Mechanically tunable elastomeric hydrogels made from melt-fabricated photoreactive block copolymer micelles

NASA Astrophysics Data System (ADS)

Huq, Nabila; Bailey, Travis

Recently, our group has developed a range of novel elastomeric hydrogels using thermoplastic elastomer design concepts. These have been traditionally formed using two-component blends of AB diblock and ABA triblock copolymer designed to self-assemble into micelle-like domains in the melt. Vitrification of the micelle cores (A blocks) followed by swelling in aqueous media leads to an elastic network of spheres tethered by the population of bridging ABA chains in the blend. The concentration of ABA used has a strong influence on the mechanical properties exhibited by the hydrogels. We have built on this by replacing the traditional AB with a photoreactive AB-p. This construct provides flexibility to install specific concentrations of ABA tethering molecules at any point in the fabrication process as well as at any location simply through intensity-controlled, spatially directed irradiation with UV light. Increasing UV exposure time results in greater ABA concentrations, reinforcing the area of exposure. In this presentation we explore the influence of patterned ABA installation on shape, surface topography, and mechanical properties of the resulting hydrogels.

“Uncontrolled” Preparation of Disperse Poly(lactide)- block -poly(styrene)- block -poly(lactide) for Nanopatterning Applications

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

Vanderlaan, Marie E.; Hillmyer, Marc A.

We report the facile synthesis of well-defined ABA poly(lactide)-block-poly(styrene)-block-poly(lactide) (LSL) triblock copolymers having a disperse poly(styrene) midblock (Ð = 1.27–2.24). The direct synthesis of telechelic α,ω-hydroxypoly(styrene) (HO-PS-OH) midblocks was achieved using a commercially available difunctional free radical diazo initiator 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]. Poly(lactide) (PLA) end blocks were subsequently grown from HO-PS-OH macroinitiators via ring-opening transesterification polymerization of (±)-lactide using the most common and prevalent catalyst system available, tin(II) 2-ethylhexanoate. Fourteen LSL triblock copolymers with total molar masses Mn,total = 24–181 kg/mol and PLA volume fractions fPLA = 0.15–0.68 were synthesized and thoroughly characterized. The self-assembly of symmetric triblocks was analyzed in themore » bulk using small-angle X-ray scattering and in thin films using grazing incidence small-angle X-ray scattering and atomic force microscopy. We demonstrate both the bulk and thin film self-assembly of LSL disperse triblocks gave well-organized nanostructures with uniform domain sizes suitable for nanopatterning applications.« less

Flexible Epoxy Resin Formed Upon Blending with a Triblock Copolymer through Reaction-Induced Microphase Separation

PubMed Central

Chu, Wei-Cheng; Lin, Wei-Sheng; Kuo, Shiao-Wei

2016-01-01

In this study, we used diglycidyl ether bisphenol A (DGEBA) as a matrix, the ABA block copolymer poly(ethylene oxide–b–propylene oxide–b–ethylene oxide) (Pluronic F127) as an additive, and diphenyl diaminosulfone (DDS) as a curing agent to prepare flexible epoxy resins through reaction-induced microphase separation (RIMPS). Fourier transform infrared spectroscopy confirmed the existence of hydrogen bonding between the poly(ethylene oxide) segment of F127 and the OH groups of the DGEBA resin. Small-angle X-ray scattering, atomic force microscopy, and transmission electron microscopy all revealed evidence for the microphase separation of F127 within the epoxy resin. Glass transition temperature (Tg) phenomena and mechanical properties (modulus) were determined through differential scanning calorimetry and dynamic mechanical analysis, respectively, of samples at various blend compositions. The modulus data provided evidence for the formation of wormlike micelle structures, through a RIMPS mechanism, in the flexible epoxy resin upon blending with the F127 triblock copolymer. PMID:28773571

Single-ion triblock copolymer electrolytes based on poly(ethylene oxide) and methacrylic sulfonamide blocks for lithium metal batteries

NASA Astrophysics Data System (ADS)

Porcarelli, Luca; Aboudzadeh, M. Ali; Rubatat, Laurent; Nair, Jijeesh R.; Shaplov, Alexander S.; Gerbaldi, Claudio; Mecerreyes, David

2017-10-01

Single-ion conducting polymer electrolytes represent the ideal solution to reduce concentration polarization in lithium metal batteries (LMBs). This paper reports on the synthesis and characterization of single-ion ABA triblock copolymer electrolytes comprising PEO and poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) blocks, poly(LiMTFSI). Block copolymers are prepared by reversible addition-fragmentation chain transfer polymerization, showing low glass transition temperature (-55 to 7 °C) and degree of crystallinity (51-0%). Comparatively high values of ionic conductivity are obtained (up to ≈ 10-4 S cm-1 at 70 °C), combined with a lithium-ion transference number close to unity (tLi+ ≈ 0.91) and a 4 V electrochemical stability window. In addition to these promising features, solid polymer electrolytes are successfully tested in lithium metal cells at 70 °C providing long lifetime up to 300 cycles, and stable charge/discharge cycling at C/2 (≈100 mAh g-1).

Directed self-assembly of high-chi block copolymer for nano fabrication of bit patterned media via solvent annealing

NASA Astrophysics Data System (ADS)

Xiong, Shisheng; Chapuis, Yves-Andre; Wan, Lei; Gao, He; Li, Xiao; Ruiz, Ricardo; Nealey, Paul F.

2016-10-01

We report the formation of nanoimprint master templates that can be used for the fabrication of bit patterned media (BPM). The template was formed by directed self-assembly, with solvent annealing, of a symmetric ABA triblock copolymer to form perpendicularly oriented lamellae on chemical patterns. We used a high-χ block copolymer, poly(2-vinyl pyridine)-block-polystyrene-block-poly(2-vinyl pyridine) to achieve smaller feature sizes than are possible with polystyrene-block-poly(methyl methacrylate). The work shows that triblock copolymers can provide a large processing window in terms of pitch commensurability. Using block-selective infiltration (atomic layer deposition with sequential long soaking/purge cycles), an alumina composite with high etch resistance was specifically incorporated into the polar and hydrophilic P2VP domains. Subsequently, the surface pattern was successfully transferred into underlying Si substrates by etching with a fluorine-containing plasma to create a nanoimprint master. The line/space pattern of the nanoimprint master met the BPM fabrication requirement of defectivity <10-3. For demonstration purposes, the nanoimprint master was used to imprint a replica pattern of photoresist on a quartz wafer.

Self-assembly behavior of pH- and thermosensitive amphiphilic triblock copolymers in solution: experimental studies and self-consistent field theory simulations.

PubMed

Cai, Chunhua; Zhang, Liangshun; Lin, Jiaping; Wang, Liquan

2008-10-09

We investigated, both experimentally and theoretically, the self-assembly behaviors of pH- and thermosensitive poly(L-glutamic acid)- b-poly(propylene oxide)-b-poly(L-glutamic acid) (PLGA-b-PPO-b-PLGA) triblock copolymers in aqueous solution by means of transmission electron microscopy (TEM), scanning electron microscopy (SEM), dynamic light scattering (DLS), circular dichroism (CD), and self-consistent field theory (SCFT) simulations. Vesicles were observed when the hydrophilic PLGA block length is shorter or the pH value of solution is lower. The vesicles were found to transform to spherical micelles when the PLGA block length increases or its conformation changes from helix to coil with increasing the pH value. In addition, increasing temperature gives rise to a decrease in the size of aggregates, which is related to the dehydration of the PPO segments at higher temperatures. The SCFT simulation results show that the vesicles transform to the spherical micelles with increasing the fraction or statistical length of A block in model ABA triblock copolymer, which corresponds to the increase in the PLGA length or its conformation change from helix to coil in experiments, respectively. The SCFT calculations also provide chain distribution information in the aggregates. On the basis of both experimental and SCFT results, the mechanism of the structure change of the PLGA- b-PPO- b-PLGA aggregates was proposed.

Diverse 2D structures obtained by adsorption of charged ABA triblock copolymer on different surfaces

NASA Astrophysics Data System (ADS)

Kontturi, Katri S.; Vesterinen, Arja-Helena; Seppälä, Jukka; Laine, Janne

2012-11-01

In the larger context of 2D polymeric structures, the morphologies obtained by adsorption and subsequent drying of charged, ABA type amphiphilic triblock copolymer of poly[2-(dimethylamino)ethyl metacrylate] (PDMAEMA) and poly(propylene oxide) (PPO) were investigated with atomic force microscopy and X-ray photoelectron spectroscopy as well as in situ adsorption analysis with quartz crystal microbalance with dissipation monitoring. Hydrophilic silica and hydrophobic polystyrene (PS) were used as substrates for adsorption. The structures emerging from the self-assembly of adsorbing polymer were profoundly influenced by composition of the aqueous solution and the choice of substrate. When adsorbed from dilute polymer solution where the concentration is so low that the polymer does not yet show surface-active behavior, the triblock copolymer unimers associated on hydrophilic silica surface forming large, irregular clustered aggregates, with sizes increasing with electrolyte concentration of the solution. On a hydrophobic PS substrate, on the other hand, unimers spread much more evenly, forming clear surface patterns. The roughness of these patterned structures was tuned with the electrolyte concentration of the solution. Adsorption from a more concentrated polymer solution, where the surface-activity of the polymer is perceptible, resulted in the formation of a smooth film with complete coverage over the hydrophilic silica substrate when the electrolyte concentration was high. On PS, on the other hand, nucleation of evenly scattered globular, disk-like micelles was induced. Besides the dry film morphology, the even distribution of the irreversibly adsorbed polymer over the PS surface was likely to serve as an optimal platform for the build-up of reversible hydrophobically bound multilayers at high electrolyte concentration. The multilayer formation was reversible because a decrease in the electrolyte concentration of the solution re-introduces strong electrostatic repulsion between the multilayered polymer coils which results in breakdown of the layer.

Morphological characterization of microspheres, films and implants prepared from poly(lactide-co-glycolide) and ABA triblock copolymers: is the erosion controlled by degradation, swelling or diffusion?

PubMed

Witt, C; Kissel, T

2001-05-01

Erosion of biodegradable parenteral delivery systems (PDS) based on ABA copolymers consisting of poly(L-lactide-co-glycolide) (PLGA) A-blocks attached to polyethylene oxide (PEO) B-blocks, or PLGA is important for the release of macromolecular drugs. The degradation behavior of four types of PDS, namely extruded rods, tablets, films and microspheres, was studied with respect to molecular weight, mass, polymer composition and shape and microstructure of the PDS. For each device the onset time of bulk erosion (t(on)) and the apparent rate of mass loss (k(app)) were calculated. In the case of PLGA, the t(on) was 16.2 days for microspheres, 19.2 days for films and 30.1 days for cylindrical implants and tablets. The k(app) was 0.04 days(-1) for microspheres, 0.09 days(-1) for films, 0.11 days(-1) for implants and 0.10 days(-1) for tablets. The degradation rates were in the same range irrespective of the geometry and the micrographs of eroding PDS demonstrated pore formation; therefore, a complex pore diffusion mechanism seems to control the erosion of PLGA devices. In contrast, PDS based on ABA copolymers showed swelling, followed by a parallel process of molecular weight degradation and polymer erosion, independent of the geometry. The contact angles of ABA films increased either with decreasing PEO content or with increasing chain length of the PEO B-blocks. In summary, the insertion of a hydrophilic B-block leads to an erosion controlled by degradation of ABA copolymers, whereas for PLGA a complex pore diffusion of degradation products controls the rate of bulk erosion.

A Triblock Copolymer Design Leads to Robust Hybrid Hydrogels for High-Performance Flexible Supercapacitors.

PubMed

Zhang, Guangzhao; Chen, Yunhua; Deng, Yonghong; Wang, Chaoyang

2017-10-18

We report here an intriguing hybrid conductive hydrogel as electrode for high-performance flexible supercapacitor. The key is using a rationally designed water-soluble ABA triblock copolymer (termed as IAOAI) containing a central poly(ethylene oxide) block (A) and terminal poly(acrylamide) (PAAm) block with aniline moieties randomly incorporated (B), which was synthesized by reversible additional fragment transfer polymerization. The subsequent copolymerization of aniline monomers with the terminated aniline moieties on the IAOAI polymer generates a three-dimensional cross-linking hybrid network. The hybrid hydrogel electrode demonstrates robust mechanical flexibility, remarkable electrochemical capacitance (919 F/g), and cyclic stability (90% capacitance retention after 1000 cycles). Moreover, the flexible supercapacitor based on this hybrid hydrogel electrode presents a large specific capacitance (187 F/g), superior to most reported conductive hydrogel-based supercapacitors. With the demonstrated additional favorable cyclic stability and excellent capacitive and rate performance, this hybrid hydrogel-based supercapacitor holds great promise for flexible energy-storage device.

Photo-Patterned Ion Gel Electrolyte-Gated Thin Film Transistors

NASA Astrophysics Data System (ADS)

Choi, Jae-Hong; Gu, Yuanyan; Hong, Kihyun; Frisbie, C. Daniel; Lodge, Timothy P.

2014-03-01

We have developed a novel fabrication route to pattern electrolyte thin films in electrolyte-gated transistors (EGTs) using a chemically crosslinkable ABA-triblock copolymer ion gel. In the self-assembly of poly[(styrene-r-vinylbenzylazide)-b-ethylene oxide-b-(styrene-r-vinylbenzylazide)] (SOS-N3) triblock copolymer and the ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]), the azide groups of poly(styrene-r-vinylbenzylazide) (PS-N3) end-blocks in the cores can be chemically cross-linked via UV irradiation (λ = 254 nm). Impedance spectroscopy and small-angle X-ray scattering confirmed that ion transport and microstructure of the ion gel are not affected by UV cross-linking. Using this chemical cross-linking strategy, we demonstrate a photo-patterning of ion gels through a patterned mask and the fabricated electrolyte-gated thin film transistors with photo-patterned ion gels as high-capacitance gate insulators exhibited high device performance (low operation voltages and high on/off current ratios).

Communication: Molecular-level insights into asymmetric triblock copolymers: Network and phase development

NASA Astrophysics Data System (ADS)

Tallury, Syamal S.; Mineart, Kenneth P.; Woloszczuk, Sebastian; Williams, David N.; Thompson, Russell B.; Pasquinelli, Melissa A.; Banaszak, Michal; Spontak, Richard J.

2014-09-01

Molecularly asymmetric triblock copolymers progressively grown from a parent diblock copolymer can be used to elucidate the phase and property transformation from diblock to network-forming triblock copolymer. In this study, we use several theoretical formalisms and simulation methods to examine the molecular-level characteristics accompanying this transformation, and show that reported macroscopic-level transitions correspond to the onset of an equilibrium network. Midblock conformational fractions and copolymer morphologies are provided as functions of copolymer composition and temperature.

Sustainable Elastomers from Renewable Biomass.

PubMed

Wang, Zhongkai; Yuan, Liang; Tang, Chuanbing

2017-07-18

Sustainable elastomers have undergone explosive growth in recent years, partly due to the resurgence of biobased materials prepared from renewable natural resources. However, mounting challenges still prevail: How can the chemical compositions and macromolecular architectures of sustainable polymers be controlled and broadened? How can their processability and recyclability be enabled? How can they compete with petroleum-based counterparts in both cost and performance? Molecular-biomass-derived polymers, such as polymyrcene, polymenthide, and poly(ε-decalactone), have been employed for constructing thermoplastic elastomers (TPEs). Plant oils are widely used for fabricating thermoset elastomers. We use abundant biomass, such as plant oils, cellulose, rosin acids, and lignin, to develop elastomers covering a wide range of structure-property relationships in the hope of delivering better performance. In this Account, recent progress in preparing monomers and TPEs from biomass is first reviewed. ABA triblock copolymer TPEs were obtained with a soft middle block containing a soybean-oil-based monomer and hard outer blocks containing styrene. In addition, a combination of biobased monomers from rosin acids and soybean oil was formulated to prepare triblock copolymer TPEs. Together with the above-mentioned approaches based on block copolymers, multigraft copolymers with a soft backbone and rigid side chains are recognized as the first-generation and second-generation TPEs, respectively. It has been recently demonstrated that multigraft copolymers with a rigid backbone and elastic side chains can also be used as a novel architecture of TPEs. Natural polymers, such as cellulose and lignin, are utilized as a stiff, macromolecular backbone. Cellulose/lignin graft copolymers with side chains containing a copolymer of methyl methacrylate and butyl acrylate exhibited excellent elastic properties. Cellulose graft copolymers with biomass-derived polymers as side chains were further explored to enhance the overall sustainability. Isoprene polymers were grafted from a cellulosic backbone to afford Cell-g-polyisoprene copolymers. Via cross-linking of these graft copolymers, human-skin-mimic elastomers and high resilient elastomers with a well-defined network structure were achieved. The mechanical properties of these resilient elastomers could be finely controlled by tuning the cellulose content. As isoprene can be produced by engineering of microorganisms, these elastomers could be a renewable alternative to petroleum products. In summary, triblock copolymer and graft copolymer TPEs with biomass components, skin-mimic elastomers, high resilient biobased elastomers, and engineering of macromolecular architectures for elastomers are discussed. These approaches and design provide us knowledge on the potential to make sustainable elastomers for various applications to compete with petroleum-based counterparts.

Effects of PEO-PPO-PEO Triblock Copolymers on Phospholipid Membrane Integrity under Osmotic Stress

PubMed Central

Wang, Jia-Yu; Chin, Jaemin; Marks, Jeremy D.; Lee, Ka Yee C.

2010-01-01

The effects of PEO-PPO-PEO triblock copolymers, mainly Poloxamer 188, on phospholipid membrane integrity under osmotic gradients were explored using giant unilamellar vesicles (GUVs). Fluorescence leakage assays showed two opposing effects of P188 on the structural integrity of GUVs depending on the duration of their incubation time. A two-state transition mechanism of interaction between the triblock copolymers and the phospholipid membrane is proposed: an adsorption (I) and an insertion (II) state. While the triblock copolymer in state I acts to moderately retard the leakage, their insertion in state II perturbs the lipid packing, thus increasing the membrane permeability. Our results suggest that the biomedical application of PEO-PPO-PEO triblock copolymers, either as cell membrane resealing agents or as accelerators for drug delivery, is directed by the delicate balance between these two states. PMID:20666423

Molecular Design of Sulfonated Triblock Copolymer Permselective Membranes

DTIC Science & Technology

2008-07-03

factors governing sorption and permeability ofphosphoorganic agents in PEM made of sulfonated triblock copolymers of styrene and lower olefins by means...membrane morphology at environmental conditions, and the membrane sorption and transport properties with respect to water and nerve gas simulant...and chemical factors governing sorption and permeability of phosphoorganic agents in PEM made of sulfonated triblock copolymers of styrene and lower

Micelle Morphology and Mechanical Response of Triblock Gels

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

Seitz, Michelle E.; Burghardt, Wesley R.; Shull, Kenneth R.

2010-01-12

The effect of polymer concentration on mechanical response and micelle morphology of ABA and AB copolymers in B-selective solvents has been systematically studied. Micelle morphology was determined using a combination of small-angle X-ray scattering, shear, and birefringence while mechanical response at low and high strains was determined using indentation techniques. Self-consistent field theory calculations were used to determine micelle volume fraction profiles and to construct an equilibrium phase map. The transition from spherical to cylindrical micelles increases the triblock gel modulus and energy dissipation. Combining knowledge of gel relaxation time, which determines the rate at which the gel can equilibratemore » its micelle structure, with the equilibrium phase map allows estimation of the experimental temperatures and time scales over which kinetic trapping will arrest micelle structure evolution. Kinetic trapping enables cylindrical morphologies to be obtained at significantly lower polymer fractions than is possible in equilibrated systems.« less

Use of amphiphilic triblock copolymers for enhancing removal efficiency of organic pollutant from contaminated media

NASA Astrophysics Data System (ADS)

Lee, Jun Hyup; Lee, Byungsun; Son, Intae; Kim, Jae Hong; Kim, Chunho; Yoo, Ji Yong; Wu, Jong-Pyo; Kim, Younguk

2015-11-01

We have studied amphiphilic triblock copolymers poly(ethylene glycol)- b-poly(propylene glycol)- b-poly(ethylene glycol) (PEG- b-PPG- b-PEG) and poly(propylene glycol)- b-poly(ethylene glycol)- b-poly(propylene glycol) (PPG- b-PEG- b-PPG) as possible substitutes for sodium dodecyl sulfate as anionic surfactants for the removal of hydrophobic contaminants. The triblock copolymers were compared with sodium dodecyl sulfate in terms of their abilities to remove toluene as hydrophobic contaminant in fuel, and the effects of polymer structure, PEG content, and concentration were studied. The PEG- b-PPG- b-PEG copolymer containing two hydrophilic PEG blocks was more effective for the removal of hydrophobic contaminant at extremely high concentration. We also measured the removal capabilities of the triblock copolymers having various PEG contents and confirmed that removal capability was greatest at 10% PEG content regardless of polymer structure. As with sodium dodecyl sulfate, the removal efficiency of a copolymer has a positive correlation with its concentration. Finally, we proposed the amphiphilic triblock copolymer of PPG- b-PEG- b-PPG bearing 10% PEG content that proved to be the most effective substitute for sodium dodecyl sulfate.

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

Block copolymer micelles with a dual-stimuli-responsive core for fast or slow degradation.

PubMed

Han, Dehui; Tong, Xia; Zhao, Yue

2012-02-07

We report the design and demonstration of a dual-stimuli-responsive block copolymer (BCP) micelle with increased complexity and control. We have synthesized and studied a new amphiphilic ABA-type triblock copolymer whose hydrophobic middle block contains two types of stimuli-sensitive functionalities regularly and repeatedly positioned in the main chain. Using a two-step click chemistry approach, disulfide and o-nitrobenzyle methyl ester groups are inserted into the main chain, which react to reducing agents and light, respectively. With the end blocks being poly(ethylene oxide), micelles formed by this BCP possess a core that can be disintegrated either rapidly via photocleavage of o-nitrobenzyl methyl esters or slowly through cleavage of disulfide groups by a reducing agent in the micellar solution. This feature makes possible either burst release of an encapsulated hydrophobic species from disintegrated micelles by UV light, or slow release by the action of a reducing agent, or release with combined fast-slow rate profiles using the two stimuli.

Hydrogen Bonding-Mediated Microphase Separation during the Formation of Mesoporous Novolac-Type Phenolic Resin Templated by the Triblock Copolymer, PEO-b-PPO-b-PEO

PubMed Central

Chu, Wei-Cheng; Chiang, Shih-Fan; Li, Jheng-Guang; Kuo, Shiao-Wei

2013-01-01

After blending the triblock copolymer, poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (PEO-b-PPO-b-PEO) with novolac-type phenolic resin, Fourier transform infrared spectroscopy revealed that the ether groups of the PEO block were stronger hydrogen bond acceptors for the OH groups of phenolic resin than were the ether groups of the PPO block. Thermal curing with hexamethylenetetramine as the curing agent resulted in the triblock copolymer being incorporated into the phenolic resin, forming a nanostructure through a mechanism involving reaction-induced microphase separation. Mild pyrolysis conditions led to the removal of the PEO-b-PPO-b-PEO triblock copolymer and formation of mesoporous phenolic resin. This approach provided a variety of composition-dependent nanostructures, including disordered wormlike, body-centered-cubic spherical and disorder micelles. The regular mesoporous novolac-type phenolic resin was formed only at a phenolic content of 40–60 wt %, the result of an intriguing balance of hydrogen bonding interactions among the phenolic resin and the PEO and PPO segments of the triblock copolymer. PMID:28788378

Adsorption of non-ionic ABC triblock copolymers: Surface modification of TiO2 suspensions in aqueous and non-aqueous medium

NASA Astrophysics Data System (ADS)

Lerch, Jean-Philippe; Atanase, Leonard Ionut; Riess, Gérard

2017-10-01

A series of non-ionic ABC triblock copolymers, such as poly(butadiene)-b-poly(2-vinylpyrridine)-b-poly(ethylene oxide) (PB-P2VP-PEO) were synthesized by sequential anionic polymerizations. For these copolymers comprising an organo-soluble PB and a water-soluble PEO block, their P2VP middle block has been selected for its anchoring capacity on solid surfaces. The adsorption isotherms on TiO2 were obtained in heptane and in aqueous medium, as selective solvents. In both of these cases, the P2VP middle block provides the surface anchoring, whereas PB and PEO sequences are acting as stabilizing moieties in heptane and water respectively. By extension to ABC triblock copolymers of the scaling theory developed for diblock copolymers, the density of adsorbed chains could be correlated with the molecular characteristics of the PB-P2VP-PEO triblock copolymers. From a practical point a view, it could be demonstrated that these copolymers are efficient dispersing agents for the TiO2 pigments in both aqueous and non-aqueous medium.

Phase behavior and dynamics of a micelle-forming triblock copolymer system

NASA Astrophysics Data System (ADS)

Mohan, P. Harsha; Bandyopadhyay, Ranjini

2008-04-01

Synperonic F-108 (generic name, “pluronic”) is a micelle forming triblock copolymer of type ABA , where A is polyethylene oxide (PEO) and B is polypropylene oxide (PPO). At high temperatures, the hydrophobicity of the PPO chains increase, and the pluronic molecules, when dissolved in an aqueous medium, self-associate into spherical micelles with dense PPO cores and hydrated PEO coronas. At appropriately high concentrations, these micelles arrange in a face centered cubic lattice to show inverse crystallization, with the samples exhibiting high-temperature crystalline and low-temperature fluidlike phases. By studying the evolution of the elastic and viscous moduli as temperature is increased at a fixed rate, we construct the concentration-temperature phase diagram of Synperonic F-108. For a certain range of temperatures and at appropriate sample concentrations, we observe a predominantly elastic response. Oscillatory strain amplitude sweep measurements on these samples show pronounced peaks in the loss moduli, a typical feature of soft solids. The soft solidlike nature of these materials is further demonstrated by measuring their frequency-dependent mechanical moduli. The storage moduli are significantly larger than the loss moduli and are almost independent of the applied angular frequency. Finally, we perform strain rate frequency superposition experiments to measure the slow relaxation dynamics of this soft solid.

