. When confined to thin films and directed to assemble with interfaces perpendicular to the substrate, two-dimensional domains are formed between the free surface and the substrate, and selective removal of a single block creates a nanostructured polymeric template. The substrate exposed between the polymeric features can subsequently be modified through standard top-down microfabrication processes to generate novel nanostructured materials. Despite tremendous progress in our understanding of block copolymer self-assembly, continuous two-dimensional materials have not yet been fabricated via this robust technique, which may enable nanostructured material combinations that cannot be fabricated through bottom-up methods. This thesis aims to study the effects of block copolymer composition and processing on the lamellar network morphology of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) and utilize this knowledge to fabricate continuous two-dimensional materials through top-down methods. First, block copolymer composition was varied through homopolymer blending to explore the physical phenomena surrounding lamellar network continuity. After establishing a framework for tuning the continuity, the effects of various processing parameters were explored to engineer the network connectivity via defect annihilation processes. Precisely controlling the connectivity and continuity of lamellar networks through defect engineering and optimizing the block copolymer lithography process thus enabled the top-down fabrication of continuous two-dimensional gold networks with nanoscale properties. The lamellar structure of these networks was found to confer unique mechanical properties on the nanowire networks and suggests that materials templated via this method may be excellent candidates for integration into stretchable and flexible devices.

Examining water in model membranes by near infrared spectroscopy and multivariate analysis.

PubMed

Wenz, Jorge J

2018-03-01

By exploiting the sensitivity of the NIR spectrum, particularly the first overtone of water, to the number and strength of hydrogen bonds, the hydrogen bond network and water polymerization in membranes of DMPA (1,2-dimyristoyl-sn-glycero-3-phosphate) and DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) was investigated as a function of the temperature and the presence of this two phospholipids having the same tail but different polar head. Principal components analysis performed on the spectra was used to disclose subtle spectral changes that mirror the alteration of the vibrational energy of the water O-H bonds, as a measure of the H-bond network. Temperature showed a dominating effect on the H-bond network. Increasing temperatures diminished the number of strongly H-bonded water molecules and increased the number of weakly H-bonded waters. This main effect of temperature was missing after the subtraction of the pure water spectra from the lipid-containing ones. An intriguing secondary effect of temperature was also revealed. Phospholipids exhibited an effect qualitatively similar to that of the temperature. DMPA, and particularly DMPC, disrupted the H-bond network in the neighboring lipid-water interface, reducing water polymerization and strengthening the water O-H bonds. The type of the polar head affects the H-bonds more than duplicate the concentration of the lipid. A connection between head group structure and the effect on the H-bonds network, and the existence of two populations of water molecules are discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Nanoparticle Control of Void Formation and Expansion in Polymeric and Composite Systems

DTIC Science & Technology

2007-02-01

facilities of GloCal Network Corporation, a Delaware legal entity with facilities in Seattle, Washington. The team succeeded at performing work in the State of...Delaware and Washington concurrently. After December 1, 2006, Professor Seferis and his team will continue the research, exclusively through GloCal

Nanoreinforced biocompatible hydrogels from wood hemicelluloses and cellulose whiskers

Treesearch

Muzaffer Ahmet Karaaslan; Mandla A. Tshabalala; Daniel J. Yelle; Gisela Buschle-Diller

2011-01-01

Nanoreinforced hydrogels with a unique network structure were prepared from wood cellulose whiskers coated with chemically modified wood hemicelluloses. The hemicelluloses were modified with 2-hydroxyethylmethacrylate prior to adsorption onto the cellulose whiskers in aqueous medium. Synthesis of the hydrogels was accomplished by in situ radical polymerization of the...

EFFECT OF MOLECULAR ARCHITECTURE ON DBS-INDUCED BLOCK COPOLYMER GELS: A RHEOLOGICAL STUDY

EPA Science Inventory

Dibenzylidene sorbitol (DBS) is capable of gelling a variety of organic solvents and polymeric materials by forming a rigid, 3-D hydrogen-bonded network. In this work, two poly(siloxane)/poly(propylene oxide) segmented copolymers of equal composition and molecular weight, but di...

Taming Prebiotic Chemistry: The Role of Heterogeneous and Interfacial Catalysis in the Emergence of a Prebiotic Catalytic/Information Polymer System

PubMed Central

Monnard, Pierre-Alain

2016-01-01

Cellular life is based on interacting polymer networks that serve as catalysts, genetic information and structural molecules. The complexity of the DNA, RNA and protein biochemistry suggests that it must have been preceded by simpler systems. The RNA world hypothesis proposes RNA as the prime candidate for such a primal system. Even though this proposition has gained currency, its investigations have highlighted several challenges with respect to bulk aqueous media: (1) the synthesis of RNA monomers is difficult; (2) efficient pathways for monomer polymerization into functional RNAs and their subsequent, sequence-specific replication remain elusive; and (3) the evolution of the RNA function towards cellular metabolism in isolation is questionable in view of the chemical mixtures expected on the early Earth. This review will address the question of the possible roles of heterogeneous media and catalysis as drivers for the emergence of RNA-based polymer networks. We will show that this approach to non-enzymatic polymerizations of RNA from monomers and RNA evolution cannot only solve some issues encountered during reactions in bulk aqueous solutions, but may also explain the co-emergence of the various polymers indispensable for life in complex mixtures and their organization into primitive networks. PMID:27827919

Platelet factor 4 (CXCL4) seals blood clots by altering the structure of fibrin.

PubMed

Amelot, Aymeric A; Tagzirt, Madjid; Ducouret, Guylaine; Kuen, René Lai; Le Bonniec, Bernard F

2007-01-05

Platelet factor-4 (PF4/CXCL4) is an orphan chemokine released in large quantities in the vicinity of growing blood clots. Coagulation of plasma supplemented with a matching amount of PF4 results in a translucent jelly-like clot. Saturating amounts of PF4 reduce the porosity of the fibrin network 4.4-fold and decrease the values of the elastic and loss moduli by 31- and 59-fold, respectively. PF4 alters neither the cleavage of fibrinogen by thrombin nor the cross-linking of protofibrils by activated factor XIII but binds to fibrin and dramatically transforms the structure of the ensuing network. Scanning electron microscopy showed that PF4 gives rise to a previously unreported pattern of polymerization where fibrin assembles to form a sealed network. The subunits constituting PF4 form a tetrahedron having at its corners a RPRH motif that mimics (in reverse orientation) the Gly-His-Arg-Pro-amide peptides that co-crystallize with fibrin. Molecular modeling showed that PF4 could be docked to fibrin with remarkable complementarities and absence of steric clashes, allowing the assembly of irregular polymers. Consistent with this hypothesis, as little as 50 microm the QVRPRHIT peptide derived from PF4 affects the polymerization of fibrin.

Wound Tissue Can Utilize a Polymeric Template to Synthesize a Functional Extension of Skin

NASA Astrophysics Data System (ADS)

Yannas, I. V.; Burke, J. F.; Orgill, D. P.; Skrabut, E. M.

1982-01-01

Prompt and long-term closure of full-thickness skin wounds in guinea pigs and humans is achieved by applying a bilayer polymeric membrane. The membrane comprises a top layer of a silicone elastomer and a bottom layer of a porous cross-linked network of collagen and glycosaminoglycan. The bottom layer can be seeded with a small number of autologous basal cells before grafting. No immunosuppression is used and infection, exudation, and rejection are absent. Host tissue utilizes the sterile membrane as a culture medium to synthesize neoepidermal and neodermal tissue. A functional extension of skin over the entire wound area is formed in about 4 weeks.

Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures

DOEpatents

Pekala, R.W.

1996-09-17

The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes {<=}1,000{angstrom}, and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1,050 C to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors. 8 figs.

Ion conducting organic/inorganic hybrid polymers

NASA Technical Reports Server (NTRS)

Meador, Maryann B. (Inventor); Kinder, James D. (Inventor)

2010-01-01

This invention relates to a series of organic/inorganic hybrid polymers that are easy to fabricate into dimensionally stable films with good ion-conductivity over a wide range of temperatures for use in a variety of applications. The polymers are prepared by the reaction of amines, preferably diamines and mixtures thereof with monoamines with epoxy-functionalized alkoxysilanes. The products of the reaction are polymerized by hydrolysis of the alkoxysilane groups to produce an organic-containing silica network. Suitable functionality introduced into the amine and alkoxysilane groups produce solid polymeric membranes which conduct ions for use in fuel cells, high-performance solid state batteries, chemical sensors, electrochemical capacitors, electro-chromic windows or displays, analog memory devices and the like.

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.

Structure and Dynamics of an Arp2/3 Complex-independent Component of the Lamellipodial Actin Network

PubMed Central

Henson, John H.; Cheung, David; Fried, Christopher A.; Shuster, Charles B.; McClellan, Mary K.; Voss, Meagen K.; Sheridan, John T.; Oldenbourg, Rudolf

2010-01-01

Sea urchin coelomocytes contain an unusually broad lamellipodial region and have served as a useful model experimental system for studying the process of actin-based retrograde/centripetal flow. In the current study the small molecule drug 2,3-butanedione monoxime (BDM) was employed as a means of delocalizing the Arp2/3 complex from the cell edge in an effort to investigate the Arp2/3 complex-independent aspects of retrograde flow. Digitally-enhanced phase contrast, fluorescence and polarization light microscopy, along with rotary shadow TEM methods demonstrated that BDM treatment resulted in the centripetal displacement of the Arp2/3 complex and the associated dendritic lamellipodial (LP) actin network from the cell edge. In its wake there remained an array of elongate actin filaments organized into concave arcs that displayed retrograde flow at approximately one quarter the normal rate. Actin polymerization inhibitor experiments indicated that these arcs were generated by polymerization at the cell edge, while active myosin-based contraction in BDM treated cells was demonstrated by localization with anti-phospho-MRLC antibody, the retraction of the cytoskeleton in the presence of BDM, and the response of the BDM arcs to laser-based severing. The results suggest that BDM treatment reveals an Arp2/3 complex-independent actin structure in coelomocytes consisting of elongate filaments integrated into the LP network and that these filaments represent a potential connection between the LP network and the central cytoskeleton. PMID:19530177

Dynamic tubulation of mitochondria drives mitochondrial network formation.

PubMed

Wang, Chong; Du, Wanqing; Su, Qian Peter; Zhu, Mingli; Feng, Peiyuan; Li, Ying; Zhou, Yichen; Mi, Na; Zhu, Yueyao; Jiang, Dong; Zhang, Senyan; Zhang, Zerui; Sun, Yujie; Yu, Li

2015-10-01

Mitochondria form networks. Formation of mitochondrial networks is important for maintaining mitochondrial DNA integrity and interchanging mitochondrial material, whereas disruption of the mitochondrial network affects mitochondrial functions. According to the current view, mitochondrial networks are formed by fusion of individual mitochondria. Here, we report a new mechanism for formation of mitochondrial networks through KIF5B-mediated dynamic tubulation of mitochondria. We found that KIF5B pulls thin, highly dynamic tubules out of mitochondria. Fusion of these dynamic tubules, which is mediated by mitofusins, gives rise to the mitochondrial network. We further demonstrated that dynamic tubulation and fusion is sufficient for mitochondrial network formation, by reconstituting mitochondrial networks in vitro using purified fusion-competent mitochondria, recombinant KIF5B, and polymerized microtubules. Interestingly, KIF5B only controls network formation in the peripheral zone of the cell, indicating that the mitochondrial network is divided into subzones, which may be constructed by different mechanisms. Our data not only uncover an essential mechanism for mitochondrial network formation, but also reveal that different parts of the mitochondrial network are formed by different mechanisms.

Stabilization, not polymerization, of microtubules inhibits the nuclear translocation of STATs in adipocytes.

PubMed

Gleason, Evanna L; Hogan, Jessica C; Stephens, Jacqueline M

2004-12-17

Signal transducers and activators of transcriptions (STATs) are a family of latent transcription factors which are activated by a variety of growth factors and cytokines in many cell types. However, the mechanism by which these transcription factors translocate to the nucleus is poorly understood. The goal of this study was to determine the requirement of microfilaments and microtubules for cytokine induced STAT activation in cultured adipocytes. We used seven different actin-specific and microtubule-specific agents that are well-established effectors of these cytoskeletal networks. Our results clearly demonstrate that inhibition of microfilaments or the prevention of microtubule polymerization has no effect on the ability of STATs to be tyrosine phosphorylated or to translocate to the nucleus. However, we observed that paclitaxel, a microtubule stabilizer, resulted in a significant decrease in the nuclear translocation of STATs without affecting the cytosolic tyrosine phosphorylation of these transcription factors. In summary, our results demonstrate that the dynamic instability, but not the polymerization, of microtubules contributes to nuclear translocation of STAT proteins in adipocytes.

Multi input single output model predictive control of non-linear bio-polymerization process

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

Arumugasamy, Senthil Kumar; Ahmad, Z.

This paper focuses on Multi Input Single Output (MISO) Model Predictive Control of bio-polymerization process in which mechanistic model is developed and linked with the feedforward neural network model to obtain a hybrid model (Mechanistic-FANN) of lipase-catalyzed ring-opening polymerization of ε-caprolactone (ε-CL) for Poly (ε-caprolactone) production. In this research, state space model was used, in which the input to the model were the reactor temperatures and reactor impeller speeds and the output were the molecular weight of polymer (M{sub n}) and polymer polydispersity index. State space model for MISO created using System identification tool box of Matlab™. This state spacemore » model is used in MISO MPC. Model predictive control (MPC) has been applied to predict the molecular weight of the biopolymer and consequently control the molecular weight of biopolymer. The result shows that MPC is able to track reference trajectory and give optimum movement of manipulated variable.« less

PEG Molecular Net-Cloth Grafted on Polymeric Substrates and Its Bio-Merits

NASA Astrophysics Data System (ADS)

Zhao, Changwen; Lin, Zhifeng; Yin, Huabing; Ma, Yuhong; Xu, Fujian; Yang, Wantai

2014-05-01

Polymer brushes and hydrogels are sensitive to the environment, which can cause uncontrolled variations on their performance. Herein, for the first time, we report a non-swelling ``PEG molecular net-cloth'' on a solid surface, fabricated using a novel ``visible light induced surface controlled graft cross-linking polymerization'' (VSCGCP) technique. Via this method, we show that 1) the 3D-network structure of the net-cloth can be precisely modulated and its thickness controlled; 2) the PEG net-cloth has excellent resistance to non-specific protein adsorption and cell adhesion; 3) the mild polymerization conditions (i.e. visible light and room temperature) provided an ideal tool for in situ encapsulation of delicate biomolecules such as enzymes; 4) the successive grafting of reactive three-dimensional patterns on the PEG net-cloth enables the creation of protein microarrays with high signal to noise ratio. Importantly, this strategy is applicable to any C-H containing surface, and can be easily tailored for a broad range of applications.

Unveiling the molecular mechanism of self-healing in a telechelic, supramolecular polymer network

PubMed Central

Yan, Tingzi; Schröter, Klaus; Herbst, Florian; Binder, Wolfgang H.; Thurn-Albrecht, Thomas

2016-01-01

Reversible polymeric networks can show self-healing properties due to their ability to reassemble after application of stress and fracture, but typically the relation between equilibrium molecular dynamics and self-healing kinetics has been difficult to disentangle. Here we present a well-characterized, self-assembled bulk network based on supramolecular assemblies, that allows a clear distinction between chain dynamics and network relaxation. Small angle x-ray scattering and rheological measurements provide evidence for a structurally well-defined, dense network of interconnected aggregates giving mechanical strength to the material. Different from a covalent network, the dynamic character of the supramolecular bonds enables macroscopic flow on a longer time scale and the establishment of an equilibrium structure. A combination of linear and nonlinear rheological measurements clearly identifies the terminal relaxation process as being responsible for the process of self-healing. PMID:27581380

Experimental and modeling study of Newtonian and non-Newtonian fluid flow in pore network micromodels.

PubMed

Perrin, Christian L; Tardy, Philippe M J; Sorbie, Ken S; Crawshaw, John C

2006-03-15

The in situ rheology of polymeric solutions has been studied experimentally in etched silicon micromodels which are idealizations of porous media. The rectangular channels in these etched networks have dimensions typical of pore sizes in sandstone rocks. Pressure drop/flow rate relations have been measured for water and non-Newtonian hydrolyzed-polyacrylamide (HPAM) solutions in both individual straight rectangular capillaries and in networks of such capillaries. Results from these experiments have been analyzed using pore-scale network modeling incorporating the non-Newtonian fluid mechanics of a Carreau fluid. Quantitative agreement is seen between the experiments and the network calculations in the Newtonian and shear-thinning flow regions demonstrating that the 'shift factor,'alpha, can be calculated a priori. Shear-thickening behavior was observed at higher flow rates in the micromodel experiments as a result of elastic effects becoming important and this remains to be incorporated in the network model.

Effect of a non-thermal, atmospheric-pressure, plasma brush on conversion of model self-etch adhesive formulations compared to conventional photo-polymerization

PubMed Central

Chen, Mingsheng; Zhang, Ying; Yao, Xiaomei; Li, Hao; Yu, Qingsong; Wang, Yong

2012-01-01

Objective To determine the effectiveness and efficiency of non-thermal, atmospheric plasmas for inducing polymerization of model dental self-etch adhesives. Methods The monomer mixtures used were bis-[2-(methacryloyloxy)ethyl] phosphate (2MP) and 2-hydroxyethyl methacrylate (HEMA), with mass ratios of 70/30, 50/50 and 30/70. Water was added to the above formulations: 10–30 wt%. These monomer/water mixtures were treated steadily for 40 s under a non-thermal atmospheric plasma brush working at temperatures from 32° to 35°C. For comparison, photo-initiators were added to the above formulations for photo-polymerization studies, which were light-cured for 40 s. The degree of conversion (DC) of both the plasma- and light-cured samples was measured using FTIR spectroscopy with an attenuated total reflectance attachment. Results The non-thermal plasma brush was effective in inducing polymerization of the model self-etch adhesives. The presence of water did not negatively affect the DC of plasma-cured samples. Indeed, DC values slightly increased, with increasing water content in adhesives: from 58.3% to 68.7% when the water content increased from 10% to 30% in the adhesives with a 50/50 (2MP/HEMA) mass ratio. Conversion values of the plasma-cured groups were higher than those of light-cured samples with the same mass ratio and water content. Spectral differences between the plasma- and light-cured groups indicate subtle structural distinctions in the resultant polymer networks. Significance This research if the first to demonstrate that the non-thermal plasma brush induces polymerization of model adhesives under clinical settings by direct/indirect energy transfer. This device shows promise for polymerization of dental composite restorations having enhanced properties and performance. PMID:23018084

Kinetics of bulk photo-initiated copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerizations.

PubMed

Song, Han Byul; Baranek, Austin; Bowman, Christopher N

2016-01-21

Photoinitiation of polymerizations based on the copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction enables spatio-temporal control and the formation of mechanically robust, highly glassy photopolymers. Here, we investigated several critical factors influencing photo-CuAAC polymerization kinetics via systematic variation of reaction conditions such as the physicochemical nature of the monomers; the copper salt and photoinitiator types and concentrations; light intensity; exposure time and solvent content. Real time Fourier transform infrared spectroscopy (FTIR) was used to monitor the polymerization kinetics in situ . Six different di-functional azide monomers and four different tri-functional alkyne monomers containing either aliphatic, aromatic, ether and/or carbamate substituents were synthesized and polymerized. Replacing carbamate structures with ether moieties in the monomers enabled an increase in conversion from 65% to 90% under similar irradiation conditions. The carbamate results in stiffer monomers and higher viscosity mixtures indicating that chain mobility and diffusion are key factors that determine the CuAAC network formation kinetics. Photoinitiation rates were manipulated by altering various aspects of the photo-reduction step; ultimately, a loading above 3 mol% per functional group for both the copper catalyst and the photoinitiator showed little or no rate dependence on concentration while a loading below 3 mol% exhibited 1 st order rate dependence. Furthermore, a photoinitiating system consisting of camphorquinone resulted in 60% conversion in the dark after only 1 minute of 75 mW cm -2 light exposure at 400-500 nm, highlighting a unique characteristic of the CuAAC photopolymerization enabled by the combination of the copper(i)'s catalytic lifetime and the nature of the step-growth polymerization.

Synthesis of Size-Tunable CO2-Philic Imprinted Polymeric Particles (MIPs) for Low-Pressure CO2 Capture Using Oil-in-Oil Suspension Polymerization.

PubMed

Nabavi, Seyed Ali; Vladisavljević, Goran T; Zhu, Yidi; Manović, Vasilije

2017-10-03

Highly selective molecularly imprinted poly[acrylamide-co-(ethylene glycol dimethacrylate)] polymer particles (MIPs) for CO 2 capture were synthesized by suspension polymerization via oil-in-oil emulsion. Creation of CO 2 -philic, amide-decorated cavities in the polymer matrix led to a high affinity to CO 2 . At 0.15 bar CO 2 partial pressure, the CO 2 /N 2 selectivity was 49 (corresponding to 91% purity of the gas stream after regeneration), and reached 97 at ultralow CO 2 partial pressures. The imprinted polymers showed considerably higher CO 2 uptakes compared to their nonimprinted counterparts, and the maximum equilibrium CO 2 capture capacity of 1.1 mmol g -1 was achieved at 273 K. The heat of adsorption was below 32 kJ mol -1 and the temperature of onset of intense thermal degradation was 351-376 °C. An increase in monomer-to-cross-linker molar ratio in the dispersed phase up to 1:2.5 led to a higher affinity toward CO 2 due to higher density of selective amide groups in the polymer network. MIPs are a promising option for industrial packed and fluidized bed CO 2 capture systems due to large particles with a diameter up to 1200 μm and irregular oblong shapes formed due to arrested coalescence during polymerization, occurring as a result of internal elasticity of the partially polymerized semisolid drops.

Microwave-assisted synthesis of sucrose polyurethanes and their semi-interpenetrating polymer networks with polycaprolactane and soybean oil

USDA-ARS?s Scientific Manuscript database

Because of the current interest in sustainability, environmental stewardship, and green chemistry, there has been a lot of interest in using agrobased raw materials for the design of polymeric materials. One of the promising biorenewable materials is sucrose, which is inexpensive and widely availabl...

Synthesis of wheat straw cellulose-g-poly (potassium acrylate)/PVA semi-IPNs superabsorbent resin.

PubMed

Liu, Jia; Li, Qian; Su, Yuan; Yue, Qinyan; Gao, Baoyu; Wang, Rui

2013-04-15

To better use wheat straw and minimize its negative impact on environment, a novel semi-interpenetrating polymer networks (semi-IPNs) superabsorbent resin (SAR) composed of wheat straw cellulose-g-poly (potassium acrylate) (WSC-g-PKA) network and linear polyvinyl alcohol (PVA) was prepared by polymerization in the presence of a redox initiating system. The structure and morphology of semi-IPNs SAR were characterized by means of FTIR, SEM and TGA, which confirmed that WSC and PVA participated in the graft polymerization reaction with acrylic acid (AA). The factors that can influence the water absorption of the semi-IPNs SAR were investigated and optimized, including the weight ratios of AA to WSC and PVA to WSC, the content of initiator and crosslinker, neutralization degree (ND) of AA, reaction temperature and time. The semi-IPNs SAR prepared under optimized synthesis condition gave the best water absorption of 266.82 g/g in distilled water and 34.32 g/g in 0.9 wt% NaCl solution. Copyright © 2013 Elsevier Ltd. All rights reserved.

Investigating the Release of a Hydrophobic Peptide from Matrices of Biodegradable Polymers: An Integrated Method Approach

PubMed Central

Gubskaya, Anna V.; Khan, I. John; Valenzuela, Loreto M.; Lisnyak, Yuriy V.; Kohn, Joachim

2013-01-01

The objectives of this work were: (1) to select suitable compositions of tyrosine-derived polycarbonates for controlled delivery of voclosporin, a potent drug candidate to treat ocular diseases, (2) to establish a structure-function relationship between key molecular characteristics of biodegradable polymer matrices and drug release kinetics, and (3) to identify factors contributing in the rate of drug release. For the first time, the experimental study of polymeric drug release was accompanied by a hierarchical sequence of three computational methods. First, suitable polymer compositions used in subsequent neural network modeling were determined by means of response surface methodology (RSM). Second, accurate artificial neural network (ANN) models were built to predict drug release profiles for fifteen polymers located outside the initial design space. Finally, thermodynamic properties and hydrogen-bonding patterns of model drug-polymer complexes were studied using molecular dynamics (MD) technique to elucidate a role of specific interactions in drug release mechanism. This research presents further development of methodological approaches to meet challenges in the design of polymeric drug delivery systems. PMID:24039300

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.

Photopolymer Electrolytes for Sustainable, Upscalable, Safe, and Ambient-Temperature Sodium-Ion Secondary Batteries.

PubMed

Bella, Federico; Colò, Francesca; Nair, Jijeesh R; Gerbaldi, Claudio

2015-11-01

The first example of a photopolymerized electrolyte for a sodium-ion battery is proposed herein. By means of a preparation process free of solvents, catalysts, purification steps, and separation steps, it is possible to obtain a three-dimensional polymeric network capable of efficient sodium-ion transport. The thermal properties of the resulting solid electrolyte separator, characterized by means of thermogravimetric and calorimetric techniques, are excellent for use in sustainable energy systems conceived for safe large-scale grid storage. The photopolymerized electrolyte shows a wide electrochemical stability window up to 4.8 V versus Na/Na(+) along with the highest ionic conductivity (5.1 mS cm(-1) at 20 °C) obtained in the field of Na-ion polymer batteries so far and stable long-term constant-current charge/discharge cycling. Moreover, the polymeric networks are also demonstrated for the in situ fabrication of electrode/electrolyte composites with excellent interfacial properties, which are ideal for all-solid-state, safe, and easily upscalable device assembly. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Identification of cation-binding sites on actin that drive polymerization and modulate bending stiffness

PubMed Central

Kang, Hyeran; Bradley, Michael J.; McCullough, Brannon R.; Pierre, Anaëlle; Grintsevich, Elena E.; Reisler, Emil; De La Cruz, Enrique M.

2012-01-01

The assembly of actin monomers into filaments and networks plays vital roles throughout eukaryotic biology, including intracellular transport, cell motility, cell division, determining cellular shape, and providing cells with mechanical strength. The regulation of actin assembly and modulation of filament mechanical properties are critical for proper actin function. It is well established that physiological salt concentrations promote actin assembly and alter the overall bending mechanics of assembled filaments and networks. However, the molecular origins of these salt-dependent effects, particularly if they involve nonspecific ionic strength effects or specific ion-binding interactions, are unknown. Here, we demonstrate that specific cation binding at two discrete sites situated between adjacent subunits along the long-pitch helix drive actin polymerization and determine the filament bending rigidity. We classify the two sites as “polymerization” and “stiffness” sites based on the effects that mutations at the sites have on salt-dependent filament assembly and bending mechanics, respectively. These results establish the existence and location of the cation-binding sites that confer salt dependence to the assembly and mechanics of actin filaments. PMID:23027950

Polymeric nanoparticulate system augmented the anticancer therapeutic efficacy of gemcitabine.

PubMed

Arias, José L; Reddy, L Harivardhan; Couvreur, Patrick

2009-09-01

Gemcitabine hydrochloride is an anticancer nucleoside analogue indicated in clinic for the treatment of various solid tumors. Although this drug has been demonstrated to display anticancer activity against a wide variety of tumors, it is needed to be administered at high doses to elicit the required therapeutic response, simultaneously leading to severe adverse effects. We hypothesized that the efficient delivery of gemcitabine to tumors using a biodegradable carrier system could reduce the dose required to elicit sufficient therapeutic response. Thus, we have developed a nanoparticle formulation of gemcitabine suitable for parenteral administration based on the biodegradable polymer poly(octylcyanoacrylate) (POCA). The nanoparticles were synthesized by anionic polymerization of the corresponding monomer. Two drug loading methods were analyzed: the first one based on gemcitabine surface adsorption onto the preformed nanoparticles, and the second method being gemcitabine addition before the polymerization process leading to drug entrapment in the polymeric network. A detailed investigation of the capabilities of the polymer particles to load this drug is described. Gemcitabine entrapment into the polymer matrix yielded a higher drug loading and a slower drug release profile as compared with drug adsorption procedure. The main factors determining the gemcitabine incorporation to the polymer network were the nanoparticles preparation procedure, the monomer concentration, the surfactant concentration, the pH, and the drug concentration. The release kinetic of gemcitabine was found to be controlled by the pH and the type of drug incorporation. The cytotoxicity studies performed on L1210 tumor cells revealed a similar anticancer activity of the gemcitabine-loaded POCA (GPOCA) nanoparticle as free gemcitabine. Following intravenous administration into the mice bearing L1210 wt subcutaneous tumor, the GPOCA nanoparticles displayed significantly greater anticancer activity compared to free gemcitabine; this has been additionally confirmed by histology and immunohistochemistry studies, suggesting the potential of GPOCA for the efficient treatment of cancer.

Kinetics of sorption of polyaromatic hydrocarbons onto granular activated carbon and Macronet hyper-cross-linked polymers (MN200).

PubMed

Valderrama, C; Cortina, J L; Farran, A; Gamisans, X; Lao, C

2007-06-01

Polymeric supports are presented as an alternative to granular activated carbon (GAC) for organic contaminant removal from groundwater using permeable reactive barriers (PRB). The search for suitable polymeric sorbents for hydrocarbon extraction from aqueous streams has prompted the synthesis of new resins incorporating new functionalities or modifying the polymer network properties that solve many of the existing problems. Between them, the new type of polymeric sorbents Macronet Hypersol containing a styrene-divinylbenzene macroporous hyperreticulated network has been evaluated. Because of their potential sorptive properties, tests were conducted to determine the feasibility of using them as a low-cost reactive material for groundwater applications. The present work describes the sorption of six polycyclic hydrocarbons (PAHs) from aqueous solution onto both Macronet polymeric sorbent MN200 and granular activated carbon. Batch experiments were performed to determine loading rates of a family of PAHs (naphthalene, fluorene, anthracene, acenaphthene, pyrene, and fluoranthene), from a simple two-rings PAH (naphthalene) up to a four-ring PAH (pyrene). The behavior of a non-functionalized Macronet support (MN200) was compared with the behavior of a recognized material, granular activated carbon (GAC). Analyses of the respective rate data with three theoretical models (pseudo-first- and pseudo-second-order reaction models and the Elovich model) were used to describe the PAH sorption kinetics. Sorption rate constants were determined by graphical analysis of the proposed models. The study showed that sorption systems followed a pseudo-first-order reaction model, although the pseudo-second-order reaction model provides an acceptable description of the sorption process. Graphical analysis showed that the sorption process with activated carbon is a more complex process than the one observed for hyper-cross-linked polymers (MN200). A simulation of the barrier thickness needed to treat a PAH-polluted plume showed that 0.1-1 m of sorption media is enough even for high water fluxes such as 0.1-2 m(3)/m(2)/day for both sorbents.

A phase-transition model for the rise and collapse of ancient civilizations: A pre-ceramic Andean case study

NASA Astrophysics Data System (ADS)

Flores, J. C.

2015-12-01

For ancient civilizations, the shift from disorder to organized urban settlements is viewed as a phase-transition simile. The number of monumental constructions, assumed to be a signature of civilization processes, corresponds to the order parameter, and effective connectivity becomes related to the control parameter. Based on parameter estimations from archaeological and paleo-climatological data, this study analyzes the rise and fall of the ancient Caral civilization on the South Pacific coast during a period of small ENSO fluctuations (approximately 4500 BP). Other examples considered include civilizations on Easter Island and the Maya Lowlands. This work considers a typical nonlinear third order evolution equation and numerical simulations.

Comparing Ullmann Coupling on Noble Metal Surfaces: On-Surface Polymerization of 1,3,6,8-Tetrabromopyrene on Cu(111) and Au(111).

PubMed

Pham, Tuan Anh; Song, Fei; Nguyen, Manh-Thuong; Li, Zheshen; Studener, Florian; Stöhr, Meike

2016-04-18

The on-surface polymerization of 1,3,6,8-tetrabromopyrene (Br4 Py) on Cu(111) and Au(111) surfaces under ultrahigh vacuum conditions was investigated by a combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. Deposition of Br4 Py on Cu(111) held at 300 K resulted in a spontaneous debromination reaction, generating the formation of a branched coordination polymer network stabilized by C-Cu-C bonds. After annealing at 473 K, the C-Cu-C bonds were converted to covalent C-C bonds, leading to the formation of a covalently linked molecular network of short oligomers. In contrast, highly ordered self-assembled two-dimensional (2D) patterns stabilized by both Br-Br halogen and Br-H hydrogen bonds were observed upon deposition of Br4 Py on Au(111) held at 300 K. Subsequent annealing of the sample at 473 K led to a dissociation of the C-Br bonds and the formation of disordered metal-coordinated molecular networks. Further annealing at 573 K resulted in the formation of covalently linked disordered networks. Importantly, we found that the chosen substrate not only plays an important role as catalyst for the Ullmann reaction, but also influences the formation of different types of intermolecular bonds and thus, determines the final polymer network morphology. DFT calculations further support our experimental findings obtained by STM and XPS and add complementary information on the reaction pathway of Br4 Py on the different substrates. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoporous thermosetting polymers.

PubMed

Raman, Vijay I; Palmese, Giuseppe R

2005-02-15

Potential applications of nanoporous thermosetting polymers include polyelectrolytes in fuel cells, separation membranes, adsorption media, and sensors. Design of nanoporous polymers for such applications entails controlling permeability by tailoring pore size, structure, and interface chemistry. Nanoporous thermosetting polymers are often synthesized via free radical mechanisms using solvents that phase separate during polymerization. In this work, a novel technique for the synthesis of nanoporous thermosets is presented that is based on the reactive encapsulation of an inert solvent using step-growth cross-linking polymerization without micro/macroscopic phase separation. The criteria for selecting such a monomer-polymer-solvent system are discussed based on FTIR analysis, observed micro/macroscopic phase separation, and thermodynamics of swelling. Investigation of resulting network pore structures by scanning electron microscopy (SEM) and small-angle X-ray scattering following extraction and supercritical drying using carbon dioxide showed that nanoporous polymeric materials with pore sizes ranging from 1 to 50 nm can be synthesized by varying the solvent content. The differences in the porous morphology of these materials compared to more common free radically polymerized analogues that exhibit phase separation were evident from SEM imaging. Furthermore, it was demonstrated that the chemical activity of the nanoporous materials obtained by our method could be tailored by grafting appropriate functional groups at the pore interface.

Guided in Situ Polymerization of MEH-PPV in Mesoporous Titania Photoanodes.

PubMed

Minar, Norma K; Docampo, Pablo; Fattakhova-Rohlfing, Dina; Bein, Thomas

2015-05-20

Incorporation of conjugated polymers into porous metal oxide networks is a challenging task, which is being pursued via many different approaches. We have developed the guided in situ polymerization of poly(2-methoxy-5-(2'-ethylhexyloxy)-p-phenylenevinylene) (MEH-PPV) in porous titania films by means of surface functionalization. The controlled polymerization via the Gilch route was induced by an alkoxide base and by increasing the temperature. The selected and specially designed surface-functionalizing linker molecules mimic the monomer or its activated form, respectively. In this way, we drastically enhanced the amount of MEH-PPV incorporated into the porous titania phase compared to nonfunctionalized samples by a factor of 6. Additionally, photovoltaic measurements were performed. The devices show shunting or series resistance limitations, depending on the surface functionalization prior to in situ polymerization of MEH-PPV. We suggest that the reason for this behavior can be found in the orientation of the grown polymer chains with respect to the titania surface. Therefore, the geometry of the anchoring via the linker molecules is relevant for exploiting the full electronic potential of the conjugated polymer in the resulting hybrid composite. This observation will help to design future synthesis methods for new hybrid materials from conjugated polymers and n-type semiconductors to take full advantage of favorable electronic interactions between the two phases.

Patterning poly(maleic anhydride-co-3,9-divinyl-2,4,8,10-tetraoxaspiro (5.5) undecane) copolymer bioconjugates for controlled release of drugs.

PubMed

Nita, Loredana E; Chiriac, Aurica P; Mititelu-Tartau, Liliana; Stoleru, Elena; Doroftei, Florica; Diaconu, Alina

2015-09-30

Owing to the special characteristics and abilities polymeric networks have received special interest for a range of biomedical applications especially for drug delivery systems. This study was devoted to preparation of new polymeric compounds based on maleic anhydride and 3,9-divinyl-2,4,8,10-tetraoxaspiro (5.5) undecane copolymer (poly maleic anhydride-co-3,9-divinyl-2,4,8,10-tetraoxaspiro (5.5) undecane) (PMAU) patterned as a network for bioconjugation and tested as drug carrier systems. The PMAU copolymer was improved in its functionality by opening the maleic anhydride ring with different amounts of erythritol, which is free of side effects in regular use and a multifunctional compound, and also confers antioxidant character for the new compounds. The new polymeric matrices were loaded with acetaminophen, codeine and their fixed dose combinations. The investigation demonstrated the capability of the new structures to be used as polymer networks for linking bioactive compounds and to perform controlled delivery. The physico-chemical investigations--Fourier transform infrared spectroscopy (FTIR) spectra, contact angle, zeta potential (ZP - z, PMAU and its derivatives samples loaded with medicines present decreased values of zeta potential attesting the bioconjugate formation and as well their stability), and hydrodynamic radius, near infrared chemical imaging evaluation (new specific bands being registered for bio-conjugate with acetaminophen around of 1150-1200 nm and 1700 nm, and also between 1150 and 1200 nm in case of the codeine bio-conjugate), scanning electron microscopy (SEM) studies, X-ray diffraction analysis--evidenced the formation of the bioconjugates in relation to the chemical composition of the polymer matrices, while in vitro release study and in vivo tests confirm the capacity for drug delivery of the prepared bioactive systems. Copyright © 2015 Elsevier B.V. All rights reserved.

Influence of conformational changes on spin crossover properties and superstructure formation in 2D coordination polymers [Fe(hbtz)2(RCN)2](ClO4)2.

PubMed

Książek, Maria; Kusz, Joachim; Białońska, Agata; Bronisz, Robert; Weselski, Marek

2015-11-14

2D structurally related iron(ii) coordination networks {[Fe(hbtz)2(RCN)2](ClO4)2}∞ featuring, besides tetrazol-2-yl rings in the first coordination sphere, also axially coordinated propionitrile or allyl cyanide molecules (R = C3H5-, 1; R = C2H5-, 2) were synthesized. Thermally induced spin crossover (SCO) in 1 takes place in two poorly resolved stages (T(1)1/2(↓) = T(1)1/2(↑) = 198 K, T(2)1/2(↓) = 170 K, T(2)1/2(↑) = 171 K) whereas in 2 complete and relatively gradual one step SCO (T1/2(↓) = T1/2(↑) = 160 K) occurs. Diversification of the SCO properties of the complexes originates from the ability of coordinated allyl cyanide in 1 to undergo conformational alterations, which is not observed for propionitrile molecules in 2. SCO in 1 is accompanied by a non-monotonic change of the contribution of allyl cyanide conformers which is related to reconstruction of the network of intermolecular contacts established between polymeric layers. The coordination network 1 exhibits extraordinary elasticity and in the second stage SCO, accompanied by conformational changes of allyl cyanide, triggers a crystallographic phase transition which leads to the formation of a superstructure. What is important, the formation of the superstructure is not caused by long range ordering of HS and LS iron(ii) ions. The structural alteration is associated with corrugation of the polymeric skeleton and disappearance of nitrile disorder. Irradiation of a single crystal of 1 at 15 K with laser light (520 nm) allowed producing a novel low temperature HS phase of 1 in which, contrary to the high temperature HS phase, disordering of anion and allyl cyanide molecules is not observed and the corrugated nature of the polymeric layer, characteristic of the LS phase, is preserved.

Polymer-stabilized liquid crystalline topological defect network for micro-pixelated optical devices

NASA Astrophysics Data System (ADS)

Araoka, Fumito; Le, Khoa V.; Fujii, Shuji; Orihara, Hiroshi; Sasaki, Yuji

2018-02-01

Spatially and temporally controlled topological defects in nematic liquid crystals (NLCs) are promising for its potential in optical applications. Utilization of self-organization is a key to fabricate complex micro- and nano-structures which are often difficult to obtain by conventional lithographic tools. Using photo-polymerization technique, here we show a polymer-stabilized NLC having a micro-pixelated structure of regularly ordered umbilical defects which are induced by an electric field. Due to the formation of polymer network, the self-organized pattern is kept stable without deterioration. Moreover, the polymer network allows to template other LCs whose optical properties can be tuned with external stimuli such as temperature and electric fields.