Aggregation behavior and complex structure between triblock copolymer and anionic surfactants

NASA Astrophysics Data System (ADS)

Li, Yiming; Bao, Mutai; Wang, Zhining; Zhang, Haixia; Xu, Guiying

2011-01-01

The aggregation behavior and complex structure of ABA triblock copolymer EO 76PO 30EO 76 (F68) with sodium dodecyl sulfate (SDS) and sodium bis(2-ethylhexyl)sulfonate (AOT) in aqueous solution were investigated by surface tension, fluorescence techniques and dynamic light-scattering (DLS) measurements. It is revealed that in certain regions of binding, surfactant/F68 complexes are formed. Structural informations and size of complexes are evaluated. When F68 is present in its nonassociated state, F68/micellar SDS complexes are formed at SDS concentrations above its critical aggregation concentration (cac). The cac is well below the critical micellar concentration (cmc) of pure SDS, and a model suggesting how complexes are formed at the cac in the presence of F68 is described. Experimental results show that SDS interacts with F68 mainly through hydrophobic forces, polypropylene oxide (PPO) groups of F68 are solubilized into SDS micellar cores and poly(ethylene oxide) (PEO) groups interact with SDS micelles. This interaction mechanism results in a "pearl-necklace" complex structure. However, a different structure occurs for F68/AOT complex at lower F68 concentrations, as nonassociated F68 interacts with AOT mainly through ion-dipole interactions. Complexes with a "wrapping" structure at lower F68 concentrations are formed.

A nanophosphor-based method for selective DNA recovery in Synthosomes.

PubMed

Nallani, Madhavan; Onaca, Ozana; Gera, Nimish; Hildenbrand, Karlheinz; Hoheisel, Werner; Schwaneberg, Ulrich

2006-01-01

A nanocompartment system composed of an ABA triblock copolymer, where A is poly(dimethylsiloxane) and B is poly(2-methyloxazoline), has been developed for selective recovery and detection of DNA. Translocation of TAMRA-labeled complementary primers into the nanocompartment system has been achieved through two deletion mutants (FhuA Delta1-129; FhuA Delta1-160) of the channel protein FhuA. Translocation was monitored by fluorescence resonance energy transfer through hybridization of the TAMRA-labeled primer to the complementary sequence of a nanophosphor-DNA-conjugate, which reduces its half-life (FhuA Delta1-129, 16.0% reduced; FhuA Delta1-160, 39.0% reduced).

Injectable Self-Healing Hydrogel with Antimicrobial and Antifouling Properties.

PubMed

Li, Lin; Yan, Bin; Yang, Jingqi; Huang, Weijuan; Chen, Lingyun; Zeng, Hongbo

2017-03-22

Microbial adhesion, biofilm formation and associated microbial infection are common challenges faced by implanted biomaterials (e.g., hydrogels) in bioengineering applications. In this work, an injectable self-healing hydrogel with antimicrobial and antifouling properties was prepared through self-assembly of an ABA triblock copolymer employing catechol functionalized polyethylene glycol (PEG) as A block and poly{[2-(methacryloyloxy)-ethyl] trimethylammonium iodide}(PMETA) as B block. This hydrogel exhibits excellent thermosensitivity, and can effectively inhibit the growth of E. coli (>99.8% killing efficiency) and prevent cell attachment. It can also heal autonomously from repeated damage, through mussel-inspired catechol-mediated hydrogen bonding and aromatic interactions, exhibiting great potential in bioengineering applications.

Simultaneous determination of the styrene unit content and assessment of molecular weight of triblock copolymers in adhesives by a size exclusion chromatography method.

PubMed

Wang, Mingfang; Wang, Yuerong; Luo, Pei; Zhang, Hongyang; Zhang, Min; Hu, Ping

2017-10-01

The content of styrene units in nonhydrogenated and hydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers significantly influences product performance. A size exclusion chromatography method was developed to determine the average styrene content of triblock copolymers blended with tackifier in adhesives. A complete separation of the triblock copolymer from the other additives was realized with size exclusion chromatography. The peak area ratio of the UV and refraction index signals of the copolymers at the same effective elution volume was correlated to the average styrene unit content using nuclear magnetic resonance spectroscopy with commercial copolymers as standards. The obtained calibration curves showed good linearity for both the hydrogenated and nonhydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers (r = 0.974 for styrene contents of 19.3-46.3% for nonhydrogenated ones and r = 0.970 for the styrene contents of 23-58.2% for hydrogenated ones). For copolymer blends, the developed method provided more accurate average styrene unit contents than nuclear magnetic resonance spectroscopy provided. These results were validated using two known copolymer blends consisting of either styrene-isoprene-styrene or hydrogenated styrene-butadiene-styrene and a hydrocarbon tackifying resin as well as an unknown adhesive with styrene-butadiene-styrene and an aromatic tackifying resin. The methodology can be readily applied to styrene-containing polymers in blends such as poly(acrylonitrile-butadiene styrene). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inducing Order from Disordered Copolymers: On Demand Generation of Triblock Morphologies Including Networks

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

Tureau, Maëva S.; Kuan, Wei-Fan; Rong, Lixia

Disordered block copolymers are generally impractical in nanopatterning applications due to their inability to self-assemble into well-defined nanostructures. However, inducing order in low molecular weight disordered systems permits the design of periodic structures with smaller characteristic sizes. Here, we have induced nanoscale phase separation from disordered triblock copolymer melts to form well-ordered lamellae, hexagonally packed cylinders, and a triply periodic gyroid network structure, using a copolymer/homopolymer blending approach, which incorporates constituent homopolymers into selective block domains. This versatile blending approach allows one to precisely target multiple nanostructures from a single disordered material and can be applied to a wide varietymore » of triblock copolymer systems for nanotemplating and nanoscale separation applications requiring nanoscale feature sizes and/or high areal feature densities.« less

Triblock copolymers based on ε-caprolactone and trimethylene carbonate for the 3D printing of tissue engineering scaffolds.

PubMed

Güney, Aysun; Malda, Jos; Dhert, Wouter J A; Grijpma, Dirk W

2017-05-09

Biodegradable PCL-b-PTMC-b-PCL triblock copolymers based on trimethylene carbonate (TMC) and ε-caprolactone (CL) were prepared and used in the 3D printing of tissue engineering scaffolds. Triblock copolymers of various molecular weights containing equal amounts of TMC and CL were prepared. These block copolymers combine the low glass transition temperature of amorphous PTMC (approximately -20°C) and the semi-crystallinity of PCL (glass transition approximately -60°C and melting temperature approximately 60°C). PCL-b-PTMC-b-PCL triblock copolymers were synthesized by sequential ring opening polymerization (ROP) of TMC and ε-CL. From these materials, films were prepared by solvent casting and porous structures were prepared by extrusion-based 3D printing. Films prepared from a polymer with a relatively high molecular weight of 62 kg/mol had a melting temperature of 58°C and showed tough and resilient behavior, with values of the elastic modulus, tensile strength and elongation at break of approximately 120 MPa, 16 MPa and 620%, respectively. Porous structures were prepared by 3D printing. Ethylene carbonate was used as a crystalizable and water-extractable solvent to prepare structures with microporous strands. Solutions, containing 25 wt% of the triblock copolymer, were extruded at 50°C then cooled at different temperatures. Slow cooling at room temperature resulted in pores with widths of 18 ± 6 μm and lengths of 221 ± 77 μm, rapid cooling with dry ice resulted in pores with widths of 13 ± 3 μm and lengths of 58 ± 12 μm. These PCL-b-PTMC-b-PCL triblock copolymers processed into porous structures at relatively low temperatures may find wide application as designed degradable tissue engineering scaffolds. In this preliminary study we prepared biodegradable triblock copolymers based on 1,3-trimethylene carbonate and ε-caprolactone and assessed their physical characteristics. Furthermore, we evaluated their potential as melt-processable thermoplastic elastomeric biomaterials in 3D printing of tissue engineering scaffolds.

Multiscale Mechanical Characterization of Biomimetic Physically Associating Gels

DTIC Science & Technology

2006-09-01

work, a ballistic gelatin and two styrene- isoprene triblock copolymer gels are tested and compared using both macroscale and microscale measurements... isoprene triblock copolymer gels are tested and compared using both macroscale and microscale measurements. A methodology is presented to conduct

Hollow carbon nanospheres using an asymmetric triblock copolymer structure directing agent.

PubMed

Li, Yunqi; Tan, Haibo; Salunkhe, Rahul R; Tang, Jing; Shrestha, Lok Kumar; Bastakoti, Bishnu Prasad; Rong, Hongpan; Takei, Toshiaki; Henzie, Joel; Yamauchi, Yusuke; Ariga, Katsuhiko

2016-12-20

We introduce a simple method to prepare hollow carbon nanospheres (HCNs) by using triblock copolymer poly(styrene-b-2-vinylpyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) micelles as a new class of soft-templates. Simply by changing the solvent we can prepare ultra-small sized micelles of the triblock copolymer PS-b-P2VP-b-PEO soft template to obtain HCNs with ultra-small diameters (43 nm) and hollow cores (19 nm). Furthermore, we use these HCNs to make electric double-layer capacitors (EDLCs) that exhibit superior performance.

Phase Behavior of Neat Triblock Copolymers and Copolymer/Homopolymer Blends Near Network Phase Windows

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

M Tureau; L Rong; B Hsiao

The phase behavior of poly(isoprene-b-styrene-b-methyl methacrylate) (ISM) copolymers near the styrene-rich network phase window was examined through the use of neat triblock copolymers and copolymer/homopolymer blends. Both end-block and middle-block blending protocols were employed using poly(isoprene) (PI), poly(methyl methacrylate) (PMMA), and poly(styrene) (PS) homopolymers. Blended specimens exhibited phase transformations to well-ordered nanostructures (at homopolymer loadings up to 26 vol % of the total blend volume). Morphological consistency between neat and blended specimens was established at various locations in the ISM phase space. Copolymer/homopolymer blending permitted the refinement of lamellar, hexagonally packed cylinder, and disordered melt phase boundaries as well asmore » the identification of double gyroid (Q{sup 230}), alternating gyroid (Q{sup 214}), and orthorhombic (O{sup 70}) network regimes. Additionally, the experimental phase diagram exhibited similar trends to those found in a theoretical ABC triblock copolymer phase diagram with symmetric interactions and statistical segments lengths generated by Tyler et al.« less

Phase behavior of model ABC triblock copolymers

NASA Astrophysics Data System (ADS)

Chatterjee, Joon

The phase behavior of poly(isoprene-b-styrene- b-ethylene oxide) (ISO), a model ABC triblock copolymer has been studied. This class of materials exhibit self-assembly, forming a large array of ordered morphologies at length scales of 5-100 nm. The formation of stable three-dimensionally continuous network morphologies is of special interest in this study. Since these nanostructures considerably impact the material properties, fundamental knowledge for designing ABC systems have high technological importance for realizing applications in the areas of nanofabrication, nanoporous media, separation membranes, drug delivery and high surface area catalysts. A comprehensive framework was developed to describe the phase behavior of the ISO triblock copolymers at weak to intermediate segregation strengths spanning a wide range of composition. Phases were characterized through a combination of characterization techniques, including small angle x-ray scattering, dynamic mechanical spectroscopy, transmission electron microscopy, and birefringence measurements. Combined with previous investigations on ISO, six different stable ordered state symmetries have been identified: lamellae (LAM), Fddd orthorhombic network (O70), double gyroid (Q230), alternating gyroid (Q214), hexagonal (HEX), and body-centered cubic (BCC). The phase map was found to be somewhat asymmetric around the fI = fO isopleth. This work provides a guide for theoretical studies and gives insight into the intricate effects of various parameters on the self-assembly of ABC triblock copolymers. Experimental SAXS data evaluated with a simple scattering intensity model show that local mixing varies continuously across the phase map between states of two- and three-domain segregation. Strategies of blending homopolymers with ISO triblock copolymer were employed for studying the swelling properties of a lamellar state. Results demonstrate that lamellar domains swell or shrink depending upon the type of homopolymer that was mixed. The results provide insight into the chain conformation of ABC triblock copolymers, where the B blocks are completely bridged across the adjacent A and C domains. In the final part of the thesis, the swelling properties were used to study the directed assembly of ABC triblock copolymers on chemically nanopatterned surfaces.

Directed Self-Assembly of Poly(2-vinylpyridine)-b-polystyrene-b-poly(2-vinylpyridine) Triblock Copolymer with Sub-15 nm Spacing Line Patterns Using a Nanoimprinted Photoresist Template.

PubMed

Sun, Zhiwei; Chen, Zhenbin; Zhang, Wenxu; Choi, Jaewon; Huang, Caili; Jeong, Gajin; Coughlin, E Bryan; Hsu, Yautzong; Yang, XiaoMin; Lee, Kim Y; Kuo, David S; Xiao, Shuaigang; Russell, Thomas P

2015-08-05

Low molecular weight P2VP-b-PS-b-P2VP triblock copolymer (poly(2-vinlypyridine)-block-polystyrene-block-poly(2-vinylpyridine)] is doped with copper chloride and microphase separated into lamellar line patterns with ultrahigh area density. Salt-doped P2VP-b-PS-b-P2VP triblock copolymer is self-assembled on the top of the nanoimprinted photoresist template, and metallic nanowires with long-range ordering are prepared with platinum-salt infiltration and plasma etching. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mixing a sol and a precipitate of block copolymers with different block ratios leads to an injectable hydrogel.

PubMed

Yu, Lin; Zhang, Zheng; Zhang, Huan; Ding, Jiandong

2009-06-08

A facile method to obtain a thermoreversible physical hydrogel was found by simply mixing an aqueous sol of a block copolymer with a precipitate of a similar copolymer but with a different block ratio. Two ABA-type triblock copolymers poly(D,L-lactic acid-co-glycolic acid)-B-poly(ethylene glycol)-B-poly(D,L-lactic acid-co-glycolic acid) (PLGA-PEG-PLGA) were synthesized. One sample in water was a sol in a broad temperature region, while the other in water was just a precipitate. The mixture of these two samples with a certain mix ratio underwent, however, a sol-to-gel-to-precipitate transition upon an increase of temperature. A dramatic tuning of the sol-gel transition temperature was conveniently achieved by merely varying mix ratio, even in the case of a similar molecular weight. Our study indicates that the balance of hydrophobicity and hydrophilicity within this sort of amphiphilic copolymers is critical to the inverse thermal gelation in water resulting from aggregation of micelles. The availability of encapsulation and sustained release of lysozyme, a model protein by the thermogelling systems was confirmed. This "mix" method provides a very convenient approach to design injectable thermogelling biomaterials with a broad adjustable window, and the novel copolymer mixture platform is potentially used in drug delivery and other biomedical applications.

Molecular and morphological characterization of midblock-sulfonated styrenic triblock copolymers

DOE PAGES

Mineart, Kenneth P.; Ryan, Justin J.; Lee, Byeongdu; ...

2017-01-11

Midblock-sulfonated triblock copolymers afford a desirable opportunity to generate network-forming amphiphilic materials that are suitable for use in a wide range of emerging technologies as fuel-cell, water-desalination, ion-exchange, photovoltaic, or electroactive membranes. Employing a previously reported synthetic strategy wherein poly( p- tert-butylstyrene) remains unreactive, we have selectively sulfonated the styrenic midblock of a poly( p- tert-butylstyrene- b-styrene- b- p- tert- butylstyrene) (TST) triblock copolymer to different extents. Comparison of the resulting sulfonated copolymers with results from our prior study provides favorable quantitative agreement and suggests that a shortened reaction time is advantageous. An ongoing challenge regarding the morphological development ofmore » charged block copolymers is the competition between microphase separation of the incompatible blocks and physical cross-linking of ionic clusters, with the latter often hindering the former. Here, we expose the sulfonated TST copolymers to solvent-vapor annealing to promote nanostructural refinement. Furthermore, the effect of such annealing on morphological characteristics, as well as on molecular free volume, is explored.« less

High temperature thermoplastic elastomers synthesized by living anionic polymerization in hydrocarbon solvent at room temperature

DOE PAGES

Schlegel, Ralf; Williams, Katherine; Voyloy, Dimitry; ...

2016-03-30

We present the synthesis and characterization of a new class of high temperature thermoplastic elastomers composed of polybenzofulvene–polyisoprene–polybenzofulvene (FIF) triblock copolymers. All copolymers were prepared by living anionic polymerization in benzene at room temperature. Homopolymerization and effects of additives on the glass transition temperature (T g) of polybenzofulvene (PBF) were also investigated. Among all triblock copolymers studied, FIF with 14 vol % of PBF exhibited a maximum stress of 14.3 ± 1.3 MPa and strain at break of 1390 ± 66% from tensile tests. The stress–strain curves of FIF-10 and 14 were analyzed by a statistical molecular approach using amore » nonaffine tube model to estimate the thermoplastic elastomer behavior. Dynamic mechanical analysis showed that the softening temperature of PBF in FIF was 145 °C, much higher than that of thermoplastic elastomers with polystyrene hard blocks. Microphase separation of FIF triblock copolymers was observed by small-angle X-ray scattering, even though long-range order was not achieved under the annealing conditions employed. Additionally, the microphase separation of the resulting triblock copolymers was examined by atomic force microscopy.« less

High temperature thermoplastic elastomers synthesized by living anionic polymerization in hydrocarbon solvent at room temperature

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

Schlegel, Ralf; Williams, Katherine; Voyloy, Dimitry

We present the synthesis and characterization of a new class of high temperature thermoplastic elastomers composed of polybenzofulvene–polyisoprene–polybenzofulvene (FIF) triblock copolymers. All copolymers were prepared by living anionic polymerization in benzene at room temperature. Homopolymerization and effects of additives on the glass transition temperature (T g) of polybenzofulvene (PBF) were also investigated. Among all triblock copolymers studied, FIF with 14 vol % of PBF exhibited a maximum stress of 14.3 ± 1.3 MPa and strain at break of 1390 ± 66% from tensile tests. The stress–strain curves of FIF-10 and 14 were analyzed by a statistical molecular approach using amore » nonaffine tube model to estimate the thermoplastic elastomer behavior. Dynamic mechanical analysis showed that the softening temperature of PBF in FIF was 145 °C, much higher than that of thermoplastic elastomers with polystyrene hard blocks. Microphase separation of FIF triblock copolymers was observed by small-angle X-ray scattering, even though long-range order was not achieved under the annealing conditions employed. Additionally, the microphase separation of the resulting triblock copolymers was examined by atomic force microscopy.« less

Manipulating the ABCs of self-assembly via low-χ block polymer design

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

Chang, Alice B.; Bates, Christopher M.; Lee, Byeongdu

Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χ ij). In this report, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χ AC ≲ 0), promotes organization into a unique mixed-domain lamellar morphology which we designate LAM P. Transmission electron microscopy indicates that LAMP exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM 3) with ABCB periods. Complementary small angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations andmore » predicts that LAM P is thermodynamically stable below a critical χ AC, above which LAM 3 emerges. Both experiments and theory expose close analogies to ABA triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. Furthermore, these conclusions provide new opportunities in block polymer design with potential consequences spanning all self-assembling soft materials.« less

Manipulating the ABCs of self-assembly via low-χ block polymer design

DOE PAGES

Chang, Alice B.; Bates, Christopher M.; Lee, Byeongdu; ...

2017-06-06

Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χ ij). In this report, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χ AC ≲ 0), promotes organization into a unique mixed-domain lamellar morphology which we designate LAM P. Transmission electron microscopy indicates that LAMP exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM 3) with ABCB periods. Complementary small angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations andmore » predicts that LAM P is thermodynamically stable below a critical χ AC, above which LAM 3 emerges. Both experiments and theory expose close analogies to ABA triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. Furthermore, these conclusions provide new opportunities in block polymer design with potential consequences spanning all self-assembling soft materials.« less

Copolymerization of Glycolide and ɛ-Caprolactone Using 12-Aminolauric Acid Modified Montmorillonite

NASA Astrophysics Data System (ADS)

Gallos, HAV; Reyes, LQ

2017-09-01

Poly(glycolide-co-ɛ-caprolactone) (PGLYCL) nanocomposites were prepared by copolymerization glycolide (GLY) and ɛ-caprolactone (ɛ-CL) in the presence of varying loadings 12-aminolauric acid (12-ALA)-modified montmorillonite. Copolymerization was successfully achieved based on the increase in polymer molecular weight after the reaction determined by gel permeation chromatography (GPC). The amount of the poly(glycolide) block and poly(ɛ-caprolactone) block units in the copolymer, identified by proton nuclear magnetic resonance (1H-NMR) spectroscopy, suggested that the increase in organo-clay loading cause a reduction GLYL: ɛ-CLL ratio. The arrangement of the monomers in the polymer products was elucidated to have an ABA triblock structure, where PCL block is the central block and the PGLY is found at both end of the copolymer. The presence of intercalated and exfoliated silicates in the nanocomposites were observed by x-ray diffraction (XRD) analysis. The biocompatibility of the nanocomposites with NCTC 292 mouse normal fibroblast was high relative to untreated cell cultures using tetrazolium bromide (MTT)-dye reduction assay.

Formulation of benzoporphyrin derivatives in Pluronics.

PubMed

Chowdhary, Rubinah K; Chansarkar, Namrata; Sharif, Isha; Hioka, Noboru; Dolphin, David

2003-03-01

This study investigates the potential of Pluronics for the formulation of tetrapyrrole-based photosensitizers, with a particular focus on B-ring benzoporphyrin derivatives. The B-ring derivatives have a high tendency to aggregate in aqueous solutions, and this poses a significant formulation problem. Pluronics are ABA-type triblock copolymers composed of a central hydrophobic polypropylene oxide section with two hydrophilic polyethylene oxide sections of equal length at either end. Out of a range of different commercially available block copolymers studied, it was found that the longer the hydrophobic block, the better the stabilization of tetrapyrrolic drugs in monomeric form in aqueous suspensions. Of these the best performance was observed in the micelle-forming Pluronic P123. Micelle size determination by laser light scattering confirmed that particle size in stable Pluronic formulations was around 20 nm. Pluronics such as L122 formed emulsions spontaneously without the need for emulsion stabilizers; emulsions were highly stable at ambient temperatures over several days and also highly effective as potential drug delivery agents.

Study of structural morphologies of thermoresponsive diblock AB and triblock BAB copolymers (A = poly(N-isopropylacrylamide), B = polystyrene)

NASA Astrophysics Data System (ADS)

Rodríguez-Hidalgo, María del Rosario; Soto-Figueroa, César; Vicente, Luis

2018-03-01

Structural morphologies of diblock AB and triblock BAB copolymers (A = poly(N-isopropylacrylamide), B = polystyrene) in aqueous environment have been investigated by dissipative particle dynamics (DPD). In triblock copolymers insoluble PS blocks contract while soluble pNIPAM blocks stay at the periphery forming looped chains as corona. As the temperature is increased there is a continuous morphological transition and micelles form ellipsoidal structures with segregated polymer zones. The phase transition of looped pNIPAM chains occurs at lower temperature than for linear chains and within broader temperature range. It is discussed how the chain topology of pNIPAM affects the phase transition.

Measurement of Diffusion in Entangled Rod-Coil Triblock Copolymers

NASA Astrophysics Data System (ADS)

Olsen, B. D.; Wang, M.

2012-02-01

Although rod-coil block copolymers have attracted increasing attention for functional nanomaterials, their dynamics relevant to self-assembly and processing have not been widely investigated. Because the rod and coil blocks have different reptation behavior and persistence lengths, the mechanism by which block copolymers will diffuse is unclear. In order to understand the effect of the rigid block on reptation, tracer diffusion of a coil-rod-coil block copolymer through an entangled coil polymer matrix was experimentally measured. A monodisperse, high molecular weight coil-rod-coil triblock was synthesized using artificial protein engineering to prepare the helical rod and bioconjugaiton of poly(ethylene glycol) coils to produce the final triblock. Diffusion measurements were performed using Forced Rayleigh scattering (FRS), at varying ratios of the rod length to entanglement length, where genetic engineering is used to control the protein rod length and the polymer matrix concentration controls the entanglement length. As compared to PEO homopolymer tracers, the coil-rod-coil triblocks show markedly slower diffusion, suggesting that the mismatch between rod and coil reptation mechanisms results in hindered diffusion of these molecules in the entangled state.

Mesoscopic Simulations of Adsorption and Association of PEO-PPO-PEO Triblock Copolymers on a Hydrophobic Surface: From Mushroom Hemisphere to Rectangle Brush.

PubMed

Song, Xianyu; Zhao, Shuangliang; Fang, Shenwen; Ma, Yongzhang; Duan, Ming

2016-11-08

The dissipative particle dynamics (DPD) method is used to investigate the adsorption behavior of PEO-PPO-PEO triblock copolymers at the liquid/solid interface. The effect of molecular architecture on the self-assembled monolayer adsorption of PEO-PPO-PEO triblock copolymers on hydrophobic surfaces is elucidated by the adsorption process, film properties, and adsorption morphologies. The adsorption thicknesses on hydrophobic surfaces and the diffusion coefficient as well as the aggregation number of Pluronic copolymers in aqueous solution observed in our simulations agree well with previous experimental and numerical observations. The radial distribution function revealed that the ability of self-assembly on hydrophobic surfaces is P123 > P84 > L64 > P105 > F127, which increased with the EO ratio of the Pluronic copolymers. Moreover, the shape parameter and the degree of anisotropy increase with increasing molecular weight and mole ratio of PO of the Pluronic copolymers. Depending on the conformation of different Pluronic copolymers, the morphology transition of three regimes on hydrophobic surfaces is present: mushroom or hemisphere, progressively semiellipsoid, and rectangle brush regimes induced by decreasing molecular weight and mole ratio of EO of Pluronic copolymers.

Micellar Packing in Aqueous Solutions of As-Received and Pure Pluronic Block Copolymers

NASA Astrophysics Data System (ADS)

Ryu, Chang; Park, Han Jin

2013-03-01

Pluronic block copolymers (Pluronics) are produced on a commercial scale to enable wide range of novel applications from emulsification and colloidal stabilization as nonionic surfactants. While the Pluronic block copolymers offer the advantages of being readily available for such applications, it contains non-micellizable low molecular weight (MW) impurities that would interfere with the self-assembly and micellar packing of PEO-PPO-PEO triblock copolymers in aqueous solutions. The impacts of the low MW impurities will be discussed on the micellar packing of Pluronics F108 and F127 solutions, which form BCC and FCC. While as-received Pluronic samples typically contain about 20 wt.% low MW impurities, we were able to reduce the impurity level to less than 2 wt.% using our large scale purification technique. Comparative studies on small angle x-ray scattering (SAXS) experiments on as-received and purified Pluronics solutions revealed that the contents of triblock copolymers in solutions essentially governs the inter-micellar distance of Pluronic cubic structures. A universal relationship between triblock copolymer concentration and SAXS-based domain spacing has been finally discussed. Funding from Agency for Defense Development, Korea.

Phase Behavior of Binary Blends of High Molecular Weight Diblock Copolymers with a Low Molecular Weight Triblock

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

Mickiewicz, Rafal A.; Ntoukas, Eleftherios; Avgeropoulos, Apostolos

2009-08-26

Binary blends of four different high molecular weight poly(styrene-b-isoprene) (SI) diblock copolymers with a lower molecular weight poly(styrene-b-isoprene-b-styrene) (SIS) triblock copolymer were prepared, and their morphology was characterized by transmission electron microscopy and ultra-small-angle X-ray scattering. All the neat block copolymers have nearly symmetric composition and exhibit the lamellar morphology. The SI diblock copolymers had number-average molecular weights, Mn, in the range 4.4 x 10{sup 5}--1.3 x 10{sup 6} g/mol and volume fractions of poly(styrene), {Phi}{sub PS}, in the range 0.43--0.49, and the SIS triblock had a molecular weight of Mn 6.2 x 10{sup 4} g/mol with {Phi}{sub PS} =more » 0.41. The high molecular weight diblock copolymers are very strongly segregating, with interaction parameter values, {chi}N, in the range 470--1410. A morphological phase diagram in the parameter space of molecular weight ratio (R = M{sub n}{sup diblock}/1/2M{sub n}{sup triblock}) and blend composition was constructed, with R values in the range between 14 and 43, which are higher than previously reported. The phase diagram revealed a large miscibility gap for the blends, with macrophase separation into two distinct types of microphase-separated domains for weight fractions of SI, w{sub SI} < 0.9, implying virtually no solubility of the much higher molecular weight diblocks in the lower molecular weight triblock. For certain blend compositions, above R 30, morphological transitions from the lamellar to cylindrical and bicontinuous structures were also observed.« less

Thermally Switchable Thin Films of an ABC Triblock Copolymer of Poly(n-butyl methacrylate)-poly(methyl methacrylate)-poly(2-fluoroethyl methacrylate)

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

Zhang, Shanju; Liu, Zhan; Bucknall, David G.

2011-01-01

The thermo-responsive behavior of polymer films consisting of novel linear triblock copolymers of poly(n-butyl methacrylate)-poly(methyl methacrylate)-poly(2-fluoroethyl methacrylate) (PnBuMA-PMMA-P2FEMA) are reported using differential scanning calorimetry (DSC), atomic forcing microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and contacting angle (CA) measurements. The surface morphology, wettability and chemical structure of thin films of these triblock copolymers on silicon wafers as a function of temperature have been investigated. It has been shown that the wettability of the films is thermally switchable. Detailed structural analysis shows that thermo-responsive surface composition changes are produced. The underlying mechanism of the thermoresponsive behavior is discussed.

All-Atom Molecular Dynamics-Based Analysis of Membrane-Stabilizing Copolymer Interactions with Lipid Bilayers Probed under Constant Surface Tensions.

PubMed

Houang, Evelyne M; Bates, Frank S; Sham, Yuk Y; Metzger, Joseph M

2017-11-30

An all-atom phospholipid bilayer and triblock copolymer model was developed for molecular dynamics (MD) studies. These were performed to investigate the mechanism of interaction between membrane-stabilizing triblock copolymer P188 and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC) lipid bilayers under applied lateral surface tension (γ) to model membrane mechanical stress. Results showed that P188 insertion is driven by the hydrophobic poly(propylene oxide) (PPO) core and dependent on bilayer area per lipid. Moreover, insertion of P188 increased the bilayer's resistance to mechanical rupture, as observed by a significant increase in the absolute lateral pressure required to disrupt the bilayer. To further investigate the specific chemical features of P188 underlying membrane stabilizer function, a series of MD simulations with triblock copolymers of the same class as P188 but of varying chemical composition and sizes were performed. Results showed that triblock copolymer insertion into the lipid bilayer is dependent on overall copolymer hydrophobicity, with higher copolymer hydrophobicity requiring a reduced bilayer area per lipid ratio for insertion. Further analysis revealed that the effect of copolymer insertion on membrane mechanical integrity was also dependent on hydrophobicity. Here, P188 insertion significantly increased the absolute apparent lateral pressure required to rupture the POPC bilayer, thereby protecting the membrane against mechanical stress. In marked contrast, highly hydrophobic copolymers decreased the lateral pressure necessary for membrane rupture and thus rendering the membrane significantly more susceptible to mechanical stress. These new in silico findings align with recent experimental findings using synthetic lipid bilayers and in muscle cells in vitro and mouse models in vivo. Collectively, these data underscore the importance of PEO-PPO-PEO copolymer chemical composition in copolymer-based muscle membrane stabilization in vitro and in vivo. All-atom modeling with MD simulations holds promise for investigating novel copolymers with enhanced membrane interacting properties.

Membrane-Based Gas Separation Accelerated by Hollow Nanosphere Architectures

DOE PAGES

Zhang, Jinshui; Schott, Jennifer Ann; Univ. of Tennessee, Knoxville, TN; ...

2016-11-15

We report that the coupling of hollow carbon nanospheres with triblock copolymers is a promising strategy to fabricate mixed-matrix membranes, because the symmetric microporous shells combine with the hollow space to promote gas transport and the unique soft-rigid molecular structure of triblock copolymers can accommodate a high loading of fillers without a significant loss of mechanical strength.

Modified release from lipid bilayer coated mesoporous silica nanoparticles using PEO–PPO–PEO triblock copolymers [Modified release from lipid bilayer coated mesoporous silica nanoparticles using PEO PPO PEO triblock copolymers

DOE PAGES

Rahman, Masoud; Yu, Erick; Forman, Evan; ...

2014-08-20

Triblock copolymers comprised of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, or trade name Pluronic) interact with lipid bilayers to increase their permeability. Here we demonstrate a novel application of Pluronic L61 and L64 as modification agents in tailoring the release rate of a molecular indicator species from 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) bilayer-coated superparamagnetic Fe 3O 4/mesoporous silica coreshell nanoparticles. Lastly, we show there is a direct relationship between Pluronic concentration and the indicator molecule release, suggesting Pluronic may be useful for the controlled release of drugs from lipid bilayer-coated carriers.

Asymmetric Membranes from Two Chemically Distinct Triblock Terpolymers Blended during Standard Membrane Fabrication.

PubMed

Li, Yuk Mun; Srinivasan, Divya; Vaidya, Parth; Gu, Yibei; Wiesner, Ulrich

2016-10-01

Deviating from the traditional formation of block copolymer derived isoporous membranes from one block copolymer chemistry, here asymmetric membranes with isoporous surface structure are derived from two chemically distinct block copolymers blended during standard membrane fabrication. As a first proof of principle, the fabrication of asymmetric membranes is reported, which are blended from two chemically distinct triblock terpolymers, poly(isoprene-b-styrene-b-(4-vinyl)pyridine) (ISV) and poly(isoprene-b-styrene-b-(dimethylamino)ethyl methacrylate) (ISA), differing in the pH-responsive hydrophilic segment. Using block copolymer self-assembly and nonsolvent induced phase separation process, pure and blended membranes are prepared by varying weight ratios of ISV to ISA. Pure and blended membranes exhibit a thin, selective layer of pores above a macroporous substructure. Observed permeabilities at varying pH values of blended membranes depend on relative triblock terpolymer composition. These results open a new direction for membrane fabrication through the use of mixtures of chemically distinct block copolymers enabling the tailoring of membrane surface chemistries and functionalities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational Design of Biomimetic Gels With Properties of Human Tissues

DTIC Science & Technology

2008-12-01

poly(styrene-block- isoprene -block-styrene) copolymer or SIS in the I-selective solvent has been chosen as a model triblock copolymer for this study...our model. A A B B B RC Fig. 2. Schematic representation of A1B3A1 triblock copolymer mapped on DPD model. Poly(styrene-block- isoprene -block...Pa making G 2.25 times higher for c changes from 0.16 to 0.33 (density of styrene and isoprene blocks are taken to be 1.04 and 0.913 g/cm3

Experimental measurement of coil-rod-coil block copolymer tracer diffusion through entangled coil homopolymers

PubMed Central

Wang, Muzhou; Timachova, Ksenia; Olsen, Bradley D.

2014-01-01

The diffusion of coil-rod-coil triblock copolymers in entangled coil homopolymers is experimentally measured and demonstrated to be significantly slower than rod or coil homopolymers of the same molecular weight. A model coil-rod-coil triblock was prepared by expressing rodlike alanine-rich α-helical polypeptides in E. coli and conjugating coillike poly(ethylene oxide) (PEO) to both ends to form coil-rod-coil triblock copolymers. Tracer diffusion through entangled PEO homopolymer melts was measured using forced Rayleigh scattering at various rod lengths, coil molecular weights, and coil homopolymer concentrations. For rod lengths, L, that are close to the entanglementh length, a, the ratio between triblock diffusivity and coil homopolymer diffusivity decreases monotonically and is only a function of L/a, in quantitative agreement with previous simulation results. For large rod lengths, diffusion follows an arm retraction scaling, which is also consistent with previous theoretical predictions. These experimental results support the key predictions of theory and simulation, suggesting that the mismatch in curvature between rod and coil entanglement tubes leads to the observed diffusional slowing. PMID:25484454

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

Lu, Wei; Goodwin, Andrew; Wang, Yangyang

All-acrylic multigraft copolymers made by a facile synthesis procedure exhibit elongation at break >1700% and strain recovery behavior far exceeding those of commercial acrylic and styrenic triblock copolymers.

Formation of integral asymmetric membranes of AB diblock and ABC triblock copolymers by phase inversion.

PubMed

Jung, Adina; Filiz, Volkan; Rangou, Sofia; Buhr, Kristian; Merten, Petra; Hahn, Janina; Clodt, Juliana; Abetz, Clarissa; Abetz, Volker

2013-04-12

The formation of integral asymmetric membranes from ABC triblock terpolymers by non-solvent-induced phase separation is shown. They are compared with the AB diblock copolymer precursors. Triblock terpolymers of polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO) with two compositions are investigated. The third block supports the formation of a membrane in a case, where the corresponding diblock copolymer does not form a good membrane. In addition, the hydrophilicity is increased by the third block and due to the hydroxyl group the possibility of post-functionalization is given. The morphologies are imaged by scanning electron microscopy. The influence of the PEO on the membrane properties is analyzed by water flux, retention, and dynamic contact angle measurements. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A nanocompartment system (Synthosome) designed for biotechnological applications.

PubMed

Nallani, Madhavan; Benito, Samantha; Onaca, Ozana; Graff, Alexandra; Lindemann, Marcus; Winterhalter, Mathias; Meier, Wolfgang; Schwaneberg, Ulrich

2006-05-03

A nanocompartment system based on two deletion mutants of the large channel protein FhuA (FhuA Delta1-129; FhuA Delta1-160) and an ABA triblock copolymer (PMOXA-PDMS-PMOXA) has been developed for putative biotechnological applications. FhuA is ideally suited for applications in biotechnology due to its monomeric structure, large pore diameter (39-46 A elliptical cross-section) that ensures rapid compound flux, and solved crystallographic structure. Two areas of application were targeted as proof of principle: (A) selective product recovery in nanocompartments and (B) enzymatic conversion in nanocompartments. Selective recovery of negatively charged compounds has been achieved on the example of sulforhodamine B by using positively charged polylysine molecules as trap inside the nanocompartment. Conversion in nanocompartments has been achieved by 3,3',5,5'-tetramethylbenzidine oxidation employing horseradish peroxidase (HRP).

Self-assembled micellar aggregates based monomethoxyl poly(ethylene glycol)-b-poly(ε-caprolactone)-b-poly(aminoethyl methacrylate) triblock copolymers as efficient gene delivery vectors.

PubMed

Ma, Ming; Li, Feng; Liu, Xiu-hong; Yuan, Zhe-fan; Chen, Fu-jie; Zhuo, Ren-xi

2010-10-01

Amphiphilic triblock copolymers monomethoxyl poly(ethylene glycol) (mPEG)-b-poly(ε-caprolactone) (PCL)-b-poly(aminoethyl methacrylate)s (PAMAs) (mPECAs) were synthesized as gene delivery vectors. They exhibited lower cytotoxicity and higher transfection efficiency in COS-7 cells in presence of serum compared to 25 kDa bPEI. The influence of mPEG and PCL segments in mPECAs was evaluated by comparing with corresponding diblock copolymers. The studies showed the incorporation of the hydrophobic PCL segment in triblock copolymers affected the binding capability to pDNA and surface charges of complexes due to the formation of micelles increasing the local charges. The presence of mPEG segment in gene vector decreased the surface charges of the complexes and increased the stability of the complexes in serum because of the steric hindrance effect. It was also found that the combination of PEG and PCL segments into one macromolecule might lead to synergistic effect for better transfection efficiency in serum.

ABC triblock copolymer vesicles with mesh-like morphology.

PubMed

Zhao, Wei; Chen, Dian; Hu, Yunxia; Grason, Gregory M; Russell, Thomas P

2011-01-25

Polymer vesicles made from poly(isoprene-b-styrene-b-2-vinyl pyridine) (PI-b-PS-b-P2VP) triblock copolymer confined within the nanopores of an anodic aluminum oxide (AAO) membrane are studied. It was found that these vesicles have well-defined, nanoscopic size, and complex microphase-separated hydrophobic membranes, comprised of the PS and PI blocks, while the coronas are formed by the P2VP block. Vesicle formation was tracked using both transmission and scanning electron microscopy. A mesh-like morphology formed in the membrane at a well-defined composition of the three blocks that can be tuned by changing the copolymer composition. The nanoscale confinement, copolymer composition, and subtle molecular interactions contribute to the generation of these vesicles with such unusual morphologies.

PEO-PPO-PEO Tri-Block Copolymers for Gene Delivery Applications in Human Regenerative Medicine—An Overview

PubMed Central

Cucchiarini, Magali

2018-01-01

Lineal (poloxamers or Pluronic®) or X-shaped (poloxamines or Tetronic®) amphiphilic tri-block copolymers of poly(ethylene oxide) and poly(propylene oxide) (PEO-PPO-PEO) have been broadly explored for controlled drug delivery in different regenerative medicine approaches. The ability of these copolymers to self-assemble as micelles and to undergo sol-to-gel transitions upon heating has endowed the denomination of “smart” or “intelligent” systems. The use of PEO-PPO-PEO copolymers as gene delivery systems is a powerful emerging strategy to improve the performance of classical gene transfer vectors. This review summarizes the state of art of the application of PEO-PPO-PEO copolymers in both nonviral and viral gene transfer approaches and their potential as gene delivery systems in different regenerative medicine approaches. PMID:29518011

Gel Phase Formation in Dilute Triblock Copolyelectrolyte Complexes

NASA Astrophysics Data System (ADS)

Srivastava, Samanvaya; Andreev, Marat; Prabhu, Vivek; de Pablo, Juan; Tirrell, Matthew

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at extremely low polymer concentrations (<1 % by mass) has been observed in scattering experiments and molecular dynamics simulations. In contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing polymer concentrations, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assemblies of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously upon solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of triblock copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries not only contribute to our fundamental understanding of the structure and pathways of complexation driven assemblies, but also raise intriguing prospects for formation of gel structures at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

Bicomponent Block Copolymers Derived from One or More Random Copolymers as an Alternative Route to Controllable Phase Behavior

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

Ashraf, Arman R.; Ryan, Justin J.; Satkowski, Michael M.

Block copolymers have been extensively studied due to their ability to spontaneously self-organize into a wide variety of morphologies that are valuable in energy-, medical- and conservation-related (nano)technologies. While the phase behavior of bicomponent diblock and triblock copolymers is conventionally governed by temperature and individual block masses, we demonstrate that their phase behavior can alternatively be controlled through the use of blocks with random monomer sequencing. Block random copolymers (BRCs), i.e., diblock copolymers wherein one or both blocks is a random copolymer comprised of A and B repeat units, have been synthesized, and their phase behavior, expressed in terms ofmore » the order-disorder transition (ODT), has been investigated. Our results establish that, depending on the block composition contrast and molecular weight, BRCs can microphase-separate. We also report that the predicted ODT can be generated at relatively constant molecular weight and temperature with these new soft materials. This sequence-controlled synthetic strategy is extended to thermoplastic elastomeric triblock copolymers differing in chemistry and possessing a random-copolymer midblock.« less

Mechanistic analysis of Zein nanoparticles/PLGA triblock in situ forming implants for glimepiride.

PubMed

Ahmed, Osama Abdelhakim Aly; Zidan, Ahmed Samir; Khayat, Maan

2016-01-01

The study aims at applying pharmaceutical nanotechnology and D-optimal fractional factorial design to screen and optimize the high-risk variables affecting the performance of a complex drug delivery system consisting of glimepiride-Zein nanoparticles and inclusion of the optimized formula with thermoresponsive triblock copolymers in in situ gel. Sixteen nanoparticle formulations were prepared by liquid-liquid phase separation method according to the D-optimal fractional factorial design encompassing five variables at two levels. The responses investigated were glimepiride entrapment capacity (EC), particle size and size distribution, zeta potential, and in vitro drug release from the prepared nanoparticles. Furthermore, the feasibility of embedding the optimized Zein-based glimepiride nanoparticles within thermoresponsive triblock copolymers poly(lactide-co-glycolide)-block-poly(ethylene glycol)-block-poly(lactide-co-glycolide) in in situ gel was evaluated for controlling glimepiride release rate. Through the systematic optimization phase, improvement of glimepiride EC of 33.6%, nanoparticle size of 120.9 nm with a skewness value of 0.2, zeta potential of 11.1 mV, and sustained release features of 3.3% and 17.3% drug released after 2 and 24 hours, respectively, were obtained. These desirability functions were obtained at Zein and glimepiride loadings of 50 and 75 mg, respectively, utilizing didodecyldimethylammonium bromide as a stabilizer at 0.1% and 90% ethanol as a common solvent. Moreover, incorporating this optimized formulation in triblock copolymers-based in situ gel demonstrated pseudoplastic behavior with reduction of drug release rate as the concentration of polymer increased. This approach to control the release of glimepiride using Zein nanoparticles/triblock copolymers-based in situ gel forming intramuscular implants could be useful for improving diabetes treatment effectiveness.

Controlled Sol-Gel Transitions of a Thermoresponsive Polymer in a Photoswitchable Azobenzene Ionic Liquid as a Molecular Trigger.

PubMed

Wang, Caihong; Hashimoto, Kei; Tamate, Ryota; Kokubo, Hisashi; Watanabe, Masayoshi

2018-01-02

Producing ionic liquids (ILs) that function as molecular trigger for macroscopic change is a challenging issue. Photoisomerization of an azobenzene IL at the molecular level evokes a macroscopic response (light-controlled mechanical sol-gel transitions) for ABA triblock copolymer solutions. The A endblocks, poly(2-phenylethyl methacrylate), show a lower critical solution temperature in the IL mixture containing azobenzene, while the B midblock, poly(methyl methacrylate), is compatible with the mixture. In a concentrated polymer solution, different gelation temperatures were observed in it under dark and UV conditions. Light-controlled sol-gel transitions were achieved by a photoresponsive solubility change of the A endblocks upon photoisomerization of the azobenzene IL. Therefore, an azobenzene IL as a molecular switch can tune the self-assembly of a thermoresponsive polymer, leading to macroscopic light-controlled sol-gel transitions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic confinement and alpha-helix persistence length in poly(gamma-benzyl-L-glutamate)-b-poly(dimethyl siloxane)-b-poly(gamma-benzyl-L-glutamate) triblock copolymers.

PubMed

Papadopoulos, P; Floudas, G; Schnell, I; Lieberwirth, I; Nguyen, T Q; Klok, H-A

2006-02-01

The structure and the associated dynamics of a series of poly(gamma-benzyl-L-glutamate)-b-poly(dimethyl siloxane)-b-poly(gamma-benzyl-L-glutamate) (PBLG-b-PDMS-b-PBLG) triblock copolymers were investigated using small- and wide-angle X-ray scattering, NMR, transmission electron microscopy, and dielectric spectroscopy, respectively. The structural analysis revealed phase separation in the case of the longer blocks with defected alpha-helical segments embedded within the block copolymer nanodomains. The alpha-helical persistence length was found to depend on the degree of segregation; thermodynamic confinement and chain stretching results in the partial annihilation of helical defects.

Compression and Instrumented Indentation Measurements on Biomimetic Polymers

DTIC Science & Technology

2006-09-01

styrene- isoprene triblock copolymer gels are tested and compared using both macro-scale and micro-scale measurements. A methodology is presented to...at stress states and strain rates not available to bulk measurement equipment. In this work, a ballistic gelatin and two styrene- isoprene triblock

Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations

DOE PAGES

Zhang, Wenxu; Liu, Ye; Jackson, Aaron C.; ...

2016-06-22

Triblock and diblock copolymers based on isoprene (Ip) and chloromethylstyrene (CMS) were synthesized in this paper by sequential polymerization using reversible addition–fragmentation chain transfer radical polymerization (RAFT). The block copolymers were quaternized with tris(2,4,6-trimethoxyphenyl)phosphine (Ar 3P) to prepare soluble ionomers. The ionomers were cast from chloroform to form anion exchange membranes (AEMs) with highly ordered morphologies. At low volume fractions of ionic blocks, the ionomers formed lamellar morphologies, while at moderate volume fractions (≥30% for triblock and ≥22% for diblock copolymers) hexagonal phases with an ionic matrix were observed. Ion conductivities were higher through the hexagonal phase matrix than inmore » the lamellar phases. Finally, promising chloride conductivities (20 mS/cm) were achieved at elevated temperatures and humidified conditions.« less

Non-Covalent Microgel Particles Containing Functional Payloads: Coacervation of PEG-Based Triblocks via Microfluidics.

PubMed

Wang, Cynthia X; Utech, Stefanie; Gopez, Jeffrey D; Mabesoone, Mathijs F J; Hawker, Craig J; Klinger, Daniel

2016-07-06

Well-defined microgel particles were prepared by combining coacervate-driven cross-linking of ionic triblock copolymers with the ability to control particle size and encapsulate functional cargos inherent in microfluidic devices. In this approach, the efficient assembly of PEO-based triblock copolymers with oppositely charged end-blocks allows for bioinspired cross-linking under mild conditions in dispersed aqueous droplets. This strategy enables the integration of charged cargos into the coacervate domains (e.g., the loading of anionic model compounds through electrostatic association with cationic end-blocks). Distinct release profiles can be realized by systematically varying the chemical nature of the payload and the microgel dimensions. This mild and noncovalent assembly method represents a promising new approach to tunable microgels as scaffolds for colloidal biomaterials in therapeutics and regenerative medicine.

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

PubMed

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

2011-10-18

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

ABC Triblock Copolymer Vesicles with Mesh-like Morphology

NASA Astrophysics Data System (ADS)

Zhao, Wei; Russell, Thomas; Grason, Gregory

2010-03-01

Polymer vesicles can be made from poly(isoprene-b-styrene-b-2-vinylpyridene) (PI-b-PS-b-P2VP) triblock copolymer under the confinement of anodic aluminum oxide (AAO) membrane. It was found that these vesicles have well-defined, nanoscopic size and a microphase-separated hydrophobic core, comprised of PS and PI blocks. Vesicle formation was tracked using both transmission and scanning electron microscopy. A mesh-like morphology formed in the core at a well-defined composition of three blocks. Confinement played an important role in generating these vesicles with such an unusual morphology.

Aggregate morphologies of amphiphilic ABC triblock copolymer in dilute solution using self-consistent field theory.

PubMed

Wang, Rong; Tang, Ping; Qiu, Feng; Yang, Yuliang

2005-09-15

The complex microstructures of amphiphilic ABC linear triblock copolymers in which one of the end blocks is relatively short and hydrophilic, and the other two blocks B and C are hydrophobic in a dilute solution, have been investigated by the real-space implementation of self-consistent field theory (SCFT) in two dimensions (2D). In contrast to diblock copolymers in solution, the aggregation of triblock copolymers are more complicated due to the presence of the second hydrophobic blocks and, hence, big ranges of parameter space controlling the morphology. By tailoring the hydrophobic degree and its difference between the blocks B and C, the various shapes of vesicles, circlelike and linelike micelles possibly corresponding to spherelike, and rodlike micelles in 3D, and especially, peanutlike micelles not found in diblock copolymers are observed. The transition from vesicles to circlelike micelles occurs with increasing the hydrophobicity of the blocks B and C, while the transition from circlelike micelles to linelike micelles or from the mixture of micelles and vesicles to the long linelike micelles takes place when the repulsive interaction of the end hydrophobic block C is stronger than that of the middle hydrophobic block B. Furthermore, it is favorable for dispersion of the block copolymer in the solvent into aggregates when the repulsion of the solvent to the end hydrophobic block is larger than that of the solvent to the middle hydrophobic block. Especially when the bulk block copolymers are in a weak segregation regime, the competition between the microphase separation and macrophase separation exists and the large compound micelle-like aggregates are found due to the macrophase separation with increasing the hydrophobic degree of blocks B and C, which is absent in diblock copolymer solution. The simulation results successfully reproduce the existing experimental ones.