Advancing reversible shape memory by tuning the polymer network architecture

DOE PAGES

Li, Qiaoxi; Zhou, Jing; Vatankhah-Varnoosfaderani, Mohammad; ...

2016-02-02

Because of counteraction of a chemical network and a crystalline scaffold, semicrystalline polymer networks exhibit a peculiar behavior—reversible shape memory (RSM), which occurs naturally without applying any external force and particular structural design. There are three RSM properties: (i) range of reversible strain, (ii) rate of strain recovery, and (iii) decay of reversibility with time, which can be improved by tuning the architecture of the polymer network. Different types of poly(octylene adipate) networks were synthesized, allowing for control of cross-link density and network topology, including randomly cross-linked network by free-radical polymerization, thiol–ene clicked network with enhanced mesh uniformity, and loosemore » network with deliberately incorporated dangling chains. It is shown that the RSM properties are controlled by average cross-link density and crystal size, whereas topology of a network greatly affects its extensibility. In conclusion, we have achieved 80% maximum reversible range, 15% minimal decrease in reversibility, and fast strain recovery rate up to 0.05 K –1, i.e., ca. 5% per 10 s at a cooling rate of 5 K/min.« less

Noisy Oscillations in the Actin Cytoskeleton of Chemotactic Amoeba.

PubMed

Negrete, Jose; Pumir, Alain; Hsu, Hsin-Fang; Westendorf, Christian; Tarantola, Marco; Beta, Carsten; Bodenschatz, Eberhard

2016-09-30

Biological systems with their complex biochemical networks are known to be intrinsically noisy. Here we investigate the dynamics of actin polymerization of amoeboid cells, which are close to the onset of oscillations. We show that the large phenotypic variability in the polymerization dynamics can be accurately captured by a generic nonlinear oscillator model in the presence of noise. We determine the relative role of the noise with a single dimensionless, experimentally accessible parameter, thus providing a quantitative description of the variability in a population of cells. Our approach, which rests on a generic description of a system close to a Hopf bifurcation and includes the effect of noise, can characterize the dynamics of a large class of noisy systems close to an oscillatory instability.

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.

Noisy Oscillations in the Actin Cytoskeleton of Chemotactic Amoeba

NASA Astrophysics Data System (ADS)

Negrete, Jose; Pumir, Alain; Hsu, Hsin-Fang; Westendorf, Christian; Tarantola, Marco; Beta, Carsten; Bodenschatz, Eberhard

2016-09-01

Biological systems with their complex biochemical networks are known to be intrinsically noisy. Here we investigate the dynamics of actin polymerization of amoeboid cells, which are close to the onset of oscillations. We show that the large phenotypic variability in the polymerization dynamics can be accurately captured by a generic nonlinear oscillator model in the presence of noise. We determine the relative role of the noise with a single dimensionless, experimentally accessible parameter, thus providing a quantitative description of the variability in a population of cells. Our approach, which rests on a generic description of a system close to a Hopf bifurcation and includes the effect of noise, can characterize the dynamics of a large class of noisy systems close to an oscillatory instability.

Hydroxycinnamic acid-derived polymers constitute the polyaromatic domain of suberin

NASA Technical Reports Server (NTRS)

Bernards, M. A.; Lopez, M. L.; Zajicek, J.; Lewis, N. G.

1995-01-01

Suberin is an abundant, complex, intractable, plant cell wall polymeric network that forms both protective and wound-healing layers. Its function is, therefore, critical to the survival of all vascular plants. Its chemical structure and biosynthesis are poorly defined, although it is known to consist of both aromatic and aliphatic domains. While the composition of the aliphatic component has been fairly well characterized, that of the phenolic component has not. Using a combination of specific carbon-13 labeling techniques, and in situ solid state 13C NMR spectroscopic analysis, we now provide the first direct evidence for the nature of the phenolic domain of suberin and report here that it is almost exclusively comprised of a covalently linked, hydroxycinnamic acid-derived polymeric matrix.

Effects of High-Temperature-Pressure Polymerized Resin-Infiltrated Ceramic Networks on Oral Stem Cells

PubMed Central

Nassif, Ali; Berbar, Tsouria; Le Goff, Stéphane; Berdal, Ariane; Sadoun, Michael; Fournier, Benjamin P. J.

2016-01-01

Objectives The development of CAD—CAM techniques called for new materials suited to this technique and offering a safe and sustainable clinical implementation. The infiltration of resin in a ceramic network under high pressure and high temperature defines a new class of hybrid materials, namely polymer infiltrated ceramics network (PICN), for this purpose which requires to be evaluated biologically. We used oral stem cells (gingival and pulpal) as an in vitro experimental model. Methods Four biomaterials were grinded, immersed in a culture medium and deposed on stem cells from dental pulp (DPSC) and gingiva (GSC): Enamic (VITA®), Experimental Hybrid Material (EHM), EHM with initiator (EHMi) and polymerized Z100™ composite material (3M®). After 7 days of incubation; viability, apoptosis, proliferation, cytoskeleton, inflammatory response and morphology were evaluated in vitro. Results Proliferation was insignificantly delayed by all the tested materials. Significant cytotoxicity was observed in presence of resin based composites (MTT assay), however no detectable apoptosis and some dead cells were detected like in PICN materials. Cell morphology, major cytoskeleton and extracellular matrix components were not altered. An intimate contact appeared between the materials and cells. Clinical Significance The three new tested biomaterials did not exhibit adverse effects on oral stem cells in our experimental conditions and may be an interesting alternative to ceramics or composite based CAD—CAM blocks. PMID:27196425

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

Larsen, Michael B.; Van Horn, J. David; Wu, Fei

The synthesis of microporous polymers generally requires postpolymerization modification via hyper-cross-linking to trap the polymeric network in a state with high void volume. An alternative approach utilizes rigid, sterically demanding monomers to inhibit efficient packing, thus leading to a high degree of free volume between polymer side groups and main chains. Herein we combine polymers of intrinsic microporosity with polymerization-induced microphase separation (PIMS), a versatile methodology for the synthesis of nanostructured materials that can be rendered mesoporous. Copolymerization of various styrenic monomers with divinylbenzene in the presence of a poly(lactide) terminated with a chain-transfer agent (PLA-CTA) results in kinetic trappingmore » of a microphase-separated state. Subsequent etching of PLA provides a bicontinuous mesoporous network. Using equilibrium and kinetic nitrogen sorption experiments as well as positron annihilation lifetime spectroscopy (PALS), we demonstrate that variations in the steric characteristics of the styrenic monomer impart the network with microporosity, resulting in hierarchically (meso and micro) porous materials. Additionally, structure–property relationships of the styrenic monomer with total surface area and pore volume indicate that the glass transition temperature (Tg) of the corresponding styrenic homopolymers provides a reasonable measure of the steric interactions and resultant microporosity in these systems. Finally, PALS provides insight into micro- and mesoscopic void volume differences between porous monoliths containing either tert-butyl or TMS-modified styrenic monomers compared to the parent, unmodified styrene.« less

Synthesis characterization and in vitro drug release from acrylamide and sodium alginate based superporous hydrogel devices

PubMed Central

Nagpal, Manju; Singh, Shailendra Kumar; Mishra, Dinanath

2013-01-01

Objective: Present investigation was aimed at developing gastroretentive superporous hydrogels (SPHs) having desired mechanical characteristics with sustained release. Materials and Methods: The acrylamide based SPHs of various generations (1st, 2nd and 3rd) were synthesized by gas blowing technique. The prepared SPHs were evaluated for swelling, mechanical strength studies and scanning electron microscopy studies. Verapamil hydrochloride was loaded into selected SPHs by aqueous drug loading method and characterized via Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (X-RD), differential scanning calorimetry (DSC), nuclear magnetic resonance (NMR) and in vitro drug release studies. Results: SPHs of third generation were observed to have desired mechanical strength with sufficient swelling properties. Integrity of the drug was maintained in hydrogel polymeric network as indicated by FTIR, X-RD, and DSC and NMR studies. Initially, fast drug release (up to 60%) was observed in 30 min in formulation batches containing pure drug only (A, C and E), which was further sustained untill 24 h. Discussion: The increase in mechanical strength was due to the chemical cross-linking of secondary polymer in hydrogel network. The initial burst release was due to the presence of free drug at the surface and later sustained drug release was due to diffusion of entrapped drug in polymeric network. Significant decrease in drug release was observed by the addition of hydroxypropyl methyl cellulose. Conclusion: SPH interpenetrating networks with fast swelling and sufficient mechanical strength were prepared, which can be potentially exploited for designing gastroretentive drug delivery devices. PMID:24167785

Microfluidic approaches for the fabrication of gradient crosslinked networks based on poly(ethylene glycol) and hyperbranched polymers for manipulation of cell interactions

PubMed Central

Pedron, S; Peinado, C; Bosch, P; Benton, J A; Anseth, K S

2011-01-01

High-throughput methods allow rapid examination of parameter space to characterize materials and develop new polymeric formulations for biomaterials applications. One limitation is the difficulty of preparing libraries and performing high-throughput screening with conventional instrumentation and sample preparation. Here, we describe the fabrication of substrate materials with controlled gradients in composition by a rapid method of micromixing followed by a photopolymerization reaction. Specifically, poly(ethylene glycol) dimethacrylate was copolymerized with a hyperbranched multimethacrylate (P1000MA or H30MA) in a gradient manner. The extent of methacrylate conversion and the final network composition were determined by near-infrared spectroscopy, and mechanical properties were measured by nanoindentation. A relationship was observed between the elastic modulus and network crosslinking density. Roughness and hydrophilicity were increased on surfaces with a higher concentration of P1000MA. These results likely relate to a phase segregation process of the hyperbranched macromer that occurs during the photopolymerization reaction. On the other hand, the decrease in the final conversion in H30MA polymerization reactions was attributed to the lower termination rate as a consequence of the softening of the network. Valvular interstitial cell attachment was evaluated on these gradient substrates as a demonstration of studying cell morphology as a function of the local substrate properties. Data revealed that the presence of P1000MA affects cell–material interaction with a higher number of adhered cells and more cell spreading on gradient regions with a higher content of the multifunctional crosslinker. PMID:21105168

Novel fabrication of silicon carbide based ceramics for nuclear applications

NASA Astrophysics Data System (ADS)

Singh, Abhishek Kumar

Advances in nuclear reactor technology and the use of gas-cooled fast reactors require the development of new materials that can operate at the higher temperatures expected in these systems. These materials include refractory alloys based on Nb, Zr, Ta, Mo, W, and Re; ceramics and composites such as SiC--SiCf; carbon--carbon composites; and advanced coatings. Besides the ability to handle higher expected temperatures, effective heat transfer between reactor components is necessary for improved efficiency. Improving thermal conductivity of the fuel can lower the center-line temperature and, thereby, enhance power production capabilities and reduce the risk of premature fuel pellet failure. Crystalline silicon carbide has superior characteristics as a structural material from the viewpoint of its thermal and mechanical properties, thermal shock resistance, chemical stability, and low radioactivation. Therefore, there have been many efforts to develop SiC based composites in various forms for use in advanced energy systems. In recent years, with the development of high yield preceramic precursors, the polymer infiltration and pyrolysis (PIP) method has aroused interest for the fabrication of ceramic based materials, for various applications ranging from disc brakes to nuclear reactor fuels. The pyrolysis of preceramic polymers allow new types of ceramic materials to be processed at relatively low temperatures. The raw materials are element-organic polymers whose composition and architecture can be tailored and varied. The primary focus of this study is to use a pyrolysis based process to fabricate a host of novel silicon carbide-metal carbide or oxide composites, and to synthesize new materials based on mixed-metal silicocarbides that cannot be processed using conventional techniques. Allylhydridopolycarbosilane (AHPCS), which is an organometal polymer, was used as the precursor for silicon carbide. Inert gas pyrolysis of AHPCS produces near-stoichiometric amorphous silicon carbide (a-SiC) at 900--1150 °C. Results indicated that this processing technique can be effectively used to fabricate various silicon carbide composites with UC or UO2 as the nuclear component.

Joining of Silicon Carbide-Based Ceramics by Reaction Forming Method

NASA Technical Reports Server (NTRS)

Singh, M.; Kiser, J. D.

1997-01-01

Recently, there has been a surge of interest in the development and testing of silicon-based ceramics and composite components for a number of aerospace and ground based systems. The designs often require fabrication of complex shaped parts which can be quite expensive. One attractive way of achieving this goal is to build up complex shapes by joining together geometrically simple shapes. However, the joints should have good mechanical strength and environmental stability comparable to the bulk materials. These joints should also be able to maintain their structural integrity at high temperatures. In addition, the joining technique should be practical, reliable, and affordable. Thus, joining has been recognized as one of the enabling technologies for the successful utilization of silicon carbide based ceramic components in high temperature applications. Overviews of various joining techniques, i.e., mechanical fastening, adhesive bonding, welding, brazing, and soldering have been provided in recent publications. The majority of the techniques used today are based on the joining of monolithic ceramics with metals either by diffusion bonding, metal brazing, brazing with oxides and oxynitrides, or diffusion welding. These techniques need either very high temperatures for processing or hot pressing (high pressures). The joints produced by these techniques have different thermal expansion coefficients than the ceramic materials, which creates a stress concentration in the joint area. The use temperatures for these joints are around 700 C. Ceramic joint interlayers have been developed as a means of obtaining high temperature joints. These joint interlayers have been produced via pre-ceramic polymers, in-situ displacement reactions, and reaction bonding techniques. Joints produced by the pre-ceramic polymer approach exhibit a large amounts of porosity and poor mechanical properties. On the other hand, hot pressing or high pressures are needed for in-situ displacement reactions and reaction bonding techniques. Due to the equipment required, these techniques are impractical for joining large or complex shaped components.

Improving the fit of implant prosthetics: an in vitro study.

PubMed

Yannikakis, Stavros; Prombonas, Anthony

2013-01-01

Accurate and passive fit between a prosthesis and its supporting implants has been considered a prerequisite for successful long-term osseointegration. The objective of this in vitro study was to evaluate the strain development during tightening of a five-unit screw-retained superstructure constructed using five different methods. Five-unit screw-retained fixed partial prostheses (n = 25) were fabricated on three implants embedded in an epoxy resin block using five different methods: (1) cobalt-chromium (Co-Cr), plastic cylinders, one-piece cast; (2) Co-Cr, plastic cylinders, framework sectioned, preceramic laser-welding soldering; (3) gold-platinum (Au-Pt), gold cylinders, one-piece cast; (4) Au-Pt, gold cylinders, framework sectioned, preceramic laser-welding soldering; (5) Co-Cr, one-piece cast, and cementation to "passive abutments" (Southern Implants) after final finishing and polishing. Strain gauges (SG) were attached to the fixed partial prosthesis (FPP) and to the resin block to measure the stress created during screw tightening. The combination of Co-Cr alloy and plastic cylinders in a one-piece cast showed such an inadequate fit among the fabricated methods that this group was excluded from the remainder of the experiment. Specimens of Au-Pt cast on gold cylinders in one piece showed higher strain development than the other groups used in this study, with strains ranging from 223.1 to 2,198.1 Μm/m. Sectioning and soldering significantly improved the overall fit. FPPs of Co-Cr in a one-piece cast cemented to "passive abutments" produced the best level of fit, with the least strain development in the prosthesis and the resin block (59 to 204.6 Μm/m). Absolute fit of superstructures on implants is not possible using conventional laboratory procedures. Cementing FPPs onto prefabricated cylinders directly onto the implants significantly reduces strain development compared to the other fabrication methods.

Evolutionarily conserved coupling of adaptive and excitable networks mediates eukaryotic chemotaxis

NASA Astrophysics Data System (ADS)

Tang, Ming; Wang, Mingjie; Shi, Changji; Iglesias, Pablo A.; Devreotes, Peter N.; Huang, Chuan-Hsiang

2014-10-01

Numerous models explain how cells sense and migrate towards shallow chemoattractant gradients. Studies show that an excitable signal transduction network acts as a pacemaker that controls the cytoskeleton to drive motility. Here we show that this network is required to link stimuli to actin polymerization and chemotactic motility and we distinguish the various models of chemotaxis. First, signalling activity is suppressed towards the low side in a gradient or following removal of uniform chemoattractant. Second, signalling activities display a rapid shut off and a slower adaptation during which responsiveness to subsequent test stimuli decline. Simulations of various models indicate that these properties require coupled adaptive and excitable networks. Adaptation involves a G-protein-independent inhibitor, as stimulation of cells lacking G-protein function suppresses basal activities. The salient features of the coupled networks were observed for different chemoattractants in Dictyostelium and in human neutrophils, suggesting an evolutionarily conserved mechanism for eukaryotic chemotaxis.

SYNTHESIS AND IN VITRO CHARACTERIZATION OF HYDROXYPROPYL METHYLCELLULOSE-GRAFT-POLY (ACRYLIC ACID/2-ACRYLAMIDO-2-METHYL-1-PROPANESULFONIC ACID) POLYMERIC NETWORK FOR CONTROLLED RELEASE OF CAPTOPRIL.

PubMed

Furqan Muhammad, Iqbal; Mahmood, Ahmad; Aysha, Rashid

2016-01-01

A super-absorbent hydrogel was developed by crosslinking of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and acrylic acid with hydroxypropyl methylcellulose (HPMC) for controlled release drug delivery of captopril, a well known antihypertensive drug. Acrylic acid and AMPS were polymerized and crosslinked with HPMC by free radical polymerization, a widely used chemical crosslinking method. N,N'-methylenebisacrylamide (MBA) and potassium persulfate (KPS) were added as cross-linker and initiator, respectively. The hydrogel formulation was loaded with captopril (as model drug). The concentration of captopril was monitored at 205 nm using UV spectrophotometer. Equilibrium swelling ratio was determined at pH 2, 4.5 and 7.4 to evaluate the pH responsiveness of the formed hydrogel. The super-absorbent hydrogels were evaluated by FTIR, SEM, XRD, and thermal analysis (DSC and TGA). The formation of new copolymeric network was determined by FTIR, XRD, TGA and DSC analysis. The hydrogel formulations with acrylic acid and AMPS ratio of 4: 1 and lower amounts of crosslinker had shown maximum swelling. Moreover, higher release rate of captopril was observed at pH 7.4 than at pH 2, because of more swelling capacity of copolymer with increasing pH of the aqueous medium. The present research work confirms the development of a stable hydrogel comprising of HPMC with acrylic acid and AMPS. The prepared hydrogels exhibited pH sensitive behav-ior. This superabsorbent composite prepared could be a successful drug carrier for treating hypertension.

Chemistry and Processing of Nanostructured Materials

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

Fox, G A; Baumann, T F; Hope-Weeks, L J

2002-01-18

Nanostructured materials can be formed through the sol-gel polymerization of inorganic or organic monomer systems. For example, a two step polymerization of tetramethoxysilane (TMOS) was developed such that silica aerogels with densities as low as 3 kg/m{sup 3} ({approx} two times the density of air) could be achieved. Organic aerogels based upon resorcinol-formaldehyde and melamine-formaldehyde can also be prepared using the sol-gel process. Materials of this type have received significant attention at LLNL due to their ultrafine cell sizes, continuous porosity, high surface area and low mass density. For both types of aerogels, sol-gel polymerization depends upon the transformation ofmore » these monomers into nanometer-sized clusters followed by cross-linking into a 3-dimensional gel network. While sol-gel chemistry provides the opportunity to synthesize new material compositions, it suffers from the inability to separate the process of cluster formation from gelation. This limitation results in structural deficiencies in the gel that impact the physical properties of the aerogel, xerogel or nanocomposite. In order to control the properties of the resultant gel, one should be able to regulate the formation of the clusters and their subsequent cross-linking. Towards this goal, we are utilizing dendrimer chemistry to separate the cluster formation from the gelation so that new nanostructured materials can be produced. Dendrimers are three-dimensional, highly branched macromolecules that are prepared in such a way that their size, shape and surface functionality are readily controlled. The dendrimers will be used as pre-formed clusters of known size that can be cross-linked to form an ordered gel network.« less

Lithium conductivity in glasses of the Li2O-Al2O3-SiO2 system.

PubMed

Ross, Sebastian; Welsch, Anna-Maria; Behrens, Harald

2015-01-07

To improve the understanding of Li-dynamics in oxide glasses, i.e. the effect of [AlO4](-) tetrahedra and non-bridging oxygens on the potential landscape, electrical conductivity of seven fully polymerized and partly depolymerized lithium aluminosilicate glasses was investigated using impedance spectroscopy (IS). Lithium is the only mobile particle in these materials. Data derived from IS, i.e. activation energies, pre-exponential factors and diffusivities for lithium, are interpreted in light of Raman spectroscopic analyses of local structures in order to identify building units, which are crucial for lithium dynamics and migration. In polymerized glasses (compositional join LiAlSiO4-LiAlSi4O10) the direct current (DC) electrical conductivity continuously increases with increasing lithium content while lithium diffusivity is not affected by the Al/Si ratio in the glasses. Hence, the increase in electrical conductivity can be solely assigned to lithium concentration in the glasses. An excess of Li with respect to Al, i.e. the introduction of non-bridging oxygen into the network, causes a decrease in lithium mobility in the glasses. Activation energies in polymerized glasses (66 to 70 kJ mol(-1)) are significantly lower than those in depolymerized networks (76 to 78 kJ mol(-1)) while pre-exponential factors are nearly constant across all compositions. Comparison of the data with results for lithium silicates from the literature indicates a minimum in lithium diffusivity for glasses containing both aluminium tetrahedra and non-bridging oxygens. The findings allow a prediction of DC conductivity for a large variety of lithium aluminosilicate glass compositions.

UV-Vis/FT-NIR in situ monitoring of visible-light induced polymerization of PEGDA hydrogels initiated by eosin/triethanolamine/O2.

PubMed

Kaastrup, Kaja; Aguirre-Soto, Alan; Wang, Chen; Bowman, Christopher N; Stansbury, Jeffery; Sikes, Hadley D

In conjunction with a tertiary amine coinitiator, eosin, a photoreducible dye, has been shown to successfully circumvent oxygen inhibition in radical photopolymerization reactions. However, the role of O 2 in the initiation and polymerization processes remains inconclusive. Here, we employ a UV-Vis/FT-NIR analytical tool for real-time, simultaneous monitoring of chromophore and monomer reactive group concentrations to investigate the eosin-activated photopolymerization of PEGDA-based hydrogels under ambient conditions. First, we address the challenges associated with spectroscopic monitoring of the polymerization of hydrogels using UV-Vis and FT-NIR, proposing metrics for quantifying the extent of signal loss from reflection and scattering, and showing their relation to microgelation and network formation. Second, having established a method for extracting kinetic information by eliminating the effects of changing refractive index and scattering, the coupled UV-Vis/FT-NIR system is applied to the study of eosin-activated photopolymerization of PEGDA in the presence of O 2 . Analysis of the inhibition time, rate of polymerization, and rate of eosin consumption under ambient and purged conditions indicates that regeneration of eosin in the presence of oxygen and consumption of oxygen occur via a nonchain process. This suggests that the uniquely high O 2 resilience is due to alternative processes such as energy transfer from photo-activated eosin to oxygen. Uncovering the intricacies of the role of O 2 in eosin-mediated initiation aids the design of O 2 resistant free radical polymerization systems relevant to photonics, optoelectronics, biomaterials, and biosensing.

UV-Vis/FT-NIR in situ monitoring of visible-light induced polymerization of PEGDA hydrogels initiated by eosin/triethanolamine/O2

PubMed Central

Kaastrup, Kaja; Aguirre-Soto, Alan; Wang, Chen; Bowman, Christopher N.; Stansbury, Jeffery; Sikes, Hadley D.

2016-01-01

In conjunction with a tertiary amine coinitiator, eosin, a photoreducible dye, has been shown to successfully circumvent oxygen inhibition in radical photopolymerization reactions. However, the role of O2 in the initiation and polymerization processes remains inconclusive. Here, we employ a UV-Vis/FT-NIR analytical tool for real-time, simultaneous monitoring of chromophore and monomer reactive group concentrations to investigate the eosin-activated photopolymerization of PEGDA-based hydrogels under ambient conditions. First, we address the challenges associated with spectroscopic monitoring of the polymerization of hydrogels using UV-Vis and FT-NIR, proposing metrics for quantifying the extent of signal loss from reflection and scattering, and showing their relation to microgelation and network formation. Second, having established a method for extracting kinetic information by eliminating the effects of changing refractive index and scattering, the coupled UV-Vis/FT-NIR system is applied to the study of eosin-activated photopolymerization of PEGDA in the presence of O2. Analysis of the inhibition time, rate of polymerization, and rate of eosin consumption under ambient and purged conditions indicates that regeneration of eosin in the presence of oxygen and consumption of oxygen occur via a nonchain process. This suggests that the uniquely high O2 resilience is due to alternative processes such as energy transfer from photo-activated eosin to oxygen. Uncovering the intricacies of the role of O2 in eosin-mediated initiation aids the design of O2 resistant free radical polymerization systems relevant to photonics, optoelectronics, biomaterials, and biosensing. PMID:26755925

New hybrid latexes from a soybean oil-based waterborne polyurethane and acrylics via emulsion polymerization.

PubMed

Lu, Yongshang; Larock, Richard C

2007-10-01

A series of new waterborne polyurethane (PU)/acrylic hybrid latexes have been successfully synthesized by the emulsion polymerization of acrylic monomers (butyl acrylate and methyl methacrylate) in the presence of a soybean oil-based waterborne PU dispersion using potassium persulfate as an initiator. The waterborne PU dispersion has been synthesized by a polyaddition reaction of toluene 2,4-diisocyanate and a soybean oil-based polyol (SOL). The resulting hybrid latexes, containing 15-60 wt % SOL as a renewable resource, are very stable and exhibit uniform particle sizes of 125 +/- 20 nm as determined by transmittance electronic microscopy. The structure, thermal, and mechanical properties of the resulting hybrid latex films have been investigated by Fourier transform infrared spectroscopy, solid state 13C NMR spectroscopy, dynamic mechanical analysis, extraction, and mechanical testing. Grafting copolymerization of the acrylic monomers onto the PU network occurs during the emulsion polymerization, leading to a significant increase in the thermal and mechanical properties of the resulting hybrid latexes. This work provides a new way of utilizing renewable resources to prepare environmentally friendly hybrid latexes with high performance for coating applications.

Vital microscopic analysis of polymeric micelle extravasation from tumor vessels: macromolecular delivery according to tumor vascular growth stage.

PubMed

Hori, Katsuyoshi; Nishihara, Masamichi; Yokoyama, Masayuki

2010-01-01

Particles larger than a specific size have been thought to extravasate from tumor vessels but not from normal vessels. Therefore, various nanoparticles incorporating anticancer drugs have been developed to realize selective drug delivery to solid tumors. However, it is not yet clear whether nanoparticles extravasate readily from all tumor vessels including vessels of microtumors. To answer this question, we synthesized new polymeric micelles labeled with fluorescein isothiocyanate (FITC) and injected them into the tail vein of rats with implanted skinfold transparent chambers. We also analyzed, by means of time-lapse vital microscopy with image analysis, extravasation of FITC micelles from tumor vessels at different stages of growth of Yoshida ascites sarcoma LY80. Polymeric micelles readily leaked from vessels at the interface between normal and tumor tissues and those at the interface between tumor tissues and necrotic areas. The micelles showed negligible extravasation, however, from the vascular network of microtumors less than 1 mm in diameter and did not accumulate in the microtumor. Our results suggest that we must develop a novel therapeutic strategy that can deliver sufficient nanomedicine to microtumors.

Recyclable crosslinked polymer networks with full property recovery made via one-step controlled radical polymerization

NASA Astrophysics Data System (ADS)

Jin, Kailong; Li, Lingqiao; Torkelson, John

Rubber tires illustrate well the issues ranging from economic loss to environmental problems and sustainability issues that arise with spent, covalently crosslinked polymers. A nitroxide-mediated polymerization (NMP) strategy has been developed that allows for one-step synthesis of recyclable crosslinked polymers from monomers or polymers that contain carbon-carbon double bonds amenable to radical polymerization. Resulting materials possess dynamic alkoxyamine crosslinks that undergo reversible decrosslinking as a function of temperature. Using polybutadiene as starting material, and styrene, an appropriate nitroxide molecule and bifunctional initiator for initial crosslinking, a model for tire rubber can be produced by reaction at temperatures comparable to those employed in tire molding. Upon cooling, the crosslinks are made permanent due to the extraordinarily strong temperature dependence of the reverisible nitroxide capping and uncapping reaction. Based on thermomechanical property characterization, when the original crosslinked model rubber is chopped into bits and remolded in the melt state, a well-consolidated material is obtained which exhibits full recovery of properties reflecting crosslink density after multiple recycling steps.

ERK reinforces actin polymerization to power persistent edge protrusion during motility

PubMed Central

Mendoza, Michelle C.; Vilela, Marco; Juarez, Jesus E.; Blenis, John; Danuser, Gaudenz

2016-01-01

Cells move through perpetual protrusion and retraction cycles at the leading edge. These cycles are coordinated with substrate adhesion and retraction of the cell rear. Here, we tracked spatial and temporal fluctuations in the molecular activities of individual moving cells to elucidate how extracellular regulated kinase (ERK) signaling controlled the dynamics of protrusion and retraction cycles. ERK is activated by many cell-surface receptors and we found that ERK signaling specifically reinforced cellular protrusions so that they translated into rapid, sustained forward motion of the leading edge. Using quantitative fluorescent speckle microscopy (qFSM) and cross-correlation analysis, we showed that ERK controlled the rate and timing of actin polymerization by promoting the recruitment of the actin nucleator Arp2/3 to the leading edge. Arp2/3 activity generates branched actin networks that can produce pushing force. These findings support a model in which surges in ERK activity induced by extracellular cues enhance Arp2/3-mediated actin polymerization to generate protrusion power phases with enough force to counteract increasing membrane tension and to promote sustained motility. PMID:25990957

Constructing novel dihydrofuran and dihydroisoxazole analogues of isocombretastatin-4 as tubulin polymerization inhibitors through [3+2] reactions.

PubMed

Song, Ming-Yu; Cao, Chen-Yu; He, Qiu-Rui; Dong, Qing-Miao; Li, Ding; Tang, Jiang-Jiang; Gao, Jin-Ming

2017-10-15

[3+2] reactions play a key role in constructing various pharmaceutical moleculars. In this study, using Mn(OAc) 3 mediated and 1,3-dipolar [3+2] cyclization reactions, 38 novel dihydrofuran and dihydroisoxazole analogues of isoCA-4 were synthesized as inhibitors of tubulin polymerization. Among them, compound 6g was found to be the most potent cytotoxic agents against PC-3 cells with IC 50 value of 0.47μM, and compound 5p exhibted highest activity on HeLa cells with IC 50 vaule of 2.32µM. Tubulin polymerization assay revealed that 6g was a dose-dependent and effective inhibitor of tubulin assembly. Immunohistochemistry studies and cell cycle distribution analysis indicated that 6g severely disrupted microtubule network and significantly arrested most cells in the G2/M phase of the cell cycle in PC-3 cells. In addition, molecular docking studies showed that two chiral isomers of 6g can bind efficiently and similarly at colchicine binding site of tubulin. Copyright © 2017 Elsevier Ltd. All rights reserved.

Formation of a Crack-Free, Hybrid Skin Layer with Tunable Surface Topography and Improved Gas Permeation Selectivity on Elastomers Using Gel–Liquid Infiltration Polymerization

DOE PAGES

Wang, Mengyuan; Gorham, Justin M.; Killgore, Jason P.; ...

2017-07-31

Surface modifications of elastomers and gels are crucial for emerging applications such as soft robotics and flexible electronics, in large part because they provide a platform to control wettability, adhesion, and permeability. Current surface modification methods via ultraviolet-ozone (UVO) and/or O2 plasma, atomic layer deposition (ALD), plasmas deposition, and chemical treatment impart a dense polymer or inorganic layer on the surface that is brittle and easy to fracture at low strain levels. This paper presents a new method, based on gel–liquid infiltration polymerization, to form hybrid skin layers atop elastomers. The method is unique in that it allows for controlmore » of the skin layer topography, with tunable feature sizes and aspect ratios as high as 1.8 without fracture. Unlike previous techniques, the skin layer formed here dramatically improves the barrier properties of the elastomer, while preserving skin layer flexibility. Furthermore, the method is versatile and likely applicable to most interfacial polymerization systems and network polymers on flat and patterned surfaces.« less

Formation of a Crack-Free, Hybrid Skin Layer with Tunable Surface Topography and Improved Gas Permeation Selectivity on Elastomers Using Gel–Liquid Infiltration Polymerization

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

Wang, Mengyuan; Gorham, Justin M.; Killgore, Jason P.

Surface modifications of elastomers and gels are crucial for emerging applications such as soft robotics and flexible electronics, in large part because they provide a platform to control wettability, adhesion, and permeability. Current surface modification methods via ultraviolet-ozone (UVO) and/or O2 plasma, atomic layer deposition (ALD), plasmas deposition, and chemical treatment impart a dense polymer or inorganic layer on the surface that is brittle and easy to fracture at low strain levels. This paper presents a new method, based on gel–liquid infiltration polymerization, to form hybrid skin layers atop elastomers. The method is unique in that it allows for controlmore » of the skin layer topography, with tunable feature sizes and aspect ratios as high as 1.8 without fracture. Unlike previous techniques, the skin layer formed here dramatically improves the barrier properties of the elastomer, while preserving skin layer flexibility. Furthermore, the method is versatile and likely applicable to most interfacial polymerization systems and network polymers on flat and patterned surfaces.« less

Thiol-vinyl systems as shape memory polymers and novel two-stage reactive polymer systems

NASA Astrophysics Data System (ADS)

Nair, Devatha P.

2011-12-01

The focus of this research was to formulate, characterize and tailor the reaction methodologies and material properties of thiol-vinyl systems to develop novel polymer platforms for a range of engineering applications. Thiol-ene photopolymers were demonstrated to exhibit several advantageous characteristics for shape memory polymer systems for a range of biomedical applications. The thiol-ene shape memory polymer systems were tough and flexible as compared to the acrylic control systems with glass transition temperatures between 30 and 40 °C; ideal for actuation at body temperature. The thiol-ene polymers also exhibited excellent shape fixity and a rapid and distinct shape memory actuation response along with free strain recoveries of greater than 96% and constrained stress recoveries of 100%. Additionally, two-stage reactive thiol-acrylate systems were engineered as a polymer platform technology enabling two independent sets of polymer processing and material properties. There are distinct advantages to designing polymer systems that afford two distinct sets of material properties -- an intermediate polymer that would enable optimum handling and processing of the material (stage 1), while maintaining the ability to tune in different, final properties that enable the optimal functioning of the polymeric material (stage 2). To demonstrate the range of applicability of the two-stage reactive systems, three specific applications were demonstrated; shape memory polymers, lithographic impression materials, and optical materials. The thiol-acrylate reactions exhibit a wide range of application versatility due to the range of available thiol and acrylate monomers as well as reaction mechanisms such as Michael Addition reactions and free radical polymerizations. By designing a series of non-stoichiometeric thiol-acrylate systems, a polymer network is initially formed via a base catalyzed 'click' Michael addition reaction. This self-limiting reaction results in a Stage 1 polymer with excess acrylic functional groups within the network. At a later point in time, the photoinitiated, free radical polymerization of the excess acrylic functional groups results in a highly crosslinked, robust material system. By varying the monomers within the system as well as the stoichiometery of thiol to acrylate functional groups, the ability of the two-stage reactive systems to encompass a wide range of properties at the end of both the stage 1 and stage 2 polymerizations was demonstrated. The thiol-acrylate networks exhibited intermediate Stage 1 rubbery moduli and glass transition temperatures that range from 0.5 MPa and -10 ºC to 22 MPa and 22 ºC respectively. The same polymer networks can then attain glass transition temperatures that range from 5 ºC to 195 ºC and rubbery moduli of up to 200 MPa after the subsequent photocure stage. Two-stage reactive polymer composite systems were also formulated and characterized for thermomechanical and mechanical properties. Thermomechanical analysis showed that the fillers resulted in a significant increase in the modulus at both stage 1 and stage 2 polymerizations without a significant change in the glass transition temperatures (Tg). The two-stage reactive matrix composite formed with a hexafunctional acrylate matrix and 20 volume % silica particles showed a 125% increase in stage 1 modulus and 101% increase in stage 2 modulus, when compared with the modulus of the neat matrix. Finally, the two-stage reactive polymeric devices were formulated and designed as orthopedic suture anchors for arthroscopic surgeries and mechanically characterized. The Stage 1 device was designed to exhibit properties ideal for arthroscopic delivery and device placement with glass transition temperatures 25 -- 30 °C and rubbery moduli ˜ 95 MPa. The subsequent photopolymerization generated Stage 2 polymers designed to match the local bone environment with moduli ranging up to 2 GPa. Additionally, pull-out strengths of 140 N were demonstrated and are equivalent to the pull-strengths achieved by other commercially available suture anchors.

Dual Sulfide-Disulfide Crosslinked Networks with Rapid and Room Temperature Self-Healability.

PubMed

An, So Young; Noh, Seung Man; Nam, Joon Hyun; Oh, Jung Kwon

2015-07-01

Polymer-based crosslinked networks with intrinsic self-repairing ability have emerged due to their built-in ability to repair physical damages. Here, novel dual sulfide-disulfide crosslinked networks (s-ssPxNs) are reported exhibiting rapid and room temperature self-healability within seconds to minutes, with no extra healing agents and no change under any environmental conditions. The method to synthesize these self-healable networks utilizes a combination of well-known crosslinking chemistry: photoinduced thiol-ene click-type radical addition, generating lightly sulfide-crosslinked polysulfide-based networks with excess thiols, and their oxidation, creating dynamic disulfide crosslinkages to yield the dual s-ssPxNs. The resulting s-ssPxN networks show rapid self-healing within 30 s to 30 min at room temperature, as well as self-healing elasticity with reversible viscoelastic properties. These results, combined with tunable self-healing kinetics, demonstrate the versatility of the method as a new means to synthesize smart multifunctional polymeric materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Conductive Ionic-Liquid Gels Prepared with Orthogonal Double Networks of a Low-Molecular-Weight Gelator and Cross-Linked Polymer.

PubMed

Kataoka, Toshikazu; Ishioka, Yumi; Mizuhata, Minoru; Minami, Hideto; Maruyama, Tatsuo

2015-10-21

We prepared a heterogeneous double-network (DN) ionogel containing a low-molecular-weight gelator network and a polymer network that can exhibit high ionic conductivity and high mechanical strength. An imidazolium-based ionic liquid was first gelated by the molecular self-assembly of a low-molecular-weight gelator (benzenetricarboxamide derivative), and methyl methacrylate was polymerized with a cross-linker to form a cross-linked poly(methyl methacrylate) (PMMA) network within the ionogel. Microscopic observation and calorimetric measurement revealed that the fibrous network of the low-molecular-weight gelator was maintained in the DN ionogel. The PMMA network strengthened the ionogel of the low-molecular-weight gelator and allowed us to handle the ionogel using tweezers. The orthogonal DNs produced ionogels with a broad range of storage elastic moduli. DN ionogels with low PMMA concentrations exhibited high ionic conductivity that was comparable to that of a neat ionic liquid. The present study demonstrates that the ionic conductivities of the DN and single-network, low-molecular-weight gelator or polymer ionogels strongly depended on their storage elastic moduli.

Structure and properties of semi-interpenetrating network hydrogel based on starch.

PubMed

Zhu, Baodong; Ma, Dongzhuo; Wang, Jian; Zhang, Shuang

2015-11-20

Starch-g-P(acrylic acid-co-acrylamide)/PVA semi-interpenetrating network (semi-IPN) hydrogels were prepared by aqueous solution polymerization method. Starch grafting copolymerization reaction, semi-IPN structure and crystal morphology were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The PVA in the form of partial crystallization distributing in the gel matrix uniformly were observed by Field emission scanning electron microscope (FESEM). The space network structure, finer microstructure and pore size in the interior of hydrogel were presented by biomicroscope. The results demonstrated that absorption ratio of water and salt generated different degree changes with the effect of PVA. In addition, the mechanical strength of hydrogel was improved. Copyright © 2015 Elsevier Ltd. All rights reserved.