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

PubMed

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

2012-01-31

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

Triblock copolymer micelles as templates for preparation of mesoporous niobia thin films

NASA Astrophysics Data System (ADS)

Georgiev, R.; Christova, D.; Todorova, L.; Georgieva, B.; Vasileva, M.; Novakov, Ch; Babeva, T.

2018-03-01

The micelle formation of commercially available Pluronic PE 6800 (PEO-PPO-PEO triblock copolymer) was studied by means of a dye solubilization method, and the solubility of 1,6-diphenyl-1,3,5-hexatriene in aqueous solutions of the copolymer with concentrations ranging from 0.05 to 20 % w/v was studied by recording the transmission and emission spectra of the solutions using UV-VIS and photoluminescence spectroscopy, respectively. Further, mesoporous Nb2O5 films using PE 6800 micelles templates were obtained through sol-gel using spin-coating; their morphology, structure and optical properties were studied by TEM, SAED and nonlinear fitting of reflectance measurements. The possible application of the films in optical sensing of vapors was demonstrated and discussed.

Nature of Interactions between PEO-PPO-PEO Triblock Copolymers and Lipid Membranes: (I) The Effect of Polymer Hydrophobicity on Its Ability to Protect Liposomes from Peroxidation

PubMed Central

Wang, Jia-Yu; Marks, Jeremy; Lee, Ka Yee C.

2013-01-01

PEO-PPO-PEO triblock copolymers have opposing effects on lipid membrane integrity- they can behave either as membrane sealants or as membrane permeabilizers. To gain insights into their biomembrane activities, the fundamental interactions between a series of PEO-based polymers and phospholipid vesicles were investigated. Specifically, the effect of copolymer hydrophobicity on its ability to prevent liposomes from peroxidation was evaluated, and partitioning free energy and coefficient involved in the interactions were derived. Our results show that the high degree of hydrophilicity is a key feature of the copolymers that can effectively protect liposomes from peroxidation and the protective effect of the copolymers stems from their adsorption at the membrane surface without penetrating into the bilayer core. The origin of this protective effect induced by polymer absorption is attributed to the retardation of membrane hydration dynamics, which is further illustrated in the accompany study on dynamic nuclear polarization (DNP)-derived hydration dynamics1. PMID:22808900

Polydiacetylene/triblock copolymer nanoblend applied as a sensor for micellar casein: A thermodynamic approach.

PubMed

de Souza, Luana Cypriano; de Paula Rezende, Jaqueline; Pires, Ana Clarissa dos Santos; da Silva, Luis Henrique Mendes; da Silva, Maria do Carmo Hespanhol; Castrillon, Elkin Dario Castellon; de Andrade, Nélio José

2016-04-15

Polydiacetylene (PDA) and triblock copolymer nanoblends were synthesized to detect micellar casein (MC), the main milk protein and an indicator of milk quality. UV-Vis spectrum showed that MC induced blue-to-red transition in nanoblends. When nanoblends and MC were separated by dialysis membrane colorimetric response (CR) was similar, whereas a remarkable CR reduction was noticed after addition of dialyzed-MC, suggesting that small molecules present in MC (salts) caused PDA color change. Interaction enthalpy variation between nanoblends and MC showed an abrupt increase that coincided with MC concentration when colorimetric transition occurred. Copolymer hydrophobic/hydrophilic balance and presence of other molecules in the system affected nanoblends CR. MC salts were found to interact with nanoblends leading to color changes. MC concentration, MC salt release, copolymer hydrophobic/hydrophilic balance, and presence of other molecules in the system affected responses of the sensors. These results contribute to future applications of PDA/copolymer nanosensors to dairy models. Copyright © 2015 Elsevier Ltd. All rights reserved.

Chain exchange in triblock copolymer micelles

NASA Astrophysics Data System (ADS)

Lu, Jie; Lodge, Timothy; Bates, Frank

2015-03-01

Block polymer micelles offer a host of technological applications including drug delivery, viscosity modification, toughening of plastics, and colloidal stabilization. Molecular exchange between micelles directly influences the stability, structure and access to an equilibrium state in such systems and this property recently has been shown to be extraordinarily sensitive to the core block molecular weight in diblock copolymers. The dependence of micelle chain exchange dynamics on molecular architecture has not been reported. The present work conclusively addresses this issue using time-resolved small-angle neutron scattering (TR-SANS) applied to complimentary S-EP-S and EP-S-EP triblock copolymers dissolved in squalane, a selective solvent for the EP blocks, where S and EP refer to poly(styrene) and poly(ethylenepropylene), respectively. Following the overall SANS intensity as a function of time from judiciously deuterium labelled polymer and solvent mixtures directly probes the rate of molecular exchange. Remarkably, the two triblocks display exchange rates that differ by approximately ten orders of magnitude, even though the solvophobic S blocks are of comparable size. This discovery is considered in the context of a model that successfully explains S-EP diblock exchange dynamics.

Novel Pentablock Copolymers as Thermosensitive Self-Assembling Micelles for Ocular Drug Delivery

PubMed Central

Alami-Milani, Mitra; Zakeri-Milani, Parvin; Valizadeh, Hadi; Salehi, Roya; Salatin, Sara; Naderinia, Ali; Jelvehgari, Mitra

2017-01-01

Many studies have focused on how drugs are formulated in the sol state at room temperature leading to the formation of in situ gel at eye temperature to provide a controlled drug release. Stimuli-responsive block copolymer hydrogels possess several advantages including uncomplicated drug formulation and ease of application, no organic solvent, protective environment for drugs, site-specificity, prolonged and localized drug delivery, lower systemic toxicity, and capability to deliver both hydrophobic and hydrophilic drugs. Self-assembling block copolymers (such as diblock, triblock, and pentablock copolymers) with large solubility variation between hydrophilic and hydrophobic segments are capable of making temperature-dependent micellar assembles, and with further increase in the temperature, of jellifying due to micellar aggregation. In general, molecular weight, hydrophobicity, and block arrangement have a significant effect on polymer crystallinity, micelle size, and in vitro drug release profile. The limitations of creature triblock copolymers as initial burst release can be largely avoided using micelles made of pentablock copolymers. Moreover, formulations based on pentablock copolymers can sustain drug release for a longer time. The present study aims to provide a concise overview of the initial and recent progresses in the design of hydrogel-based ocular drug delivery systems. PMID:28507933

Synthetic strategy for preparing chiral double-semicrystalline polyether block copolymers

DOE PAGES

McGrath, Alaina J.; Shi, Weichao; Rodriguez, Christina G.; ...

2014-12-11

Here, we report an effective strategy for the synthesis of semi-crystalline block copolyethers with well-defined architecture and stereochemistry. As an exemplary system, triblock copolymers containing either atactic (racemic) or isotactic ( R or S) poly(propylene oxide) end blocks with a central poly(ethylene oxide) mid-block were prepared by anionic ring-opening procedures. Stereochemical control was achieved by an initial hydrolytic kinetic resolution of racemic terminal epoxides followed by anionic ring-opening polymerization of the enantiopure monomer feedstock. The resultant triblock copolymers were highly isotactic (meso triads [ mm]% ~ 90%) with optical microscopy, differential scanning calorimetry, wide angle x-ray scattering and small anglemore » x-ray scattering being used to probe the impact of the isotacticity on the resultant polymer and hydrogel properties.« less

Triblock copolymer matrix-based capillary electrophoretic microdevice for high-resolution multiplex pathogen detection.

PubMed

Kim, Se Jin; Shin, Gi Won; Choi, Seok Jin; Hwang, Hee Sung; Jung, Gyoo Yeol; Seo, Tae Seok

2010-03-01

Rapid and simple analysis for the multiple target pathogens is critical for patient management. CE-SSCP analysis on a microchip provides high speed, high sensitivity, and a portable genetic analysis platform in molecular diagnostic fields. The capability of separating ssDNA molecules in a capillary electrophoretic microchannel with high resolution is a critical issue to perform the precise interpretation in the electropherogram. In this study, we explored the potential of poly(ethyleneoxide)-poly(propyleneoxide)-poly(ethyleneoxide) (PEO-PPO-PEO) triblock copolymer as a sieving matrix for CE-SSCP analysis on a microdevice. To demonstrate the superior resolving power of PEO-PPO-PEO copolymers, 255-bp PCR amplicons obtained from 16S ribosomal RNA genes of four bacterial species, namely Proteus mirabilis, Haemophilus ducreyi, Pseudomonas aeruginosa, and Neisseria meningitidis, were analyzed in the PEO-PPO-PEO matrix in comparison with 5% linear polyacrylamide and commercial GeneScan gel. Due to enhanced dynamic coating and sieving ability, PEO-PPO-PEO copolymer displayed fourfold enhancement of resolving power in the CE-SSCP to separate same-sized DNA molecules. Fivefold input of genomic DNA of P. aeruginosa and/or N. meningitidis produced proportionally increased corresponding amplicon peaks, enabling correct quantitative analysis in the pathogen detection. Besides the high-resolution sieving capability, a facile loading and replenishment of gel in the microchannel due to thermally reversible gelation property makes PEO-PPO-PEO triblock copolymer an excellent matrix in the CE-SSCP analysis on the microdevice.

De Novo Synthesis of Phosphorylated Triblock Copolymers with Pathogen Virulence-Suppressing Properties That Prevent Infection-Related Mortality

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

Mao, Jun; Zaborin, Alexander; Poroyko, Valeriy

Phosphate is a key and universal "cue" in response to which bacteria either enhance their virulence when local phosphate is scarce or downregulate it when phosphate is adundant. Phosphate becomes depleted in the mammalian gut following physiologic stress and serves as a major trigger for colonizing bacteria to express virulence. This process cannot be reversed with oral supplementation of inorganic phosphate because it is nearly completely absorbed in the proximal small intestine. In the present study, we describe the de novo synthesis of phosphorylated polyethylene glycol compounds with three defined ABA (hydrophilic/-phobic/-philic) structures, ABA-PEG10k-Pi10, ABA-PEG16k-Pi14, and ABA-PEG20k-Pi20, and linear polymermore » PEG20k-Pi20 absent of the hydrophobic block. The 10k, 16k, and 20k demonstrate the molecular weights of the poly(ethylene glycol) block, and Pi10, Pi14, and Pi20 represent the repeating units of phosphate. Polymers were tested for their efficacy against Pseudomonas aeruginosa virulence in vitro and in vivo by assessing the expression of the phosphate sensing protein PstS, the production of key virulence factor pyocyanin, and Caenorhabditis elegans killing assays. Results indicate that all phosphorylated polymers suppressed phosphate sensing, virulence expression, and lethality in P. aeruginosa. Among all of the phosphorylated polymers, ABA-PEG20kPi20 displayed the greatest degree of protection against P. aeruginosa. To define the role of the hydrophobic core in ABA-PEG20k-Pi20 in the above response, we synthesized PEG20k-Pi20 in which the hydrophobic core is absent. Results indicate that the hypdrophobic core of ABA-PEG20k-Pi20 is a key structure in its protective effect against P. aeruginosa, in part due to its ability to coat the surface of bacteria. Taken together, the synthesis of novel polymers with defined structures and levels of phosphorylation may elucidate their antivirulence action against clinically important and lethal pathogens such as P. aeruginosa« less

New Linear and Star-Shaped Thermogelling Poly([R]-3-hydroxybutyrate) Copolymers.

PubMed

Barouti, Ghislaine; Liow, Sing Shy; Dou, Qingqing; Ye, Hongye; Orione, Clément; Guillaume, Sophie M; Loh, Xian Jun

2016-07-18

The synthesis of multi-arm poly([R]-3-hydroxybutyrate) (PHB)-based triblock copolymers (poly([R]-3-hydroxybutyrate)-b-poly(N-isopropylacrylamide)-b-[[poly(methyl ether methacrylate)-g-poly(ethylene glycol)]-co-[poly(methacrylate)-g-poly(propylene glycol)

Synthesis and characterization of nanocomposite scaffolds based on triblock copolymer of L-lactide, ε-caprolactone and nano-hydroxyapatite for bone tissue engineering.

PubMed

Torabinejad, Bahman; Mohammadi-Rovshandeh, Jamshid; Davachi, Seyed Mohammad; Zamanian, Ali

2014-09-01

The employment of biodegradable polymer scaffolds is one of the main approaches for achieving a tissue engineered construct to reproduce bone tissues, which provide a three dimensional template to regenerate desirable tissues for different applications. The main goal of this study is to design a novel triblock scaffold reinforced with nano-hydroxyapatite (nHA) for hard tissue engineering using gas foaming/salt leaching method with minimum solvent usage. With this end in view, the biodegradable triblock copolymers of l-lactide and ε-caprolactone with different mol% were synthesized by ring-opening polymerization method in the presence of Sn(Oct)2 catalyst as initiator and ethylene glycol as co-initiator. The chemical compositions of biodegradable copolymers were characterized by means of FTIR and NMR. The thermal and crystallization behaviors of copolymers were characterized using TGA and DSC thermograms. Moreover, nano-hydroxyapatite was synthesized by the chemical precipitation process and was thoroughly characterized by FTIR, XRD and TEM. Additionally, the nanocomposites with different contents of nHA were prepared by mixing triblock copolymer with nHA. Mechanical properties of the prepared nanocomposites were evaluated by stress-strain measurements. It was found that the nanocomposite with 30% of nHA showed the optimum result. Therefore, nanocomposite scaffolds with 30% nHA were fabricated by gas foaming/salt leaching method and SEM images were used to observe the microstructure and morphology of nanocomposites and nanocomposite scaffolds before and after cell culture. The in-vitro and cell culture tests were also carried out to further evaluate the biological properties. The results revealed that the porous scaffolds were biocompatible to the osteoblast cells because the cells spread and grew well. The resultant nanocomposites could be considered as good candidates for use in bone tissue engineering. Copyright © 2014 Elsevier B.V. All rights reserved.

How ABA block polymers activate cytochrome c in toluene: molecular dynamics simulation and experimental observation.

PubMed

Chen, Gong; Kong, Xian; Zhu, Jingying; Lu, Diannan; Liu, Zheng

2015-04-28

While the conjugation of enzymes with ABA copolymers has resulted in increased enzymatic activities in organic solvents, by several orders of magnitude, the underpinning mechanism has not been fully uncovered, particularly at the molecular level. In the present work, a coarse-grained molecular dynamics simulation of cytochrome c (Cyt c) conjugated with a PEO-PPO-PEO block copolymer (ABA) in toluene was simulated with Cyt c as a control. It is shown that the hydrophilic segments (PEO) of the conjugated block copolymer molecules tend to entangle around the hydrophilic patch of Cyt c, while the hydrophobic segments (PPO) extend into the toluene. At a lower temperature, the PEO tails tend to form a hairpin structure outside the conjugated protein, whereas the Cyt c-ABA conjugates tend to form larger aggregates. At a higher temperature, however, the PEO tails tend to adsorb onto the hydrophilic protein surface, thus improving the suspension of the Cyt c-ABA conjugates and, consequently, the contact with the substrate. Moreover, the temperature increase drives the conformational transition of the active site of Cyt c-ABA from an "inactive state" to an "activated state" and thus results in an enhanced activity. To validate the above simulations, Cyt c was conjugated to F127, an extensively used ABA copolymer. By elevating the temperature, a decrease in the average size of the Cyt c-F127 conjugates along with a great increase in the apparent activity in toluene was observed, as can be predicted from the molecular dynamics simulation. The above mentioned molecular simulations offer a molecular insight into the temperature-responsive behaviour of protein-ABA copolymers, which is helpful for the design and application of enzyme-polymer conjugates for industrial biocatalysis.

Adsorption and association of a symmetric PEO-PPO-PEO triblock copolymer on polypropylene, polyethylene, and cellulose surfaces.

PubMed

Li, Yan; Liu, Hongyi; Song, Junlong; Rojas, Orlando J; Hinestroza, Juan P

2011-07-01

The association of a symmetric polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO(19)-PPO(29)-PEO(19)) triblock copolymer adsorbed from aqueous solutions onto polypropylene (PP), polyethylene (PE), and cellulose surfaces was probed using Atomic Force Microscopy (AFM). Significant morphological differences between the polyolefin substrates (PP and PE) and the cellulose surfaces were observed after immersion of the films in the PEO(19)-PPO(29)-PEO(19) solutions. When the samples were scanned, while immersed in solutions of the triblock copolymer, it was revealed that the structures adsorbed on the polyolefin surfaces were smoothed by the adsorbed PEO(19)-PPO(29)-PEO(19). In contrast, those structures on the hydrophilic cellulose surfaces were sharpened. These observations were related to the roughness of the substrate and the energy of interaction between the surfaces and the PEO and PPO polymer segments. The interaction energy between each of the blocks and the surface was calculated using molecular dynamics simulations. It is speculated that the associative structures amply reported in aqueous solution at concentrations above the critical micelle concentration, CMC, are not necessarily preserved upon adsorption; instead, it appears that molecular arrangements of the anchor-buoy type and hemimicelles prevail. The reported data suggests that the roughness of the surface, as well as its degree of hydrophobicity, have a large influence on the nature of the resulting adsorbed layer. The reported observations are valuable in explaining the behavior of finishing additives and lubricants commonly used in textile and fiber processing, as well as the effect of the morphology of the boundary layers on friction and wear, especially in the case of symmetric triblock copolymers, which are commonly used as antifriction, antiwear additives.

Gel phase formation in dilute triblock copolyelectrolyte complexes

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

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chainmore » aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.« less

Gel phase formation in dilute triblock copolyelectrolyte complexes

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

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chainmore » aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Finally, our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.« less

Gel phase formation in dilute triblock copolyelectrolyte complexes

DOE PAGES

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; ...

2017-02-23

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chainmore » aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Finally, our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.« less

Gel phase formation in dilute triblock copolyelectrolyte complexes

NASA Astrophysics Data System (ADS)

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; Goldfeld, David J.; Mao, Jun; Heller, William T.; Prabhu, Vivek M.; de Pablo, Juan J.; Tirrell, Matthew V.

2017-02-01

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

Anatomy of triply-periodic network assemblies: characterizing skeletal and inter-domain surface geometry of block copolymer gyroids.

PubMed

Prasad, Ishan; Jinnai, Hiroshi; Ho, Rong-Ming; Thomas, Edwin L; Grason, Gregory M

2018-05-09

Triply-periodic networks (TPNs), like the well-known gyroid and diamond network phases, abound in soft matter assemblies, from block copolymers (BCPs), lyotropic liquid crystals and surfactants to functional architectures in biology. While TPNs are, in reality, volume-filling patterns of spatially-varying molecular composition, physical and structural models most often reduce their structure to lower-dimensional geometric objects: the 2D interfaces between chemical domains; and the 1D skeletons that thread through inter-connected, tubular domains. These lower-dimensional structures provide a useful basis of comparison to idealized geometries based on triply-periodic minimal, or constant-mean curvature surfaces, and shed important light on the spatially heterogeneous packing of molecular constituents that form the networks. Here, we propose a simple, efficient and flexible method to extract a 1D skeleton from 3D volume composition data of self-assembled networks. We apply this method to both self-consistent field theory predictions as well as experimental electron microtomography reconstructions of the double-gyroid phase of an ABA triblock copolymer. We further demonstrate how the analysis of 1D skeleton, 2D inter-domain surfaces, and combinations therefore, provide physical and structural insight into TPNs, across multiple length scales. Specifically, we propose and compare simple measures of network chirality as well as domain thickness, and analyze their spatial and statistical distributions in both ideal (theoretical) and non-ideal (experimental) double gyroid assemblies.

Synthesis and Characterization of Fatty Acid/Amino Acid Self-Assemblies

PubMed Central

Gajowy, Joanna; Bolikal, Durgadas; Kohn, Joachim; El Fray, Miroslawa

2014-01-01

In this paper, we discuss the synthesis and self-assembling behavior of new copolymers derived from fatty acid/amino acid components, namely dimers of linoleic acid (DLA) and tyrosine derived diphenols containing alkyl ester pendent chains, designated as “R” (DTR). Specific pendent chains were ethyl (E) and hexyl (H). These poly(aliphatic/aromatic-ester-amide)s were further reacted with poly(ethylene glycol) (PEG) and poly(ethylene glycol methyl ether) of different molecular masses, thus resulting in ABA type (hydrophilic-hydrophobic-hydrophilic) triblock copolymers. We used Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies to evaluate the chemical structure of the final materials. The molecular masses were estimated by gel permeation chromatography (GPC) measurements. The self-organization of these new polymeric systems into micellar/nanospheric structures in aqueous environment was evaluated using ultraviolet/visible (UV-VIS) spectroscopy, dynamic light scattering (DLS) and transmission electron microscopy (TEM). The polymers were found to spontaneously self-assemble into nanoparticles with sizes in the range 196–239 nm and critical micelle concentration (CMC) of 0.125–0.250 mg/mL. The results are quite promising and these materials are capable of self-organizing into well-defined micelles/nanospheres encapsulating bioactive molecules, e.g., vitamins or antibacterial peptides for antibacterial coatings on medical devices. PMID:25347356

Fabrication of biofunctional nanomaterials via Escherichia coli OmpF protein air/water interface insertion/integration with copolymeric amphiphiles.

PubMed

Ho, Dean; Chang, Stacy; Montemagno, Carlo D

2006-06-01

Fabrication of next-generation biologically active materials will involve the integration of proteins with synthetic membrane materials toward a wide spectrum of applications in nanoscale medicine, including high-throughput drug testing, energy conversion for powering medical devices, and bio-cloaking films for mimicry of cellular membrane surfaces toward the enhancement of implant biocompatibility. We have used ABA triblock copolymer membranes (PMOXA-PDMS-PMOXA) of varied thicknesses as platform materials for Langmuir film-based functionalization with the OmpF pore protein from Escherichia coli by fabricating monolayers of copolymer amphiphile-protein complexes on the air/water interface. Here we demonstrate that the ability for protein insertion at the air/water interface during device fabrication is dependent upon the initial surface coverage with the copolymer as well as copolymer thickness. Methacrylate-terminated block copolymer structures that were 4 nm (4METH) and 8 nm (8METH) in length were used as the protein reconstitution matrix, whereas a 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) lipid (~4 nm thickness) was used as a comparison to demonstrate the effects of copolymer length on protein integration capabilities. Wilhemy surface pressure measurements (mN/m) revealed a greater protein insertion in the 4METH and POPC structures compared with the 8METH structure, indicating that shorter copolymer chains possess enhanced biomimicry of natural lipid-based membranes. In addition, comparisons between the isothermal characteristics of the 4METH, 8METH, and POPC membranes reveal that phase transitions of the 4METH resemble a blend of the 8METH and POPC materials, indicating that the 4METH chain may possess hybrid properties of both copolymers and lipids. Furthermore, we have shown that following the deposition of the amphiphilic materials on the air/water interface, the OmpF can be deposited directly on top of the amphiphiles (surface addition), thus effectively further enhancing protein insertion because of the buoying effects of the membranes. These characteristics of Langmuir-Blodgett-based fabrication of copolymer-biomolecule hybrids represent a synthesis strategy for next-generation biomedical materials.

Poly(lactide)-block-poly([epsilon]-caprolactone-co-[epsilon]-decalactone)-block-poly(lactide) copolymer elastomers

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

Schneiderman, Deborah K.; Hill, Erin M.; Martello, Mark T.

Batch ring opening transesterification copolymerization of ε-caprolactone and ε-decalactone was used to generate statistical copolymers over a wide range of compositions and molar masses. Reactivity ratios determined for this monomer pair, r CL = 5.9 and r DL = 0.03, reveal ε-caprolactone is added preferentially regardless of the propagating chain end. Relative to poly(ε-caprolactone) the crystallinity and melting point of these statistical copolymers were depressed by the addition of ε-decalactone; copolymers containing greater than 31 mol% (46 wt%) ε-decalactone were amorphous. Poly(lactide)-block-poly(ε-caprolactone-co-ε-decalactone)-block-poly(lactide) triblock polymers were also prepared and used to explore the influence of midblock composition on the temperature dependentmore » Flory-Huggins interaction parameter (χ). In addition, uniaxial extension tests were used to determine the effects of midblock composition, poly(lactide) content, and molar mass on the mechanical properties of these new elastomeric triblocks.« less

UCST-Type Thermoresponsive Polymers in Synthetic Lubricating Oil Polyalphaolefin (PAO)

DOE PAGES

Fu, Wenxin; Bai, Wei; Jiang, Sisi; ...

2018-02-20

Here, this article reports a family of UCST-type thermoresponsive polymers, poly(alkyl methacrylate)s with an appropriate alkyl pendant length, in an industrially important non-volatile organic liquid polyalphaolefin (PAO). The cloud point (CP) can be readily tuned over a wide temperature range by changing the alkyl pendant length; at a concentration of 1 wt% and similar polymer molecular weights, the CP varies linearly with the (average) number of carbon atoms in the alkyl pendant. PAO solutions of ABA triblock copolymers, composed of a PAO-philic middle block and thermoresponsive outer blocks with appropriate block lengths, undergo thermoreversible sol-gel transitions at sufficiently high concentrations.more » The discovery of thermoresponsive polymers in PAO makes it possible to explore new applications by utilizing PAO’s unique characteristics such as thermal stability, non-volatility, superior lubrication properties, etc. Lastly, two examples are presented: thermoresponsive physical gels for control of optical transmittance and injectable gel lubricants.« less

UCST-Type Thermoresponsive Polymers in Synthetic Lubricating Oil Polyalphaolefin (PAO)

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

Fu, Wenxin; Bai, Wei; Jiang, Sisi

Here, this article reports a family of UCST-type thermoresponsive polymers, poly(alkyl methacrylate)s with an appropriate alkyl pendant length, in an industrially important non-volatile organic liquid polyalphaolefin (PAO). The cloud point (CP) can be readily tuned over a wide temperature range by changing the alkyl pendant length; at a concentration of 1 wt% and similar polymer molecular weights, the CP varies linearly with the (average) number of carbon atoms in the alkyl pendant. PAO solutions of ABA triblock copolymers, composed of a PAO-philic middle block and thermoresponsive outer blocks with appropriate block lengths, undergo thermoreversible sol-gel transitions at sufficiently high concentrations.more » The discovery of thermoresponsive polymers in PAO makes it possible to explore new applications by utilizing PAO’s unique characteristics such as thermal stability, non-volatility, superior lubrication properties, etc. Lastly, two examples are presented: thermoresponsive physical gels for control of optical transmittance and injectable gel lubricants.« less

Modeling and self-assembly behavior of PEG-PLA-PEG triblock copolymers in aqueous solution

NASA Astrophysics Data System (ADS)

Wu, Xiaohan; Li, Suming; Coumes, Fanny; Darcos, Vincent; Lai Kee Him, Joséphine; Bron, Patrick

2013-09-01

A series of poly(ethylene glycol)-polylactide-poly(ethylene glycol) (PEG-PLA-PEG) triblock copolymers with symmetric or asymmetric chain structures were synthesized by combination of ring-opening polymerization and copper-catalyzed click chemistry. The resulting copolymers were used to prepare self-assembled aggregates by dialysis. Various architectures such as nanotubes, polymersomes and spherical micelles were observed from transmission electron microscopy (TEM), cryo-TEM and atomic force microscopy (AFM) measurements. The formation of diverse aggregates is explained by modeling from the angle of both geometry and thermodynamics. From the angle of geometry, a ``blob'' model based on the Daoud-Cotton model for star polymers is proposed to describe the aggregate structures and structural changes with copolymer composition and molar mass. In fact, the copolymer chains extend in aqueous medium to form single layer polymersomes to minimize the system's free energy if one of the two PEG blocks is short enough. The curvature of polymersomes is dependent on the chain structure of copolymers, especially on the length of PLA blocks. A constant branch number of aggregates (f) is thus required to preserve the morphology of polymersomes. Meanwhile, the aggregation number (Nagg) determined from the thermodynamics of self-assembly is roughly proportional to the total length of polymer chains. Comparing f to Nagg, the aggregates take the form of polymersomes if Nagg ~ f, and change to nanotubes if Nagg > f to conform to the limits from both curvature and aggregation number. The length of nanotubes is mainly determined by the difference between Nagg and f. However, the hollow structure becomes unstable when both PEG segments are too long, and the aggregates eventually collapse to yield spherical micelles. Therefore, this work gives new insights into the self-assembly behavior of PEG-PLA-PEG triblock copolymers in aqueous solution which present great interest for biomedical and pharmaceutical applications.A series of poly(ethylene glycol)-polylactide-poly(ethylene glycol) (PEG-PLA-PEG) triblock copolymers with symmetric or asymmetric chain structures were synthesized by combination of ring-opening polymerization and copper-catalyzed click chemistry. The resulting copolymers were used to prepare self-assembled aggregates by dialysis. Various architectures such as nanotubes, polymersomes and spherical micelles were observed from transmission electron microscopy (TEM), cryo-TEM and atomic force microscopy (AFM) measurements. The formation of diverse aggregates is explained by modeling from the angle of both geometry and thermodynamics. From the angle of geometry, a ``blob'' model based on the Daoud-Cotton model for star polymers is proposed to describe the aggregate structures and structural changes with copolymer composition and molar mass. In fact, the copolymer chains extend in aqueous medium to form single layer polymersomes to minimize the system's free energy if one of the two PEG blocks is short enough. The curvature of polymersomes is dependent on the chain structure of copolymers, especially on the length of PLA blocks. A constant branch number of aggregates (f) is thus required to preserve the morphology of polymersomes. Meanwhile, the aggregation number (Nagg) determined from the thermodynamics of self-assembly is roughly proportional to the total length of polymer chains. Comparing f to Nagg, the aggregates take the form of polymersomes if Nagg ~ f, and change to nanotubes if Nagg > f to conform to the limits from both curvature and aggregation number. The length of nanotubes is mainly determined by the difference between Nagg and f. However, the hollow structure becomes unstable when both PEG segments are too long, and the aggregates eventually collapse to yield spherical micelles. Therefore, this work gives new insights into the self-assembly behavior of PEG-PLA-PEG triblock copolymers in aqueous solution which present great interest for biomedical and pharmaceutical applications. Electronic supplementary information (ESI) available: 1H-NMR, DOSY, FTIR, and GPC measurements, methods and results of the copolymers in PEG-PLA-PEG synthesis. See DOI: 10.1039/c3nr02899b

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

Bolton, Justin; Rzayev, Javid

Polystyrene–poly(methyl methacrylate)–polylactide (PS–PMMA–PLA) triblock bottlebrush copolymer with nearly symmetric volume fractions was synthesized by grafting from a symmetrical triblock backbone and the resulting melt was characterized by scanning electron microscopy and small-angle X-ray scattering. The copolymer backbone was prepared by sequential reversible addition–fragmentation chain transfer (RAFT) polymerization of solketal methacrylate (SM), 2-(bromoisobutyryl)ethyl methacrylate (BIEM), and 5-(trimethylsilyl)-4-pentyn-1-ol methacrylate (TPYM). PMMA branches were grafted by atom transfer radical polymerization from the poly(BIEM) segment, PS branches were grafted by RAFT polymerization from the poly(TPYM) block after installment of the RAFT agents, while PLA side chains were grafted from the deprotected poly(SM) block. Themore » resulting copolymer was found to exhibit a lamellae morphology with a domain spacing of 79 nm. Differential scanning calorimetry analysis indicated that PMMA was preferentially mixing with PS while phase separating from PLA domains.« less

Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers

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

Margulis, Katherine; Zhang, Xiangyi; Joubert, Lydia -Marie

Template–free fabrication of non–spherical polymeric nanoparticles is desirable for various applications, but has had limited success owing to thermodynamic favorability of sphere formation. Herein we present a simple way to prepare cubic nanoparticles of block copolymers by self–assembly from aqueous solutions at room temperature. Nanocubes with edges of 40–200 nm are formed spontaneously on different surfaces upon water evaporation from micellar solutions of triblock copolymers containing a central poly(ethylene oxide) block and terminal trimethylene carbonate/dithiolane blocks. These polymers self–assemble into 28±5 nm micelles in water. Upon drying, micelle aggregation and a kinetically controlled crystallization of central blocks evidently induce solidmore » cubic particle formation. An approach for preserving the structures of these cubes in water by thiol– or photo–induced crosslinking was developed. In conclusion, the ability to solubilize a model hydrophobic drug, curcumin, was also explored.« less

Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers

DOE PAGES

Margulis, Katherine; Zhang, Xiangyi; Joubert, Lydia -Marie; ...

2017-10-27

Template–free fabrication of non–spherical polymeric nanoparticles is desirable for various applications, but has had limited success owing to thermodynamic favorability of sphere formation. Herein we present a simple way to prepare cubic nanoparticles of block copolymers by self–assembly from aqueous solutions at room temperature. Nanocubes with edges of 40–200 nm are formed spontaneously on different surfaces upon water evaporation from micellar solutions of triblock copolymers containing a central poly(ethylene oxide) block and terminal trimethylene carbonate/dithiolane blocks. These polymers self–assemble into 28±5 nm micelles in water. Upon drying, micelle aggregation and a kinetically controlled crystallization of central blocks evidently induce solidmore » cubic particle formation. An approach for preserving the structures of these cubes in water by thiol– or photo–induced crosslinking was developed. In conclusion, the ability to solubilize a model hydrophobic drug, curcumin, was also explored.« less

Peptide surface modification of P(HEMA-co-MMA)-b-PIB-b-P(HEMA-co-MMA) block copolymers.

PubMed

Ojha, Umaprasana; Feng, Dingsong; Chandekar, Amol; Whitten, James E; Faust, Rudolf

2009-06-02

Peptide surface modification of poly[(methyl methacrylate-co-hydroxyethyl methacrylate)-b-isobutylene-b-(methyl methacrylate-co-hydroxyethyl methacrylate)] P(MMA-co-HEMA)-b-PIB-b-P(MMA-co-HEMA) triblock copolymers with different HEMA/MMA ratios has been accomplished using an efficient synthetic procedure. The triblock copolymers were reacted with 4-fluorobenzenesulfonyl chloride (fosyl chloride) in pyridine to obtain the activated polymers [poly{(methyl methacrylate-co-fosyloxyethyl methacrylate)-b-isobutylene-b-(methyl methacrylate-co-fosyloxyethyl methacrylate)}] P(MMA-co-FEMA)-b-PIB-b-P(MMA-co-FEMA), with an activating efficiency of 80-90%. The resulting polymers were soluble in chloroform, and their solutions were used to coat thin uniform films with a predetermined thickness on smooth steel surfaces. The presence of reactive activating groups on the film surface was confirmed by X-ray photoelectron spectroscopy (XPS), dye labeling, and confocal laser scanning microscopic studies. Activation of the triblock copolymer films was also achieved under heterogeneous conditions in polar (acetonitrile) and nonpolar (hexanes) media. The extent of activation was controlled by varying the dipping time and polarity of the medium. Peptide attachment was accomplished by immersing the coated steel strips into aqueous buffer solution of Gly-Gly or GYIGSR. XPS and solubility studies revealed successful attachment of peptides to the polymer surface. Virtually all remaining activating groups were successfully replaced in the subsequent step by a treatment with Tris(hydroxymethyl)amino methane in a buffered methanol/water mixture.

Thermoreversible hydrogels based on triblock copolymers of poly(ethylene glycol) and carboxyl functionalized poly(ε-caprolactone): The effect of carboxyl group substitution on the transition temperature and biocompatibility in plasma.

PubMed

Safaei Nikouei, Nazila; Vakili, Mohammad Reza; Bahniuk, Markian S; Unsworth, Larry; Akbari, Ali; Wu, Jianping; Lavasanifar, Afsaneh

2015-01-01

In this study we report on the development, characterization and plasma protein interaction of novel thermoresponsive in situ hydrogels based on triblock copolymers of poly(ethylene glycol) (PEG) and poly(α-carboxyl-co-benzyl carboxylate)-ε-caprolactone (PCBCL) having two different degrees of carboxyl group substitution on the PCBCL block. Block copolymers were synthesized through ring-opening polymerization of α-benzyl carboxylate-ε-caprolactone by dihydroxy PEG, leading to the production of poly(α-benzyl carboxylate-ε-caprolactone)-PEG-poly(α-benzyl carboxylate-ε-caprolactone) (PBCL-PEG-PBCL). This was followed by partial debenzylation of PBCL blocks under controlled conditions, leading to the preparation of PCBCL-PEG-PCBCL triblock copolymers with 30 and 54mol.% carboxyl group substitution. Prepared PCBCL-PEG-PCBCL block copolymers have been shown to have a concentration-dependent sol to gel transition as a result of an increase in temperature above ∼29°C, as evidenced by the inverse flow method, differential scanning calorimetry and dynamic mechanical analysis. The sol-gel transition temperature/concentration and dynamic mechanical properties of the gel were found to be dependent on the level of carboxyl group substitution. Both hydrogels (30 and 54mol.% carboxyl group substitution) showed similar amounts of protein adsorption but striking differences in the profiles of the adsorbed proteome. Additionally, the two systems showed similarities in their clot formation kinetics but substantial differences in clot endpoints. The results show great promise for the above-mentioned thermoreversible in situ hydrogels as biocompatible materials for biomedical applications. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Thermal Annealing to Modulate the Shape Memory Behavior of a Biobased and Biocompatible Triblock Copolymer Scaffold in the Human Body Temperature Range.

PubMed

Merlettini, Andrea; Gigli, Matteo; Ramella, Martina; Gualandi, Chiara; Soccio, Michelina; Boccafoschi, Francesca; Munari, Andrea; Lotti, Nadia; Focarete, Maria Letizia

2017-08-14

A biodegradable and biocompatible electrospun scaffold with shape memory behavior in the physiological temperature range is here presented. It was obtained starting from a specifically designed, biobased PLLA-based triblock copolymer, where the central block is poly(propylene azelate-co-propylene sebacate) (P(PAz60PSeb40)) random copolymer. Shape memory properties are determined by the contemporary presence of the low melting crystals of the P(PAz60PSeb40) block, acting as switching segment, and of the high melting crystal phase of PLLA blocks, acting as physical network. It is demonstrated that a straightforward annealing process applied to the crystal phase of the switching element gives the possibility to tune the shape recovery temperature from about 25 to 50 °C, without the need of varying the copolymer's chemical structure. The thermal annealing approach here presented can be thus considered a powerful strategy for "ad hoc" programming the same material for applications requiring different recovery temperatures. Fibroblast culture experiments demonstrated scaffold biocompatibility.

Using tethered triblock copolymers to mediate the interaction between substrates

NASA Astrophysics Data System (ADS)

Chern, Shyh-Shi; Zhulina, Ekaterina B.; Pickett, Galen T.; Balazs, Anna C.

1998-04-01

Using scaling analysis and a self-consistent field (SCF) theory, we compress two copolymer-coated surfaces and isolate conditions that yield multiple, distinct minima in the interaction profile. We focus on planar surfaces that are coated with ABC triblock copolymers. Tethered to the surface by the last monomer in the C block, the copolymers are grafted at relatively low densities. The surrounding solution is a poor solvent for both the A and C blocks, and is a good solvent for the B blocks. Through scaling theory, we pinpoint the parameters that yield two minima in the interaction profile. The SCF calculations reveal the changes in the morphology of the polymers as the layers are compressed. Through both studies, we determine how the morphological changes give rise to the observed surface interactions. The results provide guidelines for creating polymer-coated colloidal systems that can form two stable crystal structures. Such systems could be used for bistable, optical switches. The findings also yield a prescription for creating systems that exhibit additional minima in the free energy of interaction.

Macroscopic Modeling of A3B15A3 Triblock Copolymers in B Solvent

DTIC Science & Technology

2010-11-01

matrix composed of the midblock (2). Some examples of TPEs are poly[styrene-butadiene-styrene] (SBS), poly[styrene- isoprene -styrene] (SIS), poly[styrene...92. 19. Hadziioannou, G.; Skoulios, A. Molecular Weight Dependence of Lamellar Structure in Styrene Isoprene Two- and Three-block Copolymers...Microphase Seperation in Styrene- Isoprene Block Copolymers. Macromolecules 1994, 27. 42. Mckay, K. W.; Gros, W. A.; Diehl, C. F. The Influence of

Triblock copolyampholytes from 5-(N,N-dimethyl amino)isoprene styrene, and methacrylic acid: Synthesis and solution properties

NASA Astrophysics Data System (ADS)

Bieringer, R.; Abetz, V.; Müller, A. H. E.

ABC triblock copolymers of the type poly[5-(N,N-dimethyl amino)isoprene]-block-polystyrene-block-poly(tert-butyl methacrylate) (AiST) were synthesized and hydrolyzed to yield poly[5-(N,N-dimethyl amino)isoprene]-block-polystyrene-block-poly(methacrylic acid) (AiSA) triblock copolyampholytes. Due to a complex solubility behavior the solution properties of these materials had to be investigated in THF/water solvent mixtures. Potentiometric titrations of AiSA triblock copolyampholytes showed two inflection points with the A block being deprotonated prior to the Ai hydrochloride block thus forming a polyzwitterion at the isoelectric point (iep). The aggregation behavior was studied by dynamic light scattering (DLS) and freeze-fracture/transmission electron microscopy (TEM). Large vesicular structures with almost pH-independent radii were observed.

The development and characterization of degradable poly(vinyl ester) and poly(vinyl ester)/PEO block copolymers

NASA Astrophysics Data System (ADS)

Lipscomb, Corinne Elizabeth

The development of biodegradable materials is a challenging and important problem in polymer science. A review of the state of the art in degradable materials is presented, which reveals that current biodegradable materials do not exhibit the thermal or mechanical properties necessary for widespread applications. One strategy for toughening polymeric materials, which has previously been applied to non-degradable thermoplastics and thermoplastic elastomers, is the formation of block copolymers. Poly(vinyl esters) (PVE) homopolymers are known to have a wide range of properties, but PVE block copolymers comprise a class of inexpensive and (bio)degradable materials that were previously unknown. Therefore, the synthesis and properties of these block copolymers were explored in an effort to develop robust degradable materials. This thesis research probes the reaction conditions necessary for the reversible-addition fragmentation chain transfer (RAFT) polymerization and chain extension reactions of vinyl ester monomers. PVE di- and triblock copolymers are synthesized and studied, and the triblock copolymers display extremely poor toughness due to their relatively low molecular weights in light of the high entanglement molecular weight of the poly(vinyl acetate) center block. Attempts to improve the mechanical properties of these materials focus on the incorporation of poly(ethylene oxide) (PEO) as a low entanglement molecular weight and biocompatible center block in PVE-containing triblock copolymers. Depending on the choice of PVE endblocks and the overall polymer composition, crystallization of the PEO block can be controlled, confined, or inhibited. Polymers in which PEO crystallization is completely inhibited exhibit enhanced mechanical properties and behave as weak thermoplastics. In order to understand the relationship between the inhibition of PEO crystallization and the mechanical properties of PVE/PEO materials, these polymers were studied using dynamic mechanical spectroscopy, wide angle X-ray scattering, small angle X-ray scattering, differential scanning calorimetry, and uniaxial tensile tests. By combining insights gained from these techniques, a complex picture emerges that explains the enhanced mechanical properties of these materials based on the type and location of thermal transitions, amorphous PEO entanglements, and the strain-induced crystallization of PEO. This work represents an important step toward developing robust materials with tunable properties containing (bio)degradable components.

Nanostructured DPA-MPC-DPA triblock copolymer gel for controlled drug release of ketoprofen and spironolactone.

PubMed

Azmy, Bahaa; Standen, Guy; Kristova, Petra; Flint, Andrew; Lewis, Andrew L; Salvage, Jonathan P

2017-08-01

Uncontrolled rapid release of drugs can reduce their therapeutic efficacy and cause undesirable toxicity; however, controlled release from reservoir materials helps overcome this issue. The aims of this study were to determine the release profiles of ketoprofen and spironolactone from a pH-responsive self-assembling DPA-MPC-DPA triblock copolymer gel and elucidate underlying physiochemical properties. Drug release profiles from DPA 50 -MPC 250 -DPA 50 gel (pH 7.5), over 32 h (37 °C), were determined using UV-Vis spectroscopy. Nanoparticle size was measured by dynamic light scattering (DLS) and critical micelle concentration (CMC) by pyrene fluorescence. Polymer gel viscosity was examined via rheology, nanoparticle morphology investigated using scanning transmission electron microscopy (STEM) and the gel matrix observed using cryo-scanning electron microscopy (Cryo-SEM). DPA 50 -MPC 250 -DPA 50 copolymer (15% w/v) formed a free-standing gel (pH 7.5) that controlled drug release relative to free drugs. The copolymer possessed a low CMC, nanoparticle size increased with copolymer concentration, and DLS data were consistent with STEM. The gel displayed thermostable viscosity at physiological temperatures, and the gel matrix was a nanostructured aggregation of smaller nanoparticles. The DPA 50 -MPC 250 -DPA 50 copolymer gel could be used as a drug delivery system to provide the controlled drug release of ketoprofen and spironolactone. © 2017 Royal Pharmaceutical Society.

Temperature-dependent optical properties of gold nanoparticles coated with a charged diblock copolymer and an uncharged triblock copolymer.

PubMed

Volden, Sondre; Kjøniksen, Anna-Lena; Zhu, Kaizheng; Genzer, Jan; Nyström, Bo; Glomm, Wilhelm R

2010-02-23

We demonstrate that the optical properties of gold nanoparticles can be used to detect and follow stimuli-induced changes in adsorbed macromolecules. Specifically, we investigate thermal response of anionic diblock and uncharged triblock copolymers based on poly(N-isopropylacrylamide) (PNIPAAM) blocks adsorbed onto gold nanoparticles and planar gold surfaces in a temperature range between 25 and 60 degrees C. By employing a palette of analytical probes, including UV-visible spectroscopy, dynamic light scattering, fluorescence, and quartz crystal microbalance with dissipation monitoring, we establish that while the anionic copolymer forms monolayers at both low and high temperature, the neutral copolymer adsorbs as a monolayer at low temperatures and forms multilayers above the cloud point (T(C)). Raising the temperature above T(C) severely affects the optical properties of the gold particle/polymer composites, expelling associated water and altering the immediate surroundings of the gold nanoparticles. This effect, stronger for the uncharged polymer, is related to the amount of polymer adsorbed on the surface, where a denser shell influences the surface plasmon band to a greater degree. This is corroborated with light scattering experiments, which reveal that flocculation of the neutral polymer-coated particles occurs at high temperatures. The flocculation behavior of the neutral copolymer on planar gold surfaces results in multilayer formation. The observed effects are discussed within the framework of the Mie-Drude theory.

Combinatorial and high-throughput screening of the effect of siloxane composition on the surface properties of crosslinked siloxane-polyurethane coatings.

PubMed

Ekin, Abdullah; Webster, Dean C

2007-01-01

Libraries of siloxane-polyurethane coatings were designed, formulated, and screened using high-throughput experimentation. Four independent variables that were analyzed were the molecular weight of poly(dimethylsiloxane) (PDMS), presence or absence of poly(epsilon-caprolactone) (PCL) blocks attached to the PDMS backbone, the length of the PCL blocks, and the siloxane polymer level in the coating formulations. In addition to the siloxane libraries (3-aminopropyl-terminated PDMS and poly(epsilon-caprolactone)-poly(dimethylsiloxane)-poly(epsilon-caprolactone) (PCL-PDMS-PCL) triblock copolymers), the coating formulation included a trifunctional isocyanate crosslinker, trifunctional poly(epsilon-caprolactone) polyol, 2,4-pentanedione (pot-life extender), dibutyltin diacetate (catalyst), and a blend of solvents. The resulting coatings were analyzed for their surface energy and pseudobarnacle adhesion both before and after aging the coatings for 30 days in water. The water and methylene iodide contact angle averages increase with increasing molecular weight of PDMS. Coatings prepared from PCL-PDMS-PCL triblock copolymers have lower surface energies than coatings prepared from 3-aminopropyl-terminated PDMS; however, lower pseudobarnacle adhesion results were obtained for the coatings prepared from 3-aminopropyl-terminated PDMS than coatings prepared from PCL-PDMS-PCL triblock copolymers. The siloxane polymer level in the coating formulations does not have a significant effect on the surface energy of the coatings, but it resulted in higher pseudobarnacle adhesion.

Hard Pd Nanorods in the Soft Surfactant Mixture of CTAB and Pluronics: Seedless Synthesis and Their Self-Assembly.

PubMed

Song, Hyon-Min; Zink, Jeffrey I

2018-04-10

Seedless synthesis of Pd nanorods and their self-assembly into the layered smectic ordering are described. Aqueous Pluronic triblock copolymers (14.3-35.7%) are used as a soft template along with cetyltrimethylammonium bromide for inducing one-dimensional growth of Pd nanorods. Pluronic triblock copolymers are probably the most used polymer surfactants, and they are composed of poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO triblocks. Neither pH adjustment nor AgNO 3 and other additives, such as poly(vinyl pyrrolidone) and ethylene glycol, are required to obtain Pd nanorods. Sonochemical synthesis at 43 °C, followed by thermal annealing for 1 h at 65 °C produces Pd nanorods with the aspect ratio from 3.1 (17.9%, Pluronic L-64) to 6.7 (35.7%, Pluronic P-123). Two-dimensional self-assembly of the nanorods is observed, and both nematic ordering between the mesogens and smectic ordering between the layers is identified. Micellar hydrophobic PPO with hydrated PEO coronas are known to self-assemble into many crystalline orders, including cubic, hexagonal, lamellar, and inverse hexagonal mesophases, which extend into cylindrical micelles with increasing temperature. Relatively small size of Pluronic copolymers with regard to general polymers, but rather large size of their micelles and their tendency to organize into crystalline mesophases are thought to contribute to the anisotropic growth of Pd nanorods.

Double network physical gels from elastin-like polypeptide block copolymers: nanoscale control of thermoresponsive reinforcement

NASA Astrophysics Data System (ADS)

Glassman, Matthew; Olsen, Bradley

2014-03-01

Triblock copolymers with associative protein midblocks and thermoresponsive endblocks form shear thinning hydrogels with a low yield stress at low temperatures, but can be reinforced by a self-assembled network of the endblock aggregates. Here, we compare the use of bioengineered elastin-like polypeptides (ELPs) to synthetic poly(N-isopropylacrylamide) (PNIPAM) as endblocks to control the self-assembly of the reinforcing network. The temperature dependence of the mechanics of these hydrogels is a strong function of the domain size and morphology in the endblock network. Despite the architectural similarities, triblock ELP fusions and PNIPAM bioconjugates exhibit distinct reinforcement maxima at fixed block composition and polymer concentration, and these differences can be attributed to the nanostructural features of the two systems. Furthermore, in ELP fusions, the amino acid sequence can be readily modified to manipulate the solvation kinetics of the endblock domains. Finally, various endblocks have been combined to form triblock terpolymer hydrogels, demonstrating how the choice of thermoresponsive blocks can be used to tune the reinforcement of shear thinning hydrogels.

Self-Assembly and Responsiveness of Polypeptide-Based Star and Triblock Copolymers

NASA Astrophysics Data System (ADS)

Savin, Daniel

This study involves the bottom-up design and tunability of responsive, peptide-based block polymers. The self-assembly of amphiphilic block polymers is dictated primarily by the balance between the hydrophobic core volume and the hydrophilic corona. In these studies, amphiphilic triblock and star copolymers containing poly(lysine) (PK), poly(leucine) (PL) and poly(glutamic acid) (PE) were synthesized and their solution properties studied using dynamic light scattering, circular dichroism spectroscopy and transmission electron microscopy. The peptide block in these structures can serve to introduce pH responsiveness (in the case of PK and PE), or can facilitate the formation of elongated or kinetically-trapped structures (in the case of PL.) This talk will present some recent studies in solution morphology transitions that occur in these materials under varying solution conditions. As the topological complexity of the polymers increases from diblock to linear triblock or star polymers, the solution morphology and response becomes much more complex. We present a systematic series of structures, with increasing complexity, that have applications as passive and active delivery vehicles, hydrogels, and responsive viscosity modifiers. NSF CHE-1539347.