Structure and performance of polymer-derived bulk ceramics determined by method of filler incorporation

NASA Astrophysics Data System (ADS)

Konegger, T.; Schneider, P.; Bauer, V.; Amsüss, A.; Liersch, A.

2013-12-01

The effect of four distinct methods of incorporating fillers into a preceramic polymer matrix was investigated with respect to the structural and mechanical properties of the resulting materials. Investigations were conducted with a polysiloxane/Al2O3/ZrO2 model system used as a precursor for mullite/ZrO2 composites. A quantitative evaluation of the uniformity of filler distribution was obtained by employing a novel image analysis. While solvent-free mixing led to a heterogeneous distribution of constituents resulting in limited mechanical property values, a strong improvement of material homogeneity and properties was obtained by using solvent-assisted methods. The results demonstrate the importance of the processing route on final characteristics of polymer-derived ceramics.

Synthesis of organosilicon compounds

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

Zhao, G.

1996-01-01

Silicon-containing polymers have been a focus of synthesis and study in Dr. Barton`s group because of their chemistry and properties which are not offered by other systems or materials. For example, the polymer -[-SiMe 2C≡C-] n-can be easily processed to films or fibers from melt or solution, and thermally converted to a SiC-containing ceramic in high yield at high temperature. In recent years, carbosilane dendritic polymers have been of great interests in many research groups. However, no synthesis of carbosilane dendrimers with functionalties both inside and outside the dendrimer has been reported. Functionality is very important in the synthesis ofmore » preceramic polymers. This thesis will be devoted to exploring several new organosilicon polymer systems.« less

The earliest settlers of Mesoamerica date back to the late Pleistocene.

PubMed

Stinnesbeck, Wolfgang; Becker, Julia; Hering, Fabio; Frey, Eberhard; González, Arturo González; Fohlmeister, Jens; Stinnesbeck, Sarah; Frank, Norbert; Terrazas Mata, Alejandro; Benavente, Martha Elena; Avilés Olguín, Jerónimo; Aceves Núñez, Eugenio; Zell, Patrick; Deininger, Michael

2017-01-01

Preceramic human skeletal remains preserved in submerged caves near Tulum in the Mexican state of Quintana Roo, Mexico, reveal conflicting results regarding 14C dating. Here we use U-series techniques for dating a stalagmite overgrowing the pelvis of a human skeleton discovered in the submerged Chan Hol cave. The oldest closed system U/Th age comes from around 21 mm above the pelvis defining the terminus ante quem for the pelvis to 11311±370 y BP. However, the skeleton might be considerable older, probably as old as 13 ky BP as indicated by the speleothem stable isotope data. The Chan Hol individual confirms a late Pleistocene settling of Mesoamerica and represents one of the oldest human osteological remains in America.

The earliest settlers of Mesoamerica date back to the late Pleistocene

PubMed Central

Becker, Julia; Hering, Fabio; Frey, Eberhard; González, Arturo González; Fohlmeister, Jens; Stinnesbeck, Sarah; Frank, Norbert; Terrazas Mata, Alejandro; Benavente, Martha Elena; Avilés Olguín, Jerónimo; Aceves Núñez, Eugenio; Zell, Patrick; Deininger, Michael

2017-01-01

Preceramic human skeletal remains preserved in submerged caves near Tulum in the Mexican state of Quintana Roo, Mexico, reveal conflicting results regarding 14C dating. Here we use U-series techniques for dating a stalagmite overgrowing the pelvis of a human skeleton discovered in the submerged Chan Hol cave. The oldest closed system U/Th age comes from around 21 mm above the pelvis defining the terminus ante quem for the pelvis to 11311±370 y BP. However, the skeleton might be considerable older, probably as old as 13 ky BP as indicated by the speleothem stable isotope data. The Chan Hol individual confirms a late Pleistocene settling of Mesoamerica and represents one of the oldest human osteological remains in America. PMID:28854194

Cryptosporidium, Giardia, and Cyclospora in ancient Peruvians.

PubMed

Ortega, Ynes R; Bonavia, Duccio

2003-06-01

Twenty-two coprolites of human origin, collected from excavations along the north-central coast of Peru, were examined using fluorescent microscopy for the presence of fecal parasites, with emphasis on Cryptosporidium sp., Giardia sp., and Cyclospora sp. Three samples were positive. One coprolite dated between ca. 2,375 and 1,525 BC contained Giardia sp. cysts. This coprolite corresponded to the Peruvian preceramic period. Another positive coprolite ca. AD 770-830 corresponded to Epoch 3 of the Middle Horizon and contained Cryptosporidium sp. oocysts. The third positive coprolite (corresponding to the Middle Horizon. ca. AD 500-900) contained Giardia sp. cysts. This report demonstrates that Giardia sp. and Cryptosporidium sp. were present in Peruvian coastal populations for at least 4,300 and 1,100 BP.

Methods of repairing a substrate

NASA Technical Reports Server (NTRS)

Riedell, James A. (Inventor); Easler, Timothy E. (Inventor)

2011-01-01

A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium boride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

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

Remendable Polymeric Materials Using Reversible Covalent Bonds

DTIC Science & Technology

2008-12-01

Synthesis and characterization of melamine - urea - formaldehyde microcapsules containing ENB-based self-healing agents. International Conference on Smart...R. Wang, X. He, W. Liu, and H. Hao, 2007: Preparation and characterization of self-healing poly ( urea - formaldehyde ) microcapsules. International...captured much attention. In one method, polymer networks are made to self-heal by adding particles filled with uncured resin . The resin held

Graphene Quantum Dot-Aerogel: From Nanoscopic to Macroscopic Fluorescent Materials. Sensing Polyaromatic Compounds in Water.

PubMed

Martín-Pacheco, Ana; Del Río Castillo, Antonio Esaú; Martín, Cristina; Herrero, María Antonia; Merino, Sonia; García Fierro, José Luis; Díez-Barra, Enrique; Vázquez, Ester

2018-05-30

Fluorescence based on quantum confinement is a property restricted to the nanoscopic range. The incorporation of nanoparticles in a three-dimensional polymeric network could afford macroscopic scaffolds that show nanoscopic properties. Moreover, if these scaffolds are based on strong bonds, the stability of the resulting materials can be preserved, thus enhancing their final applications. We report for the first time the preparation of a graphene quantum dot (GQD) composite based on a cationic covalent network. This new material has unusual features: (i) the final composite remains stable after several swelling-deswelling cycles, thus demonstrating strong interactions between GQDs and the polymeric material, and therefore it could be used as a portable system. (ii) Fluorescence emission in the composite and in solution is quasi-independent to the excitation wavelength. (iii) However, and in contrast to the behavior observed in GQD solutions, the fluorescence of the composite remains unaltered over a wide pH range and in the presence of different ions commonly found in tap water. (iv) Fluorescence quenching is only observed as a consequence of molecules that bear aromatic systems, and this could be applied to the preparation of in situ water sensors.

Control of actin-based motility through localized actin binding

PubMed Central

Banigan, Edward J.; Lee, Kun-Chun; Liu, Andrea J.

2014-01-01

A wide variety of cell biological and biomimetic systems use actin polymerization to drive motility. It has been suggested that an object such as a bacterium can propel itself by self-assembling a high concentration of actin behind it if it is repelled by actin. However, it is also known that it is essential for the moving object to bind actin. Therefore, a key question is how the actin tail can propel an object when it both binds and repels the object. We present a physically consistent Brownian dynamics model for actin-based motility that includes the minimal components of the dendritic nucleation model and allows for both attractive and repulsive interactions between actin and a moveable disk. We find that the concentration gradient of filamentous actin generated by polymerization is sufficient to propel the object, even with moderately strong binding interactions. Additionally, actin binding can act as a biophysical cap, and may directly control motility through modulation of network growth. Overall, this mechanism is robust in that it can drive motility against a load up to a stall pressure that depends on the Young’s modulus of the actin network and can explain several aspects of actin-based motility. PMID:24225232

Actin growth profile in clathrin-mediated endocytosis

NASA Astrophysics Data System (ADS)

Tweten, D. J.; Bayly, P. V.; Carlsson, A. E.

2017-05-01

Clathrin-mediated endocytosis in yeast is driven by a protein patch containing close to 100 different types of proteins. Among the proteins are 5000 -10 000 copies of polymerized actin, and successful endocytosis requires growth of the actin network. Since it is not known exactly how actin network growth drives endocytosis, we calculate the spatial distribution of actin growth required to generate the force that drives the process. First, we establish the force distribution that must be supplied by actin growth, by combining membrane-bending profiles obtained via electron microscopy with established theories of membrane mechanics. Next, we determine the profile of actin growth, using a continuum mechanics approach and an iterative procedure starting with an actin growth profile obtained from a linear analysis. The profile has fairly constant growth outside a central hole of radius 45-50 nm, but very little growth in this hole. This growth profile can reproduce the required forces if the actin shear modulus exceeds 80 kPa, and the growing filaments can exert very large polymerization forces. The growth profile prediction could be tested via electron-microscopy or super-resolution experiments in which the turgor pressure is suddenly turned off.

The Formation Mechanism of Hydrogels.

PubMed

Lu, Liyan; Yuan, Shiliang; Wang, Jing; Shen, Yun; Deng, Shuwen; Xie, Luyang; Yang, Qixiang

2017-06-12

Hydrogels are degradable polymeric networks, in which cross-links play a vital role in structure formation and degradation. Cross-linking is a stabilization process in polymer chemistry that leads to the multi-dimensional extension of polymeric chains, resulting in network structures. By cross-linking, hydrogels are formed into stable structures that differ from their raw materials. Generally, hydrogels can be prepared from either synthetic or natural polymers. Based on the types of cross-link junctions, hydrogels can be categorized into two groups: the chemically cross-linked and the physically cross-linked. Chemically cross-linked gels have permanent junctions, in which covalent bonds are present between different polymer chains, thus leading to excellent mechanical strength. Although chemical cross-linking is a highly resourceful method for the formation of hydrogels, the cross-linkers used in hydrogel preparation should be extracted from the hydrogels before use, due to their reported toxicity, while, in physically cross-linked gels, dissolution is prevented by physical interactions, such as ionic interactions, hydrogen bonds or hydrophobic interactions. Physically cross-linked methods for the preparation of hydrogels are the alternate solution for cross-linker toxicity. Both methods will be discussed in this essay. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Applications of UV/Vis Spectroscopy in Characterization and Catalytic Activity of Noble Metal Nanoparticles Fabricated in Responsive Polymer Microgels: A Review.

PubMed

Begum, Robina; Farooqi, Zahoor H; Naseem, Khalida; Ali, Faisal; Batool, Madeeha; Xiao, Jianliang; Irfan, Ahmad

2018-11-02

Noble metal nanoparticles loaded smart polymer microgels have gained much attention due to fascinating combination of their properties in a single system. These hybrid systems have been extensively used in biomedicines, photonics, and catalysis. Hybrid microgels are characterized by using various techniques but UV/Vis spectroscopy is an easily available technique for characterization of noble metal nanoparticles loaded microgels. This technique is widely used for determination of size and shape of metal nanoparticles. The tuning of optical properties of noble metal nanoparticles under various stimuli can be studied using UV/Vis spectroscopic method. Time course UV/Vis spectroscopy can also be used to monitor the kinetics of swelling and deswelling of microgels and hybrid microgels. Growth of metal nanoparticles in polymeric network or growth of polymeric network around metal nanoparticle core can be studied by using UV/Vis spectroscopy. This technique can also be used for investigation of various applications of hybrid materials in catalysis, photonics, and sensing. This tutorial review describes the uses of UV/Vis spectroscopy in characterization and catalytic applications of responsive hybrid microgels with respect to recent research progress in this area.

Advantages and drawbacks of Thiol-ene based resins for 3D-printing

NASA Astrophysics Data System (ADS)

Leonards, Holger; Engelhardt, Sascha; Hoffmann, Andreas; Pongratz, Ludwig; Schriever, Sascha; Bläsius, Jana; Wehner, Martin; Gillner, Arnold

2015-03-01

The technology of 3D printing is conquering the world and awakens the interest of many users in the most varying of applications. New formulation approaches for photo-sensitive thiol-ene resins in combination with various printing technologies, like stereolithography (SLA), projection based printing/digital light processing (DLP) or two-photon polymerization (TPP) are presented. Thiol-ene polymerizations are known for its fast and quantitative reaction and to form highly homogeneous polymer networks. As the resins are locally and temporally photo-curable the polymerization type is very promising for 3D-printing. By using suitable wavelengths, photoinitiator-free fabrication is feasible for single- and two photon induced polymerization. In this paper divinyl ethers of polyethylene glycols in combination with star-shaped tetrathiols were used to design a simple test-system for photo-curable thiol-ene resins. In order to control and improve curing depth and lateral resolution in 3D-polymerization processes, either additives in chemical formulation or process parameters can be changed. The achieved curing depth and resolution limits depend on the applied fabrication method. While two-/multiphoton induced lithography offers the possibility of micron- to sub-micron resolution it lacks in built-up speed. Hence single-photon polymerization is a fast alternative with optimization potential in sub-10-micron resolution. Absorber- and initiator free compositions were developed in order to avoid aging, yellowing and toxicity of resulting products. They can be cured with UV-laser radiation below 300 nm. The development at Fraunhofer ILT is focusing on new applications in the field of medical products and implants, technical products with respect to mechanical properties or optical properties of 3D-printed objects. Recent process results with model system (polyethylene glycol divinylether/ Pentaerithrytol tetrakis (3-mercaptopropionat), Raman measurements of polymer conversion and surface modifications using bifunctional crosslinkers are presented with advantages, drawbacks and a general outlook.

Accelerated cell-sheet recovery from a surface successively grafted with polyacrylamide and poly(N-isopropylacrylamide).

PubMed

Akiyama, Yoshikatsu; Kikuchi, Akihiko; Yamato, Masayuki; Okano, Teruo

2014-08-01

A double polymeric nanolayer consisting of poly(N-isopropylacrylamide) (PIPAAm) and hydrophilic polyacrylamide (PAAm) was deposited on tissue culture polystyrene (TCPS) surfaces using electron beam irradiation to form a new temperature-responsive cell culture surface in which the basal hydrophilic PAAm component in the double polymeric layer promotes the hydration of the upper PIPAAm layer and induces rapid cell detachment compared to a conventional temperature-responsive cell culture surface, PIPAAm-grafted TCPS (PIPAAm-TCPS). Take-off angle-dependent X-ray photoelectron spectroscopy spectral analysis demonstrated that the grafted PIPAAm and PAAm components were located in the upper and basal regions of the double polymeric layer, respectively, suggesting that the double polymeric layer forms an inter-penetrating-network-like structure with PAAm at the basal portion of the PIPAAm grafted chains. The wettability of the temperature-responsive cell culture surfaces with the double polymeric layer tended to be more hydrophilic, with an increase in the basal PAAm graft density at a constant PIPAAm graft density. However, when the graft densities of the upper PIPAAm and basal PAAm were optimized, the resulting temperature-responsive cell culture surface with the double polymeric layer exhibited rapid cell detachment while maintaining cell adhesive character comparable to that of PIPAAm-TCPS. The cell adhesive character was altered from cell-adhesive to cell-repellent with increasing PAAm or PIPAAm graft density. The cell adhesive character of the temperature-responsive cell culture surfaces was relatively consistent with their contact angles. These results strongly suggest that the basal PAAm surface properties affect the degree of hydration and dehydration of the subsequently grafted PIPAAm. In addition, the roles of the hydrophilic component in accelerating cell detachment are further discussed in terms of the mobility of the grafted PIPAAm chains. Applications of this insight might be useful for designing temperature-responsive cell culture surfaces for achieving efficient cell culture and quick target cell detachment. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Synthesis and redox activity of "clicked" triazolylbiferrocenyl polymers, network encapsulation of gold and silver nanoparticles and anion sensing.

PubMed

Rapakousiou, Amalia; Deraedt, Christophe; Irigoyen, Joseba; Wang, Yanlan; Pinaud, Noël; Salmon, Lionel; Ruiz, Jaime; Moya, Sergio; Astruc, Didier

2015-03-02

The design of redox-robust polymers is called for in view of interactions with nanoparticles and surfaces toward applications in nanonetwork design, sensing, and catalysis. Redox-robust triazolylbiferrocenyl (trzBiFc) polymers have been synthesized with the organometallic group in the side chain by ring-opening metathesis polymerization using Grubbs-III catalyst or radical polymerization and with the organometallic group in the main chain by Cu(I) azide alkyne cycloaddition (CuAAC) catalyzed by [Cu(I)(hexabenzyltren)]Br. Oxidation of the trzBiFc polymers with ferricenium hexafluorophosphate yields the stable 35-electron class-II mixed-valent biferrocenium polymer. Oxidation of these polymers with Au(III) or Ag(I) gives nanosnake-shaped networks (observed by transmission electron microscopy and atomic force microscopy) of this mixed-valent Fe(II)Fe(III) polymer with encapsulated metal nanoparticles (NPs) when the organoiron group is located on the side chain. The factors that are suggested to be synergistically responsible for the NP stabilization and network formation are the polymer bulk, the trz coordination, the nearby cationic charge of trzBiFc, and the inter-BiFc distance. For instance, reduction of such an oxidized trzBiFc-AuNP polymer to the neutral trzBiFc-AuNP polymer with NaBH4 destroys the network, and the product flocculates. The polymers easily provide modified electrodes that sense, via the oxidized Fe(II)Fe(III) and Fe(III)Fe(III) polymer states, respectively, ATP(2-) via the outer ferrocenyl units of the polymer and Pd(II) via the inner Fc units; this recognition works well in dichloromethane, but also to a lesser extent in water with NaCl as the electrolyte.

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.

Paradoxes of thermodynamics of swelling equilibria of polymers in liquids and vapors.

PubMed

Davankov, Vadim A; Pastukhov, Alexander V

2011-12-29

An automatic registration of the changing size of a single spherical microbead of a cross-linked polymer was applied for studying the swelling process of the bead by the sorption of vapors and/or liquids. Many representatives of all three basic types of polymeric networks, gel-type, hypercrosslinked, and macroporous, were examined. Only the first two display large volume changes and prove suitable for following the kinetics and extent of swelling by the above dilatometric technique. The results unambiguously prove that swelling of all polymeric networks in liquids is always higher than in corresponding saturated vapors (Schroeder's paradox). The general nature of this phenomenon implies that the absolute activity of any sorbate in its liquid form is always larger than in the form of its saturated vapor. Surprisingly, gels with any solvent contents, which fall into the broad range between the vapor-equilibrated and liquid-equilibrated extreme contents, retain their volumes constant in the saturated vapor atmosphere. This paradox of a wide range of gels swollen to a different extent and, nevertheless, standing in equilibrium with saturated vapor is explained by the specificity of the network polymers, namely, that the energy of the solvent-polymer interactions is easily compensated by the energy of remaining between-chain interactions at any solvent content in the above range. Therefore, the strain-free swollen gels do not generate enhanced vapor pressure, but neither display the ability to take up more sorbate from its vapor. © 2011 American Chemical Society

Prediction of composite fatigue life under variable amplitude loading using artificial neural network trained by genetic algorithm

NASA Astrophysics Data System (ADS)

Rohman, Muhamad Nur; Hidayat, Mas Irfan P.; Purniawan, Agung

2018-04-01

Neural networks (NN) have been widely used in application of fatigue life prediction. In the use of fatigue life prediction for polymeric-base composite, development of NN model is necessary with respect to the limited fatigue data and applicable to be used to predict the fatigue life under varying stress amplitudes in the different stress ratios. In the present paper, Multilayer-Perceptrons (MLP) model of neural network is developed, and Genetic Algorithm was employed to optimize the respective weights of NN for prediction of polymeric-base composite materials under variable amplitude loading. From the simulation result obtained with two different composite systems, named E-glass fabrics/epoxy (layups [(±45)/(0)2]S), and E-glass/polyester (layups [90/0/±45/0]S), NN model were trained with fatigue data from two different stress ratios, which represent limited fatigue data, can be used to predict another four and seven stress ratios respectively, with high accuracy of fatigue life prediction. The accuracy of NN prediction were quantified with the small value of mean square error (MSE). When using 33% from the total fatigue data for training, the NN model able to produce high accuracy for all stress ratios. When using less fatigue data during training (22% from the total fatigue data), the NN model still able to produce high coefficient of determination between the prediction result compared with obtained by experiment.

Actin-myosin network is required for proper assembly of influenza virus particles

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

Kumakura, Michiko; Kawaguchi, Atsushi, E-mail: ats-kawaguchi@md.tsukuba.ac.jp; Nagata, Kyosuke, E-mail: knagata@md.tsukuba.ac.jp

Actin filaments are known to play a central role in cellular dynamics. After polymerization of actin, various actin-crosslinking proteins including non-muscle myosin II facilitate the formation of spatially organized actin filament networks. The actin-myosin network is highly expanded beneath plasma membrane. The genome of influenza virus (vRNA) replicates in the cell nucleus. Then, newly synthesized vRNAs are nuclear-exported to the cytoplasm as ribonucleoprotein complexes (vRNPs), followed by transport to the beneath plasma membrane where virus particles assemble. Here, we found that, by inhibiting actin-myosin network formation, the virus titer tends to be reduced and HA viral spike protein is aggregatedmore » on the plasma membrane. These results indicate that the actin-myosin network plays an important role in the virus formation. - Highlights: • Actin-myosin network is important for the influenza virus production. • HA forms aggregations at the plasma membrane in the presence of blebbistatin. • M1 is recruited to the budding site through the actin-myosin network.« less

YSL-12, a novel microtubule-destabilizing agent, exerts potent anti-tumor activity against colon cancer in vitro and in vivo.

PubMed

Cai, De; Qiu, Zhiqing; Yao, Weimin; Liu, Yuyu; Huang, Haixiang; Liao, Sihai; Luo, Qun; Xie, Liming; Lin, Zhixiu

2016-06-01

Microtubules play a central role in various fundamental cell functions and thus become an attractive target for cancer therapy. A novel compound YSL-12 is a combretastatin A-4 (CA-4) analogue with more stability. We investigated its anti-tumor activity and mechanisms in vitro and in vivo for the first time. Cytotoxicity was evaluated by MTT method. In vitro microtubule polymerization assay was performed using a fluorescence-based method by multifunction fluorescence microplate reader. Intracellular microtubule network was detected by immunofluorescence method. Cell cycle analysis and apoptosis were measured by flow cytometry. Metabolic stability was recorded by liquid chromatography-ultraviolet detection and liquid chromatography-mass spectrometry. In vivo anti-tumor activity was assessed using HT-29 colon carcinoma xenografts established in BALB/c nude mice. YSL-12 displayed nanomolar-level cytotoxicity against various human cancer cell lines. A high selectivity toward normal cells and potent activity toward drug-resistant cells were also observed. YSL-12 was identified as tubulin polymerization inhibitor evidenced by effectively inhibits tubulin polymerization and heavily disrupted microtubule networks in living HT-29 cells. YSL-12 displayed potent disruption effect of pre-established tumor vasculature in vitro. In addition, YSL-12 treatment also caused cell cycle arrest in the G2/M phase and induced cell apoptosis in a dose-dependent manner. In vitro metabolic stability study revealed YSL-12 displayed considerable better stability than CA-4 in liver microsomes. In vivo, YSL-12 delayed tumor growth with 69.4 % growth inhibition. YSL-12 is a promising microtubule inhibitor that has great potential for the treatment of colon carcinoma in vitro and in vivo and worth being a candidate for further development of cancer therapy.

Visible light induced electropolymerization of suspended hydrogel bioscaffolds in a microfluidic chip.

PubMed

Li, Pan; Yu, Haibo; Liu, Na; Wang, Feifei; Lee, Gwo-Bin; Wang, Yuechao; Liu, Lianqing; Li, Wen Jung

2018-05-23

The development of microengineered hydrogels co-cultured with cells in vitro could advance in vivo bio-systems in both structural complexity and functional hierarchy, which holds great promise for applications in regenerative tissues or organs, drug discovery and screening, and bio-sensors or bio-actuators. Traditional hydrogel microfabrication technologies such as ultraviolet (UV) laser or multiphoton laser stereolithography and three-dimensional (3D) printing systems have advanced the development of 3D hydrogel micro-structures but need either expensive and complex equipment, or harsh material selection with limited photoinitiators. Herein, we propose a simple and flexible hydrogel microfabrication method based on a ubiquitous visible-light projection system combined with a custom-designed photosensitive microfluidic chip, to rapidly (typically several to tens of seconds) fabricate various two-dimensional (2D) hydrogel patterns and 3D hydrogel constructs. A theoretical layer-by-layer model that involves continuous polymerizing-delaminating-polymerizing cycles is presented to explain the polymerization and structural formation mechanism of hydrogels. A large area of hydrogel patterns was efficiently fabricated without the usage of costly laser systems or photoinitiators, i.e., a stereoscopic mesh-like hydrogel network with intersecting hydrogel micro-belts was fabricated via a series of dynamic-changing digital light projections. The pores and gaps of the hydrogel network are tunable, which facilitates the supply of nutrients and discharge of waste in the construction of 3D thick bio-models. Cell co-culture experiments showed the effective regulation of cell spreading by hydrogel scaffolds fabricated by the new method presented here. This visible light enabled hydrogel microfabrication method may provide new prospects for designing cell-based units for advanced biomedical studies, e.g., for 3D bio-models or bio-actuators in the future.

The Interference of Selected Cytotoxic Alkaloids with the Cytoskeleton: An Insight into Their Modes of Action.

PubMed

Wang, Xiaojuan; Tanaka, Mine; Krstin, Sonja; Peixoto, Herbenya Silva; Wink, Michael

2016-07-12

Alkaloids, the largest group among the nitrogen-containing secondary metabolites of plants, usually interact with several molecular targets. In this study, we provide evidence that six cytotoxic alkaloids (sanguinarine, chelerythrine, chelidonine, noscapine, protopine, homoharringtonine), which are known to affect neuroreceptors, protein biosynthesis and nucleic acids, also interact with the cellular cytoskeleton, such as microtubules and actin filaments, as well. Sanguinarine, chelerythrine and chelidonine depolymerized the microtubule network in living cancer cells (Hela cells and human osteosarcoma U2OS cells) and inhibited tubulin polymerization in vitro with IC50 values of 48.41 ± 3.73, 206.39 ± 4.20 and 34.51 ± 9.47 μM, respectively. However, sanguinarine and chelerythrine did not arrest the cell cycle while 2.5 μM chelidonine arrested the cell cycle in the G₂/M phase with 88.27% ± 0.99% of the cells in this phase. Noscapine and protopine apparently affected microtubule structures in living cells without affecting tubulin polymerization in vitro, which led to cell cycle arrest in the G2/M phase, promoting this cell population to 73.42% ± 8.31% and 54.35% ± 11.26% at a concentration of 80 μM and 250.9 μM, respectively. Homoharringtonine did not show any effects on microtubules and cell cycle, while the known microtubule-stabilizing agent paclitaxel was found to inhibit tubulin polymerization in the presence of MAPs in vitro with an IC50 value of 38.19 ± 3.33 μM. Concerning actin filaments, sanguinarine, chelerythrine and chelidonine exhibited a certain effect on the cellular actin filament network by reducing the mass of actin filaments. The interactions of these cytotoxic alkaloids with microtubules and actin filaments present new insights into their molecular modes of action.

Kinetics of bulk photo-initiated copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC) polymerizations†

PubMed Central

Song, Han Byul; Baranek, Austin; Bowman, Christopher N.

2016-01-01

Photoinitiation of polymerizations based on the copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC) reaction enables spatio-temporal control and the formation of mechanically robust, highly glassy photopolymers. Here, we investigated several critical factors influencing photo-CuAAC polymerization kinetics via systematic variation of reaction conditions such as the physicochemical nature of the monomers; the copper salt and photoinitiator types and concentrations; light intensity; exposure time and solvent content. Real time Fourier transform infrared spectroscopy (FTIR) was used to monitor the polymerization kinetics in situ. Six different di-functional azide monomers and four different tri-functional alkyne monomers containing either aliphatic, aromatic, ether and/or carbamate substituents were synthesized and polymerized. Replacing carbamate structures with ether moieties in the monomers enabled an increase in conversion from 65% to 90% under similar irradiation conditions. The carbamate results in stiffer monomers and higher viscosity mixtures indicating that chain mobility and diffusion are key factors that determine the CuAAC network formation kinetics. Photoinitiation rates were manipulated by altering various aspects of the photo-reduction step; ultimately, a loading above 3 mol% per functional group for both the copper catalyst and the photoinitiator showed little or no rate dependence on concentration while a loading below 3 mol% exhibited 1st order rate dependence. Furthermore, a photoinitiating system consisting of camphorquinone resulted in 60% conversion in the dark after only 1 minute of 75 mW cm−2 light exposure at 400–500 nm, highlighting a unique characteristic of the CuAAC photopolymerization enabled by the combination of the copper(i)’s catalytic lifetime and the nature of the step-growth polymerization. PMID:27429650

Feedback Interactions of Polymerized Actin with the Cell Membrane: Waves, Pulses, and Oscillations

NASA Astrophysics Data System (ADS)

Carlsson, Anders

Polymerized filaments of the protein actin have crucial functions in cell migration, and in bending the cell membrane to drive endocytosis or the formation of protrusions. The nucleation and polymerization of actin filaments are controlled by upstream agents in the cell membrane, including nucleation-promoting factors (NPFs) that activate the Arp2/3 complex to form new branches on pre-existing filaments. But polymerized actin (F-actin) also feeds back on the assembly of NPFs. We explore the effects of the resulting feedback loop of F-actin and NPFs on two phenomena: actin pulses that drive endocytosis in yeast, and actin waves traveling along the membrane of several cell types. In our model of endocytosis in yeast, the actin network is grown explicitly in three dimensions, exerts a negative feedback interaction on localized patch of NPFs in the membrane, and bends the membrane by exerting a distribution of forces. This model explains observed actin and NPF pulse dynamics, and the effects of several interventions including i) NPF mutations, ii) inhibition of actin polymerization, and iii) deletion of a protein that allows F-actin to bend the cell membrane. The model predicts that mutation of the active region of an NPF will enhance the accumulation of that NPF, and we confirm this prediction by quantitative fluorescence microscopy. For actin waves, we treat a similar model, with NPFs distributed over a larger region of the cell membrane. This model naturally generates actin waves, and predicts a transition from wave behavior to spatially localized oscillations when NPFs are confined to a small region. We also predict a transition from waves to static polarization as the negative-feedback coupling between F-actin and the NPFs is reduced. Supported by NIGMS Grant R01 GM107667.

Resilient self-assembling hydrogels from block copolypeptide amphiphiles

NASA Astrophysics Data System (ADS)

Nowak, Andrew Paul

The ability to produce well defined synthetic polypeptides has been greatly improved by the discovery of transition metal species that mediate the controlled polymerization of N-carboxyanhydrides (NCAs). These metal species create a living polymerization system by producing control over chain length, low polydispersities, and the ability to form complex block architectures. We have applied this system to the synthesis of block copolypeptide amphiphiles. Initial block copolymers synthesized were composed of hydrophilic, cationic poly(L-Lysine) combined with hydrophobic, alpha-helical poly(L-Leucine). These Lysine- block-Leucine copolypeptides were found to form stiff, clear hydrogels at low concentration (˜1 wt%) in low ionic strength water. Based on this unexpected result we used the flexibility of our transition metal polymerization chemistry to better understand the nature and mechanisms of gel formation in these materials. Systematic changes to the original Lysine-block-Leucine copolypeptides were made by altering overall chain size, relative block length, polyelectrolyte charge, and hydrophobic secondary structure. Rheological characterization revealed that the strength of these hydrogels was primarily dependent on degree of polymerization, relative block length, and a well ordered secondary structure in the hydrophobic segment. The Lysine-block-Leucine hydrogels were formed by direct addition of water to dry polypeptide material which swelled to homogeneously fill the entire volume of liquid with no special processing. CryoTEM showed a percolating cellular network at ˜100nm that appears to be comprised of both membranes and fibers. Larger length scales studied with Laser Scanning Confocal Microscopy revealed a spontaneously formed microporous network with large (˜10mum) water rich voids. These hydrogels also displayed interesting mechanical properties including rapid recovery of solid like behavior after being sheared to a liquid and mechanical stability with increased temperature (˜90°C). The behavior of the Lysine- block-Leucine system with salt was also thoroughly investigated. With proper tuning of the relative block composition it was found that hydrogels could be optimized to possess good solubility and mechanical strength in many useful ionic solutions (˜100--200mM) such as pH buffers and cell culture media.

Multi-functional Textiles for Military Applications

NASA Astrophysics Data System (ADS)

Malshe, Priyadarshini

The objective of this research was to develop the standard rip-stop weave military uniform fabric made of 50/50 nylon/cotton (NyCo) to achieve a repellent front surface and an antibacterial bulk for protection from chemical-biological warfare agents. Diallyldimethylammonium chloride (DADMAC), a quaternary ammonium salt monomer was graft polymerized on NyCo fabric to impart antimicrobial capability using atmospheric pressure glow discharge plasma. Plasma was used to induce free radical chain polymerization of the DADMAC monomer to introduce a graft polymerized network on the fabric with durable antimicrobial properties. Pentaerythritol tertraacrylate was used as a cross-linking agent to obtain a highly cross-linked, durable polymer network. The presence of polyDADMAC on the fabric surface was confirmed using acid dye staining, SEM, and TOF-SIMS. Antibacterial performance was evaluated using standard AATCC test method 100 for both gram positive and gram negative bacteria. Results showed 99.9% reduction in the bacterial activities of K. pneumoniae and S. aureus. To achieve repellency on NyCo front surface, an environmentally benign C6 fluorocarbon monomer, 2-(perfluorohexyl) ethyl acrylate was graft polymerized using plasma on the front surface of the NyCo fabric which was already grafted with polyDADMAC for anti-microbial properties. The surface was characterized by IR spectroscopy and XPS. The presence of fluorine on the surface was mapped and confirmed by TOF-SIMS. SEM images showed a uniform layer of fluorocarbon polymer on the fiber surface. High water contact angle of 144° was obtained on the surface. The surface also achieved a high AATCC Test Method 193 rating of 9 and AATCC Test Method 118 rating of 5, indicating that the surface could repel a fluid with surface tension as low as 24 dynes/cm. Appropriate experimental designs and statistical modeling of data helped identify the experimental space and optimal factor combinations for best response. The study helped create a multi-functional fabric with an anti-bacterial bulk, hydrophilic back surface and repellent front surface for enhanced protective and aesthetic values.

High Efficiency, Transparent, Reusable, and Active PM2.5 Filters by Hierarchical Ag Nanowire Percolation Network.

PubMed

Jeong, Seongmin; Cho, Hyunmin; Han, Seonggeun; Won, Phillip; Lee, Habeom; Hong, Sukjoon; Yeo, Junyeob; Kwon, Jinhyeong; Ko, Seung Hwan

2017-07-12

Air quality has become a major public health issue in Asia including China, Korea, and India. Particulate matters are the major concern in air quality. We present the first environmental application demonstration of Ag nanowire percolation network for a novel, electrical type transparent, reusable, and active PM2.5 air filter although the Ag nanowire percolation network has been studied as a very promising transparent conductor in optoelectronics. Compared with previous particulate matter air filter study using relatively weaker short-range intermolecular force in polar polymeric nanofiber, Ag nanowire percolation network filters use stronger long-range electrostatic force to capture PM2.5, and they are highly efficient (>99.99%), transparent, working on an active mode, low power consumption, antibacterial, and reusable after simple washing. The proposed new particulate matter filter can be applied for a highly efficient, reusable, active and energy efficient filter for wearable electronics application.

Assembly kinetics determine the architecture of α-actinin crosslinked F-actin networks.

PubMed

Falzone, Tobias T; Lenz, Martin; Kovar, David R; Gardel, Margaret L

2012-05-29

The actin cytoskeleton is organized into diverse meshworks and bundles that support many aspects of cell physiology. Understanding the self-assembly of these actin-based structures is essential for developing predictive models of cytoskeletal organization. Here we show that the competing kinetics of bundle formation with the onset of dynamic arrest arising from filament entanglements and crosslinking determine the architecture of reconstituted actin networks formed with α-actinin crosslinks. Crosslink-mediated bundle formation only occurs in dilute solutions of highly mobile actin filaments. As actin polymerization proceeds, filament mobility and bundle formation are arrested concomitantly. By controlling the onset of dynamic arrest, perturbations to actin assembly kinetics dramatically alter the architecture of biochemically identical samples. Thus, the morphology of reconstituted F-actin networks is a kinetically determined structure similar to those formed by physical gels and glasses. These results establish mechanisms controlling the structure and mechanics in diverse semiflexible biopolymer networks.

Network Polymers Formed Under Nonideal Conditions.

DTIC Science & Technology

1986-12-01

the system or the limited ability of the statistical model to account for stochastic correlations. The viscosity of the reacting system was measured as...based on competing reactions (ring, chain) and employs equilibrium chain statistics . The work thus far has been limited to single cycle growth on an...polymerizations, because a large number of differential equations must be solved. The Makovian approach (sometimes referred to as the statistical or

Soft nanoparticles: nano ionic networks of associated ionic polymers

DOE PAGES

Aryal, Dipak; Grest, Gary S.; Perahia, Dvora

2017-01-01

Directing the formation of nanostructures that serve as building blocks of membranes presents an immense step towards engineering controlled polymeric ion transport systems. Here, using the exquisite atomic detail captured by molecular dynamics simulations, we follow the assembly of a co-polymer that consists of polystyrene sulfonate tethered symmetrically to hydrophobic blocks, realizing a new type of long lived solvent-responsive soft nanoparticle.

Optimizing Glassy Polymer Network Morphology for Nano-particle Dispersion, Stabilization and Performance

DTIC Science & Technology

2016-10-03

dissolution, toughener dissolution and controlled chain-extension reactions in the continuous reactor high temperature “hot-zone” to advance conversion...rheology and tack. 2. Simultaneous MWCNT dispersion and stabilization in the continuous reactor low temperature “cold-zone” leading to an increased...Weight and Low Dispersity Polyacrylonitrile by Low Temperature RAFT Polymerization, Moskowitz, Jeremy, Abel, Brooks, McCormick, Charles, Wiggins

Structural Modification of Sol-Gel Materials through Retro Diels-Alder Reaction

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

SHALTOUT,RAAFAT M.; LOY,DOUGLAS A.; MCCLAIN,MARK D.

1999-12-08

Hydrolysis and condensation of organically bridged bis-triethoxysilanes, (EtO){sub 3}Si-R-Si(OEt){sub 3}, results in the formation of three dimensional organic/inorganic hybrid networks (Equation 1). Properties of these materials, including porosity, are dependent on the nature of the bridging group, R. Flexible groups (akylene-spacers longer than five carbons in length) polymerize under acidic conditions to give non-porous materials. Rigid groups (such as arylene-, alkynylene-, or alkenylene) form non-porous, microporous, and macroporous gels. In many cases the pore size distributions are quite narrow. One of the motivations for preparing hybrid organic-inorganic materials is to extend the range of properties available with sol-gel systems bymore » incorporating organic groups into the inorganic network. For example, organically modified silica gels arc either prepared by co-polymerizing an organoalkoxysilane with a silica precursor or surface silylating the inorganic gel. This can serve to increase hydrophobicity or to introduce some reactive organic functionality. However, the type and orientation of these organic functionalities is difficult to control. Furthermore, many organoalkoxysilanes can act to inhibitor even prevent gelation, limiting the final density of organic functionalities. We have devised a new route for preparing highly functionalized pores in hybrid materials using bridging groups that are thermally converted into the desired functionalities after the gel has been obtained. In this paper, we present the preparation and characterization of bridged polysilsesquioxanes with Diels-Alder adducts as the bridging groups from the sol-gel polymerization of monomers 2 and 4. The bridging groups are constructed such that the retro Diela-Alder reaction releases the dienes and leaves the dienophiles as integral parts of the network polymers. In the rigid architecture of a xerogel, this loss of organic functionality should liberate sufficient space to modify the overall porosity. Furthermore, the new porosity will be functionalized with the dienophilic olefin bridging group. We also demonstrate that by changing the type of Diels-Alder adduct used as the bridging group, we can change the temperature at which the retro-Diels-Alder reaction will occur.« less

Through the looking glass: Unraveling the network structure of coal

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

Gregory, D. M.; Stec, D. F.; Botto, R. E.