Acid-Labile Amphiphilic PEO-b-PPO-b-PEO Copolymers: Degradable Poloxamer Analogs.

PubMed

Worm, Matthias; Kang, Biao; Dingels, Carsten; Wurm, Frederik R; Frey, Holger

2016-05-01

Poly ((ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid-labile acetal moieties in the backbone of poloxamers to generate acid-cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate-protected vinyl ether to introduce acetal units. Three cleavable PEO-PPO-PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol(-1) ; Mn,PEO = 2200, 3600, 4750 g·mol(-1) ) have been synthesized using anionic ring-opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06-1.08). Surface tension measurements reveal surface-active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid-triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation "on demand." © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Utilization of Network-Forming Block Copolymers and Ionomers in the Development of Novel Nanostructures and Responsive Media

NASA Astrophysics Data System (ADS)

Mineart, Kenneth

Network forming block copolymers, i.e. thermoplastic elastomers (TPEs), are one of the highest commodity forms of block copolymers due to their competitive elasticity and extendability as well as their ability to be melt and solution processed. TPEs owe many of their advantages to a combination of hard and soft blocks. The soft blocks, which must be covalently bound at both ends to hard blocks, connect adjacent hard domains resulting in physically cross-linked systems. Herein, simulations and theory are used to provide a molecular-level depiction of the evolution from diblock copolymers, which do not contain the ability to form physical cross-links, to network forming triblock copolymers. In addition, systems with high interblock incompatibility that are within the diblock-to-triblock transition (i.e. having high molecular asymmetry) are identified to form three component (ABC triblock copolymer) phases from copolymer containing only two chemically distinct blocks. Following this work, which emphasizes the fundamental principle of TPEs, the dissertation shifts focus to physically- and chemically-modified triblock and pentablock copolymer TPEs. Recent progress has sought to broaden TPEs to include properties that are above and beyond their inherent mechanical benefits, including responsiveness to external stimuli. The first examples presented here consist of TPEs prepared in combination with amorphous hydrocarbon additives to yield TPE gels (TPEGs). The resulting TPEGs, which maintain the beneficial processing properties of TPEs, are subsequently molded into 1- and 2-D arrays of microchannels that are filled with liquid metal. The final devices exhibit strain-sensitive electrical conductivity to at least 600% strain, have tunable compliance (ease of stretching), and are fully recyclable. The substitution of the amorphous hydrocarbon component for crystalline analogues with melting points <100 °C yield TPE composites (TPECs). The TPECs gain the added capability of thermally-triggered shape-memory actuation, which results in a number of design possibilities including: (i) multiple-transition shape-memory in single a composite, (ii) complex actuation in laminates and, (iii) thermally-responsive electrical conductivity in microchannel-molded composites filled with liquid metal. These shape-memory TPECs can also be tuned to have different shape-memory response rates through the addition of an amorphous hydrocarbon tackifier, which serves to dilute the crystalline content without altering TPE concentration. The second set of functionalized TPEs examined are midblock-sulfonated block copolymers, which have substantial ion and water transport abilities, but are often restricted in thermal processability. The casting solvent-dependent morphology of a midblock sulfonated pentablock copolymer highlights the impact of solvent templating on resulting film domain structures. It is shown that film deposition from a miscible mixture of toluene and isopropanol (TIPA) leads to spherical sulfonated domains within a nonpolar matrix whereas deposition from neat tetrahydrofuran (THF) produces a combination of lamellar and hexagonally-pack cylinder nanostructures. These morphologies can both be converted to the anticipated equilibrium morphology, alternating lamellae, using THF vapor-annealing. Further, the morphology resulting from each solvent-casting approach impacts the rate and overall capacity at which films absorb water. Specifically, THF-cast copolymers swell faster and to a greater extent. However, some intrigue lies in the transformation of the TIPA-cast copolymer upon swelling, which yields disordered, but continuous, hydrophilic domains. The disordered morphology outperforms ordered analogues in solar simulation experiments indicating higher ion conductivity.

Highly stable biocompatible inorganic nanoparticles by self-assembly of triblock-copolymer ligands.

PubMed

Pöselt, Elmar; Fischer, Steffen; Foerster, Stephan; Weller, Horst

2009-12-15

A novel type of ligand for biofunctionalization of nanoparticles is presented that comprises tailor-made triblock-copolymers consisting of a polyethylene imine binding block, a hydrophobic polycaprolactone and a terminal functionalized polyethelene oxide block. Phase transfer to water occurs simply by ligand and water addition and removal of the organic solvents. It is shown that the intermediate polycaprolacton block favors the attachment to the particle surface and shields the binding groups effectively from the solution. As a consequence, the particles exhibit an outstanding stability in various aqueous media for biological studies and give easy access to specific coupling reactions at the terminal end groups of the polyethylene oxide block. Controlling the ligand exchange parameters leads to self-assembly to either individual encapsulated nanoparticles or to multifunctional nanobeads.

An alternative method to remove PEO-PPO-PEO template in organic-inorganic mesoporous nanocomposites by sulfuric acid extraction

NASA Astrophysics Data System (ADS)

Zhuang, Xin; Qian, Xufang; Lv, Jiahui; Wan, Ying

2010-06-01

Sulfuric acid is used as an extraction agent to remove PEO-PPO-PEO templates in the organic-inorganic mesoporous nanocomposites from the triconstituent co-assembly which includes the low-polymerized phenolic resins, TEOS and triblock copolymer F127. The XRD and TEM results show well ordered mesostructure after extraction with sulfuric acid. As followed from the N 2 sorption isotherms the extracted composites possess high surface areas (332-367 m 2/g), large pore volumes (0.66-0.78 cm 3/g), and large pore sizes (about 10.7 nm). The FT-IR analysis reveals almost complete elimination of triblock copolymer F127, and the maintenance of organic groups. This method shows potentials in removing templates from nanocomposites containing functional moieties.

Non-Classical Order in Sphere Forming ABAC Tetrablock Copolymers

NASA Astrophysics Data System (ADS)

Zhang, Jingwen; Sides, Scott; Bates, Frank

2013-03-01

AB diblock and ABC triblock copolymers have been studied thoroughly. ABAC tetrablock copolymers, representing the simplest variation from ABC triblock by breaking the molecular symmetry via inserting some of the A block in between B and C blocks, have been studied systematically in this research. The model system is poly(styrene-b-isoprene-b-styrene-b-ethylene oxide) (SISO) tetrablock terpolymers and the resulting morphologies were characterized by nuclear magnetic resonance, gel permeation chromatography, small-angle X-ray scattering, transmission electron microscopy, differential scanning calorimetry and dynamic mechanical spectroscopy. Two novel phases are first discovered in a single component block copolymers: hexagonally ordered spherical phase and tentatively identified dodecagonal quasicrystalline (QC) phase. In particular, the discovery of QC phase bridges the world of soft matters to that of metals. These unusual sets of morphologies will be discussed in the context of segregation under the constraints associated with the tetrablock molecular architecture. Theoretical calculations based on the assumption of Gaussian chain statistics provide valuable insights into the molecular configurations associated with these morphologies. the U.S. Department of Energy, Basic Energy Sciences, Division of Materials Science and Engineering, under contract number DEAC05-00OR22725 with UT-Battelle LLC at Oak Ridge National Lab.

Rouse-Bueche Theory and The Calculation of The Monomeric Friction Coefficient in a Filled System

NASA Astrophysics Data System (ADS)

Martinetti, Luca; Macosko, Christopher; Bates, Frank

According to flexible chain theories of viscoelasticity, all relaxation and retardation times of a polymer melt (hence, any dynamic property such as the diffusion coefficient) depend on the monomeric friction coefficient, ζ0, i.e. the average drag force per monomer per unit velocity encountered by a Gaussian submolecule moving through its free-draining surroundings. Direct experimental access to ζ0 relies on the availability of a suitable polymer dynamics model. Thus far, no method has been suggested that is applicable to filled systems, such as filled rubbers or microphase-segregated A-B-A thermoplastic elastomers at temperatures where one of the blocks is glassy. Building upon the procedure proposed by Ferry for entangled and unfilled polymer melts, the Rouse-Bueche theory is applied to an undiluted triblock copolymer to extract ζ0 from the linear viscoelastic behavior in the rubber-glass transition region, and to estimate the size of Gaussian submolecules. At iso-free volume conditions, the so-obtained matrix monomeric friction factor is consistent with the corresponding value for the homopolymer melt. In addition, the characteristic Rouse dimensions are in good agreement with independent estimates based on the Kratky-Porod worm-like chain model. These results seem to validate the proposed approach for estimating ζ0 in a filled system. Although preliminary tested on a thermoplastic elastomer of the A-B-A type, the method may be extended and applied to filled homopolymers as well.

Synthesis and characterization of PEO-PCL-PEO triblock copolymers: effects of the PCL chain length on the physical property of W(1)/O/W(2) multiple emulsions.

PubMed

Cho, Heui Kyoung; Cho, Kwang Soo; Cho, Jin Hun; Choi, Sung Wook; Kim, Jung Hyun; Cheong, In Woo

2008-08-01

A series of poly(ethylene glycol)-block-poly(epsilon-caprolactone)-block-poly(ethylene glycol) (PEO-PCL-PEO) triblock copolymers were prepared and then used for the investigation of the effects of the ratio of epsilon-caprolactone to poly(ethylene glycol) (i.e., [CL]/[EO]) on the physical properties of water-in-oil-in-water (W(1)/O/W(2)) multiple emulsions containing a model reagent, ascorbic acid-2-glucoside (AA2G). In the synthesis, the [CL]/[EO] was varied from 0.11 to 0.31. The molecular weights and compositions of PEO-PCL-PEO were determined by GPC and (1)H NMR analyses. Thermal behavior and crystal formation were studied by DSC, XRD, FT-IR, and polarized optical microscopy (POM). Aggregate behavior of PEO-PCL-PEO was confirmed by DLS, UV, and (1)H NMR. Morphology and relative stiffness of the W(1)/O/W(2) multiple emulsions in the presence of PEO-PCL-PEO were studied by confocal laser scanning microscopy (CLSM) and rheometer. Variation in the [CL]/[EO] significantly affects the crystalline temperature and spherulite morphology of PEO-PCL-PEO. As the [CL]/[EO] increases, the CMCs of PEO-PCL-PEO decreases and the slope of aggregate size reduction against the copolymer concentration becomes steeper except for the lowest [CL]/[EO] value of PEO-PCL-PEO (i.e., P-222). P-222 significantly increases the viscosity of continuous (W(2)) phase, which implies the copolymer would exist in the W(2) phase. On the other hand, the triblock copolymers with relatively high [CL]/[EO] ratios mainly contribute to the size reduction of multiple emulsions and the formation of a firm wall structure. The particle size of the multiple emulsion decreases and the elastic modulus increased as [CL]/[EO] increases, confirmed by microscopic and rheometric analyses.

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

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

Sar, B.

1992-12-31

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

Solution-processable electrochemiluminescent ion gels for flexible, low-voltage, emissive displays on plastic.

PubMed

Moon, Hong Chul; Lodge, Timothy P; Frisbie, C Daniel

2014-03-05

Ion gels comprising ABA triblock copolymers and ionic liquids have received much attention as functional materials in numerous applications, especially as gate dielectrics in organic transistors. Here we have expanded the functionality of ion gels by demonstrating low-voltage, flexible electrochemiluminescent (ECL) devices using patterned ion gels containing redox-active luminophores. The ECL devices consisted only of a 30 μm thick emissive gel and two electrodes and were fabricated on indium tin oxide-coated substrates (e.g., polyester) simply by solution-casting the ECL gel and brush-painting a top Ag electrode. The triblock copolymer employed in the gel was polystyrene-block-poly(methyl methacrylate)-block-polystyrene, where the solvophobic polystyrene end blocks associate into micellar cross-links in the versatile ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]). An ECL gel containing ~6.25 wt % Ru(bpy)3Cl2 (relative to [EMI][TFSI]) as the luminophore turned on at an AC peak-to-peak voltage as low as 2.6 V (i.e., -1.3 to +1.3 V) and showed a relatively rapid response (sub-ms). The wavelength of maximum emission was 610 nm (red-orange). With the use of an iridium(III) complex, Ir(diFppy)2(bpy)PF6 [diFppy = 2-(2',4'-difluorophenyl)pyridine; bpy = 2,2'-bipyridyl], the emitting color was tuned to a maximum wavelength of 540 nm (green). Moreover, when a blended luminophore system containing a 60:40 mixture of Ru(bpy)3(2+) and Ir(diFppy)2(bpy)(+) was used in the emissive layer, the luminance of red-orange-colored light was enhanced by a factor of 2, which is explained by the generation of the additional excited state Ru(bpy)3(2+)* by a coreactant pathway with Ir(diFppy)2(bpy)(+)* in addition to the usual annihilation pathway. This is the first time that enhanced ECL has been achieved in ion gels (or ionic liquids) using a coreactant. Overall, the results indicate that ECL ion gels are attractive multifunctional materials for printed electronics.

Fabrication of Pt/Au concentric spheres from triblock copolymer.

PubMed

Koh, Haeng-Deog; Park, Soojin; Russell, Thomas P

2010-02-23

Dispersion of an aqueous H(2)PtCl(6) solution into a trifluorotoluene (TFT) solution of a polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO) triblock copolymer produced an emulsion-induced hollow micelle (EIHM), comprising a water nanodroplet stabilized by PEO, H(2)PtCl(6)/P2VP, and PS, sequentially. The following addition of an aqueous LiAuCl(4) solution into the dispersion led to a coordination of LiAuCl(4) and PEO. The resulting spherical EIHM structure was transformed to a hollow cylindrical micelle by the fusion of spherical EIHM with the addition of methanol. This structural transition was reversible by the alternative addition of methanol and TFT. Oxygen plasma was used to generate Pt/Au concentric spheres and hollow cylindrical Pt/Au nano-objects.

Surface Plasmon Resonance Study of the Binding of PEO-PPO-PEO Triblock Copolymer and PEO Homopolymer to Supported Lipid Bilayers.

PubMed

Kim, Mihee; Vala, Milan; Ertsgaard, Christopher T; Oh, Sang-Hyun; Lodge, Timothy P; Bates, Frank S; Hackel, Benjamin J

2018-06-12

Poloxamer 188 (P188), a poly(ethylene oxide)- b-poly(propylene oxide)- b-poly(ethylene oxide) triblock copolymer, protects cell membranes against various external stresses, whereas poly(ethylene oxide) (PEO; 8600 g/mol) homopolymer lacks protection efficacy. As part of a comprehensive effort to elucidate the protection mechanism, we used surface plasmon resonance (SPR) to obtain direct evidence of binding of the polymers onto supported lipid bilayers. Binding kinetics and coverage of P188 and PEO were examined and compared. Most notably, PEO exhibited membrane association comparable to that of P188, evidenced by comparable association rate constants and coverage. This result highlights the need for additional mechanistic understanding beyond simple membrane association to explain the differential efficacy of P188 in therapeutic applications.

A simple and effective method for making multipotent/multilineage scaffolds with hydrophilic nature without any postmodification/treatment.

PubMed

Vaikkath, Dhanesh; Anitha, Rakhi; Sumathy, Babitha; Nair, Prabha D

2016-05-01

A number of biodegradable and bioresorbable materials, as well as scaffold designs, have been experimentally and/or clinically studied for tissue engineering of diverse tissue types. Cell-material responses are strongly dependent on the properties of the scaffold material. In this study, scaffolds based on polycaprolactone (PCL) and PCL blended with a triblock copolymer, Polycaprolactone-polytetrahydrofuran-polycaprolactone (PCL-PTHF-PCL) at different ratios were fabricated by electrospinning. Blending and electrospinning of the triblock copolymer with PCL generated a super hydrophilic scaffold, the mechanical and biological properties of which varied with the concentration of the triblock copolymer. The hydrophilicity of the electrospun scaffolds was determined by measurement of water-air contact angle. Cellular response to the electrospun scaffolds was studied by seeding two types of cells, L929 fibroblast cell line and rat mesenchymal stem cells (RMSC). We observed that the super hydrophilicity of the material did not prevent cell adhesion, while the cell proliferation was low or negligible for scaffolds containing higher amount of PCL-PTHF-PCL. Chondrogenic differentiation of RMSC was found to be better on the PCL blend containing 10% (w/v) of PCL-PTHF-PCL than the bare PCL. Our studies indicate that the cellular response is dependent on the biomaterial composition and highlight the importance of tailoring the scaffold properties for applications in tissue engineering and regenerative medicine. Copyright © 2015 Elsevier B.V. All rights reserved.

Biodegradable Nanoparticles of mPEG-PLGA-PLL Triblock Copolymers as Novel Non-Viral Vectors for Improving siRNA Delivery and Gene Silencing

PubMed Central

Du, Jing; Sun, Ying; Shi, Qiu-Sheng; Liu, Pei-Feng; Zhu, Ming-Jie; Wang, Chun-Hui; Du, Lian-Fang; Duan, You-Rong

2012-01-01

Degradation of mRNA by RNA interference is one of the most powerful and specific mechanisms for gene silencing. However, insufficient cellular uptake and poor stability have limited its usefulness. Here, we report efficient delivery of siRNA via the use of biodegradable nanoparticles (NPs) made from monomethoxypoly(ethylene glycol)-poly(lactic-co-glycolic acid)-poly-l-lysine (mPEG-PLGA-PLL) triblock copolymers. Various physicochemical properties of mPEG-PLGA-PLL NPs, including morphology, size, surface charge, siRNA encapsulation efficiency, and in vitro release profile of siRNA from NPs, were characterized by scanning electron microscope, particle size and zeta potential analyzer, and high performance liquid chromatography. The levels of siRNA uptake and targeted gene inhibition were detected in human lung cancer SPC-A1-GFP cells stably expressing green fluorescent protein. Examination of the cultured SPC-A1-GFP cells with fluorescent microscope and flow cytometry showed NPs loading Cy3-labeled siRNA had much higher intracellular siRNA delivery efficiencies than siRNA alone and Lipofectamine-siRNA complexes. The gene silencing efficiency of mPEG-PLGA-PLL NPs was higher than that of commercially available transfecting agent Lipofectamine while showing no cytotoxicity. Thus, the current study demonstrates that biodegradable NPs of mPEG-PLGA-PLL triblock copolymers can be potentially applied as novel non-viral vectors for improving siRNA delivery and gene silencing. PMID:22312268

Light-emitting block copolymers composition, process and use

DOEpatents

Ferraris, John P.; Gutierrez, Jose J.

2006-11-14

Generally, and in one form, the present invention is a composition of light-emitting block copolymer. In another form, the present invention is a process producing a light-emitting block copolymers that intends polymerizing a first di(halo-methyl) aromatic monomer compound in the presence of an anionic initiator and a base to form a polymer and contacting a second di(halo-methyl) aromatic monomer compound with the polymer to form a homopolymer or block copolymer wherein the block copolymer is a diblock, triblock, or star polymer. In yet another form, the present invention is an electroluminescent device comprising a light-emitting block copolymer, wherein the electroluminescent device is to be used in the manufacturing of optical and electrical devices.

Mechanically Tunable, Readily Processable Ion Gels by Self-Assembly of Block Copolymers in Ionic Liquids.

PubMed

Lodge, Timothy P; Ueki, Takeshi

2016-01-01

Room temperature ionic liquids are of great interest for many advanced applications, due to the combination of attractive physical properties with essentially unlimited tunability of chemical structure. High chemical and thermal stability, favorable ionic conductivity, and complete nonvolatility are just some of the most important physical characteristics that make ionic liquids promising candidates for emerging technologies. Examples include separation membranes, actuators, polymer gel electrolytes, supercapacitors, ion batteries, fuel cell membranes, sensors, printable plastic electronics, and flexible displays. However, in these and other applications, it is essential to solidify the ionic liquid, while retaining the liquid state properties of interest. A broadly applicable solidification strategy relies on gelation by addition of suitable triblock copolymers with the ABA architecture, producing ion gels or ionogels. In this paradigm, the A end blocks are immiscible with the ionic liquid, and consequently self-assemble into micellar cores, while some fraction of the well-solvated B midblocks bridge between micelles, forming a percolating network. The chemical structures of the A and B repeat units, the molar mass of the blocks, and the concentration of the copolymer in the ionic liquid are all independently tunable to attain desired property combinations. In particular, the modulus of the resulting ion gel can be readily varied between 100 Pa and 1 MPa, with little sacrifice of the transport properties of the ionic liquid, such as ionic conductivity or gas diffusivity. Suitable A blocks can impart thermoreversible gelation (with solidification either on heating or cooling) or even photoreversible gelation. By virtue of the nonvolatility of ionic liquids, a wide range of processing strategies can be employed directly to prepare ion gels in thin or thick film forms, including solvent casting, spin coating, aerosol jet printing, photopatterning, and transfer printing. For higher modulus ion gels it is even possible to employ a manual "cut and stick" strategy for easy device fabrication. Ion gels prepared from common triblock copolymers, for example, with A = polystyrene and B = poly(ethylene oxide) or poly(methyl methacrylate), in imidazolium based ionic liquids provide exceptional performance in membranes for separating CO 2 from N 2 or CH 4 . The same materials also are the best available gate dielectrics for printed plastic electronics, because their high capacitance endows organic transistors with milliamp output currents for sub-1 V applied bias, with switching speeds that can go well beyond 100 kHz, while being amenable to large area roll-to-roll printing. Incorporation of well-designed electroluminescent (e.g., Ru(bpy) 3 -based) or electrochromic (e.g., viologen-based) moieties into ion gels held between transparent electrodes yields flexible color displays operating with sub-1 V dc inputs.

Hierarchical Sol-Gel Transition Induced by Thermosensitive Self-Assembly of an ABC Triblock Polymer in an Ionic Liquid

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

Kitazawa, Yuzo; Ueki, Takeshi; McIntosh, Lucas D.

2016-04-29

Here we investigate a hierarchical morphology change and accompanying sol–gel transition using a doubly thermosensitive ABC-triblock copolymer in an ionic liquid (IL). The triblock copolymer contains two different lower critical solution temperature (LCST) thermosensitive polymers, poly(benzyl methacrylate) (PBnMA) and poly(2-phenylethyl methacrylate) (PPhEtMA), as the end blocks and poly(methyl methacrylate) (PMMA) as the middle block (PBnMA-b-PMMA-b-PPhEtMA: BMP). BMP undergoes a hierarchical phase transition corresponding to the self-assembly of each of the thermosensitive blocks in the IL, and a sol–gel transition was observed in concentrated, above 10 wt %, polymer solutions. The gelation behavior was affected by polymer concentration, and at 20more » wt %, the BMP/IL composite showed a phase transition, with increasing temperature, from solution through a jammed micelle suspension to a physically cross-linked gel. For each phase was formed reversibly and rapidly over the corresponding temperature range. Finally, the jammed micelle and cross-linked gel states were characterized using viscoelastic measurements and small-angle X-ray scattering (SAXS).« less

Design strategy of pH-sensitive triblock copolymer micelles for efficient cellular uptake by computer simulations

NASA Astrophysics Data System (ADS)

Xia, Qiang-sheng; Ding, Hong-ming; Ma, Yu-qiang

2018-03-01

Efficient delivery of nanoparticles into specific cell interiors is of great importance in biomedicine. Recently, the pH-responsive micelle has emerged as one potential nanocarrier to realize such purpose since there exist obvious pH differences between normal tissues and tumors. Herein, by using dissipative particle dynamics simulation, we investigate the interaction of the pH-sensitive triblock copolymer micelles composed of ligand (L), hydrophobic block (C) and polyelectrolyte block (P) with cell membrane. It is found that the structure rearrangement of the micelle can facilitate its penetration into the lower leaflet of the bilayer. However, when the ligand-receptor specific interaction is weak, the micelles may just fuse with the upper leaflet of the bilayer. Moreover, the ionization degree of polyelectrolyte block and the length of hydrophobic block also play a vital role in the penetration efficiency. Further, when the sequence of the L, P, C beads in the copolymers is changed, the translocation pathways of the micelles may change from direct penetration to Janus engulfment. The present study reveals the relationship between the molecular structure of the copolymer and the uptake of the pH-sensitive micelles, which may give some significant insights into the experimental design of responsive micellar nanocarriers for highly efficient cellular delivery.

Fabrication of Ordered Nanopattern by using ABC Triblock Copolymer with Salt in Toluene.

PubMed

Huang, Hailiang; Zhong, Benbin; Zu, Xihong; Luo, Hongsheng; Lin, Wenjing; Zhang, Minghai; Zhong, Yazhou; Yi, Guobin

2017-08-15

Ordered nanopatterns of triblock copolymer polystyrene-block-poly(2-vinylpyridine)-block- poly (ethylene oxide)(PS-b-P2VP-b-PEO) have been achieved by the addition of lithium chloride (LiCl). The morphological and structural evolution of PS-b-P2VP-b-PEO/LiCl thin films were systematically investigated by varying different experimental parameters, including the treatment for polymer solution after the addition of LiCl, the time scale of ultrasonic treatment and the molar ratio of Li + ions to the total number of oxygen atoms (O) in PEO block and the nitrogen atoms (N) in P2VP block. When toluene was used as the solvent for LiCl, ordered nanopattern with cylinders or nanostripes could be obtained after spin-coating. The mechanism of nanopattern transformation was related to the loading of LiCl in different microdomains.

Direct fabrication of ordered mesoporous carbons with super-micropore/small mesopore using mixed triblock copolymers.

PubMed

Li, Peng; Song, Yan; Tang, Zhihong; Yang, Guangzhi; Yang, Junhe

2014-01-01

Ordered mesoporous carbons (OMCs) have been prepared by the strategy of evaporation-induced organic-organic self-assembly method by employing a mixture of amphiphilic triblock copolymers poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) and reverse PPO-PEO-PPO as templates, with soluble in ethanol, low-molecular-weight phenolic resin as precursor, followed by carbonization. It has been found that the as prepared OMCs with porosity that combines super-micropore and small mesopore size distributed from 0.8 to 4 nm, which bridges the pore size from 2 to 3 nm and also for the diversification of the soft-templating synthesis of OMCs. Furthermore, the results showed that the OMCs obtained have mesophase transition from cylindrical p6 mm to centered rectangular c2 mm structure by simply tuning the ratio of PPO-PEO-PPO/PEO-PPO-PEO. Copyright © 2013 Elsevier Inc. All rights reserved.