1999-12-23

Since the original idea by Sanada and Honda of treating coal as a three-dimensional cross-linked network, coal structure has been probed by monitoring ingress of solvents using traditional volumetric or gravimetric methods. However, using these techniques has allowed only an indirect observation of the swelling process. More recently, the authors have developed magnetic resonance microscopy (MRM) approaches for studying solvent ingress in polymeric systems, about which fundamental aspects of the swelling process can be deduced directly and quantitatively. The aim of their work is to utilize solvent transport and network response parameters obtained from these methods to assess fundamental propertiesmore » of the system under investigation. Polymer and coal samples have been studied to date. Numerous swelling parameters measured by magnetic resonance microscopy are found to correlate with cross-link density of the polymer network under investigation. Use of these parameters to assess the three-dimensional network structure of coal is discussed.« less

Porous Cross-Linked Polyimide Networks

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B. (Inventor); Guo, Haiquan (Inventor)

2015-01-01

Porous cross-linked polyimide networks are provided. The networks comprise an anhydride end-capped polyamic acid oligomer. The oligomer (i) comprises a repeating unit of a dianhydride and a diamine and terminal anhydride groups, (ii) has an average degree of polymerization of 10 to 50, (iii) has been cross-linked via a cross-linking agent, comprising three or more amine groups, at a balanced stoichiometry of the amine groups to the terminal anhydride groups, and (iv) has been chemically imidized to yield the porous cross-linked polyimide network. Also provided are porous cross-linked polyimide aerogels comprising a cross-linked and imidized anhydride end-capped polyamic acid oligomer, wherein the oligomer comprises a repeating unit of a dianhydride and a diamine, and the aerogel has a density of 0.10 to 0.333 g/cm.sup.3 and a Young's modulus of 1.7 to 102 MPa. Also provided are thin films comprising aerogels, and methods of making porous cross-linked polyimide networks.

Polymerization speed and diffractive experiments in polymer network LC test cells

NASA Astrophysics Data System (ADS)

Braun, Larissa; Gong, Zhen; Habibpourmoghadam, Atefeh; Schafforz, Samuel L.; Wolfram, Lukas; Lorenz, Alexander

2018-02-01

Polymer-network liquid crystals (LCs), where the response properties of a LC can be enhanced by the presence of a porous polymer network, are investigated. In the reported experiments, liquid crystals were doped with a small amount (< 10%) of photo-curable acrylate monomers. Samples with surface grafted photoinitiators, dissolvable photoinitiators, and samples with both kinds of photoinitiators were prepared. Both conventional (planar electrodes) and diffractive (interdigitated electrodes) test cells were used. These samples were exposed with a UV light source and changes of their capacitance were investigated with an LCR meter during exposure. Due to the presence of the in-situ generated polymer network, the electro-optic response properties of photo cured samples were enhanced. For example, their continuous phase modulation properties led to more localized responses in samples with interdigitated electrodes, which caused suppression of selected diffraction orders in the diffraction patterns recorded in polymer network LC samples. Moreover, capacitance changes were investigated during photopolymerization of a blue phase LC.

Polyaniline nanowires-gold nanoparticles hybrid network based chemiresistive hydrogen sulfide sensor

NASA Astrophysics Data System (ADS)

Shirsat, Mahendra D.; Bangar, Mangesh A.; Deshusses, Marc A.; Myung, Nosang V.; Mulchandani, Ashok

2009-02-01

We report a sensitive, selective, and fast responding room temperature chemiresistive sensor for hydrogen sulfide detection and quantification using polyaniline nanowires-gold nanoparticles hybrid network. The sensor was fabricated by facile electrochemical technique. Initially, polyaniline nanowires with a diameter of 250-320 nm bridging the gap between a pair of microfabricated gold electrodes were synthesized using templateless electrochemical polymerization using a two step galvanostatic technique. Polyaniline nanowires were then electrochemically functionalized with gold nanoparticles using cyclic voltammetry technique. These chemiresistive sensors show an excellent limit of detection (0.1 ppb), wide dynamic range (0.1-100 ppb), and very good selectivity and reproducibility.

Toughening of PMR composites by semi-interpenetrating networks

NASA Technical Reports Server (NTRS)

Tiwari, S. N.; Srinivansan, K.

1991-01-01

Polymerization of monomer reactants (PMR-15) type polyimide and RP46 prepregs were drum wound using IM-7 fibers. Prepregging and processing conditions were optimized to yield good quality laminates with fiber volume fractions of 60 percent (+/- 2 percent). Samples were fabricated and tested to determine comprehensive engineering properties of both systems. These included 0 deg flexure, short beam shear, transverse flexure and tension, 0 deg tension and compression, intralaminar shear, short block compression, mode 1 and 2 fracture toughness, and compression after impact properties. Semi-2-IPN (interpenetrating polymer networks) toughened PMR-15 and RP46 laminates were also fabricated and tested for the same properties.

Interpenetrating polymer network approach to tougher and more microcracking resistant high temperature polymers. I - LaRC-RP40

NASA Technical Reports Server (NTRS)

Pater, Ruth H.; Morgan, Cassandra D.

1988-01-01

Interpenetrating polymer networks in the form of the LaRC-RP40 resin, prepared by the in situ polymerization of a thermosetting imide prepolymer and thermoplastic monomer reactants, are presently used to obtain toughness and microcracking resistance in a high-temperature polymer. Attention is presently given to the processing, physical, and mechanical properties, as well as the thermooxidative stability, of both the neat resin and the resin as a graphite fiber-reinforced matrix. Microcracking after thermal cycling was also tested. LaRC-RP40 exhibits significant resin fracture toughness improvements over the PMR-15 high-temperature matrix resin.

Interpenetrating polymer network approach to tougher and more microcracking resistant high temperature polymers. I. LaRC-RP40

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

Pater, R.H.; Morgan, C.D.

1988-10-01

Interpenetrating polymer networks in the form of the LaRC-RP40 resin, prepared by the in situ polymerization of a thermosetting imide prepolymer and thermoplastic monomer reactants, are presently used to obtain toughness and microcracking resistance in a high-temperature polymer. Attention is presently given to the processing, physical, and mechanical properties, as well as the thermooxidative stability, of both the neat resin and the resin as a graphite fiber-reinforced matrix. Microcracking after thermal cycling was also tested. LaRC-RP40 exhibits significant resin fracture toughness improvements over the PMR-15 high-temperature matrix resin. 16 references.

Modeling liquid crystal polymeric devices

NASA Astrophysics Data System (ADS)

Gimenez Pinto, Vianney Karina

The main focus of this work is the theoretical and numerical study of materials that combine liquid crystal and polymer. Liquid crystal elastomers are polymeric materials that exhibit both the ordered properties of the liquid crystals and the elastic properties of rubbers. Changing the order of the liquid crystal molecules within the polymer network can induce shape change. These materials are very valuable for applications such as actuators, sensors, artificial muscles, haptic displays, etc. In this work we apply finite element elastodynamics simulations to study the temperature induced shape deformation in nematic elastomers with complex director microstructure. In another topic, we propose a novel numerical method to model the director dynamics and microstructural evolution of three dimensional nematic and cholesteric liquid crystals. Numerical studies presented in this work are in agreement with experimental observations and provide insight into the design of application devices.

Smart Polymeric Gels: Redefining the Limits of Biomedical Devices.

PubMed

Chaterji, Somali; Kwon, Il Keun; Park, Kinam

2007-08-01

This review describes recent progresses in the development and applications of smart polymeric gels, especially in the context of biomedical devices. The review has been organized into three separate sections: defining the basis of smart properties in polymeric gels; describing representative stimuli to which these gels respond; and illustrating a sample application area, namely, microfluidics. One of the major limitations in the use of hydrogels in stimuli-responsive applications is the diffusion rate limited transduction of signals. This can be obviated by engineering interconnected pores in the polymer structure to form capillary networks in the matrix and by downscaling the size of hydrogels to significantly decrease diffusion paths. Reducing the lag time in the induction of smart responses can be highly useful in biomedical devices, such as sensors and actuators. This review also describes molecular imprinting techniques to fabricate hydrogels for specific molecular recognition of target analytes. Additionally, it describes the significant advances in bottom-up nanofabrication strategies, involving supramolecular chemistry. Learning to assemble supramolecular structures from nature has led to the rapid prototyping of functional supramolecular devices. In essence, the barriers in the current performance potential of biomedical devices can be lowered or removed by the rapid convergence of interdisciplinary technologies.

Smart Polymeric Gels: Redefining the Limits of Biomedical Devices

PubMed Central

Chaterji, Somali; Kwon, Il Keun; Park, Kinam

2007-01-01

This review describes recent progresses in the development and applications of smart polymeric gels, especially in the context of biomedical devices. The review has been organized into three separate sections: defining the basis of smart properties in polymeric gels; describing representative stimuli to which these gels respond; and illustrating a sample application area, namely, microfluidics. One of the major limitations in the use of hydrogels in stimuli–responsive applications is the diffusion rate limited transduction of signals. This can be obviated by engineering interconnected pores in the polymer structure to form capillary networks in the matrix and by downscaling the size of hydrogels to significantly decrease diffusion paths. Reducing the lag time in the induction of smart responses can be highly useful in biomedical devices, such as sensors and actuators. This review also describes molecular imprinting techniques to fabricate hydrogels for specific molecular recognition of target analytes. Additionally, it describes the significant advances in bottom–up nanofabrication strategies, involving supramolecular chemistry. Learning to assemble supramolecular structures from nature has led to the rapid prototyping of functional supramolecular devices. In essence, the barriers in the current performance potential of biomedical devices can be lowered or removed by the rapid convergence of interdisciplinary technologies. PMID:18670584

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.

Mechanisms of the cytopathic action of actin-ADP-ribosylating toxins.

PubMed

Aktories, K; Wegner, A

1992-10-01

Clostridium botulinum C2 toxin, Clostridium perfringens iota toxin, and Clostridium spiroforme toxin ADP-ribosylate actin monomers. Toxin-induced ADP-ribosylation disturbs the cellular equilibrium between monomeric and polymeric actin and traps monomeric actin in its unpolymerized form, thereby depolymerizing actin filaments and destroying the microfilament network. Furthermore, the toxins ADP-ribosylate gelsolin actin complexes. These modifications may contribute to the cytopathic action of the toxins.

Organic Crystal Engineering of Thermosetting Cyanate Ester Monomers: Influence of Structure on Melting Point

DTIC Science & Technology

2016-05-27

often discussed in the field of thermosetting materials, crystal engineering1-4 plays a key role in facilitating the successful utilization of these...not to alter the desirable properties of the polymerized networks. Fortunately, the field of crystal engineering provides examples where even very...Chickos and Acree.26 For molecular modeling, methods ranging from atomistic simulations with semi-empirical force fields to density functional

Waterborne Polymeric Films.

DTIC Science & Technology

1979-12-01

resin types: 1) acrylic latex, 2) acrylic solution polymer, 3) epoxy emulsions, 4) polyurethane, 5) butadiene elastomeric latex, 6) polyester/ alkyd , 7...emulsions and the class of polyester/ alkyd resins were evaluated only as network, crosslinked films. -53- j z I, ACRYLIC SOLUTIONLATEX URE THANE ACRYLIC ...amount of "plasticizing" monomer such as ethyl acrylate . 2.3.1.3 Aqueous Polyester Alkyd Resins As indicated in section 2.2.7 of this report,

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.

Cyanide bridged hetero-metallic polymeric complexes: Syntheses, vibrational spectra, thermal analyses and crystal structures of complexes [M(1,2-dmi)2Ni(μ-CN)4]n (M = Zn(II) and Cd(II))

NASA Astrophysics Data System (ADS)

Kürkçüoğlu, Güneş Süheyla; Sayın, Elvan; Şahin, Onur

2015-12-01

Two cyanide bridged hetero-metallic complexes of general formula, [M(1,2-dmi)2Ni(μ-CN)4]n (1,2-dmi = 1,2-dimethylimidazole and M = Zn(II) or Cd(II)) have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal analyses and elemental analyses. The crystallographic analyses reveal that the complexes, [Zn(1,2-dmi)2Ni(μ-CN)4] (1) and [Cd(1,2-dmi)2Ni(μ-CN)4] (2), have polymeric 2D networks. In the complexes, four cyanide groups of [Ni(CN)4]2- coordinated to the adjacent M(II) ions and distorted octahedral geometries of complexes are completed by two nitrogen atoms of trans 1,2-dmi ligands. The structures of 1 and 2 are similar and linked via intermolecular hydrogen bonding, C-H⋯Ni interactions to give rise to 3D networks. Vibration assignments are given for all the observed bands and the spectral features also supported to the crystal structures of heteronuclear complexes. The FT-IR and Raman spectra of the complexes are very much consistent with the structural data presented.

Modulation of electrostatic interactions to improve controlled drug delivery from nanogels.

PubMed

Mauri, Emanuele; Chincarini, Giulia M F; Rigamonti, Riccardo; Magagnin, Luca; Sacchetti, Alessandro; Rossi, Filippo

2017-03-01

The synthesis of nanogels as devices capable to maintain the drug level within a desired range for a long and sustained period of time is a leading strategy in controlled drug delivery. However, with respect to the good results obtained with antibodies and peptides there are a lot of problems related to the quick and uncontrolled diffusion of small hydrophilic molecules through polymeric network pores. For these reasons research community is pointing toward the use of click strategies to reduce release rates of the linked drugs to the polymer chains. Here we propose an alternative method that considers the electrostatic interactions between polymeric chains and drugs to tune the release kinetics from nanogel network. The main advantage of these systems lies in the fact that the carried drugs are not modified and no chemical reactions take place during their loading and release. In this work we synthesized PEG-PEI based nanogels with different protonation degrees and the release kinetics with charged and uncharged drug mimetics (sodium fluorescein, SF, and rhodamine B, RhB) were studied. Moreover, also the effect of counterion used to induce protonation was taken into account in order to build a tunable drug delivery system able to provide multiple release rates with the same device. Copyright © 2016 Elsevier B.V. All rights reserved.

Mechanisms of fibrin polymerization and clinical implications

PubMed Central

Litvinov, Rustem I.

2013-01-01

Research on all stages of fibrin polymerization, using a variety of approaches including naturally occurring and recombinant variants of fibrinogen, x-ray crystallography, electron and light microscopy, and other biophysical approaches, has revealed aspects of the molecular mechanisms involved. The ordered sequence of fibrinopeptide release is essential for the knob-hole interactions that initiate oligomer formation and the subsequent formation of 2-stranded protofibrils. Calcium ions bound both strongly and weakly to fibrin(ogen) have been localized, and some aspects of their roles are beginning to be discovered. Much less is known about the mechanisms of the lateral aggregation of protofibrils and the subsequent branching to yield a 3-dimensional network, although the αC region and B:b knob-hole binding seem to enhance lateral aggregation. Much information now exists about variations in clot structure and properties because of genetic and acquired molecular variants, environmental factors, effects of various intravascular and extravascular cells, hydrodynamic flow, and some functional consequences. The mechanical and chemical stability of clots and thrombi are affected by both the structure of the fibrin network and cross-linking by plasma transglutaminase. There are important clinical consequences to all of these new findings that are relevant for the pathogenesis of diseases, prophylaxis, diagnosis, and treatment. PMID:23305734

Fabrication of lead zirconate titanate actuator via suspension polymerization casting

NASA Astrophysics Data System (ADS)

Miao, Weiguo

2000-10-01

The research presented herein has focused on the fabrication of a lead zirconate titanate (PZT) telescopic actuator from Suspension Polymerization Casting (SPC). Two systems were studied: an acrylamide-based hydrogel, and an acrylate-based nonaqueous system. Analytical tools such as thermomechanical analysis (TMA), differential scanning calorimetry (DSC), chemorheology, thermogravimetric analysis (TGA), and differential thermal analysis (DTA) were used to investigate the polymerization and burnout processes. The acrylamide hydrogel polymerization casting process used hydroxymethyl acrylamide (HMAM) monofunctional monomer with methylenebisacrylamide (MBAM) difunctional monomer, or used methacrylamide (MAM) as monofunctional monomer. High solid loading PZT slurries with low viscosities were obtained by optimizing the amounts of dispersant and the PZT powders. The overall activation energy of gelation was calculated to be 60--76 kJ/mol for the monomer solution, this energy was increased to 91 kJ/mol with the addition of PZT powder. The results show that the PZT powder has a retardation effect on gelation. Although several PZT tubes were made using the acrylamide-based system, the demolding and drying difficulties made this process unsuitable for building internal structures, such as the telescopic actuator. The acrylate-based system was used successfully to build telescopic actuator. Efforts were made to study the influence of composition and experimental conditions on the polymerization process. Temperature was found to have the largest impact on polymerization. To adjust the polymerization temperature and time, initiator and/or catalyst were used. PZT powder has a catalytic effect on the polymerization process. Compared with acrylamide systems, acrylate provided a strong polymer network to support the ceramic green body. This high strength is beneficial for the demolding process, but it can easily cause cracks during the burnout process. To solve the burnout issue, non-reactive decalin was used as a solvent to lower the stress inside the green body. The addition of decalin has no large impact on the polymerization process. With 15 wt% decalin in the monomer solution, the burnout process was successfully solved. The burnout process was monitored by TGA/DTA and TMA. A 51 vol% PZT filled acrylate slurry was cast into a mold made by Stereolithography (SLA), and after curing, the telescopic actuator was removed from the mold. This indirect SLA method provides an efficient way to build ceramic parts. PZT samples were sintered at 1275°C for 4 hours, with density over 98%. SEM analysis showed the sample made by SPC has a uniform microstructure, which may be beneficial to the electric properties. The sample made by polymerization has a d33 value about 680 pm/V, which is better than the literature value (580 pm/V). The electric tests showed this telescopic actuator produced a maximum deflection of 24.7 mum at 250 kV/m, in line with theoretical calculations. Compared with actuators made by other methods, the actuator made by SPC provides a comparable structural factor (187.5). The distortion in actuators is caused by fabrication and sintering.

Correlating Free-Volume Hole Distribution to the Glass Transition Temperature of Epoxy Polymers.

PubMed

Aramoon, Amin; Breitzman, Timothy D; Woodward, Christopher; El-Awady, Jaafar A

2017-09-07

A new algorithm is developed to quantify the free-volume hole distribution and its evolution in coarse-grained molecular dynamics simulations of polymeric networks. This is achieved by analyzing the geometry of the network rather than a voxelized image of the structure to accurately and efficiently find and quantify free-volume hole distributions within large scale simulations of polymer networks. The free-volume holes are quantified by fitting the largest ellipsoids and spheres in the free-volumes between polymer chains. The free-volume hole distributions calculated from this algorithm are shown to be in excellent agreement with those measured from positron annihilation lifetime spectroscopy (PALS) experiments at different temperature and pressures. Based on the results predicted using this algorithm, an evolution model is proposed for the thermal behavior of an individual free-volume hole. This model is calibrated such that the average radius of free-volumes holes mimics the one predicted from the simulations. The model is then employed to predict the glass-transition temperature of epoxy polymers with different degrees of cross-linking and lengths of prepolymers. Comparison between the predicted glass-transition temperatures and those measured from simulations or experiments implies that this model is capable of successfully predicting the glass-transition temperature of the material using only a PDF of the initial free-volume holes radii of each microstructure. This provides an effective approach for the optimized design of polymeric systems on the basis of the glass-transition temperature, degree of cross-linking, and average length of prepolymers.

Design and development of data glove based on printed polymeric sensors and Zigbee networks for Human-Computer Interface.

PubMed

Tongrod, Nattapong; Lokavee, Shongpun; Watthanawisuth, Natthapol; Tuantranont, Adisorn; Kerdcharoen, Teerakiat

2013-03-01

Current trends in Human-Computer Interface (HCI) have brought on a wave of new consumer devices that can track the motion of our hands. These devices have enabled more natural interfaces with computer applications. Data gloves are commonly used as input devices, equipped with sensors that detect the movements of hands and communication unit that interfaces those movements with a computer. Unfortunately, the high cost of sensor technology inevitably puts some burden to most general users. In this research, we have proposed a low-cost data glove concept based on printed polymeric sensor to make pressure and bending sensors fabricated by a consumer ink-jet printer. These sensors were realized using a conductive polymer (poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) [PEDOT:PSS]) thin film printed on glossy photo paper. Performance of these sensors can be enhanced by addition of dimethyl sulfoxide (DMSO) into the aqueous dispersion of PEDOT:PSS. The concept of surface resistance was successfully adopted for the design and fabrication of sensors. To demonstrate the printed sensors, we constructed a data glove using such sensors and developed software for real time hand tracking. Wireless networks based on low-cost Zigbee technology were used to transfer data from the glove to a computer. To our knowledge, this is the first report on low cost data glove based on paper pressure sensors. This low cost implementation of both sensors and communication network as proposed in this paper should pave the way toward a widespread implementation of data glove for real-time hand tracking applications.

Effects of terrestrial UV radiation on selected outdoor materials: an interdisciplinary approach

NASA Astrophysics Data System (ADS)

Heikkilä, A.; Kazadzis, S.; Tolonen-Kivimäki, O.; Meinander, O.; Lindfors, A.; Lakkala, K.; Koskela, T.; Kaurola, J.; Sormanen, A.; Kärhä, P.; Naula-Iltanen, A.; Syrjälä, S.; Kaunismaa, M.; Juhola, J.; Ture, T.; Feister, U.; Kouremeti, N.; Bais, A.; Vilaplana, J. M.; Rodriguez, J. J.; Guirado, C.; Cuevas, E.; Koskinen, J.

2009-08-01

Modern polymeric materials possess an ever increasing potential in a large variety of outdoor objects and structures offering an alternative for many traditional materials. In outdoor applications, however, polymers are subject to a phenomenon called weathering. This is primarily observed as unwanted property changes: yellowing or fading, chalking, blistering, and even severe erosion of the material surface. One of the major weathering factors is UV radiation. In spring 2005, the Finnish Meteorological Institute with its research and industrial partners launched a five-year material research project named UVEMA (UV radiation Effects on MAterials). Within the framework of the project, a weathering network of seven European sites was established. The network extends from the Canary Islands of Spain (latitude 28.5°N) to the Lapland of Finland (latitude 67.4°N), covering a wide range of UV radiation conditions. Since autumn 2005, the sites of the network have been maintaining weathering platforms of specimens of different kinds of polymeric materials. At the same time, the sites have been maintaining their long-term monitoring programmes for spectrally resolved UV radiation. Within UVEMA, these data are used for explaining the differences between the degradation rates of the materials at each site and for correlating the UV conditions in accelerated ageing tests to those under the Sun. We will present the objectives of the UVEMA project aiming at deeper understanding of the ageing of polymers and more reliable assessments for their service life time. Methodologies adopted within the project and the first results of the project will be summarized.

Reduced graphene oxide aerogel networks with soft interfacial template for applications in bone tissue regeneration

NASA Astrophysics Data System (ADS)

Asha, S.; Ananth, A. Nimrodh; Jose, Sujin P.; Rajan, M. A. Jothi

2018-05-01

Reduced Graphene Oxide aerogels (A-RGO), functionalized with chitosan, were found to induce and/or accelerate the mineralization of hydroxyapatite. The functionalized chitosan acts as a soft interfacial template on the surface of A-RGO assisting the growth of hydroxyapatite particles. The mineralization on these soft aerogel networks was performed by soaking the aerogels in simulated body fluid, relative to time. Polymer-induced mineralization exhibited an ordered arrangement of hydroxyapatite particles on reduced graphene oxide aerogel networks with a higher crystalline index (IC) of 1.7, which mimics the natural bone formation indicating the importance of the polymeric interfacial template. These mineralized aerogels which mimic the structure and composition of natural bone exhibit relatively higher rate of cell proliferation, osteogenic differentiation and osteoid matrix formation proving it to be a potential scaffold for bone tissue regeneration.

Improved C/SiC Ceramic Composites Made Using PIP

NASA Technical Reports Server (NTRS)

Easler, Timothy

2007-01-01

Improved carbon-fiber-reinforced SiC ceramic-matrix composite (C/SiC CMC) materials, suitable for fabrication of thick-section structural components, are producible by use of a combination of raw materials and processing conditions different from such combinations used in the prior art. In comparison with prior C/SiC CMC materials, these materials have more nearly uniform density, less porosity, and greater strength. The majority of raw-material/processing-condition combinations used in the prior art involve the use of chemical vapor infiltration (CVI) for densifying the matrix. In contrast, in synthesizing a material of the present type, one uses a combination of infiltration with, and pyrolysis of, a preceramic polymer [polymer infiltration followed by pyrolysis (PIP)]. PIP processing is performed in repeated, tailored cycles of infiltration followed by pyrolysis. Densification by PIP processing takes less time and costs less than does densification by CVI. When one of these improved materials was tested by exposure to a high-temperature, inert-gas environment that caused prior C/SiC CMCs to lose strength, this material did not lose strength. (Information on the temperature and exposure time was not available at the time of writing this article.) A material of the present improved type consists, more specifically, of (1) carbon fibers coated with an engineered fiber/matrix interface material and (2) a ceramic matrix, containing SiC, derived from a pre-ceramic polymer with ceramic powder additions. The enhancements of properties of these materials relative to those of prior C/SiC CMC materials are attributable largely to engineering of the fiber/ matrix interfacial material and the densification process. The synthesis of a material of this type includes processing at an elevated temperature to a low level of open porosity. The approach followed in this processing allows one to fabricate not only simple plates but also more complexly shaped parts. The carbon fiber reinforcement in a material of this type can be in any of several alternative forms, including tow, fabric, or complex preforms containing fibers oriented in multiple directions.

Electrospinning of ceramic nanofibers

NASA Astrophysics Data System (ADS)

Eick, Benjamin M.

Silicon Carbide (SiC) nanofibers of diameters as low as 20 nm are fabricated. The fibers were produced through the electrostatic spinning of the preceramic poly(carbomethylsilane) with pyrolysis to ceramic. A new technique was used where the preceramic was blended with polystyrene (PS) and, subsequent to electrospinning, was exposed to UV to crosslink the PS and prevent fibers flowing during pyrolysis. Electrospun SiC fibers were characterized by FTIR, TGA-DTA, SEM, TEM, XRD, and SAED. Fibers were shown to be polycrystalline and nanograined with alpha-SiC 15R polytype being dominant, where commercial fiber production methods form beta-SiC 3C. Pyrolysis of the bulk polymer blend to SiC produced alpha-SiC 15R as the dominant polytype with larger grains showing that electrospinning nanofibers affects resultant crystallinity. Fibers produced were shown to have a core-shell structure of an oxide scale that was variable by pyrolysis conditions. Metal oxide powders (chromium oxide, cobalt oxide, iron oxide, silicon oxide, tantalum oxide, titanium oxide, tungsten oxide, vanadium oxide, and zirconium oxide), were converted to metal carbide powders and metal nitride powders by the process of carbothermal reduction (CTR). Synthetic pitch was explored as an alternative to graphite which is a common carbon source for CTR. It was shown via characterization with XRD that pitch performs as well and in some cases better than graphite and is therefore a viable alternative in CTR. Conversion of metal oxide powders with pitch led to conversion of sol-gel based metal oxide nanofibers produced by electrospinning. Pitch was soluble in the solutions xv that were electrospun allowing for intimate contact between the sol-gel and the carbon source for CTR. This method became a two step processing method to produce metal carbide and nitride nanofibers: first electrospin sol-gel based metal oxide nanofibers and subsequently pyrolize them in the manner of CTR to transform them. Results indicate that this method was capable of transforming hafnium, niobium, tantalum, titanium, vanadium, and zirconium sol-gel nanofibers to metal carbides and nitrides.

Formation of porous networks on polymeric surfaces by femtosecond laser micromachining

NASA Astrophysics Data System (ADS)

Assaf, Youssef; Kietzig, Anne-Marie

2017-02-01

In this study, porous network structures were successfully created on various polymer surfaces by femtosecond laser micromachining. Six different polymers (poly(tetrafluoroethylene) (PTFE), poly(methyl methacrylate) (PMMA), high density poly(ethylene) (HDPE), poly(lactic acid) (PLA), poly(carbonate) (PC), and poly(ethylene terephthalate) (PET)) were machined at different fluences and pulse numbers, and the resulting structures were identified and compared by lacunarity analysis. At low fluence and pulse numbers, porous networks were confirmed to form on all materials except PLA. Furthermore, all networks except for PMMA were shown to bundle up at high fluence and pulse numbers. In the case of PC, a complete breakdown of the structure at such conditions was observed. Operation slightly above threshold fluence and at low pulse numbers is therefore recommended for porous network formation. Finally, the thickness over which these structures formed was measured and compared to two intrinsic material dependent parameters: the single pulse threshold fluence and the incubation coefficient. Results indicate that a lower threshold fluence at operating conditions favors material removal over structure formation and is hence detrimental to porous network formation. Favorable machining conditions and material-dependent parameters for the formation of porous networks on polymer surfaces have thus been identified.

Hopping Diffusion of Nanoparticles in Polymer Matrices

PubMed Central

2016-01-01

We propose a hopping mechanism for diffusion of large nonsticky nanoparticles subjected to topological constraints in both unentangled and entangled polymer solids (networks and gels) and entangled polymer liquids (melts and solutions). Probe particles with size larger than the mesh size ax of unentangled polymer networks or tube diameter ae of entangled polymer liquids are trapped by the network or entanglement cells. At long time scales, however, these particles can diffuse by overcoming free energy barrier between neighboring confinement cells. The terminal particle diffusion coefficient dominated by this hopping diffusion is appreciable for particles with size moderately larger than the network mesh size ax or tube diameter ae. Much larger particles in polymer solids will be permanently trapped by local network cells, whereas they can still move in polymer liquids by waiting for entanglement cells to rearrange on the relaxation time scales of these liquids. Hopping diffusion in entangled polymer liquids and networks has a weaker dependence on particle size than that in unentangled networks as entanglements can slide along chains under polymer deformation. The proposed novel hopping model enables understanding the motion of large nanoparticles in polymeric nanocomposites and the transport of nano drug carriers in complex biological gels such as mucus. PMID:25691803

[THROMBIN-MEDIATED EFFECTS OF BLOOD MICROPARTICLES ON FORMATION, STRUCTURE, AND STABILITY OF FIBRIN CLOTS].

PubMed

Nabiullina, R M; Mustafin, I G; Ataullakhanov, F I; Litvinov, R I; Zubairova, L D

2015-07-01

The effects of blood microparticles (MPs) on the dynamics of fibrin polymerization, clot structure and susceptibility to fibrinolysis were studied. Kinetics of fibrin polymerization, fibrinolysis, thrombin generation in platelet-free, microparticle-depleted and microparticle-depleted plasma replenished with cephalin, from healthy donors were analyzed in parallel. MPs have profound effects on all stages of fibrin formation, decrease its turbidity. All parameters obtained in the absence of MPs were recovered after reconstitution of phospholipids. Thrombin generation rates were reduced in the absence of MPs. In the presence of MPs the fibrin networks had less poro us structures with thinner fibers, while clots formed in the absence of MPs had larger pores and were built of thicker fibers. Clots formed in the presence of MPs were significantly more resistant to fibrinolysis. Results show that normally circulating MPs can support the formation of stable clots at the sites of vascular injury.

Electrostatic-Assisted Liquefaction of Porous Carbons

DOE PAGES

Li, Peipei; Schott, Jennifer A.; Zhang, Jinshui; ...

2017-10-10

Porous liquids are a newly developed porous material that combine unique fluidity with permanent porosity, which exhibit promising functionalities for a variety of applications. However, the apparent incompatibility between fluidity and permanent porosity makes the stabilization of porous nanoparticle with still empty pores in the dense liquid phase a significant challenging. For this study, by exploiting the electrostatic interaction between carbon networks and polymerized ionic liquids, we demonstrate that carbon-based porous nanoarchitectures can be well stabilized in liquids to afford permanent porosity, and thus opens up a new approach to prepare porous carbon liquids. Furthermore, we hope this facile synthesismore » strategy can be widely applicated to fabricate other types of porous liquids, such as those (e.g., carbon nitride, boron nitride, metal–organic frameworks, covalent organic frameworks etc.) also having the electrostatic interaction with polymerized ionic liquids, evidently advancing the development and understanding of porous liquids.« less

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.

Synthesis, structure, and magnetic properties of two 1-D helical coordination polymeric Cu(II) complexes

NASA Astrophysics Data System (ADS)

Bian, He-Dong; Yang, Xiao-E.; Yu, Qing; Chen, Zi-Lu; Liang, Hong; Yan, Shi-Ping; Liao, Dai-Zheng

2008-01-01

Two helical coordination polymeric copper(II) complexes bearing amino acid Schiff bases HL or HL', which are condensed from 2-hydroxy-1-naphthaldehyde with 2-aminobenzoic acid or L-valine, respectively, have been prepared and characterised by X-ray crystallography. In [CuL] n ( 1) the copper(II) atoms are bridged by syn- anti carboxylate groups giving infinite 1-D right-handed helical chains which are further connected by weak C-H⋯Cu interactions to build a 2-D network. While in [CuL'] n ( 2) the carboxylate group acts as a rare monatomic bridge to connect the adjacent copper(II) atoms leading to the formation of a left-handed helical chain. Magnetic susceptibility measurements indicate that 1 exhibits weak ferromagnetic interactions whereas an antiferromagnetic coupling is established for 2. The magnetic behavior can be satisfactorily explained on the basis of the structural data.

Complex Networks

DTIC Science & Technology

2006-11-01

The Internet architecture was designed w/o a “theory” • Many academic theorists said it would never work • Recent “emergent” theories are wildly...architecture was designed w/o a “theory” • Many academic theorists said it would never work • Recent “emergent” theories are wildly wrong (there have...Co-factors Fatty acids Sug ars Nucleotides Amino A cids Catabolism Polymerization and complex assembly Proteins P r e c u r s o r s Autocatalytic

Systematic Investigations of Biomimetic Catalysts in the Synthesis of Reactive Metal Oxide Nanoparticle Networks

DTIC Science & Technology

2012-09-01

dioxide and aluminum oxide. Numerous polymeric templates (Table 1), such as polyallyamine (PAA), were investigated, along with amine- functionalized ...SephadexTM LH60 (an anionic functionalized resin) and SephadexTM G-100 (unfunctionalized) were used as the functionalized surface. The reaction conditions...formed with all of the polymers tested and from some of the functionalized surface. SEM images (Figure 1) show that with the exception of the

One-Pot Enzymatic Production of Lignin-Composites.

PubMed

Ion, Sabina; Opris, Cristina; Cojocaru, Bogdan; Tudorache, Madalina; Zgura, Irina; Galca, Aurelian C; Bodescu, Adina M; Enache, Madalin; Maria, Gabriel-Mihai; Parvulescu, Vasile I

2018-01-01

A novel and efficient one-pot system for green production of artificial lignin bio-composites has been developed. Monolignols such as sinapyl (SA) and coniferyl (CA) alcohols were linked together with caffeic acid (CafAc) affording a polymeric network similar with natural lignin. The interaction of the dissolved SA/CA with CafAc already bound on a solid support (S C2 /S C6 -CafAc) allowed the attachment of the polymeric product direct on the support surface (S C2 /S C6 -CafAc-L 1 and S C2 /S C6 -CafAc-L 2 , from CA and SA, respectively). Accordingly, this procedure offers the advantage of a simultaneous polymer production and deposition. Chemically, oxi-copolymerization of phenolic derivatives (SA/CA and CAfAc) was performed with H 2 O 2 as oxidation reagent using peroxidase enzyme (2-1B mutant of versatile peroxidase from Pleurotus eryngii ) as catalyst. The system performance reached a maximum of conversion for SA and CA of 71.1 and 49.8%, respectively. The conversion is affected by the system polarity as resulted from the addition of a co-solvent (e.g., MeOH, EtOH, or THF). The chemical structure, morphology, and properties of the bio-composites surface were investigated using different techniques, e.g., FTIR, TPD-NH 3 , TGA, contact angle, and SEM. Thus, it was demonstrated that the SA monolignol favored bio-composites with a dense polymeric surface, high acidity, and low hydrophobicity, while CA allowed the production of thinner polymeric layers with high hydrophobicity.

Thiol-Ene functionalized siloxanes for use as elastomeric dental impression materials

PubMed Central

Cole, Megan A.; Jankousky, Katherine C.; Bowman, Christopher N.

2014-01-01

Objectives Thiol- and allyl-functionalized siloxane oligomers are synthesized and evaluated for use as a radical-mediated, rapid set elastomeric dental impression material. Thiol-ene siloxane formulations are crosslinked using a redox-initiated polymerization scheme, and the mechanical properties of the thiol-ene network are manipulated through the incorporation of varying degrees of plasticizer and kaolin filler. Formulations with medium and light body consistencies are further evaluated for their ability to accurately replicate features on both the gross and microscopic levels. We hypothesize that thiol-ene functionalized siloxane systems will exhibit faster setting times and greater detail reproduction than commercially available polyvinylsiloxane (PVS) materials of comparable consistencies. Methods Thiol-ene functionalized siloxane mixtures formulated with varying levels of redox initiators, plasticizer, and kaolin filler are made and evaluated for their polymerization speed (FTIR), consistency (ISO4823.9.2), and surface energy (goniometer). Feature replication is evaluated quantitatively by SEM. The Tg, storage modulus, and creep behavior are determined by DMA. Results Increasing redox initiation rate increases the polymerization rate but at high levels also limits working time. Combining 0.86 wt% oxidizing agent with up to 5 wt% plasticizer gave a working time of 3 min and a setting time of 2 min. The selected medium and light body thiol-ene formulations also achieved greater qualitative detail reproduction than the commercial material and reproduced micrometer patterns with 98% accuracy. Significance Improving detail reproduction and setting speed is a primary focus of dental impression material design and synthesis. Radical-mediated polymerizations, particularly thiol-ene reactions, are recognized for their speed, reduced shrinkage, and ‘click’ nature. PMID:24553250

Fabrication of AlN/BN bishell hollow nanofibers by electrospinning and atomic layer deposition

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

Haider, Ali; Kayaci, Fatma; Uyar, Tamer

2014-09-01

Aluminum nitride (AlN)/boron nitride (BN) bishell hollow nanofibers (HNFs) have been fabricated by successive atomic layer deposition (ALD) of AlN and sequential chemical vapor deposition (CVD) of BN on electrospun polymeric nanofibrous template. A four-step fabrication process was utilized: (i) fabrication of polymeric (nylon 6,6) nanofibers via electrospinning, (ii) hollow cathode plasma-assisted ALD of AlN at 100 °C onto electrospun polymeric nanofibers, (iii) calcination at 500 °C for 2 h in order to remove the polymeric template, and (iv) sequential CVD growth of BN at 450 °C. AlN/BN HNFs have been characterized for their chemical composition, surface morphology, crystal structure, and internal nanostructuremore » using X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and selected area electron diffraction. Measurements confirmed the presence of crystalline hexagonal BN and AlN within the three dimensional (3D) network of bishell HNFs with relatively low impurity content. In contrast to the smooth surface of the inner AlN layer, outer BN coating showed a highly rough 3D morphology in the form of BN nano-needle crystallites. It is shown that the combination of electrospinning and plasma-assisted low-temperature ALD/CVD can produce highly controlled multi-layered bishell nitride ceramic hollow nanostructures. While electrospinning enables easy fabrication of nanofibrous template, self-limiting reactions of plasma-assisted ALD and sequential CVD provide control over the wall thicknesses of AlN and BN layers with sub-nanometer accuracy.« less

Rapid shape memory TEMPO-oxidized cellulose nanofibers/polyacrylamide/gelatin hydrogels with enhanced mechanical strength.

PubMed

Li, Nan; Chen, Wei; Chen, Guangxue; Tian, Junfei

2017-09-01

TEMPO-oxidized cellulose nanofibers/polyacrylamide/gelatin shape memory hydrogels were successfully fabricated through a facile in-situ free-radical polymerization method, and double network was formed by chemically cross-linked polyacrylamide (PAM) network and physically cross-linked gelatin network. TEMPO-oxidized cellulose nanofibers (TOCNs) were introduced to improve the mechanical properties of the hydrogel. The structure, shape memory behaviors and mechanical properties of the resulting composite gels with varied gel compositions were investigated. The results obtained from those different studies revealed that TOCNs, gelatin, and PAM could mix with each other homogeneously. Due to the thermoreversible nature of the gelatin network, the composite hydrogels exhibited attractive thermo-induced shape memory properties. In addition, good mechanical properties (strength >200kPa, strain >650%) were achieved. Such composite hydrogels with good shape memory behavior and enhanced mechanical strength would be an attractive candidate for a wide variety of applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Assembly Kinetics Determine the Architecture of α-actinin Crosslinked F-actin Networks

PubMed Central

Falzone, Tobias T.; Lenz, Martin; Kovar, David R.; Gardel, Margaret L.

2013-01-01

The actin cytoskeleton is organized into diverse meshworks and bundles that support many aspects of cell physiology. Understanding the self-assembly of these actin-based structures is essential for developing predictive models of cytoskeletal organization. Here we show that the competing kinetics of bundle formation with the onset of dynamic arrest arising from filament entanglements and cross-linking determine the architecture of reconstituted actin networks formed with α-actinin cross-links. Cross-link mediated bundle formation only occurs in dilute solutions of highly mobile actin filaments. As actin polymerization proceeds, filament mobility and bundle formation are arrested concomitantly. By controlling the onset of dynamic arrest, perturbations to actin assembly kinetics dramatically alter the architecture of biochemically identical samples. Thus, the morphology of reconstituted F-actin networks is a kinetically determined structure similar to those formed by physical gels and glasses. These results establish mechanisms controlling the structure and mechanics in diverse semi-flexible biopolymer networks. PMID:22643888

A biochemical network can control formation of a synthetic material by sensing numerous specific stimuli

NASA Astrophysics Data System (ADS)

Hun Yeon, Ju; Chan, Karen Y. T.; Wong, Ting-Chia; Chan, Kelvin; Sutherland, Michael R.; Ismagilov, Rustem F.; Pryzdial, Edward L. G.; Kastrup, Christian J.

2015-05-01

Developing bio-compatible smart materials that assemble in response to environmental cues requires strategies that can discriminate multiple specific stimuli in a complex milieu. Synthetic materials have yet to achieve this level of sensitivity, which would emulate the highly evolved and tailored reaction networks of complex biological systems. Here we show that the output of a naturally occurring network can be replaced with a synthetic material. Exploiting the blood coagulation system as an exquisite biological sensor, the fibrin clot end-product was replaced with a synthetic material under the biological control of a precisely regulated cross-linking enzyme. The functions of the coagulation network remained intact when the material was incorporated. Clot-like polymerization was induced in indirect response to distinct small molecules, phospholipids, enzymes, cells, viruses, an inorganic solid, a polyphenol, a polysaccharide, and a membrane protein. This strategy demonstrates for the first time that an existing stimulus-responsive biological network can be used to control the formation of a synthetic material by diverse classes of physiological triggers.

Early pre-Hispanic use of indigo blue in Peru.

PubMed

Splitstoser, Jeffrey C; Dillehay, Tom D; Wouters, Jan; Claro, Ana

2016-09-01

Archaeological research has identified the use of cultivated cotton (Gossypium barbadense) in the ancient Andes dating back to at least 7800 years ago. Because of unusual circumstances of preservation, 6000-year-old cotton fabrics from the Preceramic site of Huaca Prieta on the north coast of Peru retained traces of a blue pigment that was analyzed and positively identified as an indigoid dye (indigotin), making it the earliest known use of indigo in the world, derived most likely from Indigofera spp. native to South America. This predates by ~1500 years the earliest reported use of indigo in the Old World, from Fifth Dynasty Egypt [ca. 4400 BP (before present)]. Indigo is one of the most valued and most globally widespread dyes of antiquity and of the present era (it being the blue of blue jeans).

Ceramic Foams for TPS Applications

NASA Technical Reports Server (NTRS)

Stockpoole, Mairead

2003-01-01

Ceramic foams have potential in many areas of Thermal Protection Systems (TPS) including acreage and tile leading edges as well as being suitable as a repair approach for re-entry vehicles. NASA Ames is conducting ongoing research in developing lower-density foams from pre-ceramic polymer routes. One of the key factors to investigate, when developing new materials for re-entry applications, is their oxidation behavior in the appropriate re-entry environment which can be simulated using ground based arc jet (plasma jet) testing. Arc jet testing is required to provide the appropriate conditions (stagnation pressures, heat fluxes, enthalpies, heat loads and atmospheres) encountered during flight. This work looks at the response of ceramic foams (Si systems) exposed to simulated reentry environments and investigates the influence of microstructure and composition on the material? response. Other foam properties (mechanical and thermal) will also be presented.

Early pre-Hispanic use of indigo blue in Peru

PubMed Central

Splitstoser, Jeffrey C.; Dillehay, Tom D.; Wouters, Jan; Claro, Ana

2016-01-01

Archaeological research has identified the use of cultivated cotton (Gossypium barbadense) in the ancient Andes dating back to at least 7800 years ago. Because of unusual circumstances of preservation, 6000-year-old cotton fabrics from the Preceramic site of Huaca Prieta on the north coast of Peru retained traces of a blue pigment that was analyzed and positively identified as an indigoid dye (indigotin), making it the earliest known use of indigo in the world, derived most likely from Indigofera spp. native to South America. This predates by ~1500 years the earliest reported use of indigo in the Old World, from Fifth Dynasty Egypt [ca. 4400 BP (before present)]. Indigo is one of the most valued and most globally widespread dyes of antiquity and of the present era (it being the blue of blue jeans). PMID:27652337

Overview of ARPA low-cost ceramic composites (LC{sup 3}) program

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

Adler, P.N.

1996-12-31

Grumman is currently leading an approximate $10M ARPA cost-shared program aimed at developing low-cost fabrication methodology for manufacturing ceramic matrix composite (CMC) structural components. One of the program goals is to demonstrate the effectiveness of an advanced materials partnership. A vertically integrated collaboration now exists that combines the talents of three large private sector organizations, two smaller private sector organizations, three universities, and three federal government laboratories. Work in progress involves preceramic polymer (Blackglas{trademark}) CMC materials technology, RTM and pyrolysis process modeling & simulation, and utilization of low-cost approaches for fabricating a CMC demonstration engine seal component. This paper reviewsmore » the program organization, functioning, and some of the highlights of the technical work, which is of interest to the DoD as well as the commercial sector.« less

Mechanical Detection of a Long-Range Actin Network Emanating from a Biomimetic Cortex

PubMed Central

Bussonnier, Matthias; Carvalho, Kevin; Lemière, Joël; Joanny, Jean-François; Sykes, Cécile; Betz, Timo

2014-01-01

Actin is ubiquitous globular protein that polymerizes into filaments and forms networks that participate in the force generation of eukaryotic cells. Such forces are used for cell motility, cytokinesis, and tissue remodeling. Among those actin networks, we focus on the actin cortex, a dense branched network beneath the plasma membrane that is of particular importance for the mechanical properties of the cell. Here we reproduce the cellular cortex by activating actin filament growth on a solid surface. We unveil the existence of a sparse actin network that emanates from the surface and extends over a distance that is at least 10 times larger than the cortex itself. We call this sparse actin network the “actin cloud” and characterize its mechanical properties with optical tweezers. We show, both experimentally and theoretically, that the actin cloud is mechanically relevant and that it should be taken into account because it can sustain forces as high as several picoNewtons (pN). In particular, it is known that in plant cells, actin networks similar to the actin cloud have a role in positioning the nucleus; in large oocytes, they play a role in driving chromosome movement. Recent evidence shows that such networks even prevent granule condensation in large cells. PMID:25140420

Relationship between Eu{sup 3+} reduction and glass polymeric structure in Al{sub 2}O{sub 3}-modified borate glasses under air atmosphere

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

Jiao, Qing; Yu, Xue; Xu, Xuhui

2013-06-15

The reduction of Eu{sup 3+} to Eu{sup 2+} is realized efficiently in Eu{sub 2}O{sub 3}-doped borate glasses prepared under air condition by melting-quenching method. Luminescent spectra show an increasing tendency of Eu{sup 2+} emission with increasing Al{sub 2}O{sub 3} concentration in B{sub 2}O{sub 3}–Na{sub 2}O glasses. It is interesting that significant enhancement appeared of Eu{sup 2+} luminescence in the Al{sub 2}O{sub 3}-rich sample comparing to the samples of Al{sub 2}O{sub 3} less than 6 mol%. FTIR and Raman scattering measurements indicated that some new vibration modes assigned to the low-polymerized structure groups decomposed from the slight Al{sub 2}O{sub 3} dopantmore » samples. These results demonstrated that the polymerization of the glass structure decreased with increasing incorporation of Al{sub 2}O{sub 3} into the borate glasses, linking to the efficiency of Eu{sup 3+} self-reduction in air at high temperature. - graphical abstract: A novel europium valence reduction phenomenon occurred in Al{sub 2}O{sub 3} modified borate glasses, FTIR and Raman measurements revealed that high polymeric groups were destroyed to low polymery structures with Al{sub 2}O{sub 3} addition. - Highlights: • The efficient reduction of Eu{sup 3+} to Eu{sup 2+} is observed in the B{sub 2}O{sub 3}–Na{sub 2}O glasses. • Eu{sup 2+} luminescence is significant enhanced in the Al{sub 2}O{sub 3}-rich glasses. • The introduction of Al{sub 2}O{sub 3} changed the network structure of the borate glasses. • High polymeric borate groups in the glass matrix may be destroyed to the lower ones.« less

Evolutionary Importance of the Intramolecular Pathways of Hydrolysis of Phosphate Ester Mixed Anhydrides with Amino Acids and Peptides

NASA Astrophysics Data System (ADS)

Liu, Ziwei; Beaufils, Damien; Rossi, Jean-Christophe; Pascal, Robert

2014-12-01

Aminoacyl adenylates (aa-AMPs) constitute essential intermediates of protein biosynthesis. Their polymerization in aqueous solution has often been claimed as a potential route to abiotic peptides in spite of a highly efficient CO2-promoted pathway of hydrolysis. Here we investigate the efficiency and relevance of this frequently overlooked pathway from model amino acid phosphate mixed anhydrides including aa-AMPs. Its predominance was demonstrated at CO2 concentrations matching that of physiological fluids or that of the present-day ocean, making a direct polymerization pathway unlikely. By contrast, the occurrence of the CO2-promoted pathway was observed to increase the efficiency of peptide bond formation owing to the high reactivity of the N-carboxyanhydride (NCA) intermediate. Even considering CO2 concentrations in early Earth liquid environments equivalent to present levels, mixed anhydrides would have polymerized predominantly through NCAs. The issue of a potential involvement of NCAs as biochemical metabolites could even be raised. The formation of peptide-phosphate mixed anhydrides from 5(4H)-oxazolones (transiently formed through prebiotically relevant peptide activation pathways) was also observed as well as the occurrence of the reverse cyclization process in the reactions of these mixed anhydrides. These processes constitute the core of a reaction network that could potentially have evolved towards the emergence of translation.

Influence of residual composition on the structure and properties of extracellular matrix derived hydrogels.

PubMed

Claudio-Rizo, Jesús A; Rangel-Argote, Magdalena; Castellano, Laura E; Delgado, Jorge; Mata-Mata, José L; Mendoza-Novelo, Birzabith

2017-10-01

In this work, hydrolysates of extracellular matrix (hECM) were obtained from rat tail tendon (TR), bovine Achilles tendon (TAB), porcine small intestinal submucosa (SIS) and bovine pericardium (PB), and they were polymerized to generate ECM hydrogels. The composition of hECM was evaluated by quantifying the content of sulphated glycosaminoglycans (sGAG), fibronectin and laminin. The polymerization process, structure, physicochemical properties, in vitro degradation and biocompatibility were studied and related to their composition. The results indicated that the hECM derived from SIS and PB were significantly richer in sGAG, fibronectin and laminin, than those derived from TAB and TR. These differences in hECM composition influenced the polymerization and the structural characteristics of the fibrillar gel network. Consequently, the swelling, mechanics and degradation of the hydrogels showed a direct relationship with the remaining composition. Moreover, the cytocompatibility and the secretion of transforming growth factor beta-1 (TGF-β1) by macrophages were enhanced in hydrogels with the highest residual content of ECM biomolecules. The results of this work evidenced the role of the ECM molecules remaining after both decellularization and hydrolysis steps to produce tissue derived hydrogels with structure and properties tailored to enhance their performance in tissue engineering and regenerative medicine applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Influence of CuO and ZnO addition on the multicomponent phosphate glasses: Spectroscopic studies

NASA Astrophysics Data System (ADS)

Szumera, Magdalena; Wacławska, Irena; Sułowska, Justyna

2016-06-01

The spectra of phosphate-silicate glasses from the P2O5-SiO2-K2O-MgO-CaO system modified with the addition of CuO or ZnO have been studied by means of FTIR, Raman and 31P MAS NMR spectroscopy. All glasses were synthesized by the conventional melt-quenching technique and their homogeneous chemical composition was controlled and confirmed. By using the aforementioned research techniques, the presence of structural units with various degrees of polymerization was shown in the structure of analyzed phosphate-silicate glasses: Q3, Q2, Q1 and Q0. It was found that an increase in the content of CuO or ZnO in the composition of analyzed glasses, which are introduced at the expense of decreasing amounts of CaO and MgO, has a different influence on the phospho-oxygen network. It was shown that copper ions cause its gradual polymerization, while zinc ions cause its depolymerization. At the same time, polymerization of the silico-oxygen subnetwork was found. Additionally, in the case of glasses containing increasing amounts of ZnO, a change of the role of zinc ions in the vitreous matrix was confirmed (from the modifier to a structure-forming component).

Nonequilibrium stabilization of an RNA/protein droplet emulsion by nuclear actin

NASA Astrophysics Data System (ADS)

Brangwynne, Clifford

2013-03-01

Actin plays a structural role in the cytoplasm. However, actin takes on new functions and structures in the nucleus that are poorly understood. The nuclei of the large oocytes of the frog X. laevisspecifically accumulate actin to reach high concentrations; however, it remains unclear if this actin polymerizes into a network, and what, if any, structural role such an actin network might play. Here, we use microrheological and confocal imaging techniques to probe the local architecture and mechanics of the nucleus. Our data show that actin forms a weak network that spatially organizes the nucleus by kinetically stabilizing embedded liquid-like RNA/protein bodies which are important for cell growth. In actin-disrupted nuclei this RNA/protein droplet emulsion is destabilized leading to homotypic coalescence into single large droplets. Our data provide intriguing new insights into why large cell nuclei require an actin-based structural scaffold.

Self-Healing Nanocomposite Hydrogel with Well-Controlled Dynamic Mechanics

NASA Astrophysics Data System (ADS)

Li, Qiaochu; Mishra, Sumeet; Chen, Pangkuan; Tracy, Joseph; Holten-Andersen, Niels

Network dynamics is a crucial factor that determines the macroscopic self-healing rate and efficiency in polymeric hydrogel materials, yet its controllability is seldom studied in most reported self-healing hydrogel systems. Inspired by mussel's adhesion chemistry, we developed a novel approach to assemble inorganic nanoparticles and catechol-decorated PEG polymer into a hydrogel network. When utilized as reversible polymer-particle crosslinks, catechol-metal coordination bonds yield a unique gel network with dynamic mechanics controlled directly by interfacial crosslink structure. Taking advantage of this structure-property relationship at polymer-particle interfaces, we next designed a hierarchically structured hybrid gel with two distinct relaxation timescales. By tuning the relative contribution of the two hierarchical relaxation modes, we are able to finely control the gel's dynamic mechanical behavior from a viscoelastic fluid to a stiff solid, yet preserving its fast self-healing property without the need for external stimuli.

Effects of Hofmeister salt series on gluten network formation: Part II. Anion series.

PubMed

Tuhumury, H C D; Small, D M; Day, L

2016-12-01

Different anion salts from the Hofmeister series were used to investigate their effects on gluten network formation. The effects of these anion salts on the mixing properties of the dough and the rheological and chemical properties of gluten samples extracted from the dough with these respective salts were compared. The aim of this work was to determine how different anion salts influence the formation of the gluten structure during dough mixing. It was found that the Hofmeister anion salts affected the gluten network formation by interacting directly with specific amino acid residues that resulted in changes in gluten protein composition, specifically the percentage of the unextractable polymeric protein fractions (%UPP). These changes consequently led to remarkable differences in the mixing profiles and microstructural features of the dough, small deformation rheological properties of the gluten and a strain hardening behaviour of both dough and gluten samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Unconventional Tough Double-Network Hydrogels with Rapid Mechanical Recovery, Self-Healing, and Self-Gluing Properties.

PubMed

Jia, Haiyan; Huang, Zhangjun; Fei, Zhaofu; Dyson, Paul J; Zheng, Zhen; Wang, Xinling

2016-11-16

Hydrogels are polymeric materials that have a relatively high capacity for holding water. Recently, a double network (DN) technique was developed to fabricate hydrogels with a toughness comparable to rubber. The mechanical properties of DN hydrogels may be attributed to the brittle sacrificial bonding network of one hydrogel, facilitating stress dispersion, combined with ductile polymer chains of a second hydrogel. Herein, we report a novel class of tunable DN hydrogels composed of a polyurethane hydrogel and a stronger, dipole-dipole and H-bonding interaction reinforced (DHIR) hydrogel. Compared to conventional DN hydrogels, these materials show remarkable improvements in mechanical recovery, modulus, and yielding, with excellent self-healing and self-gluing properties. In addition, the new DN hydrogels exhibit excellent tensile and compression strengths and possess shape-memory properties, which make them promising for applications in engineering, biomedicine, and other domains where load bearing is required.

Influence of Chirality in Ordered Block Copolymer Phases

NASA Astrophysics Data System (ADS)

Prasad, Ishan; Grason, Gregory

2015-03-01

Block copolymers are known to assemble into rich spectrum of ordered phases, with many complex phases driven by asymmetry in copolymer architecture. Despite decades of study, the influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has played a major role in prediction of physical properties of polymeric systems. Only recently, a polar orientational self-consistent field (oSCF) approach was adopted to model chiral BCP having a thermodynamic preference for cholesteric ordering in chiral segments. We implement oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar chiral interactions, and focus our study on the thermodynamic stability of bi-continuous network morphologies, and the transfer of molecular chirality to mesoscale chirality of networks. Unique photonic properties observed in butterfly wings have been attributed to presence of chiral single-gyroid networks, this has made it an attractive target for chiral metamaterial design.

Folic acid conjugated cross-linked acrylic polymer (FA-CLAP) hydrogel for site specific delivery of hydrophobic drugs to cancer cells.

PubMed

Pillai, Jisha Jayadevan; Thulasidasan, Arun Kumar Theralikattu; Anto, Ruby John; Chithralekha, Devika Nandan; Narayanan, Ashwanikumar; Kumar, Gopalakrishnapillai Sankaramangalam Vinod

2014-07-15

The hydrogel based system is found to be rarely reported for the delivery of hydrophobic drug due to the incompatibility of hydrophilicity of the polymer network and the hydrophobicity of drug. This problem can be solved by preparing semi-interpenetrating network of cross-linked polymer for tuning the hydrophilicity so as to entrap the hydrophobic drugs. The current study is to develop a folic acid conjugated cross-linked pH sensitive, biocompatible polymeric hydrogel to achieve a site specific drug delivery. For that, we have synthesized a folic acid conjugated PEG cross-linked acrylic polymer (FA-CLAP) hydrogel and investigated its loading and release of curcumin. The formed polymer hydrogel was then conjugated with folic acid for the site specific delivery of curcumin to cancer cells and then further characterized and conducted the cell uptake and cytotoxicity studies on human cervical cancer cell lines (HeLa). In this study, we synthesized folic acid conjugated cross-linked acrylic hydrogel for the delivery of hydrophobic drugs to the cancer site. Poly (ethyleneglycol) (PEG) diacrylate cross-linked acrylic polymer (PAA) was prepared via inverse emulsion polymerization technique and later conjugated it with folic acid (FA-CLAP). Hydrophobic drug curcumin is entrapped into it and investigated the entrapment efficiency. Characterization of synthesized hydogel was done by using Fourier Transform-Infrared spectroscopy (FT-IR), Transmission Electron Microscopy (TEM), Differential Scanning Calorimetry (DSC). Polymerization and folate conjugation was confirmed by FT-IR spectroscopy. The release kinetics of drug from the entrapped form was studied which showed initial burst release followed by sustained release due to swelling and increased cross-linking. In vitro cytotoxicity and cell uptake studies were conducted in human cervical cancer (HeLa) cell lines. Results showed that curcumin entrapped folate conjugated cross-linked acrylic polymer (FA-CLAP) hydrogel showed higher cellular uptake than the non folate conjugated form. So this can be suggested as a better delivery system for site specific release of hydrophobic cancer drugs.

Myocardial matrix-polyethylene glycol hybrid hydrogels for tissue engineering

NASA Astrophysics Data System (ADS)

Grover, Gregory N.; Rao, Nikhil; Christman, Karen L.

2014-01-01

Similar to other protein-based hydrogels, extracellular matrix (ECM) based hydrogels, derived from decellularized tissues, have a narrow range of mechanical properties and are rapidly degraded. These hydrogels contain natural cellular adhesion sites, form nanofibrous networks similar to native ECM, and are biodegradable. In this study, we expand the properties of these types of materials by incorporating poly(ethylene glycol) (PEG) into the ECM network. We use decellularized myocardial matrix as an example of a tissue specific ECM derived hydrogel. Myocardial matrix-PEG hybrids were synthesized by two different methods, cross-linking the proteins with an amine-reactive PEG-star and photo-induced radical polymerization of two different multi-armed PEG-acrylates. We show that both methods allow for conjugation of PEG to the myocardial matrix by gel electrophoresis and infrared spectroscopy. Scanning electron microscopy demonstrated that the hybrid materials still contain a nanofibrous network similar to unmodified myocardial matrix and that the fiber diameter is changed by the method of PEG incorporation and PEG molecular weight. PEG conjugation also decreased the rate of enzymatic degradation in vitro, and increased material stiffness. Hybrids synthesized with amine-reactive PEG had gelation rates of 30 min, similar to the unmodified myocardial matrix, and incorporation of PEG did not prevent cell adhesion and migration through the hydrogels, thus offering the possibility to have an injectable ECM hydrogel that degrades more slowly in vivo. The photo-polymerized radical systems gelled in 4 min upon irradiation, allowing 3D encapsulation and culture of cells, unlike the soft unmodified myocardial matrix. This work demonstrates that PEG incorporation into ECM-based hydrogels can expand material properties, thereby opening up new possibilities for in vitro and in vivo applications.

Conductive Polymeric Binder for Lithium-Ion Battery Anode

NASA Astrophysics Data System (ADS)

Gao, Tianxiang

Tin (Sn) has a high-specific capacity (993 mAhg-1) as an anode material for Li-ion batteries. To overcome the poor cycling performance issue caused by its large volume expansion and pulverization during the charging and discharging process, many researchers put efforts into it. Most of the strategies are through nanostructured material design and introducing conductive polymer binders that serve as matrix of the active material in anode. This thesis aims for developing a novel method for preparing the anode to improve the capacity retention rate. This would require the anode to have high electrical conductivity, high ionic conductivity, and good mechanical properties, especially elasticity. Here the incorporation of a conducting polymer and a conductive hydrogel in Sn-based anodes using a one-step electrochemical deposition via a 3-electrode cell method is reported: the Sn particles and conductive component can be electrochemically synthesized and simultaneously deposited into a hybrid thin film onto the working electrode directly forming the anode. A well-defined three dimensional network structure consisting of Sn nanoparticles coated by conducting polymers is achieved. Such a conductive polymer-hydrogel network has multiple advantageous features: meshporous polymeric structure can offer the pathway for lithium ion transfer between the anode and electrolyte; the continuous electrically conductive polypyrrole network, with the electrostatic interaction with elastic, porous hydrogel, poly (2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylonitrile) (PAMPS) as both the crosslinker and doping anion for polypyrrole (PPy) can decrease the volume expansion by creating porous scaffold and softening the system itself. Furthermore, by increasing the amount of PAMPS and creating an interval can improve the cycling performance, resulting in improved capacity retention about 80% after 20 cycles, compared with only 54% of that of the control sample without PAMPS. The cycle is performed under current of 0.1 C.

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

NASA Astrophysics Data System (ADS)

Lin, Tao

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

The elastic properties of woven polymeric fabric

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

Warren, W.E.

1989-01-01

The in-plane linear elastic constants of woven fabric are determined in terms of the specific fabric microstructure. The fabric is assumed to be a spatially periodic interlaced network of orthogonal yarns and the individual yarns are modeled as extensible elastica. These results indicate that a significant coupling of bending and stretching effects occurs during deformation. Results of this theoretical analysis compare favorable with measured in-plane elastic constants for Vincel yarn fabrics. 17 refs., 2 figs., 1 tab.

On the origins of the universal dynamics of endogenous granules in mammalian cells.

PubMed

Vanapalli, Siva A; Li, Yixuan; Mugele, Frieder; Duits, Michel H G

2009-12-01

Endogenous granules (EGs) that consist of lipid droplets and mitochondria have been commonly used to assess intracellular mechanical properties via multiple particle tracking microrheology (MPTM). Despite their widespread use, the nature of interaction of EGs with the cytoskeletal network and the type of forces driving their dynamics--both of which are crucial for the interpretation of the results from MPTM technique--are yet to be resolved. In this report, we study the dynamics of endogenous granules in mammalian cells using particle tracking methods. We find that the ensemble dynamics of EGs is diffusive in three types of mammalian cells (endothelial cells, smooth muscle cells and fibroblasts), thereby suggesting an apparent universality in their dynamical behavior. Moreover, in a given cell, the amplitude of the mean-squared displacement for EGs is an order of magnitude larger than that of injected particles. This observation along with results from ATP depletion and temperature intervention studies suggests that cytoskeletal active forces drive the dynamics of EGs. To elucidate the dynamical origin of the diffusive-like nonthermal motion, we consider three active force generation mechanisms--molecular motor transport, actomyosin contractility and microtubule polymerization forces. We test these mechanisms using pharmacological interventions. Experimental evidence and model calculations suggest that EGs are intimately linked to microtubules and that microtubule polymerization forces drive their dynamics. Thus, endogenous granules could serve as non-invasive probes for microtubule network dynamics in mammalian cells.

A novel technique using potassium permanganate and reflectance confocal microscopy to image biofilm extracellular polymeric matrix reveals non-eDNA networks in Pseudomonas aeruginosa biofilms

PubMed Central

Swearingen, Matthew C.; Mehta, Ajeet; Mehta, Amar; Nistico, Laura; Hill, Preston J.; Falzarano, Anthony R.; Wozniak, Daniel J.; Hall-Stoodley, Luanne; Stoodley, Paul

2015-01-01

Biofilms are etiologically important in the development of chronic medical and dental infections. The biofilm extracellular polymeric substance (EPS) determines biofilm structure and allows bacteria in biofilms to adapt to changes in mechanical loads such as fluid shear. However, EPS components are difficult to visualize microscopically because of their low density and molecular complexity. Here, we tested potassium permanganate, KMnO4, for use as a non-specific EPS contrast-enhancing stain using confocal laser scanning microscopy in reflectance mode. We demonstrate that KMnO4 reacted with EPS components of various strains of Pseudomonas, Staphylococcus and Streptococcus, yielding brown MnO2 precipitate deposition on the EPS, which was quantifiable using data from the laser reflection detector. Furthermore, the MnO2 signal could be quantified in combination with fluorescent nucleic acid staining. COMSTAT image analysis indicated that KMnO4 staining increased the estimated biovolume over that determined by nucleic acid staining alone for all strains tested, and revealed non-eDNA EPS networks in Pseudomonas aeruginosa biofilm. In vitro and in vivo testing indicated that KMnO4 reacted with poly-N-acetylglucosamine and Pseudomonas Pel polysaccharide, but did not react strongly with DNA or alginate. KMnO4 staining may have application as a research tool and for diagnostic potential for biofilms in clinical samples. PMID:26536894

Iron-oxide minerals affect extracellular electron-transfer paths of Geobacter spp.

PubMed

Kato, Souichiro; Hashimoto, Kazuhito; Watanabe, Kazuya

2013-01-01

Some bacteria utilize (semi)conductive iron-oxide minerals as conduits for extracellular electron transfer (EET) to distant, insoluble electron acceptors. A previous study demonstrated that microbe/mineral conductive networks are constructed in soil ecosystems, in which Geobacter spp. share dominant populations. In order to examine how (semi)conductive iron-oxide minerals affect EET paths of Geobacter spp., the present study grew five representative Geobacter strains on electrodes as the sole electron acceptors in the absence or presence of (semi)conductive iron oxides. It was found that iron-oxide minerals enhanced current generation by three Geobacter strains, while no effect was observed in another strain. Geobacter sulfurreducens was the only strain that generated substantial amounts of currents both in the presence and absence of the iron oxides. Microscopic, electrochemical and transcriptomic analyses of G. sulfurreducens disclosed that this strain constructed two distinct types of EET path; in the absence of iron-oxide minerals, bacterial biofilms rich in extracellular polymeric substances were constructed, while composite networks made of mineral particles and microbial cells (without polymeric substances) were developed in the presence of iron oxides. It was also found that uncharacterized c-type cytochromes were up-regulated in the presence of iron oxides that were different from those found in conductive biofilms. These results suggest the possibility that natural (semi)conductive minerals confer energetic and ecological advantages on Geobacter, facilitating their growth and survival in the natural environment.

Can nature's design be improved upon? High strength, transparent nacre-like nanocomposites with double network of sacrificial cross links.

PubMed

Podsiadlo, Paul; Kaushik, Amit K; Shim, Bong Sup; Agarwal, Ashish; Tang, Zhiyong; Waas, Anthony M; Arruda, Ellen M; Kotov, Nicholas A

2008-11-20

The preparation of a high-strength and highly transparent nacre-like nanocomposite via layer-by-layer assembly technique from poly(vinyl alcohol) (PVA) and Na+-montmorillonite clay nanosheets is reported in this article. We show that a high density of weak bonding interactions between the polymer and the clay particles: hydrogen, dipole-induced dipole, and van der Waals undergoing break-reform deformations, can lead to high strength nanocomposites: sigmaUTS approximately 150 MPa and E' approximately 13 GPa. Further introduction of ionic bonds into the polymeric matrix creates a double network of sacrificial bonds which dramatically increases the mechanical properties: sigmaUTS approximately 320 MPa and E' approximately 60 GPa.

Catalysis by Metallic Nanoparticles in Solution: Thermosensitive Microgels as Nanoreactors

NASA Astrophysics Data System (ADS)

Roa, Rafael; Angioletti-Uberti, Stefano; Lu, Yan; Dzubiella, Joachim; Piazza, Francesco; Ballauff, Matthias

2018-05-01

Metallic nanoparticles have been used as catalysts for various reactions, and the huge literature on the subject is hard to overlook. In many applications, the nanoparticles must be affixed to a colloidal carrier for easy handling during catalysis. These "passive carriers" (e.g. dendrimers) serve for a controlled synthesis of the nanoparticles and prevent coagulation during catalysis. Recently, hybrids from nanoparticles and polymers have been developed that allow us to change the catalytic activity of the nanoparticles by external triggers. In particular, single nanoparticles embedded in a thermosensitive network made from poly(N-isopropylacrylamide) (PNIPAM) have become the most-studied examples of such hybrids: immersed in cold water, the PNIPAM network is hydrophilic and fully swollen. In this state, hydrophilic substrates can diffuse easily through the network, and react at the surface of the nanoparticles. Above the volume transition located at 32°C, the network becomes hydrophobic and shrinks. Now hydrophobic substrates will preferably diffuse through the network and react with other substrates in the reaction catalyzed by the enclosed nanoparticle. Such "active carriers", may thus be viewed as true nanoreactors that open new ways for the use of nanoparticles in catalysis. In this review, we give a survey on recent work done on these hybrids and their application in catalysis. The aim of this review is threefold: we first review hybrid systems composed of nanoparticles and thermosensitive networks and compare these "active carriers" to other colloidal and polymeric carriers (e.g. dendrimers). In a second step we discuss the model reactions used to obtain precise kinetic data on the catalytic activity of nanoparticles in various carriers and environments. These kinetic data allow us to present a fully quantitative comparison of different nanoreactors. In a final section we shall present the salient points of recent efforts in the theoretical modeling of these nanoreactors. By accounting for the presence of a free-energy landscape for the reactants' diffusive approach towards the catalytic nanoparticle, arising from solvent-reactant and polymeric shell-reactant interactions, these models are capable of explaining the emergence of all the important features observed so far in studies of nanoreactors. The present survey also suggests that such models may be used for the design of future carrier systems adapted to a given reaction and solvent.

Cyclization Phenomena in the Sol-Gel Polymerization of a,w-Bis(triethoxysilyl)alkanes and Incorporation of the Cyclic Structures into Network Silsesquioxane Polymers

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

Alam, T.M.; Carpenter, J.P.; Dorhout, P.K.

1999-01-04

Intramolecular cyclizations during acid-catalyzed, sol-gel polymerizations of ct,co- bis(tietioxysilyl)aWmes substintidly lengtien gelties formonomers witietiylene- (l), propylene- (2), and butylene-(3)-bridging groups. These cyclizations reactions were found, using mass spectrometry and %i NMR spectroscopy, to lead preferentially to monomeric and dimeric products based on six and seven membered disilsesquioxane rings. 1,2- Bis(triethoxysilyl)ethane (1) reacts under acidic conditions to give a bicyclic drier (5) that is composed of two annelated seven membered rings. Under the same conditions, 1,3- bis(triethoxysilyl)propane (2), 1,4-bis(triethoxysilyl)butane (3), and z-1,4- bis(triethoxysilyl)but-2-ene (10) undergo an intramolecular condensation reaction to give the six membemd and seven membered cyclic disilsesquioxanes 6, 7,more » and 11. Subsequently, these cyclic monomers slowly react to form the tricyclic dirners 8,9 and 12. With NaOH as polymerization catalyst these cyclic silsesquioxanes readily ~aeted to afford gels that were shown by CP MAS z%i NMR and infr=d spectroscopes to retain some cyclic structures. Comparison of the porosity and microstructwe of xerogels prepared from the cyclic monomers 6 and 7 with gels prepared directly from their acyclic precursors 2 and 3, indicate that the final pore structure of the xerogels is markedly dependent on the nature of the precursor. In addition, despite the fact that the monomeric cyclic disilsesquioxane species can not be isolated from 1-3 under basic conditions due to their rapid rate of gelation, spectroscopic techniques also detected the presence of the cyclic structures in the resulting polymeric gels.« less

Carbon nanotube-ceramic nanocomposites: Synthesis and characterization

NASA Astrophysics Data System (ADS)

Clark, Michael David

Ceramic materials are widely used in modern society for a variety of applications including fuel cell electrolytes, bio-medical implants, and jet turbines. However, ceramics are inherently brittle making them excellent candidates for mechanical reinforcement. In this work, the feasibility of dispersing multi-walled carbon nanotubes into a silicon carbide matrix for mechanical property enhancement is explored. Prior to dispersing, nanotubes were purified using an optimized, three step methodology that incorporates oxidative treatment, acid sonication, and thermal annealing rendering near-superhydrophobic behavior in synthesized thin films. Alkyl functionalized nanotube dispersability was characterized in various solvents. Dispersability was contingent on fostering polar interactions between the functionalized nanotubes and solvent despite the purely dispersive nature of the aliphatic chains. Interpretation of these results yielded values of 45.6 +/- 1.2, 0.78 +/- 0.04, and 2 4 +/- 0.9 mJ/m2 for the Lifshitz-van der Waals, electron acceptor and electron donor surface energy components respectively. Aqueous nanotube dispersions were prepared using a number of surfactants to examine surfactant concentration and pH effects on nanotube dispersability. Increasing surfactant concentrations resulted in a solubility plateau, which was independent of the surfactant's critical micelle concentration. Deviations from neutral pH demonstrated negligible influence on non-ionic surfactant adsorption while, ionic surfactants showed substantial pH dependent behavior. These results were explained in the context of nanotube surface ionization and Debye length variation. Successful MWNT dispersion into a silicon carbide based matrix is reported by in-situ ceramic formation using two routes; sol-gel chemistry and pre-ceramic polymeric precursor workup. For the former, nanotube dispersion was assisted by PluronicRTM surfactants. Pyrolytic treatment and consolidation of formed powders yielded ceramic silicon oxycarbide glasses (SiO1.1 C0.6) attributed to incomplete carbothermal reduction. Microhardness and dynamic moduli measurements were consistent with silicon oxycarbide glasses and unaffected by nanotube loading up to 0.11 wt. %. Pyrolysis and densification of poly(methylsilyne) yielded a high density ceramic material (2.45-2.63 g/cm 3). Nanotube introduction was achieved using two separate alkylation techniques; alkyllithium replacement and organic peroxide workup. Bulk mechanical testing was deemed unreliable as powder consolidation introduced chemical inhomogeneity with pellet edges being largely composed of polycrystalline silicon and silicon carbide, while the center contained substantial oxygen contamination.

SiCO-doped carbon fibers with unique dual superhydrophilicity/superoleophilicity and ductile and capacitance properties.

PubMed

Lu, Ping; Huang, Qing; Mukherjee, Amiya; Hsieh, You-Lo

2010-12-01

Silicon oxycarbide (SiCO) glass-doped carbon fibers with an average diameter of 163 nm were successfully synthesized by electrospinning polymer mixtures of preceramic precursor polyureasilazane (PUS) and carbon precursor polyacrylonitrile (PAN) into fibers then converting to ceramic/carbon hybrid via cross-linking, stabilization, and pyrolysis at temperatures up to 1000 °C. The transformation of PUS/PAN polymer precursors to SiCO/carbon structures was confirmed by EDS and FTIR. Both carbon and SiCO/carbon fibers were amorphous and slightly oxidized. Doping with SiCO enhanced the thermal stability of carbon fibers and acquired new ductile behavior in the SiCO/carbon fibers with significantly improved flexibility and breaking elongation. Furthermore, the SiCO/carbon fibers exhibited dual superhydrophilicity and superoleophilicity with water and decane absorbing capacities of 873 and 608%, respectively. The cyclic voltammetry also showed that SiCO/carbon composite fibers possess better capacitor properties than carbon fibers.

Low temperature joining of ceramic composites

DOEpatents

Barton, Thomas J.; Anderson, Iver E.; Ijadi-Maghsoodi, Sina; Nosrati, Mohammad; Unal, Ozer

1999-01-12

A method of joining similar or dissimilar ceramic and ceramic composite materials, such as SiC continuous fiber ceramic composites, at relatively low joining temperatures uses a solventless, three component bonding agent effective to promote mechanical bond toughness and elevated temperature strength to operating temperatures of approximately 1200 degrees C. The bonding agent comprises a preceramic precursor, an aluminum bearing powder, such as aluminum alloy powder, and mixtures of aluminum metal or alloy powders with another powder, and and boron powder in selected proportions. The bonding agent is disposed as an interlayer between similar or dissimilar ceramic or cermaic composite materials to be joined and is heated in ambient air or inert atmosphere to a temperature not exceeding about 1200 degrees C. to form a strong and tough bond joint between the materials. The bond joint produced is characterized by a composite joint microstructure having relatively soft, compliant aluminum bearing particulate regions dispersed in a ceramic matrix.

Low temperature joining of ceramic composites

DOEpatents

Barton, Thomas J.; Anderson, Iver E.; Ijadi-Maghsoodi, Sina; Nosrati, Mohammad; Unal, Ozer

1999-07-13

A method of joining similar or dissimilar ceramic and ceramic composite materials, such as SiC continuous fiber ceramic composites, at relatively low joining temperatures uses a solventless, three component bonding agent effective to promote mechanical bond toughness and elevated temperature strength to operating temperatures of approximately 1200 degrees C. The bonding agent comprises a preceramic precursor, an aluminum bearing powder, such as aluminum alloy powder, and mixtures of aluminum metal or alloy powders with another powder, and and boron powder in selected proportions. The bonding agent is disposed as an interlayer between similar or dissimilar ceramic or ceramic composite materials to be joined and is heated in ambient air or inert atmosphere to a temperature not exceeding about 1200 degrees C. to form a strong and tough bond joint between the materials. The bond joint produced is characterized by a composite joint microstructure having relatively soft, compliant aluminum bearing particulate regions dispersed in a ceramic matrix.