Micellization and phase transitions in a triblock copolymer-D2O system

NASA Astrophysics Data System (ADS)

Odhner, Hosanna; Huff, Alison; Patton, Kelly; Jacobs, D. T.; Clover, Bryna; Greer, Sandra

2011-03-01

The triblock copolymer (``unimer'') of PPO-PEO-PPO (commercially known as 17R4) has hydrophobic ends and a hydrophilic center. When placed in D2 O at lower concentrations and temperatures, only a network of unimers exists. However, at higher concentrations or temperatures, micelles of different geometries can form. We have measured the micellization line marking the transition from only unimers to some micelles, as well as a one- to two-phase transition at higher temperatures. This second transition is an Ising-like, LCST critical point, based on the shape of the coexistence curve. We find the LCST to not correspond to the minimum of the cloud point curve, which indicates polydispersity as described by Sollich. We acknowledge the support from Research Corporation, NSF-REU grant DMR 0649112, The College of Wooster, and (for BC and SG) to the donors of the Petroleum Research Fund, administered by the American Chemical Society.

Biocompatible fluorinated polyglycerols for droplet microfluidics as an alternative to PEG-based copolymer surfactants.

PubMed

Wagner, Olaf; Thiele, Julian; Weinhart, Marie; Mazutis, Linas; Weitz, David A; Huck, Wilhelm T S; Haag, Rainer

2016-01-07

In droplet-based microfluidics, non-ionic, high-molecular weight surfactants are required to stabilize droplet interfaces. One of the most common structures that imparts stability as well as biocompatibility to water-in-oil droplets is a triblock copolymer surfactant composed of perfluoropolyether (PFPE) and polyethylene glycol (PEG) blocks. However, the fast growing applications of microdroplets in biology would benefit from a larger choice of specialized surfactants. PEG as a hydrophilic moiety, however, is a very limited tool in surfactant modification as one can only vary the molecular weight and chain-end functionalization. In contrast, linear polyglycerol offers further side-chain functionalization to create custom-tailored, biocompatible droplet interfaces. Herein, we describe the synthesis and characterization of polyglycerol-based triblock surfactants with tailored side-chain composition, and exemplify their application in cell encapsulation and in vitro gene expression studies in droplet-based microfluidics.

Preparation, characterization, and in vitro activity evaluation of triblock copolymer-based polymersomes for drugs delivery

NASA Astrophysics Data System (ADS)

Besada, Lucas N.; Peruzzo, Pablo; Cortizo, Ana M.; Cortizo, M. Susana

2018-03-01

Polymersomes are polymer-based vesicles that form upon hydration of amphiphilic block copolymers and display high stability and durability, due to their mechanical and physical properties. They have hydrophilic reservoirs as well as thick hydrophobic membranes; allowing to encapsulate both water-soluble bioactive agent and hydrophobic drugs. In this study, poly ethylene glycol (PEG3350 and PEG6000) were used as hydrophilic part and poly(vinyl benzoate) (PVBz) as hydrophobic block to synthesize amphiphilic triblock copolymers (PVBz- b-PEG- b-PVBz). Different proportions of hydrophilic/hydrophobic part were assayed in order to obtain polymersomes by solvent injection method. For the synthesis of the copolymers, the initial block of PEG was derived to obtain a macroinitiator through a xanthate functional group (PEGX3 or PEGX6) and the polymerization of vinyl benzoate was carried out through reversible addition-fragmentation chain transfer polymerization (RAFT). The structure of PEGX and copolymers was confirmed by Infrared, 1H-NMR and UV-Vis spectrometry, while the average molecular weight (Mw) and polydispersity index (PI) were determined by size exclusion chromatography (SEC). The structures adopted by the copolymers in aqueous solution by self-assembly were investigated using transmission electron microscopy (TEM), dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS). Both techniques confirm that polymersomes were obtained for a fraction of hydrophilic block ( f) ≈ 35 ± 10%, with a diameter of 38.3 ± 0.3 nm or 22.5 ± 0.7 nm, as determined by TEM and according to the M w of the precursor block copolymer. In addition, we analyzed the possible cytotoxicity in view of its potential application as biomedical nanocarrier. The results suggest that polymersomes seem not induce cytotoxicity during the periods of time tested.

ABA and ABC type thermoplastic elastomer toughening of epoxy matrices and its effect on carbon fiber reinforced composites

NASA Astrophysics Data System (ADS)

Pitchiaya, Gomatheeshwar

Epoxy-matrices have high modulus, strength, excellent creep resistance, but lacks ductility. One approach to improve the mechanical toughness is the addition of thermoplastic elastomers (TPEs). The TPEs investigated here are triblock copolymers of styrene-butadiene-methyl methacrylate (SBM) and methylmethacrylate-butylacrylate-methylmethacrylate (MAM) of the ABC and ABA type, respectively. The effect of concentration (1-12.5 wt %) of these TPEs on a diglycidyl ether of bisphenol-A (DGEBA) epoxy cured with metaphenylenediamine (mPDA), has been investigated. The TPE-DGEBA epoxies were characterized by TGA, DMA, SEM and impact. The flexural modulus, flexural strength and thermal resistance remained unaffected up to 5 wt% loading of TPEs, and exhibited less than 10% decrease at higher weight percent. T g was unaffected for all concentrations. Fracture toughness was improved 250% and up to 375% (when non- stoichiometric amount of curing agent was used) with TPE addition to epoxy/mPDA matrix. A SBM(1phr)EPON system was chosen to be the matrix of choice for a fiber reinforced composite system with a 4wt% aromatic epoxy sizing on a AS4 (UV-treated) carbon fiber. The 0° and 90° flexural modulus and strength of a SBM modified system was compared with the neat and their fracture surfaces were analyzed. A 89% increase in flexural strength was observed in a 90° flexural test for the modified system when compared with the neat. Novel sizing agents were also developed to enhance interfacial shear strength (IFSS) and the fiber-matrix adhesion and their birefringence pattern were analyzed.

Polymer nanoreactors shown to produce and release antibiotics locally.

PubMed

Langowska, Karolina; Palivan, Cornelia G; Meier, Wolfgang

2013-01-07

We designed and prepared nanoreactors based on a poly(2-methyloxazoline)-block-poly(dimethylsiloxane)-block-poly(2-methyloxazoline (PMOXA-b-PDMS-b-PMOXA) amphiphilic triblock copolymer encapsulating the enzyme penicillin acylase for local and controlled production of antibiotics.

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

Tang, Boxin; Schneiderman, Deborah K.; Zare Bidoky, Fazel

We have designed printable, biocompatible, and degradable ion gels by combining a novel ABA triblock aliphatic polyester, poly(ε-decalactone)-b-poly(dl-lactide)-b-poly(ε-decalactone), and a low toxicity ionic liquid, 1-butyl-1-methylpyrrolidinium bistrifluoromethanesulfonylimide ([P14][TFSI]). Due to the favorable compatibility between amorphous poly(dl-lactide) and [P14][TFSI] and the insolubility of the poly(ε-decalactone), the triblock polymer forms self-assembled micellar cross-links similar to thermoplastic elastomers, which ensures similar processing conditions and mechanical robustness during the fabrication of printed electrolyte-gated organic transistor devices. Additionally, the ester backbone in the polymer structure enables efficient hydrolytic degradation of these ion gels compared to those made previously using carbon-backbone polymers.

Model photo-responsive elastomers based on the self-assembly of side group liquid crystal triblock copolymers (Presentation Recording)

NASA Astrophysics Data System (ADS)

Kurji, Zuleikha; Kornfield, Julia A.; Kuzyk, Mark G.

2015-10-01

We report the synthesis of azobenzene-containing coil-liquid crystal-coil triblock copolymers that form uniform and highly reproducible elastomers by self-assembly. To serve as actuators to (non-invasively) steer a fiber optic, for example in deep brain stimulation, the polymers are designed to become monodomain "single liquid crystal" elastomers during the fiber-draw process and to have a large stress/strain response to stimulation with either light or heat. A fundamental scientific question that we seek to answer is how the interplay between the concentration of photoresponsive mesogens and the proximity to the nematic-isotropic transition governs the sensitivity of the material to stimuli. Specifically, a matched pair of polymers, one with ~5% azobenzene-containing side groups (~95% cyanobiphenyl side groups) and the other with 100% cyanobiphenyl side groups were synthesized from identical triblock pre-polymers (with polystyerene end blocks and 1,2-polybutadiene midblocks). These can be blended in various ratios to prepare a series of elastomers that are precisely matched in terms of the backbone length between physical crosslinks (because each polymer is derived from the same pre-polymer), while differing in % azobenzene side groups, allowing the effect of concentration of photoresponsive groups to be unambiguously determined.

Engineering Folate-Targeting Diselenide-containing Triblock Copolymer as a Redox-Responsive Shell-sheddable Micelle for Antitumor Therapy In Vivo.

PubMed

Behroozi, Farnaz; Abdkhodaie, Mohammad-Jafar; Sadeghi Abandansari, Hamid; Satarian, Leila; Molazem, Mohammad; Al-Jamal, Khuloud T; Baharvand, Hossein

2018-06-18

The oxidation-reduction (redox)-responsive micelle system is based on a diselenide-containing triblock copolymer, poly(ε-caprolactone)-bis(diselenide-methoxy poly(ethylene glycol)/poly(ethylene glycol)-folate) [PCL-(SeSe-mPEG/PEG-FA) 2 ]. This has helped in the development of tumor-targeted delivery for hydrophobic anticancer drugs. The diselenide bond, as a redox-sensitive linkage, was designed in such a manner that it is located at the hydrophilic-hydrophobic hinge to allow complete collapse of the micelle and thus efficient drug release in redox environments. The amphiphilic block copolymers self-assembled into micelles at concentrations higher than the critical micelle concentration (CMC) in an aqueous environment. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) analyses showed that the micelles were spherical with an average diameter of 120 nm. The insoluble anticancer drug paclitaxel (PTX) was loaded into micelles, and its triggered release behavior under different redox conditions was verified. Folate-targeting micelles showed an enhanced uptake in 4T1 breast cancer cells and in vitro cytotoxicity by flow cytometry and (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) (MTS) assay, respectively. Delayed tumor growth was confirmed in the subcutaneously implanted 4T1 breast cancer in mice after intraperitoneal injection. The proposed redox-responsive copolymer offers a new type of biomaterial for drug delivery into cancer cells in vivo. On-demand drug actuation is highly desired. Redox-responsive polymeric DDSs have been shown to be able to respond and release their cargo in a selective manner when encountering a significant change in the potential difference, such as that present between cancerous and healthy tissues. This study offers an added advantage to the field of redox-responsive polymers by reporting a new type of shell-sheddable micelle based on an amphiphilic triblock co-polymer, containing diselenide as a redox-sensitive linkage. The linkage was smartly located at the hydrophilic-hydrophilic bridge in the co-polymer offering complete collapse of the micelle when exposed to the right trigger. The system was able to delay tumor growth and reduce toxicity in a breast cancer tumor model following intraperitoneal injection in mice. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Translating Thermal Response of Triblock Copolymer Assemblies in Dilute Solution to Macroscopic Gelation and Phase Separation

DOE PAGES

Sun, Zhe; Tian, Ye; Hom, Wendy L.; ...

2016-12-28

The thermal response of semi-dilute solutions (5 w/w%) of two amphiphilic thermoresponsive poly(ethylene oxide)-b-poly(N,N-diethylacrylamide)-b-poly(N,N-dibutylacrylamide) (PEO 45-PDEAm x-PDBAm 12) triblock copolymers, which differ only in the size of the central responsive block, in water was examined in this paper. Aqueous PEO45-PDEAm41-PDBAm12 solutions, which undergo a thermally induced sphere-to-worm transition in dilute solution, were found to reversibly form soft (G'≈10 Pa) free-standing physical gels after 10 min at 55 °C. PEO 45-PDEAm 89-PDBAm 12 copolymer solutions, which undergo a thermally induced transition from spheres to large compound micelles (LCM) in dilute solution, underwent phase separation after heating at 55 °C for 10more » min owing to sedimentation of LCMs. The reversibility of LCM formation was investigated as a non-specific method for removal of a water-soluble dye from aqueous solution. Finally, the composition and size of the central responsive block in these polymers dictate the microscopic and macroscopic response of the polymer solutions as well as the rates of transition between assemblies.« less

Molecular Interaction Control in Diblock Copolymer Blends and Multiblock Copolymers with Opposite Phase Behaviors

NASA Astrophysics Data System (ADS)

Cho, Junhan

2014-03-01

Here we show how to control molecular interactions via mixing AB and AC diblock copolymers, where one copolymer exhibits upper order-disorder transition and the other does lower disorder-order transition. Linear ABC triblock copolymers possessing both barotropic and baroplastic pairs are also taken into account. A recently developed random-phase approximation (RPA) theory and the self-consistent field theory (SCFT) for general compressible mixtures are used to analyze stability criteria and morphologies for the given systems. It is demonstrated that the copolymer systems can yield a variety of phase behaviors in their temperature and pressure dependence upon proper mixing conditions and compositions, which is caused by the delicate force fields generated in the systems. We acknowledge the financial support from National Research Foundation of Korea and Center for Photofunctional Energy Materials.

Nanoscale patterning of two metals on silicon surfaces using an ABC triblock copolymer template.

PubMed

Aizawa, Masato; Buriak, Jillian M

2006-05-03

Patterning technologically important semiconductor interfaces with nanoscale metal films is important for applications such as metallic interconnects and sensing applications. Self-assembling block copolymer templates are utilized to pattern an aqueous metal reduction reaction, galvanic displacement, on silicon surfaces. Utilization of a triblock copolymer monolayer film, polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO), with two blocks capable of selective transport of different metal complexes to the surface (PEO and P2VP), allows for chemical discrimination and nanoscale patterning. Different regions of the self-assembled structure discriminate between metal complexes at the silicon surface, at which time they undergo the spontaneous reaction at the interface. Gold deposition from gold(III) compounds such as HAuCl4(aq) in the presence of hydrofluoric acid mirrors the parent block copolymer core structure, whereas silver deposition from Ag(I) salts such as AgNO3(aq) does the opposite, localizing exclusively under the corona. By carrying out gold deposition first and silver second, sub-100-nm gold features surrounded by silver films can be produced. The chemical selectivity was extended to other metals, including copper, palladium, and platinum. The interfaces were characterized by a variety of methods, including scanning electron microscopy, scanning Auger microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy.

Thermo-Responsive Amphiphilic Block Copolymers Stablilized Gold Nanoparticles: Synthesis and High Catalytic Properties.

PubMed

Lü, Jianhua; Yang, Yu; Gao, Junfang; Duan, Haichao; Lü, Changli

2018-06-19

A series of novel well-defined 8-hydroxyquinoline (HQ)-containing thermo-responsive amphiphilic diblock copolymers poly(styrene-co-5-(2-methacryloylethyloxy- methyl)-8-quinolinol)-b-poly(N-isopropylacrylamide) P(St-co-MQ)-b-PNIPAm (P1,2), P(NIPAm- co-MQ)-b-PSt (P3,4) and triblock copolymer poly(N-isopropylacrylamide)-b-poly(methyl- methacrylate-co-5-(2-methacryloylethyloxymethyl)-8-quinolinol)-b-polystyrene PNIPAm-b- P(MMA-co-MQ)-b-PSt (P5) were prepared by reversible addition fragmentation chain transfer (RAFT) polymerization, and their self-assembly behaviors were studied. The block copolymers P1-P5 stabilized gold nanoparticles (Au@P1-Au@P5) with small size and narrow distribution were obtained through in situ reduction of gold precursors in aqueous solution of polymer micelles with HQ as the coordination groups. The resulting Au@P nanohybrids possessed excellent catalytic activities for the reduction of nitrophenols using NaBH4. The size, morphology and surface chemistry of Au NPs could be controlled by adjusting the structure of block polymers with HQ in different block positions, which plays an important role in the catalytic properties. It was found that longer chain length of hydrophilic or hydrophobic segments of block copolymers were beneficial to elevate the catalytic activity of Au NPs for the reduction of nitrophenols, and the spherical nanoparticles (Au@P5) stabilized with triblock copolymer exhibit higher catalytic performance. Surprisingly, the gold nanowires (Au@P4) produced with P4 have a highest catalytic activity due to large abundance of grain boundaries. Excellent thermo-responsive behaviors for catalytic reaction make the as-prepared Au@P hybrids become an environmentally responsive nano-catalytic materials.

Interstitial micelles in binary blends of A B A triblock copolymers and homopolymers

NASA Astrophysics Data System (ADS)

Wołoszczuk, S.; Banaszak, M.

2018-01-01

We investigate triblock-homopolymer blends of types A1BA2/A and A1BA2/B, using a lattice Monte Carlo method. While the simulated triblock chains are compositionally symmetric in terms of the A-to-B volume ratio, the A1 block is significantly shorter than the A2 block. For the pure A1BA2 melt and the A1BA2 solutions in selective solvent the phase behavior is relatively well known, including existence and stability of the interstitial micelles which were discovered in previous Monte Carlo simulations. In this paper we study the stability of the interstitial micelles as a function of triblock volume fraction in selective homopolymers of either type A or type B, using two significantly different homopolymer chain lengths. We found that adding selective homopolymer of type A shifts the stability of the interstitial micelles into significantly higher temperatures. We also obtained, via self-assembly, intriguing new nanostructures which can be identified as ordered truncated octahedra. Finally, we established that the phase behavior of the triblock-homopolymer blends depends relatively weakly on the chain length of the added homopolymer.

Viscoelastic Properties of Alkoxy Silane-Epoxy Interpenetrating Networks

DTIC Science & Technology

2003-11-01

Owens Corning Fiberglass for supply of the epoxy film former emulsion used in the model silane formulation. The authors also wish to acknowledge the...inclusion filled composite µm- powderproperties 4 triblock copolymer surfactant. The Owens Corning Company generously provided the film former emulsion

Reversible Lifting of Surface Supported Lipid Bilayers with a Membrane-Spanning Nonionic Triblock Copolymer

DOE PAGES

Hayden, Steven C.; Junghans, Ann; Majewski, Jaroslaw; ...

2017-02-22

Neutron reflectometry was used to monitor structural variations in surface supported DMPC bilayers induced by the addition of Triton X-100, a surfactant commonly used to aid solubilization of membrane proteins, and the co-addition of a membrane spanning non-ionic amphiphilic triblock copolymer, (PEO 117-PPO 47-PE O117, Pluronic F98). Surfactant addition causes slight compression of the bilayer thickness and the creation of a distinct EO layer that increases the hydrophilic layer proximal to the supporting substrate (i.e., a water and EO gap between the lipid bilayer and quartz) to 6.8 ± 0.4 Å. Addition of the triblock copolymer into the DMPC: Tritonmore » X-100 bilayer increases the complexity (broadens) the lipid phase transition, further compresses the bilayer, and continues to expand the proximal hydrophilic layer thickness. The observed structural changes are temperature dependent with transmembrane polymer insertion achieved at 37 °C leading to a compressed membrane thickness of 39.2 ± 0.2 Å and proximal gap of 45.2 ± 0.2 Å. Temperature driven exclusion of the polymer at 15 °C causes partitioning of the polymer into the proximal space generating a large hydrogel cushion 162 ± 16 Å thick. An intermediate gap width (10 – 27 Å) is achieved at room temperature (22 – 25 °C). The temperature-driven changes in the proximal hydrophilic gap dimensions are shown to be reversible but thermal history causes variation in magnitude. Temperature-driven changes in polymer association with a supported lipid bilayer offer a facile means to reversibly control both the membrane characteristics as well as the separation between membrane and solid substrate.« less

Reversible Lifting of Surface Supported Lipid Bilayers with a Membrane-Spanning Nonionic Triblock Copolymer

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

Hayden, Steven C.; Junghans, Ann; Majewski, Jaroslaw

Neutron reflectometry was used to monitor structural variations in surface supported DMPC bilayers induced by the addition of Triton X-100, a surfactant commonly used to aid solubilization of membrane proteins, and the co-addition of a membrane spanning non-ionic amphiphilic triblock copolymer, (PEO 117-PPO 47-PE O117, Pluronic F98). Surfactant addition causes slight compression of the bilayer thickness and the creation of a distinct EO layer that increases the hydrophilic layer proximal to the supporting substrate (i.e., a water and EO gap between the lipid bilayer and quartz) to 6.8 ± 0.4 Å. Addition of the triblock copolymer into the DMPC: Tritonmore » X-100 bilayer increases the complexity (broadens) the lipid phase transition, further compresses the bilayer, and continues to expand the proximal hydrophilic layer thickness. The observed structural changes are temperature dependent with transmembrane polymer insertion achieved at 37 °C leading to a compressed membrane thickness of 39.2 ± 0.2 Å and proximal gap of 45.2 ± 0.2 Å. Temperature driven exclusion of the polymer at 15 °C causes partitioning of the polymer into the proximal space generating a large hydrogel cushion 162 ± 16 Å thick. An intermediate gap width (10 – 27 Å) is achieved at room temperature (22 – 25 °C). The temperature-driven changes in the proximal hydrophilic gap dimensions are shown to be reversible but thermal history causes variation in magnitude. Temperature-driven changes in polymer association with a supported lipid bilayer offer a facile means to reversibly control both the membrane characteristics as well as the separation between membrane and solid substrate.« less

Comprehensive two-dimensional liquid chromatographic analysis of poloxamers.

PubMed

Malik, Muhammad Imran; Lee, Sanghoon; Chang, Taihyun

2016-04-15

Poloxamers are low molar mass triblock copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), having number of applications as non-ionic surfactants. Comprehensive one and two-dimensional liquid chromatographic (LC) analysis of these materials is proposed in this study. The separation of oligomers of both types (PEO and PPO) is demonstrated for several commercial poloxamers. This is accomplished at the critical conditions for one of the block while interaction for the other block. Reversed phase LC at CAP of PEO allowed for oligomeric separation of triblock copolymers with regard to PPO block whereas normal phase LC at CAP of PPO renders oligomeric separation with respect to PEO block. The oligomeric separation with regard to PEO and PPO are coupled online (comprehensive 2D-LC) to reveal two-dimensional contour plots by unconventional 2D IC×IC (interaction chromatography) coupling. The study provides chemical composition mapping of both PEO and PPO, equivalent to combined molar mass and chemical composition mapping for several commercial poloxamers. Copyright © 2016 Elsevier B.V. All rights reserved.

Mechanical behaviour׳s evolution of a PLA-b-PEG-b-PLA triblock copolymer during hydrolytic degradation.

PubMed

Breche, Q; Chagnon, G; Machado, G; Girard, E; Nottelet, B; Garric, X; Favier, D

2016-07-01

PLA-b-PEG-b-PLA is a biodegradable triblock copolymer that presents both the mechanical properties of PLA and the hydrophilicity of PEG. In this paper, physical and mechanical properties of PLA-b-PEG-b-PLA are studied during in vitro degradation. The degradation process leads to a mass loss, a decrease of number average molecular weight and an increase of dispersity index. Mechanical experiments are made in a specific experimental set-up designed to create an environment close to in vivo conditions. The viscoelastic behaviour of the material is studied during the degradation. Finally, the mechanical behaviour is modelled with a linear viscoelastic model. A degradation variable is defined and included in the model to describe the hydrolytic degradation. This variable is linked to physical parameters of the macromolecular polymer network. The model allows us to describe weak deformations but become less accurate for larger deformations. The abilities and limits of the model are discussed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Interaction of triblock co-polymer micelles with phospholipid-bilayer: a spectroscopic investigation using a potential chloride channel blocker.

PubMed

Ganguly, Aniruddha; Ghosh, Soumen; Guchhait, Nikhil

2015-03-07

Interaction of a potential chloride channel blocker, 9-methyl anthroate (9-MA), has been studied with zwitterionic l-α-phosphatidylcholine (egg-PC) lipid vesicles, which ascertains the utility of the drug as an efficient molecular reporter for probing the microheterogeneous environment of lipid-bilayers. The effect of a non-ionic triblock co-polymer P123 on the stability of these drug-bound lipid-bilayers has also been investigated by means of steady state and time-resolved spectroscopic techniques exploiting the fluorescence properties of the drug. Experimental results reveal that the addition of P123 to the drug-bound lipid results in a preferential complexation of the drug with the Pluronic leaving the lipid vesicles aside, which has been attributed to a substantially stronger binding interaction of the drug with P123 than that with egg-PC. The result is of potential interest from a medical perspective owing to the context of excess drug desorption from bio-membranes.

Azidated Ether-Butadiene-Ether Block Copolymers as Binders for Solid Propellants

NASA Astrophysics Data System (ADS)

Cappello, Miriam; Lamia, Pietro; Mura, Claudio; Polacco, Giovanni; Filippi, Sara

2016-07-01

Polymeric binders for solid propellants are usually based on hydroxyl-terminated polybutadiene (HTPB), which does not contribute to the overall energy output. Azidic polyethers represent an interesting alternative but may have poorer mechanical properties. Polybutadiene-polyether copolymers may combine the advantages of both. Four different ether-butadiene-ether triblock copolymers were prepared and azidated starting from halogenated and/or tosylated monomers using HTPB as initiator. The presence of the butadiene block complicates the azidation step and reduces the storage stability of the azidic polymer. Nevertheless, the procedure allows modifying the binder properties by varying the type and lengths of the energetic blocks.

Controlled delivery of paclitaxel from stent coatings using poly(hydroxystyrene-b-isobutylene-b-hydroxystyrene) and its acetylated derivative.