Low temperature joining of ceramic composites

DOEpatents

Barton, Thomas J.; Anderson, Iver E.; Ijadi-Maghsoodi, Sina; Nosrati, Mohammad; Unal, Ozer

2001-04-10

A method of joining similar or dissimilar ceramic and ceramic composite materials, such as SiC continuous fiber ceramic composites, at relatively low joining temperatures uses a solventless, three component bonding agent effective to promote mechanical bond toughness and elevated temperature strength to operating temperatures of approximately 1200 degrees C. The bonding agent comprises a preceramic precursor, an aluminum bearing powder, such as aluminum alloy powder, and mixtures of aluminum metal or alloy powders with another powder, and and boron powder in selected proportions. The bonding agent is disposed as an interlayer between similar or dissimilar ceramic or cermaic composite materials to be joined and is heated in ambient air or inert atmosphere to a temperature not exceeding about 1200 degrees C. to form a strong and tough bond joint between the materials. The bond joint produced is characterized by a composite joint microstructure having relatively soft, compliant aluminum bearing particulate regions dispersed in a ceramic matrix.

Low temperature joining of ceramic composites

DOEpatents

Barton, T.J.; Anderson, I.E.; Ijadi-Maghsoodi, S.; Nosrati, M.; Unal, O.

1999-07-13

A method of joining similar or dissimilar ceramic and ceramic composite materials, such as SiC continuous fiber ceramic composites, at relatively low joining temperatures uses a solventless, three component bonding agent effective to promote mechanical bond toughness and elevated temperature strength to operating temperatures of approximately 1200 C. The bonding agent comprises a preceramic precursor, an aluminum bearing powder, such as aluminum alloy powder, and mixtures of aluminum metal or alloy powders with another powder, and boron powder in selected proportions. The bonding agent is disposed as an interlayer between similar or dissimilar ceramic or ceramic composite materials to be joined and is heated in ambient air or inert atmosphere to a temperature not exceeding about 1200 C to form a strong and tough bond joint between the materials. The bond joint produced is characterized by a composite joint microstructure having relatively soft, compliant aluminum bearing particulate regions dispersed in a ceramic matrix. 3 figs.

Low temperature joining of ceramic composites

DOEpatents

Barton, T.J.; Anderson, I.E.; Ijadi-Maghsoodi, S.; Nosrati, M.; Unal, O.

1999-01-12

A method of joining similar or dissimilar ceramic and ceramic composite materials, such as SiC continuous fiber ceramic composites, at relatively low joining temperatures uses a solventless, three component bonding agent effective to promote mechanical bond toughness and elevated temperature strength to operating temperatures of approximately 1200 degrees C. The bonding agent comprises a preceramic precursor, an aluminum bearing powder, such as aluminum alloy powder, and mixtures of aluminum metal or alloy powders with another powder, and boron powder in selected proportions. The bonding agent is disposed as an interlayer between similar or dissimilar ceramic or ceramic composite materials to be joined and is heated in ambient air or inert atmosphere to a temperature not exceeding about 1200 degrees C. to form a strong and tough bond joint between the materials. The bond joint produced is characterized by a composite joint microstructure having relatively soft, compliant aluminum bearing particulate regions dispersed in a ceramic matrix. 3 figs.

Ceramic material suitable for repair of a space vehicle component in a microgravity and vacuum environment, method of making same, and method of repairing a space vehicle component

NASA Technical Reports Server (NTRS)

Riedell, James A. (Inventor); Easler, Timothy E. (Inventor)

2009-01-01

A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium diboride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

Dynamics of Bottlebrush Networks

NASA Astrophysics Data System (ADS)

Cao, Zhen; Daniel, William; Vatankhah-Varnosfaderani, Mohammad; Sheiko, Sergei; Dobrynin, Andrey

The deformation dynamics of bottlebrush networks in a melt state is studied using a combination of theoretical, computational, and experimental techniques. Three main molecular relaxation processes are identified in these systems: (i) relaxation of the side chains, (ii) relaxation of the bottlebrush backbones on length scales shorter than the bottlebrush Kuhn length (bK) , and (iii) relaxation of the bottlebrush network strands between cross-links. The relaxation of side chains having a degree of polymerization (DP), nsc, dominates the network dynamics on the time scales τ0 < t <=τsc , where τ0 and τsc τ0 (nsc + 1)2 are the characteristic relaxation times of monomeric units and side chains, respectively. In this time interval, the shear modulus at small deformations decays with time as G0BB (t) t - 1 / 2. On time scales t >τsc, bottlebrush elastomers behave as networks of filaments with a shear modulus G0BB (t) (nsc + 1)- 1 / 4t - 1 / 2 . Finally, the response of the bottlebrush networks becomes time independent at times scales longer than the Rouse time of the bottlebrush network strands. In this time interval, the network shear modulus depends on the network molecular parameters as G0BB (t) (nsc + 1)-1N-1 . Analysis of the simulation data shows that the stress evolution in the bottlebrush networks during constant strain-rate deformation can be described by a universal function. NSF DMR-1409710, DMR-1407645, DMR-1624569, DMR-1436201.

A lead (II) 3D coordination polymer based on a marine cyclic peptide motif.

PubMed

Chakraborty, Subrata; Tyagi, Pooja; Tai, Dar-Fu; Lee, Gene-Hsiang; Peng, Shie-Ming

2013-04-26

The crystal structure of a naturally occurring cyclic tetrapeptide cyclo(Gly-L-Ser-L-Pro-L-Glu) [cyclo(GSPE)] was obtained. The conformation of synthesized cyclo(GSPE) fixes the coordination to lead ion in a 1:1 ratio. This cyclo(GSPE)-Pb complex was constructed as an asymmetric 3D network in the crystalline state. The polymerization of a heavy metal ion with a rigid asymmetric cyclic tetrapeptide represents the first example of a new class of macrocyclic complexes.

Effect of a Polymercaptan Material on the Electro-Optical Properties of Polymer-Dispersed Liquid Crystal Films.

PubMed

Sun, Yujian; Zhang, Cuihong; Zhou, Le; Fang, Hua; Huang, Jianhua; Ma, Haipeng; Zhang, Yi; Yang, Jie; Zhang, Lan-Ying; Song, Ping; Gao, Yanzi; Xiao, Jiumei; Li, Fasheng; Li, Kexuan

2016-12-30

Polymer-dispersed liquid crystal (PDLC) films were prepared by the ultraviolet-light-induced polymerization of photopolymerizable monomers in nematic liquid crystal/chiral dopant/thiol-acrylate reaction monomer composites. The effects of the chiral dopant and crosslinking agents on the electro-optical properties of the PDLC films were systematically investigate. While added the chiral dopant S811 into the PDLC films, the initial off-state transmittance of the films was decreased. It was found that the weight ratio among acrylate monomers, thiol monomer PETMP and the polymercaptan Capcure 3-800 showed great influence on the properties of the fabricated PDLC films because of the existence of competition between thiol-acrylate reaction and acrylate monomer polymerization reaction. While adding polymercaptans curing agent Capcure 3-800 with appropriate concentration into the PDLC system, lower driven voltage and higher contrast ratio were achieved. This made the polymer network and electro-optical properties of the PDLC films easily tunable by the introduction of the thiol monomers.

Radical polymerization of capillary bridges between micron-sized particles in liquid bulk phase as a low temperature route to produce porous solid materials.

PubMed

Hauf, Katharina; Riazi, Kamran; Willenbacher, Norbert; Koos, Erin

2017-10-01

We present a generic and versatile low temperature route to produce macro-porous bodies with porosity and pore size distribution that are adjustable in a wide range. Capillary suspensions, where the minor fluid is a monomer, are used as pre-cursors. The monomer is preferentially located between the particles, creating capillary bridges, resulting in a strong, percolating network. Thermally induced polymerization of these bridges at temperatures below 100 °C for less than 5 hours and subsequent removal of the bulk fluid yields macroscopic, self-supporting solid bodies with high porosity. This process is demonstrated using methylmethacrylate and hydroxyethylmethacrlyate with glass particles as a model system. The produced PMMA had a molecular weight of about 500.000 g/mol and dispersity about three. Application specific porous bodies, including PMMA particles connected by PMMA bridges, micron-sized capsules containing phase change material with high inner surface, and porous graphite membranes with high electrical conductivity, are also shown.

Waterborne polyurethane-acrylic hybrid nanoparticles by miniemulsion polymerization: applications in pressure-sensitive adhesives.

PubMed

Lopez, Aitziber; Degrandi-Contraires, Elise; Canetta, Elisabetta; Creton, Costantino; Keddie, Joseph L; Asua, José M

2011-04-05

Waterborne polyurethane-acrylic hybrid nanoparticles for application as pressure-sensitive adhesives (PSAs) were prepared by one-step miniemulsion polymerization. The addition of polyurethane to a standard waterborne acrylic formulation results in a large increase in the cohesive strength and hence a much higher shear holding time (greater than seven weeks at room temperature), which is a very desirable characteristic for PSAs. However, with the increase in cohesion, there is a decrease in the relative viscous component, and hence there is a decrease in the tack energy. The presence of a small concentration of methyl methacrylate (MMA) in the acrylic copolymer led to phase separation within the particles and created a hemispherical morphology. The tack energy was particularly low in the hybrid containing MMA because of the effects of lower energy dissipation and greater cross-linking. These results highlight the great sensitivity of the viscoelastic and adhesive properties to the details of the polymer network architecture and hence to the precise composition and synthesis conditions.

Poly[[di-μ-aqua-(μ-4-formyl-2-meth­oxy­phenol­ato)disodium] 4-formyl-2-meth­oxy­phenolate

PubMed Central

Asghar, Muhammad Nadeem; Şahin, Onur; Arshad, Muhammad Nadeem; Mazhar, Uzma; Khan, Islam Ullah; Büyükgüngör, Orhan

2010-01-01

In the title coordination polymer, {[Na2(C8H7O3)(H2O)4](C8H7O3)}n, all the non-H atoms except the water O atoms lie on a crystallographic mirror plane. One sodium cation is bonded to four water O atoms and one vanillinate O atom in a distorted square-based pyramidal arrangement; the other Na+ ion is six-coordinated by four water O atoms and two vanillinate O atoms in an irregular geometry. One of the vanillinate anions is directly bonded to two sodium ions, whilst the other only inter­acts with the polymeric network by way of hydrogen bonds. In the crystal, a two-dimensional polymeric array is formed; this is reinforced by O—H⋯O hydrogen bonds, which generate R 2 1(6) and R 2 2(20) loops. PMID:21579628

Radical polymerization of capillary bridges between micron-sized particles in liquid bulk phase as a low temperature route to produce porous solid materials

PubMed Central

Hauf, Katharina; Riazi, Kamran; Willenbacher, Norbert; Koos, Erin

2018-01-01

We present a generic and versatile low temperature route to produce macro-porous bodies with porosity and pore size distribution that are adjustable in a wide range. Capillary suspensions, where the minor fluid is a monomer, are used as pre-cursors. The monomer is preferentially located between the particles, creating capillary bridges, resulting in a strong, percolating network. Thermally induced polymerization of these bridges at temperatures below 100 °C for less than 5 hours and subsequent removal of the bulk fluid yields macroscopic, self-supporting solid bodies with high porosity. This process is demonstrated using methylmethacrylate and hydroxyethylmethacrlyate with glass particles as a model system. The produced PMMA had a molecular weight of about 500.000 g/mol and dispersity about three. Application specific porous bodies, including PMMA particles connected by PMMA bridges, micron-sized capsules containing phase change material with high inner surface, and porous graphite membranes with high electrical conductivity, are also shown. PMID:29503494

Mechanics of responsive polymers via conformationally switchable molecules

NASA Astrophysics Data System (ADS)

Brighenti, Roberto; Artoni, Federico; Vernerey, Franck; Torelli, Martina; Pedrini, Alessandro; Domenichelli, Ilaria; Dalcanale, Enrico

2018-04-01

Active materials are those capable of giving some physical reaction under external stimuli coming from the environment such as temperature, pH, light, mechanical stress, etc. Reactive polymeric materials can be obtained through the introduction of switchable molecules in their network, i.e. molecules having two distinct stable conformations: if properly linked to the hosting polymer chains, the switching from one state to the other can promote a mechanical reaction of the material, detectable at the macroscale, and thus enables us to tune the response according to a desired functionality. In the present paper, the main aspects of the mechanical behavior of polymeric materials with embedded switchable molecules-properly linked to the polymer's chains-are presented and discussed. Starting from the micro mechanisms occurring in such active material, a continuum model is developed, providing a straightforward implementation in computational approaches. Finally, some experimental outcomes related to a switchable molecules (known as quinoxaline cavitands) added to an elastomeric PDMS under chemical stimuli, are presented and quantitatively discussed through the use of the developed mechanical framework.

Experimental and theoretical investigation of vibrational spectra of coordination polymers based on TCE-TTF.

PubMed

Olejniczak, Iwona; Lapiński, Andrzej; Swietlik, Roman; Olivier, Jean; Golhen, Stéphane; Ouahab, Lahcène

2011-08-01

The room-temperature infrared and Raman spectra of a series of four isostructural polymeric salts of 2,3,6,7-tetrakis(2-cyanoethylthio)-tetrathiafulvalene (TCE-TTF) with paramagnetic (Co(II), Mn(II)) and diamagnetic (Zn(II), Cd(II)) ions, together with BF(4)(-) or ClO(4)(-) anions are reported. Infrared and Raman-active modes are identified and assigned based on theoretical calculations for neutral and ionized TCE-TTF using density functional theory (DFT) methods. It is confirmed that the TCE-TTF molecules in all the materials investigated are fully ionized and interact in the crystal structure through cyanoethylthio groups. The vibrational modes related to the C=C stretching vibrations of TCE-TTF are analyzed assuming the occurrence of electron-molecular vibration coupling (EMV). The presence of the antisymmetric C=C dimeric mode provides evidence that charge transfer takes place between TCE-TTF molecules belonging to neighboring polymeric networks. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A sol-powder coating technique for fabrication of yttria stabilised zirconia

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

Wattanasiriwech, Darunee; Wattanasiriwech, Suthee; Stevens, Ron

Yttria stabilised zirconia has been prepared using a simple sol-powder coating technique. The polymeric yttria sol, which was prepared using 1,3 propanediol as a network modifier, was homogeneously mixed with nanocrystalline zirconia powder and it showed a dual function: as a binder which promoted densification and a phase modifier which stabilised zirconia in the tetragonal and cubic phases. Thermal analysis and X-ray diffraction revealed that the polymeric yttria sol which decomposed at low temperature into yttrium oxide could change the m {sup {yields}} t phase transformation behaviour of the zirconia, possibly due to the small particle size and very highmore » surface area of both yttria and zirconia particles allowing rapid alloying. The sintered samples exhibited three crystalline phases: monoclinic, tetragonal and cubic, in which cubic and tetragonal are the major phases. The weight fractions of the individual phases present in the selected specimens were determined using quantitative Rietveld analysis.« less

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

Actin Filament Elasticity and Retrograde Flow Shape the Force-Velocity Relation of Motile Cells

PubMed Central

Zimmermann, Juliane; Brunner, Claudia; Enculescu, Mihaela; Goegler, Michael; Ehrlicher, Allen; Käs, Josef; Falcke, Martin

2012-01-01

Cells migrate through a crowded environment during processes such as metastasis or wound healing, and must generate and withstand substantial forces. The cellular motility responses to environmental forces are represented by their force-velocity relation, which has been measured for fish keratocytes but remains unexplained. Even pN opposing forces slow down lamellipodium motion by three orders of magnitude. At larger opposing forces, the retrograde flow of the actin network accelerates until it compensates for polymerization, and cell motion stalls. Subsequently, the lamellipodium adapts to the stalled state. We present a mechanism quantitatively explaining the cell's force-velocity relation and its changes upon application of drugs that hinder actin polymerization or actomyosin-based contractility. Elastic properties of filaments, close to the lamellipodium leading edge, and retrograde flow shape the force-velocity relation. To our knowledge, our results shed new light on how these migratory responses are regulated, and on the mechanics and structure of the lamellipodium. PMID:22339865

Effect of Barley β-Glucan on the Gluten Polymerization Process in Dough during Heat Treatment.

PubMed

Huang, Ze-Hua; Zhao, Yang; Zhu, Ke-Xue; Guo, Xiao-Na; Peng, Wei; Zhou, Hui-Ming

2017-07-26

Barley (Hordeum vulgare L.) β-glucan (BBG) is of interest as a result of its health benefits, but BBG presents significant disruptions on the gluten network, with a negative impact on food texture. To clarify the interaction between BBG and gluten in dough, the dynamic rheological, thermochemical process of gluten and microstructure of dough with BBG during heating were detected. The results showed that BBG delayed the gluten thermopolymerization reaction during heating and affected polymerization of specific molecular weight protein subunits. These impacts depended upon the heating temperature and time. When heating under 25-65 °C, tan δ of the dough reached the highest level at the BBG concentration of 1%. However, under the temperature of 65-95 °C, tan δ was positively correlated with the BBG content (0-3%). The differential scanning calorimetry curves revealed that the peak temperature (T P ) of the two endothermic peaks increased by 3.86 and 3.10 °C. Size-exclusion high-performance liquid chromatography analysis showed that BBG mainly affected the peak area of gliadin and glutenin. Furthermore, after 3% BBG was added, the bands of 59.8 and 64.9 kDa in sodium dodecyl sulfate-polyacrylamide gel electrophoresis patterns delayed, vanishing for 120 s when heating at 95 °C. Therefore, BBG delayed the polymerization reaction of specific molecular weight protein subunits rather than all of the proteins.

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.

Deposition of chemically reactive and repellent sites on biosensor chips for reduced non-specific binding.

PubMed

Gandhiraman, R P; Gubala, V; Le, N C H; Nam, Le Cao Hoai; Volcke, C; Doyle, C; James, B; Daniels, S; Williams, D E

2010-08-01

The performances of new polymeric materials with excellent optical properties and good machinability have led the biomedical diagnostics industry to develop cheap disposable biosensor platforms appropriate for point of care applications. Zeonor, a type of cycloolefin polymer (COP), is one such polymer that presents an excellent platform for biosensor chips. These polymer substrates have to be modified to have suitable physico-chemical properties for immobilizing proteins. In this work, we have demonstrated the amine functionalization of COP substrates, by plasma enhanced chemical vapour deposition (PECVD), through codeposition of ethylene diamine and 3-aminopropyltriethoxysilane precursors, for building chemistries on the plastic chip. The elemental composition, adhesion, ageing and reactivity of the plasma polymerized film were examined. The Si-O functionality present in amino silane contributed for a good interfacial adhesion of the coating to COP substrates and also acted as a network building layer for plasma polymerization. Wet chemical modification was then carried out on the amine functionalized chips to create chemically reactive isothiocyanate sites and protein repellent fluorinated sites on the same chip. The density of the reactive and repellent sites was altered by choosing appropriate mixtures of homofunctional phenyldiisothiocyanate (PDITC), pentafluoroisothiocyanate (5FITC) and phenylisothiocyanate (PITC) compounds. By tailoring the density of reactive binding sites and protein repellent sites, the non-specific binding of ssDNA has been decreased to a significant extent. Copyright 2010 Elsevier B.V. All rights reserved.

Probing GFP-actin diffusion in living cells using fluorescence correlation spectroscopy.

PubMed

Engelke, Hanna; Heinrich, Doris; Rädler, Joachim O

2010-12-22

The cytoskeleton of eukaryotic cells is continuously remodeled by polymerization and depolymerization of actin. Consequently, the relative content of polymerized filamentous actin (F-actin) and monomeric globular actin (G-actin) is subject to temporal and spatial fluctuations. Since fluorescence correlation spectroscopy (FCS) can measure the diffusion of fluorescently labeled actin it seems likely that FCS allows us to determine the dynamics and hence indirectly the structural properties of the cytoskeleton components with high spatial resolution. To this end we investigate the FCS signal of GFP-actin in living Dictyostelium discoideum cells and explore the inherent spatial and temporal signatures of the actin cytoskeleton. Using the free green fluorescent protein (GFP) as a reference, we find that actin diffusion inside cells is dominated by G-actin and slower than diffusion in diluted cell extract. The FCS signal in the dense cortical F-actin network near the cell membrane is probed using the cytoskeleton protein LIM and is found to be slower than cytosolic G-actin diffusion. Furthermore, we show that polymerization of the cytoskeleton induced by Jasplakinolide leads to a substantial decrease of G-actin diffusion. Pronounced fluctuations in the distribution of the FCS correlation curves can be induced by latrunculin, which is known to induce actin waves. Our work suggests that the FCS signal of GFP-actin in combination with scanning or spatial correlation techniques yield valuable information about the local dynamics and concomitant cytoskeletal properties.

Hierarchical self-assembly: Self-organized nanostructures in a nematically ordered matrix of self-assembled polymeric chains

NASA Astrophysics Data System (ADS)

Mubeena, Shaikh; Chatterji, Apratim

2015-03-01

We report many different nanostructures which are formed when model nanoparticles of different sizes (diameter σn) are allowed to aggregate in a background matrix of semiflexible self-assembled polymeric wormlike micellar chains. The different nanostructures are formed by the dynamical arrest of phase-separating mixtures of micellar monomers and nanoparticles. The different morphologies obtained are the result of an interplay of the available free volume, the elastic energy of deformation of polymers, the density (chemical potential) of the nanoparticles in the polymer matrix, and, of course, the ratio of the size of self-assembling nanoparticles and self-avoidance diameter of polymeric chains. We have used a hybrid semi-grand-canonical Monte Carlo simulation scheme to obtain the (nonequilibrium) phase diagram of the self-assembled nanostructures. We observe rodlike structures of nanoparticles which get self-assembled in the gaps between the nematically ordered chains, as well as percolating gel-like network of conjoined nanotubes. We also find a totally unexpected interlocked crystalline phase of nanoparticles and monomers, in which each crystal plane of nanoparticles is separated by planes of perfectly organized polymer chains. We identified the condition which leads to such interlocked crystal structure. We suggest experimental possibilities of how the results presented in this paper could be used to obtain different nanostructures in the laboratory.

The Sla1 adaptor-clathrin interaction regulates coat formation and progression of endocytosis.

PubMed

Tolsma, Thomas O; Cuevas, Lena M; Di Pietro, Santiago M

2018-06-01

Clathrin-mediated endocytosis is a fundamental transport pathway that depends on numerous protein-protein interactions. Testing the importance of the adaptor protein-clathrin interaction for coat formation and progression of endocytosis in vivo has been difficult due to experimental constrains. Here, we addressed this question using the yeast clathrin adaptor Sla1, which is unique in showing a cargo endocytosis defect upon substitution of 3 amino acids in its clathrin-binding motif (sla1 AAA ) that disrupt clathrin binding. Live-cell imaging showed an impaired Sla1-clathrin interaction causes reduced clathrin levels but increased Sla1 levels at endocytic sites. Moreover, the rate of Sla1 recruitment was reduced indicating proper dynamics of both clathrin and Sla1 depend on their interaction. sla1 AAA cells showed a delay in progression through the various stages of endocytosis. The Arp2/3-dependent actin polymerization machinery was present for significantly longer time before actin polymerization ensued, revealing a link between coat formation and activation of actin polymerization. Ultimately, in sla1 AAA cells a larger than normal actin network was formed, dramatically higher levels of various machinery proteins other than clathrin were recruited, and the membrane profile of endocytic invaginations was longer. Thus, the Sla1-clathrin interaction is important for coat formation, regulation of endocytic progression and membrane bending. © 2018 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Nckβ Adapter Regulates Actin Polymerization in NIH 3T3 Fibroblasts in Response to Platelet-Derived Growth Factor bb

PubMed Central

Chen, Min; She, Hongyun; Kim, Airie; Woodley, David T.; Li, Wei

2000-01-01

The SH3-SH3-SH3-SH2 adapter Nck represents a two-gene family that includes Nckα (Nck) and Nckβ (Grb4/Nck2), and it links receptor tyrosine kinases to intracellular signaling networks. The function of these mammalian Nck genes has not been established. We report here a specific role for Nckβ in platelet-derived growth factor (PDGF)-induced actin polymerization in NIH 3T3 cells. Overexpression of Nckβ but not Nckα blocks PDGF-stimulated membrane ruffling and formation of lamellipoda. Mutation in either the SH2 or the middle SH3 domain of Nckβ abolishes its interfering effect. Nckβ binds at Tyr-1009 in human PDGF receptor β (PDGFR-β) which is different from Nckα's binding site, Tyr-751, and does not compete with phosphatidylinositol-3 kinase for binding to PDGFR. Microinjection of an anti-Nckβ but not an anti-Nckα antibody inhibits PDGF-stimulated actin polymerization. Constitutively membrane-bound Nckβ but not Nckα blocks Rac1-L62-induced membrane ruffling and formation of lamellipodia, suggesting that Nckβ acts in parallel to or downstream of Rac1. This is the first report of Nckβ's role in receptor tyrosine kinase signaling to the actin cytoskeleton. PMID:11027258

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

Bowley, S.; Okumura, N; Lord, S

'A:a' knob-hole interactions and D:D interfacial interactions are important for fibrin polymerization. Previous studies with recombinant ?N308K fibrinogen, a substitution at the D:D interface, showed impaired polymerization. We examined the molecular basis for this loss of function by solving the crystal structure of ?N308K fragment D. In contrast to previous fragment D crystals, the ?N308K crystals belonged to a tetragonal space group with an unusually long unit cell (a = b = 95 Angstroms, c = 448.3 Angstroms). Alignment of the normal and ?N308K structures showed the global structure of the variant was not changed and the knob 'A' peptidemore » GPRP was bound as usual to hole 'a'. The substitution introduced an elongated positively charged patch in the D:D region. The structure showed novel, symmetric D:D crystal contacts between ?N308K molecules, indicating the normal asymmetric D:D interface in fibrin would be unstable in this variant. We examined GPRP binding to ?N308K in solution by plasmin protection assay. The results showed weaker peptide binding, suggesting that 'A:a' interactions were altered. We examined fibrin network structures by scanning electron microscopy and found the variant fibers were thicker and more heterogeneous than normal fibers. Considered together, our structural and biochemical studies indicate both 'A:a' and D:D interactions are weaker. We conclude that stable protofibrils cannot assemble from ?N308K monomers, leading to impaired polymerization.« less

Investigation of copper (Cu2+) adsorption performances and gamma radiation dose effect of polymeric hydrogel

NASA Astrophysics Data System (ADS)

Hassan, Safia; Yasin, Tariq; Imran, Zahid; Batool, Syeda Sitwat

2018-02-01

In present study, series of gamma irradiated poly(acrylic acid)/Penytriethoxytrisilane (PTES) based hydrogels were synthesized. The hydrogels were used for the adsorption of Cu2+ from the aqueous solution. Batch adsorption experiments were performed by varying contact time (0-10 hours), pH value (2-6), hydrogels weight (15-155 mg) and initial Cu2+ concentration (0.003-90 mg/L). The results indicated that lowering the gamma irradiation dose (30-15 kGy) and PTES amount (1.65-0.83 μmol) into hydrogel polymeric networks, improved the initial rate of adsorption and final adsorption capacity of hydrogel for Cu2+. AA40/15 had 143.4mg/g Cu2+ adsorption capacity higher than AA80/30 which is 106.0mg/g. Hydrogels exhibited maximum o adsorption capacity for Cu2+ within a wide pH range. All adsorption data was described by the pseudo—first order and second order kinetic model equations and isotherm data by Langmuir model. FTIR spectra analysis before and after adsorption of Cu2+ on the AA hydrogels gave detail analysis of adsorption mechanism. The behavior of adsorption expressed that the enhanced adsorption capacity was due to the porous structure and e presence of functional groups onto surface of adsorbate. It is expected this polymeric hydrogel has potential to work as alternative biomedical sorbents and environmental use as pH altered.

Synthesis, Structure, and Pressure-Induced Polymerization of Li3Fe(CN)6 Accompanied with Enhanced Conductivity.

PubMed

Li, Kuo; Zheng, Haiyan; Hattori, Takanori; Sano-Furukawa, Asami; Tulk, Christopher A; Molaison, Jamie; Feygenson, Mikhail; Ivanov, Ilia N; Yang, Wenge; Mao, Ho-Kwang

2015-12-07

Pressure-induced polymerization of charged triple-bond monomers like acetylide and cyanide could lead to formation of a conductive metal-carbon network composite, thus providing a new route to synthesize inorganic/organic conductors with tunable composition and properties. The industry application of this promising synthetic method is mainly limited by the reaction pressure needed, which is often too high to be reached for gram amounts of sample. Here we successfully synthesized highly conductive Li3Fe(CN)6 at maximum pressure around 5 GPa and used in situ diagnostic tools to follow the structural and functional transformations of the sample, including in situ X-ray and neutron diffraction and Raman and impedance spectroscopy, along with the neutron pair distribution function measurement on the recovered sample. The cyanide anions start to react around 1 GPa and bond to each other irreversibly at around 5 GPa, which are the lowest reaction pressures in all known metal cyanides and within the technologically achievable pressure range for industrial production. The conductivity of the polymer is above 10(-3) S · cm(-1), which reaches the range of conductive polymers. This investigation suggests that the pressure-induced polymerization route is practicable for synthesizing some types of functional conductive materials for industrial use, and further research like doping and heating can hence be motivated to synthesize novel materials under lower pressure and with better performances.

Injectable nano-network for glucose-mediated insulin delivery.

PubMed

Gu, Zhen; Aimetti, Alex A; Wang, Qun; Dang, Tram T; Zhang, Yunlong; Veiseh, Omid; Cheng, Hao; Langer, Robert S; Anderson, Daniel G

2013-05-28

Diabetes mellitus, a disorder of glucose regulation, is a global burden affecting 366 million people across the world. An artificial "closed-loop" system able to mimic pancreas activity and release insulin in response to glucose level changes has the potential to improve patient compliance and health. Herein we develop a glucose-mediated release strategy for the self-regulated delivery of insulin using an injectable and acid-degradable polymeric network. Formed by electrostatic interaction between oppositely charged dextran nanoparticles loaded with insulin and glucose-specific enzymes, the nanocomposite-based porous architecture can be dissociated and subsequently release insulin in a hyperglycemic state through the catalytic conversion of glucose into gluconic acid. In vitro insulin release can be modulated in a pulsatile profile in response to glucose concentrations. In vivo studies validated that these formulations provided improved glucose control in type 1 diabetic mice subcutaneously administered with a degradable nano-network. A single injection of the developed nano-network facilitated stabilization of the blood glucose levels in the normoglycemic state (<200 mg/dL) for up to 10 days.

Direct formation of reduced graphene oxide and 3D lightweight nickel network composite foam by hydrohalic acids and its application for high-performance supercapacitors.

PubMed

Huang, Haifu; Tang, Yanmei; Xu, Lianqiang; Tang, Shaolong; Du, Youwei

2014-07-09

Here, a novel graphene composite foam with 3D lightweight continuous and interconnected nickel network was successfully synthesized by hydroiodic (HI) acid using nickel foam as substrate template. The graphene had closely coated on the backbone of the 3D nickel conductive network to form nickel network supported composite foam without any polymeric binder during the HI reduction of GO process, and the nickel conductive network can be maintained even in only a small amount of nickel with 1.1 mg/cm(2) and had replaced the traditional current collector nickel foam (35 mg/cm(2)). In the electrochemical measurement, a supercapacitor device based on the 3D nickel network and graphene composite foam exhibited high rate capability of 100 F/g at 0.5 A/g and 86.7 F/g at 62.5 A/g, good cycle stability with capacitance retention of 95% after 2000 cycles, low internal resistance (1.68 Ω), and excellent flexible properties. Furthermore, the gravimetric capacitance (calculated using the total mass of the electrode) was high up to 40.9 F/g. Our work not only demonstrates high-quality graphene/nickel composite foam, but also provides a universal route for the rational design of high performance of supercapacitors.

Application of organic IR788-loaded semi-interpenetrating network dyes for photoacoustic imaging

NASA Astrophysics Data System (ADS)

Phuc Nguyen, Van; Kim, Hyejin; Kang, Mingyeong; Kwak, Minseok; Kang, Hyun Wook

2017-07-01

In this study, we present the feasibility of a biocompatible Lumogen® IR788-loaded polymeric nanoparticle (NP) as a novel photoabsorbing agent for photoacoustic (PA) imaging. The NP was fabricated through a semi-interpenetrating network (sIPN) within the core of F127 resulting in IR788-sIPN formation. To evaluate the PA sensitivity of the material, tubing phantoms were injected with various concentrations of IR788-sIPN, and H1975 lung-tumor-bearing mice were intratumorally injected with IR788-sIPN. Compared with the background, the PA contrast was enhanced up to 80 and 40% in the phantom and in vivo experiments, respectively. IR788-sIPN can be a feasible IR-absorbing material for early cancer detection.

Green polymer chemistry: Synthesis of poly(disulfide) polymers and networks

NASA Astrophysics Data System (ADS)

Rosenthal-Kim, Emily Quinn

The disulfide group is unique in that it presents a covalent bond that is easily formed and cleaved under certain biological conditions. While the ease of disulfide bond cleavage is often harnessed as a method of biodegradation, the ease of disulfide bond formation as a synthetic strategy is often overlooked. The objective this research was to synthesize poly(disulfide) polymers and disulfide crosslinked networks from a green chemistry approach. The intent of the green chemistry approach was to take advantage of the mild conditions applicable to disulfide bond synthesis from thiols. With anticipated use as biomaterials, it was also desired that the polymer materials could be degraded under biological conditions. Here, a new method of poly(disulfide) polymer synthesis is introduced which was inspired by the reaction conditions and reagents found in Nature. Ambient temperatures and aqueous mixtures were used in the new method. Hydrogen peroxide, one of the Nature's most powerful oxidizing species was used as the oxidant in the new polymerization reaction. The dithiol monomer, 3,6-dioxa-1,8-octanedithiol was first solubilized in triethylamine, which activated the thiol groups and made the monomer water soluble. At room temperature, the organic dithiol/amine solution was then mixed with dilute aqueous hydrogen peroxide (3% by weight) to make the poly(disulfide) polymers. The presence of a two phase system (organic and aqueous phases) was critical to the polymerization reaction. As the reaction progresses, a third, polymer phase appeared. At ambient temperatures and above, this phase separated from the reaction mixture and the polymer product was easily removed from the reaction solution. These polymers reach Mn > 250,000 g/mol in under two hours. Molecular weight distributions were between 1.5 and 2.0. Reactions performed in an ice bath which remain below room temperature contain high molecular weight polymers with Mn ≈ 120,000 g/mol and have a molecular weight distribution of around 1.15. However, the majority of the product consists of low molecular weight cyclic poly(disulfide) oligomers. In reactions maintained below 18°C, the organic components were miscible in the aqueous hydrogen peroxide and a milky emulsion was produced. The polymers were degraded using the disulfide-specific reducing agent, dithiothreitol. Poly(disulfide) polymer networks were also synthesized in a two-phase system. Due to the poor solubility of the crosslinker, trimethylolpropane tris(2-mercaptopropionate, organic solvents were required to obtain consistent networks. The networks were degraded using dithiothreitol in tetrahydrofuran. The networks were stable under aqueous reducing conditions. The disulfide-bearing biochemical, alpha-lipoic acid, was investigated as monomer for the new method of poly(disulfide) polymer synthesis. It was also polymerized thermally and by a new interfacial method that proceeds at the air-water interface. Polymer products were often too large to be characterized by SEC (Mn > 1,000,000 g/mol). A poly(alpha-LA) polymer sample showed mass loss in aqueous solutions of glutathione at pH = 5.2 which was used to model cytosolic conditions. Poly(alpha-LA) was decorated with PEG (2,000 g/mol) in an esterification reaction catalyzed by Candida antarctica lipase B (CALB). The decorated polymers were imaged using AFM which revealed branch-like structures. To make new alpha-lipoic acid based monomers and macromonomers, CALB-catalyzed esterification, was used to conjugate alpha-lipoic acid to a variety of glycols including: diethylene glycol monomethyl ether, tetraethylene glycol, hexaethylene glycol, and poly(ethylene glycol). The products were verified using NMR spectroscopy and mass spectrometry.

Characterization and modeling of ionic polymeric smart materials as artificial muscles and robotic swimming structures

NASA Astrophysics Data System (ADS)

Mojarrad, Mehran

2001-07-01

In this dissertation document, a thorough review and investigation of works in connection with the ionic polymeric gels as artificial muscles and electrically controllable polymeric network structures were performed. Where possible, comparisons were made with biological muscles and applications in marine propulsion using such polymeric materials were investigated. Furthermore, methods of fabrication of several chemically active ionic polymeric gel muscles such as PolyAcryloNitrile (PAN), Poly(2-Acrylamido-2-Methyl-1-PropaneSulfonic) acid (PAMPS), and PolyAcrylic-acid-bis-AcrylaMide (PAAM) as well as a new class of electrically active composite muscle such as Ion-Exchange-Metal-Composites (IEMC) or Ionic Polymer Metal Composites (IPMC) materials are introduced and investigated that resulted in two US patents regarding their fabrication and application capabilities as actuators and sensors. In this research, various forms of the IPMC fabrication were explored and reported. In addition, characterization of PAN muscles, bundling and encapsulation were investigated. Conversion of chemical to electrical artificial muscles were also investigated using chemical plating techniques as well as physical vapor deposition methods of the pH-activated muscles like PAN fibers. Experimental methods were devised to characterize contraction, expansion, and bending of various actuators using isometric, isoionic, and isotonic characterization methods. Several apparatuses for modeling and testing of the various artificial muscles were built to show the viability of the application of both chemoactive and electroactive muscles. Furthermore PAN fiber muscles in different configurations such as spring-loaded fiber bundles, biceps, triceps, ribbon type muscles, and segmented fiber bundles were fabricated to make a variety of actuators. Additionally, swimming robotic structures and associated hardware were built to incorporate IPMC as biomimetic propulsion fin actuators. In addition, various configuration of IPMC such as linear actuators and multiplayer actuators were fabricated and evaluated for load and sensing capability. Theories associated with ionic polymer gels electrodynamics and chemodynamics were proposed, analyzed and modeled for the manufactured material. Futhermore, theoretical models of swimming structures were developed and compared with biological fish propulsion models and dynamically evaluated for robotic applications.

Identification of interactive gene networks: a novel approach in gene array profiling of myometrial events during guinea pig pregnancy.

PubMed

Mason, Clifford W; Swaan, Peter W; Weiner, Carl P

2006-06-01

The transition from myometrial quiescence to activation is poorly understood, and the analysis of array data is limited by the available data mining tools. We applied functional analysis and logical operations along regulatory gene networks to identify molecular processes and pathways underlying quiescence and activation. We analyzed some 18,400 transcripts and variants in guinea pig myometrium at stages corresponding to quiescence and activation, and compared them to the nonpregnant (control) counterpart using a functional mapping tool, MetaCore (GeneGo, St Joseph, MI) to identify novel gene networks composed of biological pathways during mid (MP) and late (LP) pregnancy. Genes altered during quiescence and or activation were identified following gene specific comparisons with myometrium from nonpregnant animals, and then linked to curated pathways and formulated networks. The MP and LP networks were subtracted from each other to identify unique genomic events during those periods. For example, changes 2-fold or greater in genes mediating protein biosynthesis, programmed cell death, microtubule polymerization, and microtubule based movement were noted during the transition to LP. We describe a novel approach combining microarrays and genetic data to identify networks associated with normal myometrial events. The resulting insights help identify potential biomarkers and permit future targeted investigations of these pathways or networks to confirm or refute their importance.

Biologically Derived Soft Conducting Hydrogels Using Heparin-Doped Polymer Networks

PubMed Central

2015-01-01

The emergence of flexible and stretchable electronic components expands the range of applications of electronic devices. Flexible devices are ideally suited for electronic biointerfaces because of mechanically permissive structures that conform to curvilinear structures found in native tissue. Most electronic materials used in these applications exhibit elastic moduli on the order of 0.1–1 MPa. However, many electronically excitable tissues exhibit elasticities in the range of 1–10 kPa, several orders of magnitude smaller than existing components used in flexible devices. This work describes the use of biologically derived heparins as scaffold materials for fabricating networks with hybrid electronic/ionic conductivity and ultracompliant mechanical properties. Photo-cross-linkable heparin–methacrylate hydrogels serve as templates to control the microstructure and doping of in situ polymerized polyaniline structures. Macroscopic heparin-doped polyaniline hydrogel dual networks exhibit impedances as low as Z = 4.17 Ω at 1 kHz and storage moduli of G′ = 900 ± 100 Pa. The conductivity of heparin/polyaniline networks depends on the oxidation state and microstructure of secondary polyaniline networks. Furthermore, heparin/polyaniline networks support the attachment, proliferation, and differentiation of murine myoblasts without any surface treatments. Taken together, these results suggest that heparin/polyaniline hydrogel networks exhibit suitable physical properties as an electronically active biointerface material that can match the mechanical properties of soft tissues composed of excitable cells. PMID:24738911

A Key Role for Apoplastic H2O2 in Norway Spruce Phenolic Metabolism.

PubMed

Laitinen, Teresa; Morreel, Kris; Delhomme, Nicolas; Gauthier, Adrien; Schiffthaler, Bastian; Nickolov, Kaloian; Brader, Günter; Lim, Kean-Jin; Teeri, Teemu H; Street, Nathaniel R; Boerjan, Wout; Kärkönen, Anna

2017-07-01

Apoplastic events such as monolignol oxidation and lignin polymerization are difficult to study in intact trees. To investigate the role of apoplastic hydrogen peroxide (H 2 O 2 ) in gymnosperm phenolic metabolism, an extracellular lignin-forming cell culture of Norway spruce ( Picea abies ) was used as a research model. Scavenging of apoplastic H 2 O 2 by potassium iodide repressed lignin formation, in line with peroxidases activating monolignols for lignin polymerization. Time-course analyses coupled to candidate substrate-product pair network propagation revealed differential accumulation of low-molecular-weight phenolics, including (glycosylated) oligolignols, (glycosylated) flavonoids, and proanthocyanidins, in lignin-forming and H 2 O 2 -scavenging cultures and supported that monolignols are oxidatively coupled not only in the cell wall but also in the cytoplasm, where they are coupled to other monolignols and proanthocyanidins. Dilignol glycoconjugates with reduced structures were found in the culture medium, suggesting that cells are able to transport glycosylated dilignols to the apoplast. Transcriptomic analyses revealed that scavenging of apoplastic H 2 O 2 resulted in remodulation of the transcriptome, with reduced carbon flux into the shikimate pathway propagating down to monolignol biosynthesis. Aggregated coexpression network analysis identified candidate enzymes and transcription factors for monolignol oxidation and apoplastic H 2 O 2 production in addition to potential H 2 O 2 receptors. The results presented indicate that the redox state of the apoplast has a profound influence on cellular metabolism. © 2017 American Society of Plant Biologists. All Rights Reserved.

A Key Role for Apoplastic H2O2 in Norway Spruce Phenolic Metabolism1[OPEN

PubMed Central

Laitinen, Teresa

2017-01-01

Apoplastic events such as monolignol oxidation and lignin polymerization are difficult to study in intact trees. To investigate the role of apoplastic hydrogen peroxide (H2O2) in gymnosperm phenolic metabolism, an extracellular lignin-forming cell culture of Norway spruce (Picea abies) was used as a research model. Scavenging of apoplastic H2O2 by potassium iodide repressed lignin formation, in line with peroxidases activating monolignols for lignin polymerization. Time-course analyses coupled to candidate substrate-product pair network propagation revealed differential accumulation of low-molecular-weight phenolics, including (glycosylated) oligolignols, (glycosylated) flavonoids, and proanthocyanidins, in lignin-forming and H2O2-scavenging cultures and supported that monolignols are oxidatively coupled not only in the cell wall but also in the cytoplasm, where they are coupled to other monolignols and proanthocyanidins. Dilignol glycoconjugates with reduced structures were found in the culture medium, suggesting that cells are able to transport glycosylated dilignols to the apoplast. Transcriptomic analyses revealed that scavenging of apoplastic H2O2 resulted in remodulation of the transcriptome, with reduced carbon flux into the shikimate pathway propagating down to monolignol biosynthesis. Aggregated coexpression network analysis identified candidate enzymes and transcription factors for monolignol oxidation and apoplastic H2O2 production in addition to potential H2O2 receptors. The results presented indicate that the redox state of the apoplast has a profound influence on cellular metabolism. PMID:28522458

Fluorescent porous film modified polymer optical fiber via "click" chemistry: stable dye dispersion and trace explosive detection.

PubMed

Ma, Jiajun; Lv, Ling; Zou, Gang; Zhang, Qijin

2015-01-14

In this paper, we report a facile strategy to fabricate fluorescent porous thin film on the surface of U-bent poly(methyl methacrylate) optical fiber (U-bent POF) in situ via "click" polymerization for vapor phase sensing of explosives. Upon irradiation of evanescent UV light transmitting within the fiber under ambient condition, a porous film (POSS-thiol cross-linking film, PTCF) is synthesized on the side surface of the fiber by a thiol-ene "click" reaction of vinyl-functionalized polyhedral oligomeric silsesquioxanes (POSS-V8) and alkane dithiols. When vinyl-functionalized porphyrin, containing four allyl substituents at the periphery, is added into precursors for the polymerization, fluorescence porphyrin can be covalently bonded into the cross-linked network of PTCF. This "fastened" way reduces the aggregation-induced fluorescence self-quenching of porphyrin and enhances the physicochemical stability of the porous film on the surface of U-bent POF. Fluorescent signals of the PTCF/U-bent POF probe made by this method exhibit high fluorescence quenching toward trace TNT and DNT vapor and the highest fluorescence quenching efficiency is observed for 1, 6-hexanedimercaptan-based film. In addition, because of the presence of POSS-V8 with multi cross-linkable groups, PTCF exhibits well-organized pore network and stable dye dispersion, which not only causes fast and sensitive fluorescence quenching against vapors of nitroaromatic compounds, but also provides a repeatability of the probing performance.

Development of biopolymers based interpenetrating polymeric network of capecitabine: A drug delivery vehicle to extend the release of the model drug.

PubMed

Upadhyay, Mansi; Adena, Sandeep Kumar Reddy; Vardhan, Harsh; Yadav, Sarita K; Mishra, Brahmeshwar

2018-04-27

The research aims the development and optimization of capecitabine loaded interpenetrating polymeric network by ionotropic gelation method using polymers locust bean gum and sodium alginate by QbD approach. FMEA was performed to recognize the risks influencing CQAs. BBD was applied to study the effect of factors (polymer ratio, amount of cross-linker and curing time) on responses (particle size, % drug entrapment and % drug release). Polynomial equations and 3-D graphs were plotted to relate between factors and responses. The results of the optimized batch viz. particle size (457.92 ± 1.6 μm), % drug entrapment (74.11 ± 3.1%) and % drug release (90.23 ± 2.1%) were close to the predicted values generated by Minitab® 17. Characterization techniques SEM, EDX, FTIR, DSC and XRD were also performed for the optimized batch. To study the water transport inside IPN microbeads, swelling study was done. In vitro drug release of optimized batch showed controlled drug release for 12 h. Pharmacokinetic study carried out following oral administration in Albino Wistar rats exhibited that optimized microbeads had better PK parameters than free drug. In vitro cytotoxicity against HT-29 cells revealed significant reduction of the cell growth when treated with optimized formulation indicating IPN microbeads as effective dosage form for treating colon cancer. Copyright © 2018. Published by Elsevier B.V.

A novel technique using potassium permanganate and reflectance confocal microscopy to image biofilm extracellular polymeric matrix reveals non-eDNA networks in Pseudomonas aeruginosa biofilms.

PubMed

Swearingen, Matthew C; Mehta, Ajeet; Mehta, Amar; Nistico, Laura; Hill, Preston J; Falzarano, Anthony R; Wozniak, Daniel J; Hall-Stoodley, Luanne; Stoodley, Paul

2016-02-01

Biofilms are etiologically important in the development of chronic medical and dental infections. The biofilm extracellular polymeric substance (EPS) determines biofilm structure and allows bacteria in biofilms to adapt to changes in mechanical loads such as fluid shear. However, EPS components are difficult to visualize microscopically because of their low density and molecular complexity. Here, we tested potassium permanganate, KMnO4, for use as a non-specific EPS contrast-enhancing stain using confocal laser scanning microscopy in reflectance mode. We demonstrate that KMnO4 reacted with EPS components of various strains of Pseudomonas, Staphylococcus and Streptococcus, yielding brown MnO2 precipitate deposition on the EPS, which was quantifiable using data from the laser reflection detector. Furthermore, the MnO2 signal could be quantified in combination with fluorescent nucleic acid staining. COMSTAT image analysis indicated that KMnO4 staining increased the estimated biovolume over that determined by nucleic acid staining alone for all strains tested, and revealed non-eDNA EPS networks in Pseudomonas aeruginosa biofilm. In vitro and in vivo testing indicated that KMnO4 reacted with poly-N-acetylglucosamine and Pseudomonas Pel polysaccharide, but did not react strongly with DNA or alginate. KMnO4 staining may have application as a research tool and for diagnostic potential for biofilms in clinical samples. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Indomethacin uptake into poly(2-hydroxyethyl methacrylate-co-3,9-divinyl-2,4,8,10-tetraoxaspiro [5.5]-undecane) network: In vitro and in vivo controlled release study.

PubMed

Nita, Loredana E; Chiriac, Aurica P; Nistor, Manuela T; Tartau, Liliana

2012-04-15

Networks based on poly(2-hydroxyethyl methacrylate-co-3,9-divinyl-2,4,8,10-tetraoxaspiro [5.5]-undecane), synthesized through radical dispersion polymerization, were used as template for indomethacin (INN) as model drug. The copolymers were characterized by swelling studies at three pH values (2.4, 5.5 and 7.4) and two temperatures (room temperature 24 °C and physiological temperature 37 °C). Fourier transform infrared (FTIR) spectroscopic analysis was used to sustain the copolymer structures. Scanning electron microscopy (SEM) and thermogravimetric (TG) investigations were used to examine microstructure and appreciate the thermal stability of the polymer samples. The studies of the INN drug release from the copolymer networks were in vitro performed. The in vivo study results (biocompatibility tests, somatic nociceptive experimental model (tail flick test) and visceral nociceptive experimental model (writhing test)) are also reported in this paper. Copyright © 2012 Elsevier B.V. All rights reserved.

Three-dimensional strutted graphene grown by substrate-free sugar blowing for high-power-density supercapacitors

PubMed Central

Wang, Xuebin; Zhang, Yuanjian; Zhi, Chunyi; Wang, Xi; Tang, Daiming; Xu, Yibin; Weng, Qunhong; Jiang, Xiangfen; Mitome, Masanori; Golberg, Dmitri; Bando, Yoshio

2013-01-01

Three-dimensional graphene architectures in the macroworld can in principle maintain all the extraordinary nanoscale properties of individual graphene flakes. However, current 3D graphene products suffer from poor electrical conductivity, low surface area and insufficient mechanical strength/elasticity; the interconnected self-supported reproducible 3D graphenes remain unavailable. Here we report a sugar-blowing approach based on a polymeric predecessor to synthesize a 3D graphene bubble network. The bubble network consists of mono- or few-layered graphitic membranes that are tightly glued, rigidly fixed and spatially scaffolded by micrometre-scale graphitic struts. Such a topological configuration provides intimate structural interconnectivities, freeway for electron/phonon transports, huge accessible surface area, as well as robust mechanical properties. The graphene network thus overcomes the drawbacks of presently available 3D graphene products and opens up a wide horizon for diverse practical usages, for example, high-power high-energy electrochemical capacitors, as highlighted in this work. PMID:24336225

Three-dimensional strutted graphene grown by substrate-free sugar blowing for high-power-density supercapacitors

NASA Astrophysics Data System (ADS)

Wang, Xuebin; Zhang, Yuanjian; Zhi, Chunyi; Wang, Xi; Tang, Daiming; Xu, Yibin; Weng, Qunhong; Jiang, Xiangfen; Mitome, Masanori; Golberg, Dmitri; Bando, Yoshio

2013-12-01

Three-dimensional graphene architectures in the macroworld can in principle maintain all the extraordinary nanoscale properties of individual graphene flakes. However, current 3D graphene products suffer from poor electrical conductivity, low surface area and insufficient mechanical strength/elasticity; the interconnected self-supported reproducible 3D graphenes remain unavailable. Here we report a sugar-blowing approach based on a polymeric predecessor to synthesize a 3D graphene bubble network. The bubble network consists of mono- or few-layered graphitic membranes that are tightly glued, rigidly fixed and spatially scaffolded by micrometre-scale graphitic struts. Such a topological configuration provides intimate structural interconnectivities, freeway for electron/phonon transports, huge accessible surface area, as well as robust mechanical properties. The graphene network thus overcomes the drawbacks of presently available 3D graphene products and opens up a wide horizon for diverse practical usages, for example, high-power high-energy electrochemical capacitors, as highlighted in this work.

Clonazepam release from bioerodible hydrogels based on semi-interpenetrating polymer networks composed of poly(epsilon-caprolactone) and poly(ethylene glycol) macromer.

PubMed

Cho, C S; Han, S Y; Ha, J H; Kim, S H; Lim, D Y

1999-04-30

Poly(ethylene glycol)(PEG) macromers terminated with acrylate groups and semi-interpenetrating polymer networks (SIPNs) composed of poly(epsilon-caprolactone)(PCL) and PEG macromer were synthesized to obtain a bioerodible hydrogel. Polymerization of PEG macromer resulted in the formation of cross-linked gels due to the multifunctionality of macromer. Glass transition temperature (Tg) and melting temperature (Tm) of PEG networks and PCL in the SIPNs were inner-shifted, indicating an interpenetration of PCL and PEG chains. Water content in the SIPNs increased with increasing PEG weight fraction due to the hydrophilicity of PEG. The amount of clonazepam (CNZ) released from the SIPNs increased with higher content in the SIPNs, lower drug loading, lower concentration of PEG macromer during the SIPNs preparation, and higher molecular weight of PEG. In particular, a combination with low PEG content and low CNZ solubility in water led to long-term constant release from these matrices in vitro and in vivo. Copyright.

Template-directed assembly of metal-chalcogenide nanocrystals into ordered mesoporous networks.

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

Vamvasakis, Ioannis; Subrahmanyam, Kota S.; Kanatzidis, Mercouri G.

Although great progress in the synthesis of porous networks of metal and metal oxide nanoparticles with highly accessible pore surface and ordered mesoscale pores has been achieved, synthesis of assembled 3D mesostructures of metal-chalcogenide nanocrystals is still challenging. In this work we demonstrate that ordered mesoporous networks, which comprise well-defined interconnected metal sulfide nanocrystals, can be prepared through a polymer-templated oxidative polymerization process. The resulting self-assembled mesostructures that were obtained after solvent extraction of the polymer template impart the unique combination of light-emitting metal chalcogenide nanocrystals, three-dimensional open-pore structure, high surface area, and uniform pores. We show that the poremore » surface of these materials is active and accessible to incoming molecules, exhibiting high photocatalytic activity and stability, for instance, in oxidation of 1-phenylethanol into acetophenone. We demonstrate through appropriate selection of the synthetic components that this method is general to prepare ordered mesoporous materials from metal chalcogenide nanocrystals with various sizes and compositions.« less

Controlled release of therapeutics using interpenetrating polymeric networks.

PubMed

Aminabhavi, Tejraj M; Nadagouda, Mallikarjuna N; More, Uttam A; Joshi, Shrinivas D; Kulkarni, Venkatrao H; Noolvi, Malleshappa N; Kulkarni, Padmakar V

2015-04-01

The ever-increasing developments in pharmaceutical formulations have led to the widespread use of biodegradable polymers in various forms and configurations. In particular, interpenetrating network (IPN) and semi-IPN polymer structures that are capable of releasing drugs in a controlled manner have gained much wider importance in recent years. Recently, IPNs and semi-IPNs have emerged as innovative materials of choice in controlled release (CR) of drugs as the release from these systems depends on pH of the media and temperature in addition to the nature of the system. These networks can be prepared as smart hydrogels following chemical or physical crosslinking methods to show remarkable drug release patterns compared to single polymer systems. A large number of IPNs and semi-IPNs have been reported in the literature. The present review is focused on the preparation methods and their CR properties with reference to anticancer, anti-asthmatic, antibiotic, anti-inflammatory, anti-tuberculosis and antihypertensive drugs, as majority of these drugs have been reported to be the ideal choices for using IPNs and semi-IPNs.

Linear and Nonlinear Elasticity of Networks Made of Comb-like Polymers and Bottle-Brushes

NASA Astrophysics Data System (ADS)

Liang, H.; Dobrynin, A.; Everhart, M.; Daniel, W.; Vatankhah-Varnoosfaderani, M.; Sheiko, S.

We study mechanical properties of networks made of combs and bottle-brushes by computer simulations, theoretical calculations and experimental techniques. The networks are prepared by cross-linking backbones of combs or bottle-brushes with linear chains. This results in ``hybrid'' networks consisting of linear chains and strands of combs or bottle-brushes. In the framework of the phantom network model, the network modulus at small deformations G0 can be represented as a sum of contributions from linear chains, G0 , l, and strands of comb or bottle-brush, G0 , bb. If the length of extended backbone between crosslinks, Rmax, is much longer than the Kuhn length, bk, the modulus scales with the degree of polymerization of the side chains, nsc, and number of monomers between side chains, ng, as G0 , bb (nsc/ng + 1)-1. In the limit when bk becomes of the order of Rmax, the combs and bottle-brushes can be considered as semiflexible chains, resulting in a network modulus to be G0 , bb (nsc/ng + 1)-1(nsc2/2/ng) . In the nonlinear deformation regime, the strain-hardening behavior is described by the nonlinear network deformation model, which predicts that the true stress is a universal function of the structural modulus, G, first strain invariant, I1, and deformation ratio, β. The results of the computer simulations and predictions of the theoretical model are in a good agreement with experimental results. NSF DMR-1409710, DMR-1407645, DMR-1624569, DMR-1436201.

Micro-fluidic partitioning between polymeric sheets for chemical amplification and processing

DOEpatents

Anderson, Brian L.

2017-01-24

A system for fluid partitioning for chemical amplification or other chemical processing or separations of a sample, comprising a first dispenser of a first polymeric sheet, wherein the first polymeric sheet contains chambers; a second dispenser of a second polymeric sheet wherein the first dispenser and the second dispenser are positioned so that the first polymeric sheet and the second polymeric sheet become parallel; a dispenser of the fluid positioned to dispense the fluid between the first polymeric sheet and the second polymeric sheet; and a seal unit that seals the first polymeric sheet and the second polymeric sheet together thereby sealing the sample between the first polymeric sheet and the second polymeric sheet and partitioning the fluid for chemical amplification or other chemical processing or separations.

Micro-fluidic partitioning between polymeric sheets for chemical amplification and processing

DOEpatents

Anderson, Brian L.

2015-05-26

A system for fluid partitioning for chemical amplification or other chemical processing or separations of a sample, comprising a first dispenser of a first polymeric sheet, wherein the first polymeric sheet contains chambers; a second dispenser of a second polymeric sheet wherein the first dispenser and the second dispenser are positioned so that the first polymeric sheet and the second polymeric sheet become parallel; a dispenser of the fluid positioned to dispense the fluid between the first polymeric sheet and the second polymeric sheet; and a seal unit that seals the first polymeric sheet and the second polymeric sheet together thereby sealing the sample between the first polymeric sheet and the second polymeric sheet and partitioning the fluid for chemical amplification or other chemical processing or separations.

Polyacrylamide Ferrogels with Magnetite or Strontium Hexaferrite: Next Step in the Development of Soft Biomimetic Matter for Biosensor Applications

PubMed Central

Safronov, Alexander P.; Mikhnevich, Ekaterina A.; Blyakhman, Felix A.; Sklyar, Tatyana F.; Larrañaga Varga, Aitor; Medvedev, Anatoly I.; Fernández Armas, Sergio

2018-01-01

Magnetic biosensors are an important part of biomedical applications of magnetic materials. As the living tissue is basically a “soft matter.” this study addresses the development of ferrogels (FG) with micron sized magnetic particles of magnetite and strontium hexaferrite mimicking the living tissue. The basic composition of the FG comprised the polymeric network of polyacrylamide, synthesized by free radical polymerization of monomeric acrylamide (AAm) in water solution at three levels of concentration (1.1 M, 0.85 M and 0.58 M) to provide the FG with varying elasticity. To improve FG biocompatibility and to prevent the precipitation of the particles, polysaccharide thickeners—guar gum or xanthan gum were used. The content of magnetic particles in FG varied up to 5.2 wt % depending on the FG composition. The mechanical properties of FG and their deformation in a uniform magnetic field were comparatively analyzed. FG filled with strontium hexaferrite particles have larger Young’s modulus value than FG filled with magnetite particles, most likely due to the specific features of the adhesion of the network’s polymeric subchains on the surface of the particles. FG networks with xanthan are stronger and have higher modulus than the FG with guar. FG based on magnetite, contract in a magnetic field 0.42 T, whereas some FG based on strontium hexaferrite swell. Weak FG with the lowest concentration of AAm shows a much stronger response to a field, as the concentration of AAm governs the Young’s modulus of ferrogel. A small magnetic field magnetoimpedance sensor prototype with Co68.6Fe3.9Mo3.0Si12.0B12.5 rapidly quenched amorphous ribbon based element was designed aiming to develop a sensor working with a disposable stripe sensitive element. The proposed protocol allowed measurements of the concentration dependence of magnetic particles in gels using magnetoimpedance responses in the presence of magnetite and strontium hexaferrite ferrogels with xanthan. We have discussed the importance of magnetic history for the detection process and demonstrated the importance of remnant magnetization in the case of the gels with large magnetic particles. PMID:29337918

Self-healing multiphase polymers via dynamic metal-ligand interactions.

PubMed

Mozhdehi, Davoud; Ayala, Sergio; Cromwell, Olivia R; Guan, Zhibin

2014-11-19

A new self-healing multiphase polymer is developed in which a pervasive network of dynamic metal-ligand (zinc-imidazole) interactions are programmed in the soft matrix of a hard/soft two-phase brush copolymer system. The mechanical and dynamic properties of the materials can be tuned by varying a number of molecular parameters (e.g., backbone/brush degree of polymerization and brush density) as well as the ligand/metal ratio. Following mechanical damage, these thermoplastic elastomers show excellent self-healing ability under ambient conditions without any intervention.

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

Tiwari, Pragya; Srivastava, A. K.; Khattak, B. Q.

Polymethyl methacrylate (PMMA) is characterized for electron beam interactions in the resist layer in lithographic applications. PMMA thin films (free standing) were prepared by solvent casting method. These films were irradiated with 30keV electron beam at different doses. Structural and chemical properties of the films were studied by means of X-ray diffraction and Fourier transform infra-red (FTIR) spectroscopy The XRD results showed that the amorphization increases with electron beam irradiation dose. FTIR spectroscopic analysis reveals that electron beam irradiation promotes the scission of carbonyl group and depletes hydrogen and converts polymeric structure into hydrogen depleted carbon network.

Gelling Mechanism of Aluminum Di-Soaps in Oils

NASA Astrophysics Data System (ADS)

Wang, Xiaorong; Rackaitis, Mindaugas

2009-03-01

This work demonstrates that aluminum di-soaps form nano-sized spherical micelles in the oils and that the aggregation of these micelles forms a network that gives rise to a gel formation -- thereby refuting a long-held belief that the gel formation was the result of linear polymeric chains of aluminum association. The discovery of such aluminum nano-particles could expand application of these materials to new technologies because these materials are chemically inert, odorless and nontoxic, and have been widely used in greases, paints, gels, cosmetics, drugs and foods.

Click polymerization for the synthesis of reduction-responsive polymeric prodrug

NASA Astrophysics Data System (ADS)

Zhang, Xiaojin; Wang, Hongquan; Dai, Yu

2018-05-01

Click polymerization is a powerful polymerization technique for the construction of new macromolecules with well-defined structures and multifaceted functionalities. Here, we synthesize reduction-responsive polymeric prodrug PEG- b-(PSS- g-MTX)- b-PEG containing disulfide bonds and pendant methotrexate (MTX) via two-step click polymerization followed by conjugating MTX to pendant hydroxyl. MTX content in polymeric prodrug is 13.5%. Polymeric prodrug is able to form polymeric micelles by self-assembly in aqueous solution. Polymeric micelles are spherical nanoparticles with tens of nanometers in size. Of note, polymeric micelles are reduction-responsive due to disulfide bonds in the backbone of PEG- b-(PSS- g-MTX)- b-PEG and could release pendant drugs in the presence of the reducing agents such as dl-dithiothreitol (DTT).

Chain Reaction Polymerization.

ERIC Educational Resources Information Center

McGrath, James E.

1981-01-01

The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

Pressure-induced stable BeN4 as a high-energy density material

NASA Astrophysics Data System (ADS)

Zhang, Shoutao; Zhao, Ziyuan; Liu, Lulu; Yang, Guochun

2017-10-01

Polynitrogens are the ideal rocket fuels or propellants. Due to strong triple N≡N bond in N2, the direct polymerization of nitrogen is rather difficult (i.e. extreme high temperature and high pressure). However, the use of nitrides as precursors or the reaction of N2 with other elements has been proved to be an effective way to obtain polynitrogens. Here, with assistance of the advanced first-principles swarm-intelligence structure searches, we found that P 1 bar -BeN4, containing infinite zigzag-like polymeric nitrogen chains, can be synthesized by compressing the mixture of Be3N2 and N2 at 25.4 GPa, which is greatly lower than 110 GPa for synthesizing cubic gauche nitrogen and other polynitrogen compounds (e.g. bulk CNO at 52 GPa and SN4 at 49 GPa). Its structural stability can be attributed to the coexistence of ionic Be-N and covalent N-N bonds. Intriguingly, this phase has high kinetic stability and remains metastable at ambient pressure. The exceptional properties, including high energy density (3.60 kJ g-1), high nitrogen content (86.1%), high dynamical stability, and low polymerization pressure, make P 1 bar -structured BeN4 a promising high energy material. Infinite nitrogen chains in P 1 bar -BeN4 transform to N10 rings network in P21/c phase at 115.1 GPa. P 1 bar -BeN4 is metallic, while P21/c-BeN4 is an insulator.

Chondroitin sulfate synthase-2 is necessary for chain extension of chondroitin sulfate but not critical for skeletal development.

PubMed

Ogawa, Hiroyasu; Hatano, Sonoko; Sugiura, Nobuo; Nagai, Naoko; Sato, Takashi; Shimizu, Katsuji; Kimata, Koji; Narimatsu, Hisashi; Watanabe, Hideto

2012-01-01

Chondroitin sulfate (CS) is a linear polysaccharide consisting of repeating disaccharide units of N-acetyl-D-galactosamine and D-glucuronic acid residues, modified with sulfated residues at various positions. Based on its structural diversity in chain length and sulfation patterns, CS provides specific biological functions in cell adhesion, morphogenesis, neural network formation, and cell division. To date, six glycosyltransferases are known to be involved in the biosynthesis of chondroitin saccharide chains, and a hetero-oligomer complex of chondroitin sulfate synthase-1 (CSS1)/chondroitin synthase-1 and chondroitin sulfate synthase-2 (CSS2)/chondroitin polymerizing factor is known to have the strongest polymerizing activity. Here, we generated and analyzed CSS2(-/-) mice. Although they were viable and fertile, exhibiting no overt morphological abnormalities or osteoarthritis, their cartilage contained CS chains with a shorter length and at a similar number to wild type. Further analysis using CSS2(-/-) chondrocyte culture systems, together with siRNA of CSS1, revealed the presence of two CS chain species in length, suggesting two steps of CS chain polymerization; i.e., elongation from the linkage region up to Mr ∼10,000, and further extension. There, CSS2 mainly participated in the extension, whereas CSS1 participated in both the extension and the initiation. Our study demonstrates the distinct function of CSS1 and CSS2, providing a clue in the elucidation of the mechanism of CS biosynthesis.

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

Synthesis, Structure, and Pressure-Induced Polymerization of Li 3 Fe(CN) 6 Accompanied with Enhanced Conductivity

DOE PAGES

Li, Kuo; Zheng, Haiyan; Hattori, Takanori; ...

2015-11-17

By providing a new route to synthesize inorganic/organic conductors with tunable composition and properties, pressure-induced polymerization of charged triple-bond monomers like acetylide and cyanide could lead to formation of a conductive metal–carbon network composite. The industry application of this promising synthetic method is mainly limited by the reaction pressure needed, which is often too high to be reached for gram amounts of sample. Here we successfully synthesized highly conductive Li 3Fe(CN) 6 at maximum pressure around 5 GPa and used in situ diagnostic tools to follow the structural and functional transformations of the sample, including in situ X-ray and neutronmore » diffraction and Raman and impedance spectroscopy, along with the neutron pair distribution function measurement on the recovered sample. The cyanide anions start to react around 1 GPa and bond to each other irreversibly at around 5 GPa, which are the lowest reaction pressures in all known metal cyanides and within the technologically achievable pressure range for industrial production. Moreover, the conductivity of the polymer is above 10 –3 S·cm –1, which reaches the range of conductive polymers. Our investigation suggests that the pressure-induced polymerization route is practicable for synthesizing some types of functional conductive materials for industrial use, and further research like doping and heating can hence be motivated to synthesize novel materials under lower pressure and with better performances.« less

Copper-catalyzed azide alkyne cycloaddition polymer networks

NASA Astrophysics Data System (ADS)

Alzahrani, Abeer Ahmed

The click reaction concept, introduced in 2001, has since spurred the rapid development and reexamination of efficient, high yield reactions which proceed rapidly under mild conditions. Prior to the discovery of facile copper catalysis in 2002, the thermally activated azide-alkyne or Huisgen cycloaddition reaction was largely ignored following its discovery in large part due to its slow kinetics, requirement for elevated temperature and limited selectivity. Now, arguably, the most prolific and capable of the click reactions, the copper-catalyzed azide alkyne cycloaddition (CuAAC) reaction is extremely efficient and affords exquisite control of the reaction. The orthogonally and chemoselectivity of this reaction enable its wide utility across varied scientific fields. Despite numerous inherent advantages and widespread use for small molecule synthesis and solution-based polymer chemistry, it has only recently and rarely been utilized to form polymer networks. This work focuses on the synthesis, mechanisms, and unique attributes of the CuAAC reaction for the fabrication of functional polymer networks. The photo-reduction of a series of copper(II)/amine complexes via ligand metal charge transfer was examined to determine their relative efficiency and selectivity in catalyzing the CuAAC reaction. The aliphatic amine ligands were used as an electron transfer species to reduce Cu(II) upon irradiation with 365 nm light while also functioning as an accelerating agent and as protecting ligands for the Cu(I) that was formed. Among the aliphatic amines studied, tertiary amines such as triethylamine (TEA), tetramethyldiamine (TMDA), N,N,N',N",N"-pentamethyldiethylenetriamine (PMDTA), and hexamethylenetetramine (HMTETA) were found to be the most effective. The reaction kinetics were accelerated by increasing the PMDETA : Cu(II) ratio with a ratio of ligand to Cu(II) of 4:1 yielding the maximum conversion in the shortest time. The sequential and orthogonal nature of the photo-CuAAC reaction and a chain-growth acrylate homopolymerization were demonstrated and used to form branched polymer structures. A bulk, organic soluble initiation system consisting of a Cu(II) salt and a primary amine was also examined in both model reactions and in bulk polymerizations. The system was shown to be highly efficient, leading to nearly complete CuAAC polymerization at ambient temperature. Increasing the ratio of amine to copper from 1 to 4 increases the CuAAC reaction rate significantly from 4 mM/min for 1:1 ratio of Cu(II):hexyalmine to 14mM/min for 1:4 ratio. The concentration dependence of the amine on the reaction rate enables the polymerization rate to be controlled simply by manipulating the hexylamine concentration. Sequential thiol--acrylate and photo-CuAAC click reactions were utilized to form two-stage reactive polymer networks capable of generating wrinkles in a facile manner. The click thiol-Michael addition reaction was utilized to form a cross-linked polymer with residual, reactive alkyne sites that remained tethered throughout the network. The latent, unreacted alkyne sites are subsequently reacted with diazide monomers via a photoinduced Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction to increase the cross-link density. Increased cross-linking raised the modulus and glass transition temperature from 1.6 MPa and 2 °C after the thiol-acrylate reaction to 4.4 MPa and 22 °C after the CuAAC reaction, respectively. The double click reaction approach led to micro-wrinkles with well-controlled wavelength and amplitude of 8.50 +/- 1.6 and 1.4 μm, respectively, for a polymer with a 1280 μm total film thickness. Additionally, this approach further enables spatial selectivity of wrinkle formation by photo-patterning. The CuAAC-based polymerization was also used to design smart, responsive porous materials from well-defined CuAAC networks, which possesses a high glass transition temperature (Tg= 115°C) due to the formation of the triazole linkages. The toughness, recovery, fixity, and shape memory attributes of this material were examined. The unique recovery behavior of the porous CuAAC material is characterized by its ability to recover plastic deformation upon heating. The tough and stiff nature of the glassy CuAAC polymer networks translates into desirable high compressive strain shape memory foams. The CuAAC foam exhibited excellent shape-memory behavior and was able to recover through each of five successive cycles of 80% compression at ambient temperature, presenting a significant volume change and resistance to fracture. In addition, the glassy CuAAC foam was able to withstand more than 10 cycles of compression to 50% strain and subsequent recovery at ambient temperature, indicative of ductile behavior in the glassy state.

Concentration profiles of actin-binding molecules in lamellipodia

NASA Astrophysics Data System (ADS)

Falcke, Martin

2016-04-01

Motile cells form lamellipodia in the direction of motion, which are flat membrane protrusions containing an actin filament network. The network flows rearward relative to the leading edge of the lamellipodium due to actin polymerization at the front. Thus, actin binding molecules are subject to transport towards the rear of the cell in the bound state and diffuse freely in the unbound state. We analyze this reaction-diffusion-advection process with respect to the concentration profiles of these species and provide an analytic approximation for them. Network flow may cause a depletion zone of actin binding molecules close to the leading edge. The existence of such zone depends on the free molecule concentration in the cell body, on the ratio of the diffusion length to the distance bound molecules travel rearward with the flow before dissociating, and the ratio of the diffusion length to the width of the region with network flow and actin binding. Our calculations suggest the existence of depletion zones for the F-actin cross-linkers filamin and α-actinin in fish keratocytes (and other cell types), which is in line with the small elastic moduli of the F-actin network close to the leading edge found in measurements of the force motile cells are able to exert.

Silk Electrogel Rheology

NASA Astrophysics Data System (ADS)

Tabatabai, A. P.; Urbach, J. S.; Blair, D. L.; Kaplan, D. L.

2014-03-01

We present experimental results on the rheology on electrogels derived from aqueous solutions of reconstituted Bombyx Mori silk fibroin protein. Through electrochemistry, the silk protein solution develops local pH changes resulting in the assembly of protein into a weak gel. We determine the physical properties of the electrogels by performing rheology and observe that they exhibit the characteristics of a crosslinked biopolymer network. Interestingly, we find that these silk gels exhibit linear elasticity over a range of up to two orders of magnitude larger than most crosslinked biopolymer networks. Moreover, the nonlinear rheology exhibits a strain-stiffening behavior that is fundamentally different than the strain-stiffening observed in crosslinked biopolymers. Through rheological techniques we aim to understand this distinctive material that cannot be explained by current polymeric models. This work is supported by a grant from the AFOSR FA9550-07-1-0130.

Photoresponsive liquid crystalline epoxy networks with shape memory behavior and dynamic ester bonds

DOE PAGES

Rios, Orlando; Chen, Jihua; Li, Yuzhan; ...

2016-06-01

Functional polymers are intelligent materials that can respond to a variety of external stimuli. However, these materials have not yet found widespread real world applications because of the difficulties in fabrication and the limited number of functional building blocks that can be incorporated into a material. Here, we demonstrate a simple route to incorporate three functional building blocks (azobenzene chromophores, liquid crystals, and dynamic covalent bonds) into an epoxy-based liquid crystalline network (LCN), in which an azobenzene-based epoxy monomer is polymerized with an aliphatic dicarboxylic acid to create exchangeable ester bonds that can be thermally activated. Lastly, all three functionalmore » building blocks exhibited good compatibility, and the resulting materials exhibits various photomechanical, shape memory, and self-healing properties because of the azobenzene molecules, liquid crystals, and dynamic ester bonds, respectively.« less

ISE-based sensor array system for classification of foodstuffs

NASA Astrophysics Data System (ADS)

Ciosek, Patrycja; Sobanski, Tomasz; Augustyniak, Ewa; Wróblewski, Wojciech

2006-01-01

A system composed of an array of polymeric membrane ion-selective electrodes and a pattern recognition block—a so-called 'electronic tongue'—was used for the classification of liquid samples: milk, fruit juice and tonic. The task of this system was to automatically recognize a brand of the product. To analyze the measurement set-up responses various non-parametric classifiers such as k-nearest neighbours, a feedforward neural network and a probabilistic neural network were used. In order to enhance the classification ability of the system, standard model solutions of salts were measured (in order to take into account any variation in time of the working parameters of the sensors). This system was capable of recognizing the brand of the products with accuracy ranging from 68% to 100% (in the case of the best classifier).

Polyelectrolyte-Surfactant Complexes: A New Class of Organogelators

NASA Astrophysics Data System (ADS)

Cavicchi, Kevin; Liu, Yuqing; Guzman, Gustavo

2011-03-01

Polyelectrolyte-surfactant complexes (PE-SURFs) are a class of polymers generated by neutralizing a polyelectrolyte with an oppositely charged surfactant. It has been found that PE-SURFs composed of polystyrene sulfonate and long chain alkyl dimethyl amines act as good organogelators for a range of hydrophobic, organic solvents. Thermo-reversible organogels are formed by heating and cooling PE-SURF/solvent solutions. The gel transition temperature is influenced by the degree of polymerization, the length of the alkyl side-chain, the solubility parameter of the solvent, and the concentration of the gelator. Freeze-drying and scanning electron microscopy characterization of the resultant xerogels shows the formation of rod- and plate-like network morphologies depending on the system parameters. This behavior is consistent with gelation driven by the self-assembly of the amphiphilic PE-SURFs into micellar networks.

Model of turnover kinetics in the lamellipodium: implications of slow- and fast- diffusing capping protein and Arp2/3 complex

NASA Astrophysics Data System (ADS)

McMillen, Laura M.; Vavylonis, Dimitrios

2016-12-01

Cell protrusion through polymerization of actin filaments at the leading edge of motile cells may be influenced by spatial gradients of diffuse actin and regulators. Here we study the distribution of two of the most important regulators, capping protein and Arp2/3 complex, which regulate actin polymerization in the lamellipodium through capping and nucleation of free barbed ends. We modeled their kinetics using data from prior single molecule microscopy experiments on XTC cells. These experiments have provided evidence for a broad distribution of diffusion coefficients of both capping protein and Arp2/3 complex. The slowly diffusing proteins appear as extended ‘clouds’ while proteins bound to the actin filament network appear as speckles that undergo retrograde flow. Speckle appearance and disappearance events correspond to assembly and dissociation from the actin filament network and speckle lifetimes correspond to the dissociation rate. The slowly diffusing capping protein could represent severed capped actin filament fragments or membrane-bound capping protein. Prior evidence suggests that slowly diffusing Apr2/3 complex associates with the membrane. We use the measured rates and estimates of diffusion coefficients of capping protein and Arp2/3 complex in a Monte Carlo simulation that includes particles in association with a filament network and diffuse in the cytoplasm. We consider two separate pools of diffuse proteins, representing fast and slowly diffusing species. We find a steady state with concentration gradients involving a balance of diffusive flow of fast and slow species with retrograde flow. We show that simulations of FRAP are consistent with prior experiments performed on different cell types. We provide estimates for the ratio of bound to diffuse complexes and calculate conditions where Arp2/3 complex recycling by diffusion may become limiting. We discuss the implications of slowly diffusing populations and suggest experiments to distinguish among mechanisms that influence long range transport.

Molecular Mobility of n-Ethylene Glycol Dimethacrylate Glass Formers Upon Free Radical Polymerization

NASA Astrophysics Data System (ADS)

Plaza, Maria Teresa Viciosa

When a liquid upon cooling avoids crystallization, it enters the supercooled state. If the temperature continues to decrease, the consequent increase of viscosity is reflected in the molecular mobility in such a way that the characteristic relaxation times of cooperative motions become of the same order of the experimentally accessible timescales. Further cooling finally transforms the highly viscous liquid into a glass, in which only local motions are allowed. The monomers n-ethylene glycol dimethacrylate (n-EGDMA) for n =1 to 4, that constitutes the object of this study, easily circumvent crystallization, being good candidates to study the molecular mobility in both supercooled and glassy states. Dielectric Relaxation Spectroscopy (DRS) was the technique chosen to obtain detailed information about their molecular mobility (Chapters 1 and 2). The first part of this work consisted in the dielectric characterization of the relaxation processes present above and below the glass transition temperature (Tg), which shifts to higher values with the molecular weight ( Mw), result confirmed by Differential Scanning Calorimetry (DSC). While the cooperative alpha-process associated to the glass transition, and the secondary beta process, depend on Mw, the other found secondary process, gamma, seems to be independent from this factor (Chapter 3). In the next Chapters different strategies were carried out in order to clarify the mechanisms in the origin of these two secondary relaxations (beta and gamma), and to learn about its respective relation with the main a relaxation. Monitoring the real time isothermal free radical polymerization of TrEGDMA by Temperature Modulated Differential Scanning Calorimetry (TMDSC), carried out at temperatures below the gamma T of the final polymer network, we shown among others two important features: i) the vitrification of the polymer in formation leads to relatively low degrees of conversion, and ii) the unreacted monomer is expelled from the highly crosslinked network originating a clear phase separation (Chapter 4). Knowing that phase separation occurs upon the polymerization reaction, the next step was the separate study of the isothermal polymerization of di-, tri- and tetra- EGDMA, giving special attention to the changes in the unreacted monomer's mobility. With the restrictions imposed by the formation of chemical bonds, the alpha and beta relaxations detected in bulk monomers tend to vanish in the newly formed polymer network, while the secondary gamma relaxation kept almost unaffected. The high sensitivity of the beta relaxation to low contents of unreacted monomer was used as a probe of the reaction's advance. These different behaviours shown under polymerization allowed the assignment of the molecular origin of the secondary processes: the gamma relaxation associated to the ethylene glycol twisting motions, while the rotation of the carboxyl groups seems to be related to the beta relaxation (Chapter 5). In what concerns the polymer itself, an additional secondary process was found, betapol, namely in poly-DEGDMA, poly-TrEGDMA and poly-TeEGDMA, with similar characteristics to the one found in poly( n-alkyl methacrylates). This process was confirmed and well characterized when the copolymerization of TrEGDMA with methyl acrylate (MA) was studied varying its composition (Chapter 6). Finally, EGDMA, the smaller monomer of this family, apart from vitrifying, also shows a high tendency to crystallize by coming from both melt and glassy states. The formation of a rigid phase affects mainly the alpha-process whose intensity decreases without suffering significant changes in the temperature dependence of the characteristic relaxation time. On the other hand, the secondary beta process becomes very well defined and narrowest, indicating a more homogeneous environment around the local-motions (Chapter 7).

Carbon nanotube network evolution during deformation of PVDF-MWNT nanocomposites

NASA Astrophysics Data System (ADS)

Rizvi, Reza; Naguib, Hani E.

2013-04-01

The emergence of novel electronic systems and their requirements have necessitated the evolution of new material classes. The traditional electronic semiconductors and components are shifting from silicon based substrates to polymers and other organic compounds. Sensor components are no exceptions, where compliant polymeric materials offer the possibility of flexible electronics. This paper examines the fabrication and characterization of piezoresistive nanocomposites for pressure sensing applications. The matrix material employed was Polyvinylidene Fluoride (PVDF). The PVDF phase was reinforced with conductive particles, in order to form a conductive filler network throughout the nanocomposite. Multiwall carbon nanotubes (MWNT) were selected as conductive particles to form the networks. The composites were prepared by melt mixing the PVDF and conductive particles in compositions ranging from 0.25 to 10 wt% conductive particle in PVDF. The dielectric permittivity and electrical conductivity of the composites was characterized and the electrical percolation behavior of PVDF nanocomposites fitted to the statistical percolation model. Scanning electron was employed to understand the morphology of the filler networks in the PVDF nanocomposites. Quasi-static piezoresistance of the nanocomposites was characterized using a custom-built force-resistance measurement setup under compressive loading conditions.

Radical-Mediated Enzymatic Polymerizations

PubMed Central

Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

2016-01-01

Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

Inorganic-polymer-derived dielectric films

DOEpatents

Brinker, C.J.; Keefer, K.D.; Lenahan, P.M.

1985-02-25

A method is disclosed for coating a substrate with a thin film of a predetermined porosity. The method comprises: depositing the thin film on the substrate from a non-gelled solution comprising at least one metal alkoxide of a polymeric network forming cation, water, an alcohol compatible with the hydrolysis and the polymerization of the metal alkoxide, and an acid or a base; prior to said depositing step, controlling the porosity and structure of said coating for a given composition of said solution exclusive of the acid or base component and the water component, by adjusting each of the water content, the pH, the temperature and the time of standing of said solution, increasing/descreasing the water content or the pH to increase/decrease the pore size of said coating, and increasing/decreasing the temperature or time of standing of said solution to increase/decrease the pore size of said coating; and curing said deposited film at a temperature effective for curing whereby there is obtained a thin film coating of a predetermined porosity on the substrate.

All-SPEEK flexible supercapacitor exploiting laser-induced graphenization

NASA Astrophysics Data System (ADS)

Lamberti, A.; Serrapede, M.; Ferraro, G.; Fontana, M.; Perrucci, F.; Bianco, S.; Chiolerio, A.; Bocchini, S.

2017-09-01

Flexible supercapacitors have emerged as one of the more promising and efficient space-saving energy storage system for portable and wearable electronics. Laser-induced graphenization has been recently proposed as a powerful and scalable method to directly convert a polymeric substrate into a 3D network of few layer graphene as high-performance supercapacitor electrode. Unfortunately this outstanding process has been reported to be feasible only for few thermoplastic polymers, strongly limiting its future developments. Here we show that laser induced graphenization of sulfonated poly(ether ether ketone) (SPEEK) can be obtained and the mechanism of this novel process is proposed. The resulting material can act at the same time as binder-free electrode and current collector. Moreover SPEEK is also used both as separator and polymeric electrolyte allowing the assembling of an all-SPEEK flexible supercapacitor. Chemico-physical characterization provides deep understanding of the laser-induced graphenization process, reported on this polymer for the first time, while the device performance studied by cyclic voltammetry, charging-discharging, and impedance spectroscopy prove the enormous potential of the proposed approach.

2015 Clinical trials update in sickle cell anemia

PubMed Central

Archer, Natasha; Galacteros, Frédéric; Brugnara, Carlo

2017-01-01

Polymerization of HbS and cell sickling are the prime pathophysiological events in sickle cell disease (SCD). Over the last 30 years, a substantial understanding at the molecular level has been acquired on how a single amino acid change in the structure of the beta chain of hemoglobin leads to the explosive growth of the HbS polymer and the associated changes in red cell morphology. O2 tension and intracellular HbS concentration are the primary molecular drivers of this process, and are obvious targets for developing new therapies. However, polymerization and sickling are driving a complex network of associated cellular changes inside and outside of the erythrocyte, which become essential components of the inflammatory vasculopathy and result in a large range of potential acute and chronic organ damages. In these areas, a multitude of new targets for therapeutic developments have emerged, with several ongoing or planned new therapeutic interventions. This review outlines the key points of SCD pathophysiology as they relate to the development of new therapies, both at the pre-clinical and clinical levels. PMID:26178236

Elasticity dominated surface segregation of small molecules in polymer mixtures

NASA Astrophysics Data System (ADS)

Croce, Salvatore; Krawczyk, Jaroslaw; McLeish, Tom; Chakrabarti, Buddhapriya

When a binary polymer mixture with mobile components is left to equilibrate, the low molecular weight component migrates to the free surface. A balance between loss of translational entropy and gain in surface energy dictates the equilibrium partitioning ratio and the migrant fraction. Despite its ubiquity and several theoretical and experimental investigations, the phenomenon is not fully understood. Further, methods by which migration can be controlled are in its nascent stage of development. We propose a new phenomenological free energy functional that incorporates the elasticity of bulk polymer mixtures (reticulated networks and gels) and show (using mean field and self-consistent field theories) that the migrant fraction decreases with increasing the bulk modulus of the system. Further, a wetting transition observed otherwise for large values of miscibility parameter and polymerization index can be avoided by increasing the elastic modulus of the system. Estimated values of moduli (for the effect to be observable) are akin to those of rubbery polymers. Our work paves the way for controlling surface migration in complex industrial formulations with polymeric ingredients where this effect leads to decreased product stability and performance.

Copolymers enhance selective bacterial community colonization for potential root zone applications.

PubMed

Pham, Vy T H; Murugaraj, Pandiyan; Mathes, Falko; Tan, Boon K; Truong, Vi Khanh; Murphy, Daniel V; Mainwaring, David E

2017-11-21

Managing the impact of anthropogenic and climate induced stress on plant growth remains a challenge. Here we show that polymeric hydrogels, which maintain their hydrous state, can be designed to exploit functional interactions with soil microorganisms. This microbial enhancement may mitigate biotic and abiotic stresses limiting productivity. The presence of mannan chains within synthetic polyacrylic acid (PAA) enhanced the dynamics and selectivity of bacterial ingress in model microbial systems and soil microcosms. Pseudomonas fluorescens exhibiting high mannan binding adhesins showed higher ingress and localised microcolonies throughout the polymeric network. In contrast, ingress of Bacillus subtilis, lacking adhesins, was unaltered by mannan showing motility comparable to bulk liquids. Incubation within microcosms of an agricultural soil yielded hydrogel populations significantly increased from the corresponding soil. Bacterial diversity was markedly higher in mannan containing hydrogels compared to both control polymer and soil, indicating enhanced selectivity towards microbial families that contain plant beneficial species. Here we propose functional polymers applied to the potential root zone which can positively influence rhizobacteria colonization and potentially plant growth as a new approach to stress tolerance.

Simultaneous Measurement of Fluorescence, Conversion and Physical/mechanical Properties for Monitoring Bulk and Localized Photopolymerization Reactions in Heterogeneous Systems

PubMed Central

Medel, S.; Bosch, P.; Grabchev, I.; Shah, P. K.; Liu, J.; Aguirre-Soto, A.; Stansbury, J. W.

2016-01-01

An FT-NIR spectrometer, rheometer and fluorescence spectrophotometer were coupled for the real-time monitoring of polymerization reactions, allowing the simultaneous tracking of polymerization kinetics, storage modulus as well as fluorescence. In this study, a methacrylate functionalized dansyl chromophore (DANSMA) was synthesized and two different nanogels were made from urethane dimethacrylate and isobornyl methacrylate. Two series of resin formulations were prepared using the DANSMA probe, ethoxylated bisphenol A dimethacrylate as the matrix monomer, Irgacure® 651 as the initiator and the dispersed, monomer-swollen nanogels to give clear UV-curable resins. Placement of the fluorescent probe either throughout the resin or linked into the nanogel before its dispersion in the matrix provides a tool to study how the nanogel structure affects local network development by means of fluorescence from the DANSMA probe. We demonstrate the potential of this new technique using a composite as the two phase system (resin and polymerizable nanogel) including a dansyl derivative as a polymerizable probe to follow the reactions that are taking places in both phases. PMID:27213038

Novel Polymer Aerogel toward High Dimensional Stability, Mechanical Property, and Fire Safety.

PubMed

Shang, Ke; Yang, Jun-Chi; Cao, Zhi-Jie; Liao, Wang; Wang, Yu-Zhong; Schiraldi, David A

2017-07-12

Inorganc silica-based aerogels, the earliest and widely used aerogels, have poorer mechanical properties than their organic substitutes, which are flammable. In this study, a novel polymeric aerogel with high strength, inherent flame retardancy, and cost-effectiveness, which is based on poly(vinyl alcohol) (PVA) cross-linked with melamine-formaldehyde (MF), was prepared under aqueous condition with an ecofriendly freeze-drying and postcuring process. Combined with the additional rigid MF network and benifited from the resulting unique infrastructure of inter-cross-linked flexible PVA segments and rigid MF segments, PVA-based aerogels exibited a significantly decreased degradation rate and sharply decreased peak heat release rate (PHRR) in cone calorimeter tests (by as much as 83%) compared with neat PVA. The polymer aerogels have a limiting oxygen index (LOI) as high as 36.5% and V-0 rating in UL-94 test. Furthermore, the aerogel samples exposured to harsh temperatures maintain their dimensions (<10% change), original mechanical strength and fire safety. Therefore, this work provides a novel stragegy for preparing pure organic polymeric aerogel materials with high mechanical strength, dimensional stability, and fire safety.

PPFIA1 drives active α5β1 integrin recycling and controls fibronectin fibrillogenesis and vascular morphogenesis

PubMed Central

Mana, Giulia; Clapero, Fabiana; Panieri, Emiliano; Panero, Valentina; Böttcher, Ralph T.; Tseng, Hui-Yuan; Saltarin, Federico; Astanina, Elena; Wolanska, Katarzyna I.; Morgan, Mark R.; Humphries, Martin J.; Santoro, Massimo M.; Serini, Guido; Valdembri, Donatella

2016-01-01

Basolateral polymerization of cellular fibronectin (FN) into a meshwork drives endothelial cell (EC) polarity and vascular remodelling. However, mechanisms coordinating α5β1 integrin-mediated extracellular FN endocytosis and exocytosis of newly synthesized FN remain elusive. Here we show that, on Rab21-elicited internalization, FN-bound/active α5β1 is recycled to the EC surface. We identify a pathway, comprising the regulators of post-Golgi carrier formation PI4KB and AP-1A, the small GTPase Rab11B, the surface tyrosine phosphatase receptor PTPRF and its adaptor PPFIA1, which we propose acts as a funnel combining FN secretion and recycling of active α5β1 integrin from the trans-Golgi network (TGN) to the EC surface, thus allowing FN fibrillogenesis. In this framework, PPFIA1 interacts with active α5β1 integrin and localizes close to EC adhesions where post-Golgi carriers are targeted. We show that PPFIA1 is required for FN polymerization-dependent vascular morphogenesis, both in vitro and in the developing zebrafish embryo. PMID:27876801

Solvent-Vapor-Mitigation of Electrostatics in 3D Cyclopropenium Diblock Copolyelectrolyte Network

NASA Astrophysics Data System (ADS)

Russell, Sebastian; Kumar, Sanat; Campos, Luis

Photolithography is progressively becoming an obsolete manufacturing technique in the microelectronic industry as block copolymer (BCP) nanoassembles approach sub 10-nm features sizes. Thermodynamically, the morphology and limiting feature size, for BCP, are determined by the relative volume fraction and magnitude of the incompatibility (χN) between each block. Therefore, to achieve smaller dimensions, it is imperative to devise copolymer systems that are strongly segregating (χN >>10) by utilizing high monomer incompatibility, large χ. For synthetic cylinder forming BCPs, achieving sub-10 nm features with a high degree of lateral ordering still remains a challenge. Covalently bound ions could potentially be a route towards enhancing the segmental incompatibility and this presentation will focus on the self-assembly of post-polymerization functionalized cyclopropenium-ion diblock copolyelectrolytes (DBCPE) through solvent vapor annealing. By varying the BCPE's total degree of polymerization and charge fraction we have mapped the kinetic phase-space. This control over morphology has opened the door to sub-10nm features with tunable densities by varying the length of the neutral and polyelectrolyte block, respectively. Chemical Engineering Department.

Polymerization and Structure of Bio-Based Plastics: A Computer Simulation

NASA Astrophysics Data System (ADS)

Khot, Shrikant N.; Wool, Richard P.

2001-03-01

We recently examined several hundred chemical pathways to convert chemically functionalized plant oil triglycerides, monoglycerides and reactive diluents into high performance plastics with a broad range of properties (US Patent No. 6,121,398). The resulting polymers had linear, branched, light- and highly-crosslinked chain architectures and could be used as pressure sensitive adhesives, elastomers and high performance rigid thermoset composite resins. To optimize the molecular design and minimize the number of chemical trials in this system with excess degrees of freedom, we developed a computer simulation of the free radical polymerization process. The triglyceride structure, degree of chemical substitution, mole fractions, fatty acid distribution function, and reaction kinetic parameters were used as initial inputs on a 3d lattice simulation. The evolution of the network fractal structure was computed and used to measure crosslink density, dangling ends, degree of reaction and defects in the lattice. The molecular connectivity was used to determine strength via a vector percolation model of fracture. The simulation permitted the optimal design of new bio-based materials with respect to monomer selection, cure reaction conditions and desired properties. Supported by the National Science Foundation

21 CFR 177.2250 - Filters, microporous polymeric.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Filters, microporous polymeric. 177.2250 Section... Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in... liquid food. (a) Microporous polymeric filters consist of a suitably permeable, continuous, polymeric...

The role of living/controlled radical polymerization in the formation of improved imprinted polymers.

PubMed

Salian, Vishal D; Vaughan, Asa D; Byrne, Mark E

2012-06-01

In this work, living/controlled radical polymerization (LRP) is compared with conventional free radical polymerization in the creation of highly and weakly cross-linked imprinted poly(methacrylic acid-co-ethylene glycol dimethacrylate) networks. It elucidates, for the first time, the effect of LRP on the chain level and begins to explain why the efficiency of the imprinting process is improved using LRP. Imprinted polymers produced via LRP exhibited significantly higher template affinity and capacity compared with polymers prepared using conventional methods. The use of LRP in the creation of highly cross-linked imprinted polymers resulted in a fourfold increase in binding capacity without a decrease in affinity; whereas weakly cross-linked gels demonstrated a nearly threefold increase in binding capacity at equivalent affinity when LRP was used. In addition, by adjusting the double bond conversion, we can choose to increase either the capacity or the affinity in highly cross-linked imprinted polymers, thus allowing the creation of imprinted polymers with tailorable binding parameters. Using free radical polymerization in the creation of polymer chains, as the template-monomer ratio increased, the average molecular weight of the polymer chains decreased despite a slight increase in the double bond conversion. Thus, the polymer chains formed were shorter but greater in number. Using LRP neutralized the effect of the template. The addition of chain transfer agent resulted in slow, uniform, simultaneous chain growth, resulting in the formation of longer more monodisperse chains. Reaction analysis revealed that propagation time was extended threefold in the formation of highly cross-linked polymers when LRP techniques were used. This delayed the transition to the diffusion-controlled stage of the reaction, which in turn led to the observed enhanced binding properties, decreased polydispersity in the chains, and a more homogeneous macromolecular architecture. Copyright © 2012 John Wiley & Sons, Ltd.

Photo-responsive polymeric micelles.

PubMed

Huang, Yu; Dong, Ruijiao; Zhu, Xinyuan; Yan, Deyue

2014-09-07

Photo-responsive polymeric micelles have received increasing attention in both academic and industrial fields due to their efficient photo-sensitive nature and unique nanostructure. In view of the photo-reaction mechanism, photo-responsive polymeric micelles can be divided into five major types: (1) photoisomerization polymeric micelles, (2) photo-induced rearrangement polymeric micelles, (3) photocleavage polymeric micelles, (4) photo-induced crosslinkable polymeric micelles, and (5) photo-induced energy conversion polymeric micelles. This review highlights the recent advances of photo-responsive polymeric micelles, including the design, synthesis and applications in various biomedical fields. Especially, the influence of different photo-reaction mechanisms on the morphology, structure and properties of the polymeric micelles is emphasized. Finally, the possible future directions and perspectives in this emerging area are briefly discussed.

Thrombin-dependent Incorporation of von Willebrand Factor into a Fibrin Network*

PubMed Central

Miszta, Adam; Pelkmans, Leonie; Lindhout, Theo; Krishnamoorthy, Ganeshram; de Groot, Philip G.; Hemker, Coenraad H.; Heemskerk, Johan W. M.; Kelchtermans, Hilde; de Laat, Bas

2014-01-01

Attachment of platelets from the circulation onto a growing thrombus is a process involving multiple platelet receptors, endothelial matrix components, and coagulation factors. It has been indicated previously that during a transglutaminase reaction activated factor XIII (FXIIIa) covalently cross-links von Willebrand factor (VWF) to polymerizing fibrin. Bound VWF further recruits and activates platelets via interactions with the platelet receptor complex glycoprotein Ib (GPIb). In the present study we found proof for binding of VWF to a fibrin monomer layer during the process of fibrinogen-to-fibrin conversion in the presence of thrombin, arvin, or a snake venom from Crotalus atrox. Using a domain deletion mutant we demonstrated the involvement of the C domains of VWF in this binding. Substantial binding of VWF to fibrin monomers persisted in the presence of the FXIIIa inhibitor K9-DON, illustrating that cross-linking via factor XIII is not essential for this phenomenon and suggesting the identification of a second mechanism through which VWF multimers incorporate into a fibrin network. Under high shear conditions, platelets were shown to adhere to fibrin only if VWF had been incorporated. In conclusion, our experiments show that the C domains of VWF and the E domain of fibrin monomers are involved in the incorporation of VWF during the polymerization of fibrin and that this incorporation fosters binding and activation of platelets. Fibrin thus is not an inert end product but partakes in further thrombus growth. Our findings help to elucidate the mechanism of thrombus growth and platelet adhesion under conditions of arterial shear rate. PMID:25381443

Photoinitiator-Free Synthesis of Endothelial Cell Adhesive and Enzymatically Degradable Hydrogels

PubMed Central

Jones, Derek R.; Marchant, Roger E.; von Recum, Horst; Gupta, Anirban Sen; Kottke-Marchant, Kandice

2015-01-01

We report on a photoinitiator-free synthetic method of incorporating bioactivity into poly(ethylene glycol) (PEG) hydrogels in order to control physical properties, enzymatic biodegradability and cell-specific adhesiveness of the polymer network, while eliminating the need for UV-mediated photopolymerization. To accomplish this, hydrogel networks were polymerized using Michael addition with four-arm PEG acrylate (10 kDa), using a collagenase sensitive peptide (CSP) as a crosslinker, and introducing an endothelial cell adhesive peptide either terminally (RGD) or attached to the crosslinking peptide sequence (CSP-RGD). The efficiency of the Michael addition reactions were determined by NMR and Ellman’s assay. Successful decoupling of cell adhesivity and physical properties was demonstrated by quantifying and comparing the swelling ratios and Young’s Moduli of various hydrogel formulations. Degradation profiles were established by incubating functionalized hydrogels in collagenase solutions (0.0 – 1.0 µg/mL), demonstrating that functionalized hydrogels degraded at a rate dependent upon collagenase concentration. Moreover, it was shown that the degradation rate was independent of CSP-RGD concentration. Cell attachment and proliferation on functionalized hydrogels were compared for various RGD concentrations, providing evidence that cell attachment and proliferation were directly related to relative amounts of the CSP-RGD combination peptide. An increase in cell viability was achieved using Michael addition techniques when compared to UV-polymerization, and was assessed by a LIVE/DEAD fluorescence assay. This photoinitiator-free method shows promise in creating hydrogel-based tissue engineering scaffolds allow for decoupled cell adhesivity and physical properties and that render greater cell viability. PMID:25462848

Optimization of Polymer-ECM Composite Scaffolds for Tissue Engineering: Effect of Cells and Culture Conditions on Polymeric Nanofiber Mats

PubMed Central

Goyal, Ritu; Guvendiren, Murat; Freeman, Onyi; Mao, Yong; Kohn, Joachim

2017-01-01

The design of composite tissue scaffolds containing an extracellular matrix (ECM) and synthetic polymer fibers is a new approach to create bioactive scaffolds that can enhance cell function. Currently, studies investigating the effects of ECM-deposition and decellularization on polymer degradation are still lacking, as are data on optimizing the stability of the ECM-containing composite scaffolds during prolonged cell culture. In this study, we develop fibrous scaffolds using three polymer compositions, representing slow (E0000), medium (E0500), and fast (E1000) degrading materials, to investigate the stability, degradation, and mechanics of the scaffolds during ECM deposition and decellularization, and during the complete cellularization-decell-recell cycle. We report data on percent molecular weight (% Mw) retention of polymeric fiber mats, changes in scaffold stiffness, ECM deposition, and the presence of fibronectin after decellularization. We concluded that the fast degrading E1000 (Mw retention ≤ 50% after 28 days) was not sufficiently stable to allow scaffold handling after 28 days in culture, while the slow degradation of E0000 (Mw retention ≥ 80% in 28 days) did not allow deposited ECM to replace the polymer support. The scaffolds made from medium degrading E0500 (Mw retention about 60% at 28 days) allowed the gradual replacement of the polymer network with cell-derived ECM while maintaining the polymer network support. Thus, polymers with an intermediate rate of degradation, maintaining good scaffold handling properties after 28 days in culture, seem best suited for creating ECM-polymer composite scaffolds. PMID:28085047

Development and optimization of locust bean gum and sodium alginate interpenetrating polymeric network of capecitabine.

PubMed

Upadhyay, Mansi; Adena, Sandeep Kumar Reddy; Vardhan, Harsh; Pandey, Sureshwar; Mishra, Brahmeshwar

2018-03-01

The objective of the study was to develop interpenetrating polymeric network (IPN) of capecitabine (CAP) using natural polymers locust bean gum (LBG) and sodium alginate (NaAlg). The IPN microbeads were optimized by Box-Behnken Design (BBD) to provide anticipated particle size with good drug entrapment efficiency. The comparative dissolution profile of IPN microbeads of CAP with the marketed preparation proved an excellent sustained drug delivery vehicle. Ionotropic gelation method utilizing metal ion calcium (Ca 2+ ) as a cross-linker was used to prepare IPN microbeads. The optimization study was done by response surface methodology based Box-Behnken Design. The effect of the factors on the responses of optimized batch was exhibited through response surface and contour plots. The optimized batch was analyzed for particle size, % drug entrapment, pharmacokinetic study, in vitro drug release study and further characterized by FTIR, XRD, and SEM. To study the water uptake capacity and hydrodynamic activity of the polymers, swelling studies and viscosity measurement were performed, respectively. The particle size and % drug entrapment of the optimized batch was 494.37 ± 1.4 µm and 81.39 ± 2.9%, respectively, closer to the value predicted by Minitab 17 software. The in vitro drug release study showed sustained release of 92% for 12 h and followed anomalous drug release pattern. The derived pharmacokinetic parameters of optimized batch showed improved results than pure CAP. Thus, the formed IPN microbeads of CAP proved to be an effective extended drug delivery vehicle for the water soluble antineoplastic drug.

A Localized Complex of Two Protein Oligomers Controls the Orientation of Cell Polarity

PubMed Central

Lasker, Keren; Ahrens, Daniel G.; Eckart, Michael R.

2017-01-01

ABSTRACT Signaling hubs at bacterial cell poles establish cell polarity in the absence of membrane-bound compartments. In the asymmetrically dividing bacterium Caulobacter crescentus, cell polarity stems from the cell cycle-regulated localization and turnover of signaling protein complexes in these hubs, and yet the mechanisms that establish the identity of the two cell poles have not been established. Here, we recapitulate the tripartite assembly of a cell fate signaling complex that forms during the G1-S transition. Using in vivo and in vitro analyses of dynamic polar protein complex formation, we show that a polymeric cell polarity protein, SpmX, serves as a direct bridge between the PopZ polymeric network and the cell fate-directing DivJ histidine kinase. We demonstrate the direct binding between these three proteins and show that a polar microdomain spontaneously assembles when the three proteins are coexpressed heterologously in an Escherichia coli test system. The relative copy numbers of these proteins are essential for complex formation, as overexpression of SpmX in Caulobacter reorganizes the polarity of the cell, generating ectopic cell poles containing PopZ and DivJ. Hierarchical formation of higher-order SpmX oligomers nucleates new PopZ microdomain assemblies at the incipient lateral cell poles, driving localized outgrowth. By comparison to self-assembling protein networks and polar cell growth mechanisms in other bacterial species, we suggest that the cooligomeric PopZ-SpmX protein complex in Caulobacter illustrates a paradigm for coupling cell cycle progression to the controlled geometry of cell pole establishment. PMID:28246363

Property evolution during vitrification of dimethacrylate photopolymer networks

PubMed Central

Abu-Elenain, Dalia; Lewis, Steven H.; Stansbury, Jeffrey W.

2013-01-01

Objectives This study seeks to correlate the interrelated properties of conversion, shrinkage, modulus and stress as dimethacrylate networks transition from rubbery to glassy states during photopolymerization. Methods An unfilled BisGMA/TEGDMA resin was photocured for various irradiation intervals (7–600 s) to provide controlled levels of immediate conversion, which was monitored continuously for 10 min. Fiber optic near-infrared spectroscopy permitted coupling of real-time conversion measurement with dynamic polymerization shrinkage (linometer), modulus (dynamic mechanical analyzer) and stress (tensometer) development profiles. Results The varied irradiation conditions produced final conversion ranging from 6 % to more than 60 %. Post-irradiation conversion (dark cure) was quite limited when photopolymerization was interrupted either at very low or very high levels of conversion while significant dark cure contributions were possible for photocuring reactions suspended within the post-gel, rubbery regime. Analysis of conversion-based property evolution during and subsequent to photocuring demonstrated that the shrinkage rate increased significantly at about 40 % conversion followed by late-stage suppression in the conversion-dependent shrinkage rate that begins at about 45–50 % conversion. The gradual vitrification process over this conversion range is evident based on the broad but well-defined inflection in the modulus versus conversion data. As limiting conversion is approached, modulus and, to a somewhat lesser extent, stress rise precipitously as a result of vitrification with the stress profile showing little if any late-stage suppression as seen with shrinkage. Significance Near the limiting conversion for this model resin, the volumetric polymerization shrinkage rate slows while an exponential rise in modulus promotes the vitrification process that appears to largely dictate stress development. PMID:24080378

Synthesis of adhesive peptides similar to those found in blue mussel (Mytilus edulis) using papain and tyrosinase.

PubMed

Numata, Keiji; Baker, Peter James

2014-08-11

The blue mussel (Mytilus edulis) foot protein 5 (Mefp-5) is an adhesive protein that is mainly composed of glycine, l-lysine, and 3,4-dihydroxy-l-phenylalanine (DOPA). Thousands of adhesive pads have been analyzed in previous studies, whereby it has been found that adhesion is largely achieved by the redox-chemistry of DOPA, and that l-lysine (approximately 20 mol %) affects the formation of molecular networks. While DOPA and lysine are essential for biomimetic adhesive design, the synthesis of copolymers containing DOPA is limited, in terms of yield, by the multiple reaction steps required. Here, we synthesized adhesive peptides containing DOPA and l-lysine via two enzymatic reactions, namely, chemoenzymatic synthesis of copolypeptides of l-tyrosine and l-lysine by Papaya peptidase I (papain), as well as the enzymatic conversion from l-tyrosine to DOPA by tyrosinase. The synthesis was characterized in terms of yield, degree of polymerization, and composition of the polypeptide. In addition, the conversion of tyrosine to DOPA by tyrosinase was evaluated quantitatively by nuclear magnetic resonance and amino acid analysis. The adhesive properties of the resulting peptides, consisting of DOPA, l-lysine, and l-tyrosine, were evaluated at various pH levels with different protonation/deprotonation states. Our results show that deprotonated DOPA is required for adhesive function, and the deprotonated primary amine group of lysine induces molecular networks by varying the elastic moduli of the adhesives. In this study, we demonstrate the benefit of combining multiple enzymatic reactions, including chemoenzymatic polymerization, in obtaining new types of peptide-based materials.

Improved lignin polyurethane properties with Lewis acid treatment.

PubMed

Chung, Hoyong; Washburn, Newell R

2012-06-27

Chemical modification strategies to improve the mechanical properties of lignin-based polyurethanes are presented. We hypothesized that treatment of lignin with Lewis acids would increase the concentration of hydroxyl groups available to react with diisocyanate monomers. Under the conditions used, hydrogen bromide-catalyzed modification resulted in a 28% increase in hydroxyl group content. Associated increases in hydrophilicity of solvent-cast thin films were also recorded as evidenced by decreases in water contact angle. Polyurethanes were then prepared by first preparing a prepolymer based on mixtures of toluene-2,4-diisocyanate (TDI) and unmodified or modified lignin, then polymerization was completed through addition of polyethylene glycol (PEG), resulting in mass ratios of TDI:lignin:PEG of 43:17:40 in the compositions investigated here. The mixture of TDI and unmodified lignin resulted in a lignin powder at the bottom of the liquid, suggesting it did not react directly with TDI. However, a homogeneous solution resulted when TDI and the hydrogen bromide-treated lignin were mixed, suggesting demethylation indeed increased reactivity and resulted in better integration of lignin into the urethane network. Significant improvements in mechanical properties of modified lignin polyurethanes were observed, with a 6.5-fold increase in modulus, which were attributed to better integration of the modified lignin into the covalent polymer network due to the higher concentration of hydroxyl groups. This research indicates that chemical modification strategies can lead to significant improvements in the properties of lignin-based polymeric materials using a higher fraction of an inexpensive lignin monomer from renewable resources and a lower fraction an expensive, petroleum-derived isocyanate monomer to achieve the required material properties.

Subsistence economy of el paraiso, an early peruvian site.

PubMed

Quilter, J; E, B O; Pearsall, D M; Sandweiss, D H; Jones, J G; Wing, E S

1991-01-18

Studies of food remains from the Preceramic monumental site of E1 Paraíso, Peru (1800 to 1500 B.C.), have shed new light on a debate regarding the relative importance of seafood versus terrestrial resources and the role of cultigens in subsistence economies during the early development of Peruvian civilization. Fish was the primary animal food at the site whereas plant foods consisted of a mixture of cultivated resources (squashes, beans, peppers, and jicama) with an additional reliance on fruits (guava, lucuma, and pacae). Wild plants, especially the roots of sedges and cat-tail, also may have accounted for a substantial part of the diet. Cotton was a chief crop, used in making fishing tackle and the textiles that served as clothing and items of high value and status. As an example of the beginnings of civilization, El Paraíso is a case in which impressive architecture was built on a relatively simple subsistence economy and energy was expended in the production of resources useful in local and regional exchange systems.

Starch grains reveal early root crop horticulture in the Panamanian tropical forest.

PubMed

Piperno, D R; Ranere, A J; Holst, I; Hansell, P

2000-10-19

Native American populations are known to have cultivated a large number of plants and domesticated them for their starch-rich underground organs. Suggestions that the likely source of many of these crops, the tropical forest, was an early and influential centre of plant husbandry have long been controversial because the organic remains of roots and tubers are poorly preserved in archaeological sediments from the humid tropics. Here we report the occurrence of starch grains identifiable as manioc (Manihot esculenta Crantz), yams (Dioscorea sp.) and arrowroot (Maranta arundinacea L.) on assemblages of plant milling stones from preceramic horizons at the Aguadulce Shelter, Panama, dated between 7,000 and 5,000 years before present (BP). The artefacts also contain maize starch (Zea mays L.), indicating that early horticultural systems in this region were mixtures of root and seed crops. The data provide the earliest direct evidence for root crop cultivation in the Americas, and support an ancient and independent emergence of plant domestication in the lowland Neotropical forest.

A versatile technique for fabrication of SiC SPM probes

NASA Astrophysics Data System (ADS)

Therrien, Joel; Schmidt, Daniel; Barrot, Sheetal; Patel, Bhavin

2008-03-01

To date SPM probes have largely been fabricated via methods borrowed from the semiconductor industry for fabricating Micro Electro Mechanical Systems. Although these techniques have enabled SPM to see widespread use, the processes put significant limitations on what structures can be made. We report our progress on fabricating SPM cantilevers composed of Silicon Carbide using polymer molding techniques. A pre-ceramic polymer is molded into the desired probe shape and then converted to SiC via pyrolisys. We will also report on progress in using photo-sterolithography for fabrication of even more complex geometries. In addition to opening up a much larger set of probe structures, the use of SiC leads to improved wear resistance of the resulting probes. Among the potential applications, this method enables the fabrication of low spring constant, high resonant frequency cantilevers via cross sectional geometries not accessible to standard fabrication techniques. Such probes are required for high speed tapping and non-contact imaging.

Radiation-induced polymerization of glass-forming systems. IV. Effect of the homogeneity of polymerization phase and polymer concentration on temperature dependence of initial polymerization rate

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

Kaetsu, I.; Ito, A.; Hayashi, K.

1973-06-01

The effect of homogeneity of polymerization phase and monomer concentration on the temperature dependence of initial polymerization rate was studied in the radiation-induced radical polymerization of binary systems consisting of glass-forming monomer and solvent. In the polymerization of a completely homogeneous system such as HEMA-propylene glycol, a maximum and a minimum in polymerization rates as a function of temperature, characteristic of the polymerization in glass-forming systems, were observed for all monomer concentrations. However, in the heterogeneous polymerization systems such as HEMA-triacetin and HEMAisoamyl acetate, maximum and minimum rates were observed in monomer-rich compositions but not at low monomer concentrations. Furthermore,more » in the HEMA-dioctyl phthalate polymerization system, which is extremely heterogeneous, no maximum and minimum rates were observed at any monomer concentration. The effect of conversion on the temperature dependence of polymerization rate in homogeneous bulk polymerization of HEMA and GMA was investigated. Maximum and minimum rates were observed clearly in conversions less than 10% in the case of HEMA and less than 50% in the case of GMA, but the maximum and minimum changed to a mere inflection in the curve at higher conversions. A similar effect of polymer concentration on the temperature dependence of polymerization rate in the GMA-poly(methyl methacrylate) system was also observed. It is deduced that the change in temperature dependence of polymerization rate is attributed to the decrease in contribution of mutual termination reaction of growing chain radicals to the polymerization rate. (auth)« less

Structural environments of incompatible elements in silicate glass/melt systems: I. Zirconium at trace levels

NASA Astrophysics Data System (ADS)

Farges, Franã§Ois; Ponader, Carl W.; Brown, Gordon E., Jr.

1991-06-01

The structural environments of trace levels (2˜000 ppm) of Zr 4+ in several silicate glasses were examined as a function of melt composition and polymerization using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Glass compositions investigated were albite (NaAlSi 3O 8: AB) and a peralkaline composition (Na 3.3AlSi 7O 17: PR)- Zirconium was added to the oxide-carbonate mix prior to melting in the form of ZrO 2 (baddeleyite). A second set of Zr-silicate glasses containing 2000 ppm Zr and 1.0 to 2.4 wt% halogens (F as NaF and Cl as NaCl) was also synthesized. These included the Zr-AB and Zr-PR base-glass compositions as well as Zr-sodium trisilicate composition (Na2Si 3O 7: TS). In all glasses studied, Zr is mainly 6-coordinated by oxygen atoms ( d[Zr-O] ˜2.07 ± 0.01 Å). In the most polymerized glass (AB), a small but significant amount of Zr was also found to occur in 8-coordinated sites ( d[Zr-O] ˜2.22 Å). No clear evidence for F or Cl complexes of Zr was observed in any of the halogen-containing glasses. The regularity of the Zr site increases in the series AB < TS ˜PR. We attribute this change to an increase in the number of non-bridging oxygens in the first-coordination sphere of Zr related to the depolymerizing effects of halogens and/or sodium. Minor but significant interactions of Zr with the tetrahedral network were observed ( d[Zr-{Si, Al}] ˜3.65-3.71 Å ± 0.03 Å), which are consistent with Zr-O-{Si, Al} angles close to 160-170°, as in catapleiite (Na 2ZrSi 3O 9 · 2H 2O). Intermediaterange order, as reflected by the presence and number of second-neighbor {Si, Al} around Zr, increases significantly with increasing melt polymerization. The local environment around Zr is more strongly influenced by bonding requirements than by the network topology of the melt. Stabilization of zirconium in 6-coordinated sites in relatively depolymerized melts should act to decrease the crystal-melt partition coefficients of Zr and may explain the normally incompatible character of Zr during magmatic differentiation. The presence of Zr in sites of higher coordination (ZrO 8) in highly polymerized melts could be a precursor to the crystallization of zircon from such melts and thus may explain why Zr becomes a more compatible element, especially in the latest stages of magmatic differentiation.