PubMed

Sipos, Laszlo; Som, Abhijit; Faust, Rudolf; Richard, Robert; Schwarz, Marlene; Ranade, Shrirang; Boden, Mark; Chan, Ken

2005-01-01

A poly(styrene-b-isobutylene-b-styrene) (SIBS) triblock polymer is employed as the polymer drug carrier for the TAXUS Express2 Paclitaxel-Eluting Coronary Stent system (Boston Scientific Corp.). It has been shown that the release of paclitaxel (PTx) from SIBS can be modulated by modification of either drug-loading ratio or altering the triblock morphology by blending. In the present work, results toward achieving release modulation of PTx by chemical modification of the styrenic portion (using hydroxystyrene or its acetylated version) of the SIBS polymer system are reported. The synthesis of the precursor poly[(p-tert-butyldimethylsilyloxystyrene)]-b-isobutylene-b-[(p-tert-butyldimethylsilyloxystyrene] triblock copolymers was accomplished by living sequential block copolymerization of isobutylene (IB) and p-(tert-butyldimethylsiloxy)styrene (TBDMS) utilizing the capping-tuning technique in a one-pot procedure in methylcyclohexane/CH3Cl at -80 degrees C. This procedure involved the living cationic polymerization of IB with the 5-tert-butyl-1,3-bis(1-chloro-1-methylethyl)benzene/TiCl4 initiating system and capping of living difunctional polyisobutylene (PIB) chain ends with 1,1-ditolylethylene (DTE) followed by addition of titanium(IV) isopropoxide (Ti(OIp)4) to lower the Lewis acidity before the introduction of TBDMS. Deprotection of the product with tetrabutylammonium fluoride yielded poly(hydroxystyrene-b-isobutylene-b-hydroxystyrene), which was quantitatively acetylated to obtain the acetylated derivative. The hydroxystyrene and acetoxystyrene triblock copolymers have acceptable mechanical properties for use as drug delivery coatings for coronary stent applications. It was concluded that the hydrophilic nature of the endblocks and polarity effects on the drug/polymer miscibility lead to enhanced release of PTx from these polymers. The drug-polymer miscibility was confirmed by differential scanning calorimetry and atomic force microscopy evaluations.

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

Lu, Wei; Wang, Yangyang; Wang, Weiyu

All acrylic-based thermoplastic elastomers (TPEs) offer potential alternatives to the widely-used styrenic TPEs. However, the high entanglement molecular weight ( M e) of polyacrylates, as compared to polydienes, leads to “disappointing” mechanical performance as compared to styrenic TPEs. In this study, triblock copolymers composed of alkyl acrylates with different pendant groups and different glass transition temperatures ( T gs), i.e. 1-adamatyl acrylate (AdA) and tetrahydrofurfuryl acrylate (THFA), were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. Thermal characterization of the resulting polymers was performed using differential scanning calorimetry (DSC), and the T gs of both segments were observed for themore » block copolymers. This indication of microphase separation behavior was further demonstrated using atomic-force microscopy (AFM) and small angle X-ray scattering (SAXS). Dynamic mechanical analysis (DMA) showed that the softening temperature of the PAdA domains is 123 °C, which is higher than that of both styrenic TPEs and commercial acrylic based TPEs with poly(methyl methacrylate) (PMMA) hard block. Here, the resulting triblock copolymers also exhibited stress–strain behavior superior to that of conventional all acrylic-based TPEs composed of PMMA and poly( n-butyl acrylate) (PBA) made by controlled radical processes, while the tensile strength was lower than for products made by living anionic polymerization.« less

Controlling sub-microdomain structure in microphase-ordered block copolymers and their nanocomposites

NASA Astrophysics Data System (ADS)

Bowman, Michelle Kathleen

Block copolymers exhibit a wealth of morphologies that continue to find ubiquitous use in a diverse variety of mature and emergent (nano)technologies, such as photonic crystals, integrated circuits, pharmaceutical encapsulents, fuel cells and separation membranes. While numerous studies have explored the effects of molecular confinement on such copolymers, relatively few have examined the sub-microdomain structure that develops upon modification of copolymer molecular architecture or physical incorporation of nanoscale objects. This work will address two relevant topics in this vein: (i) bidisperse brushes formed by single block copolymer molecules and (ii) copolymer nanocomposites formed by addition of molecular or nanoscale additives. In the first case, an isomorphic series of asymmetric poly(styrene-b -isoprene-b-styrene) (S1IS2) triblock copolymers of systematically varied chain length has been synthesized from a parent SI diblock copolymer. Small-angle x-ray scattering, coupled with dynamic rheology and self-consistent field theory (SCFT), reveals that the progressively grown S2 block initially resides in the I-rich matrix and effectively reduces the copolymer incompatibility until a critical length is reached. At this length, the S2 block co-locates with the S1 block so that the two blocks generate a bidisperse brush (insofar as the S1 and S2 lengths differ). This single-molecule analog to binary block copolymer blends affords unique opportunities for materials design at sub-microdomain length scales and provides insight into the transition from diblock to triblock copolymer (and thermoplastic elastomeric nature). In the second case, I explore the distribution of molecular and nanoscale additives in microphase-ordered block copolymers and demonstrate via SCFT that an interfacial excess, which depends strongly on additive concentration, selectivity and relative size, develops. These predictions are in agreement with experimental findings. Moreover, using a poly(styrene-b-methyl methacrylate) (SM) diblock copolymer with an order-disorder transition temperature (TODT) of 186°C, we find that the addition of clustered and discrete nanoparticles of varying size and surface selectivity can cause T ODT to generally decrease, but occasionally increase. Also experimenting with a poly(styrene-b-isoprene) (SI) diblock copolymer with an TODT of 116°C, we find that the addition of smaller nanoparticles at small volume fractions effect the TODT more profoundly. The latter unexpected results are likewise predicted by SCFT and provide a unique strategy by which to improve the nanostructure stability of block copolymers by physical means.

Boundary layers of aqueous surfactant and block copolymer solutions against hydrophobic and hydrophilic solid surfaces

NASA Astrophysics Data System (ADS)

Steitz, Roland; Schemmel, Sebastian; Shi, Hongwei; Findenegg, Gerhard H.

2005-03-01

The boundary layer of aqueous surfactants and amphiphilic triblock copolymers against flat solid surfaces of different degrees of hydrophobicity was investigated by neutron reflectometry (NR), grazing incidence small angle neutron scattering (GISANS) and atomic force microscopy (AFM). Solid substrates of different hydrophobicities were prepared by appropriate surface treatment or by coating silicon wafers with polymer films of different chemical natures. For substrates coated with thin films (20-30 nm) of deuterated poly(styrene) (water contact angle \\theta_{\\mathrm {w}} \\approx 90^\\circ ), neutron reflectivity measurements on the polymer/water interface revealed a water depleted liquid boundary layer of 2-3 nm thickness and a density about 90% of the bulk water density. No pronounced depletion layer was found at the interface of water against a less hydrophobic polyelectrolyte coating (\\theta_{\\mathrm {w}} \\approx 63^\\circ ). It is believed that the observed depletion layer at the hydrophobic polymer/water interface is a precursor of the nanobubbles which have been observed by AFM at this interface. Decoration of the polymer coatings by adsorbed layers of nonionic CmEn surfactants improves their wettability by the aqueous phase at surfactant concentrations well below the critical micellar concentration (CMC) of the surfactant. Here, GISANS experiments conducted on the system SiO2/C8E4/D2O reveal that there is no preferred lateral organization of the C8E4 adsorption layers. For amphiphilic triblock copolymers (PEO-PPO-PEO) it is found that under equilibrium conditions they form solvent-swollen brushes both at the air/water and the solid/water interface. In the latter case, the brushes transform to uniform, dense layers after extensive rinsing with water and subsequent solvent evaporation. The primary adsorption layers maintain properties of the precursor brushes. In particular, their thickness scales with the number of ethylene oxide units (EO) of the block copolymer. In the case of dip-coating without subsequent rinsing, surface patterns of the presumably crystalline polymer on top of the primary adsorption layer develop upon drying under controlled conditions. The morphology depends mainly on the nominal surface coverage with the triblock copolymer. Similar morphologies are found on bare and polystyrene-coated silicon substrates, indicating that the surface patterning is mainly driven by segregation forces within the polymer layers and not by interactions with the substrate.

Multicomponent Solvated Triblock Copolymer Network Systems: Fundamental Insights and Emerging Applications

NASA Astrophysics Data System (ADS)

Krishnan, Arjun Sitaraman

Block copolymers have received significant research attention in recent times due to their ability to spontaneously self-assemble into a variety of nanostructures. Thermoplastic elastomers composed of styrenic triblock copolymers are of great importance in applications such as adhesives and vibration dampening due to their shape memory, resilience and facile processing. The swelling of these polymers by adding midblock selective solvents or oligomers provides an easy route by which to modify the morphology and mechanical behavior of these systems. We first consider a ternary blend of a poly[styrene- b-(ethylene-co-butylene)-b-styrene] triblock copolymer (SEBS) and mixtures of two midblock selective co-solvents, with significantly different physical states. We use dynamic rheology to study the viscoelastic response of a wide variety of systems under oscillatory shear. Frequency spectra acquired at ambient temperature display viscoelastic behavior that shifts in the frequency domain depending on the co-solvent composition. For each copolymer concentration, all the frequency data can be shifted by time-composition superpositioning (tCS) to yield a single master-curve. tCS fails at low frequencies due to presence of endblock pullout, which is a fundamentally different relaxation process from segmental relaxation of the midblock. As an emerging technology, we examine SEBS-oil gels as dielectric elastomers. Dielectric elastomers constitute one class of electroactive polymers (EAPs), polymeric materials that respond to an electric stimulus by changing their macroscopic dimensions, thereby converting electrical energy into mechanical work. We use standard configuration of EAP devices involving stretching, or "prestraining," the elastomer film biaxially. The effect of experimental parameters such as film thickness and amount of prestrain on the (electro)mechanical properties of the material become apparent by recasting as-obtained electroactuation data into compressive electromechanical stress-strain curves. The ultimate dielectric properties of the specimen are strongly correlated with specimen composition and experimental conditions. We shed light on the effect of biaxial prestrain on copolymer morphology. We use small-angle X-ray scattering (SAXS) to probe the nanostructure of SEBS-oil gels by systematically changing the concentration of polymer and the biaxial prestrain. Azimuthally integrated intensity profiles are used to ascertain the extent of deformation of polystyrene microdomains. The structure factor data correlates with prestrain, and is fitted using the Percus-Yevick approximation for interacting spheres. While a hard sphere interaction model is sufficient for unstrained gels, the additional attractive potentials observed in stretched samples are indicative of soft coronal interactions due to interpenetration brought about by strain.

Heat capacity anomaly in a self-aggregating system: Triblock copolymer 17R4 in water

NASA Astrophysics Data System (ADS)

Dumancas, Lorenzo V.; Simpson, David E.; Jacobs, D. T.

2015-05-01

The reverse Pluronic, triblock copolymer 17R4 is formed from poly(propylene oxide) (PPO) and poly(ethylene oxide) (PEO): PPO14 - PEO24 - PPO14, where the number of monomers in each block is denoted by the subscripts. In water, 17R4 has a micellization line marking the transition from a unimer network to self-aggregated spherical micelles which is quite near a cloud point curve above which the system separates into copolymer-rich and copolymer-poor liquid phases. The phase separation has an Ising-like, lower consolute critical point with a well-determined critical temperature and composition. We have measured the heat capacity as a function of temperature using an adiabatic calorimeter for three compositions: (1) the critical composition where the anomaly at the critical point is analyzed, (2) a composition much less than the critical composition with a much smaller spike when the cloud point curve is crossed, and (3) a composition near where the micellization line intersects the cloud point curve that only shows micellization. For the critical composition, the heat capacity anomaly very near the critical point is observed for the first time in a Pluronic/water system and is described well as a second-order phase transition resulting from the copolymer-water interaction. For all compositions, the onset of micellization is clear, but the formation of micelles occurs over a broad range of temperatures and never becomes complete because micelles form differently in each phase above the cloud point curve. The integrated heat capacity gives an enthalpy that is smaller than the standard state enthalpy of micellization given by a van't Hoff plot, a typical result for Pluronic systems.

Nanoporous polysulfone membranes via a degradable block copolymer precursor for redox flow batteries

DOE PAGES

Gindt, Brandon P.; Abebe, Daniel G.; Tang, Zhijiang J.; ...

2016-02-16

In this study, nanoporous polysulfone (PSU) membranes were fabricated via post-hydrolysis of polylactide (PLA) from PLA–PSU–PLA triblock copolymer membranes. The PSU scaffold was thermally crosslinked before sacrificing PLA blocks. The resulting nanopore surface was chemically modified with sulfonic acid moieties. The membranes were analyzed and evaluated as separators for vanadium redox flow batteries. Nanoporous PSU membranes prepared by this new method and further chemically modified to a slight degree exhibited unique behavior with respect to their ionic conductivity when exposed to solutions of increasing acid concentration.

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

Bicontinuous mesoporous carbon thin films via an order-order transition.

PubMed

Deng, Guodong; Zhang, Yuanzhong; Ye, Changhuai; Qiang, Zhe; Stein, Gila E; Cavicchi, Kevin A; Vogt, Bryan D

2014-10-28

Bicontinuous mesoporous carbon films are fabricated by cooperative self-assembly of phenolic resin and amphiphilic triblock copolymer via an order-order transition from cylinders to gyroid. The film morphology is strongly influenced by the details of processing, including age of the resol, resol : template ratio, and the solvent vapor annealing process.

Ionic Liquids in Electro-active Devices (ILED)

DTIC Science & Technology

2013-12-12

Polyesters: Structure-Property Relationships in Thermal Behavior, Ionic Conductivity , and Morphology , Advanced Functional Materials, (01 2010...and Ionic Conductivities , Macromolecular Chemistry and Physics, (10 2011): . doi: M. Green, C. Schreiner, T. Long. Thermal , Rheological, and Ion...block giving thermal stability and ionic conductivity . Table 1 shows the molecular weight analysis of the triblock copolymers with increasing

A simple and inexpensive thermal optic nanosensor formed by triblock copolymer and polydiacetylene mixture.

PubMed

Ferreira, Gabriel Max Dias; Ferreira, Guilherme Max Dias; Hespanhol, Maria do Carmo; Rezende, Jaqueline de Paula; Pires, Ana Clarissa Dos Santos; Ortega, Paulo Fernando Ribeiro; da Silva, Luis Henrique Mendes

2018-02-15

Polydiacetylene (PDA) vesicles have been applied as optical sensors in different areas, although there are difficulties in controlling their responses. In this study, we prepared nanoblends of PDA with triblock copolymers (TC) as a better sensor system for detecting temperature change. The influences of diacetylene (DA) monomer, and the TC chemical structure and concentration on the colorimetric response (CR) were examined. The TC/PDA nanoblend was remarkably more sensitive to temperature change, than classical vesicles. A higher L64 concentration of 12.0% (w/w) reduced the chromatic transition temperature (T tr ) to as low as 24°C. When using different TCs, the T tr values can be ordered as L35

Triblock copolymers encapsulated poly (aryl benzyl ether) dendrimer zinc(II) phthalocyanine nanoparticles for enhancement in vitro photodynamic efficacy.

PubMed

Huang, Yide; Yu, Huizhen; Lv, Huafei; Zhang, Hong; Ma, Dongdong; Yang, Hongqin; Xie, Shusen; Peng, Yiru

2016-12-01

A novel series of nanoparticles formed via an electrostatic interaction between the periphery of negatively charged 1-2 generation aryl benzyl ether dendrimer zinc (II) phthalocyanines and positively charged poly(L-lysin) segment of triblock copolymer, poly(L-lysin)-block-poly(ethylene glycol)-block-poly(L-lysin), was developed for the use as an effective photosensitizers in photodynamic therapy. The dynamic light scattering, atomic force microscopy showed that two nanoparticles has a relevant size of 80-150nm. The photophysical properties and singlet oxygen quantum yields of free dendrimer phthalocyanines and nanoparticles exhibited generation dependence. The intracellular uptake of dendrimer phthalocyanines in Hela cells was significantly elevated as they were incorporated into the micelles, but was inversely correlated with the generation of dendrimer phthalocyanines. The photocytotoxicity of dendrimer phthalocyanines incorporated into polymeric micelles was also increased. The presence of nanoparticles induced efficient cell death. Using a mitochondrial-sepcific dye rhodamine 123 (Rh123), our fluorescence microscopic result indicated that nanoparticles localized to the mitochondria. Copyright © 2016 Elsevier B.V. All rights reserved.

Gyroid Structures at Highly Asymmetric Volume Fractions by Blending of ABC Triblock Terpolymer and AB Diblock Copolymer

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

Ahn, Seonghyeon; Kwak, Jongheon; Choi, Chungryong

Here, we investigated, via small angle X-ray scattering and transmission electron microscopy, the morphologies of binary blend of polyisoprene- b-polystyrene- b-poly(2-vinylpyridine) (ISP) triblock terpolymer and polyisoprene-b-polystyrene (IS) diblock copolymer. An asymmetric ISP with volume fractions ( f) of 0.12, 0.75, and 0.13 for PI, PS, and P2VP blocks, respectively, showed a new morphology: Coexistence of spheres and cylinders with tetragonal packing. Asymmetric IS with f I = 0.11 and f S =0.89 showed conventional body-centered cubic spherical microdomains. Very interestingly, a binary blend of ISP and IS with overall volume fractions of f I = 0.12, f S = 0.79,more » and f P = 0.09 exhibited core-shell double gyroid (CSG: Q 230 space group), where PI consists of thin core and PS forms thick shell, while P2VP becomes thin matrix. It is very unusual to form highly asymmetric CSG with the matrix having very small volume fraction (0.09).« less

Ultrafast photoinduced electron transfer in the micelle and the gel phase of a PEO-PPO-PEO triblock copolymer

NASA Astrophysics Data System (ADS)

Mandal, Ujjwal; Ghosh, Subhadip; Dey, Shantanu; Adhikari, Aniruddha; Bhattacharyya, Kankan

2008-04-01

Ultrafast photoinduced electron transfer (PET) from N,N-dimethylaniline (DMA) to coumarin dyes is studied in the micelle and the gel phase of a triblock copolymer, (PEO)20-(PPO)70-(PEO)20 (Pluronic P123) by picosecond and femtosecond emission spectroscopies. The rate of PET in a P123 micelle and gel is found to be nonexponential and faster than the slow components of solvation dynamics. In a P123 micelle and gel, PET occurs on multiple time scales ranging from a subpicosecond time scale to a few nanoseconds. In the gel phase, the highest rate constant (9.3×109M-1s-1) of ET for C152 is about two times higher than that (3.8×109M-1s-1) observed in micelle phase. The ultrafast components of electron transfer (ET) exhibits a bell shaped dependence with the free energy change which is similar to the Marcus inversion. Possible reasons for slower PET in P123 micelle compared to other micelles and relative to P123 gel are discussed.

Gyroid Structures at Highly Asymmetric Volume Fractions by Blending of ABC Triblock Terpolymer and AB Diblock Copolymer

DOE PAGES

Ahn, Seonghyeon; Kwak, Jongheon; Choi, Chungryong; ...

2017-11-08

Here, we investigated, via small angle X-ray scattering and transmission electron microscopy, the morphologies of binary blend of polyisoprene- b-polystyrene- b-poly(2-vinylpyridine) (ISP) triblock terpolymer and polyisoprene-b-polystyrene (IS) diblock copolymer. An asymmetric ISP with volume fractions ( f) of 0.12, 0.75, and 0.13 for PI, PS, and P2VP blocks, respectively, showed a new morphology: Coexistence of spheres and cylinders with tetragonal packing. Asymmetric IS with f I = 0.11 and f S =0.89 showed conventional body-centered cubic spherical microdomains. Very interestingly, a binary blend of ISP and IS with overall volume fractions of f I = 0.12, f S = 0.79,more » and f P = 0.09 exhibited core-shell double gyroid (CSG: Q 230 space group), where PI consists of thin core and PS forms thick shell, while P2VP becomes thin matrix. It is very unusual to form highly asymmetric CSG with the matrix having very small volume fraction (0.09).« less

Zonisamide-loaded triblock copolymer nanomicelles as a novel drug delivery system for the treatment of acute spinal cord injury

PubMed Central

Li, JingLun; Deng, JiaoJiao; Yuan, JinXian; Fu, Jie; Li, XiaoLing; Tong, AiPing; Wang, YueLong; Chen, YangMei; Guo, Gang

2017-01-01

Spinal cord injury (SCI) commonly leads to lifelong disability due to the limited regenerative capacity of the adult central nervous system. Nanomicelles can be used as therapeutic systems to provide effective treatments for SCI. In this study, a novel triblock monomethyl poly(ethylene glycol)-poly(l-lactide)-poly(trimethylene carbonate) copolymer was successfully synthesized. Next, polymeric nanomicelles loaded with zonisamide (ZNS), a Food and Drug Administration-approved antiepileptic drug, were prepared and characterized. The ZNS-loaded micelles (ZNS-M) were further utilized for the treatment of SCI in vitro and in vivo. The obtained ZNS-M were ~50 nm in diameter with good solubility and dispersibility. Additionally, these controlled-release micelles showed significant antioxidative and neuron-protective effects in vitro. Finally, our results indicated that ZNS-M treatment could promote motor function recovery and could increase neuron and axon density in a hemisection SCI model. In summary, these results may provide an experimental basis for the use of ZNS-M as a clinically applicable therapeutic drug for the treatment of SCI in the future. PMID:28408816

Block copolymer self-assembly derived ultrafiltration membranes: From science to start-up

NASA Astrophysics Data System (ADS)

Wiesner, Ulrich

In the last ten years a novel method to generate asymmetric ultrafiltration membranes has been established. It is based on the combination of block copolymer self-assembly with non-solvent induced phase separation (NIPS) and is now referred to as SNIPS. NIPS as an industry proven method for the formation of phase inversion membranes opening a pathway to scale up and commercialization of these membranes. The combination of NIPS with block copolymer self-assembly leads to asymmetric membranes with narrow pore size distributions in the top surface layer (so called isoporous membranes) as well as high pore densities, thereby potentially combining high resolution with high flux in membrane separation processes. Such membranes have potential applications in the biopharmaceutical industry where a large fraction of the costs are currently associated with time-consuming non-membrane based separation processes. This talk will describe a family of isoporous ultrafiltration membranes based on the self-assembly behavior of an ABC triblock terpolymer which has led to the formation of a start-up company out of Cornell University. After introduction of the SNIPS process in general, and its application to such ABC triblock terpolymers in particular, open scientific questions associated with the formation mechanisms of the top surface separation layer in such membranes is discussed, which is at the heart of enabling high performance separation behavior. Furthermore, challenges translating scientific work into industrial settings are highlighted.

All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties

DOE PAGES

Lu, Wei; Wang, Yangyang; Wang, Weiyu; ...

2017-08-25

All acrylic-based thermoplastic elastomers (TPEs) offer potential alternatives to the widely-used styrenic TPEs. However, the high entanglement molecular weight ( M e) of polyacrylates, as compared to polydienes, leads to “disappointing” mechanical performance as compared to styrenic TPEs. In this study, triblock copolymers composed of alkyl acrylates with different pendant groups and different glass transition temperatures ( T gs), i.e. 1-adamatyl acrylate (AdA) and tetrahydrofurfuryl acrylate (THFA), were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. Thermal characterization of the resulting polymers was performed using differential scanning calorimetry (DSC), and the T gs of both segments were observed for themore » block copolymers. This indication of microphase separation behavior was further demonstrated using atomic-force microscopy (AFM) and small angle X-ray scattering (SAXS). Dynamic mechanical analysis (DMA) showed that the softening temperature of the PAdA domains is 123 °C, which is higher than that of both styrenic TPEs and commercial acrylic based TPEs with poly(methyl methacrylate) (PMMA) hard block. Here, the resulting triblock copolymers also exhibited stress–strain behavior superior to that of conventional all acrylic-based TPEs composed of PMMA and poly( n-butyl acrylate) (PBA) made by controlled radical processes, while the tensile strength was lower than for products made by living anionic polymerization.« less

Study on the mesophase development of pressure-responsive ABC triblock copolymers

NASA Astrophysics Data System (ADS)

Cho, Junhan

Here we focus on the revelation of new nanoscale morphologies for a molten compressible polymeric surfactant through a compressible self-consistent field approach. A linear ABC block copolymer is set to allow a disparity in the propensities for curved interfaces and in pressure responses of ij-pairs. Under these conditions, the copolymer evolves into noble morphologies at selected segregation levels such as networks with tetrapod connections, rectangularly packed cylinders in a 2-dimensional array, and also body-centered cubic phases. Those new structures are considered to turn up by interplay between disparity in the densities of block domains and packing frustration. Comparison with the classical mesophase structures is also given. The author acknowledges the support from the Center for Photofunctional Energy Materials (GRRC).

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.

Core-shell-corona micelles by PS-b-P2VP-b-PEO copolymers: focus on the water-induced micellization process.

PubMed

Willet, Nicolas; Gohy, Jean-François; Auvray, Loïc; Varshney, Sunil; Jérôme, Robert; Leyh, Bernard

2008-04-01

It is now well established that amphiphilic PS-b-P2VP-b-PEO linear triblock copolymers can form multilayered assemblies, thus core-shell-corona (CSC) micelles, in water. Micellization is triggered by addition of a small amount of water into a dilute solution of the PS-b-P2VP-b-PEO copolymer in a non-selective organic solvent. However, the phenomena that take place at the very beginning of this process are poorly documented. How these copolymer chains are perturbed by addition of water was investigated in this work by light and neutron scattering techniques and transmission electron microscopy. It was accordingly possible to determine the critical water concentration (CWC), the compactness of the nano-objects in solution, their number of aggregation, and their hydrodynamic diameter at each step of the micellization process.

Nanosized amorphous calcium carbonate stabilized by poly(ethylene oxide)-b-poly(acrylic acid) block copolymers.

PubMed

Guillemet, Baptiste; Faatz, Michael; Gröhn, Franziska; Wegner, Gerhard; Gnanou, Yves

2006-02-14

Particles of amorphous calcium carbonate (ACC), formed in situ from calcium chloride by the slow release of carbon dioxide by alkaline hydrolysis of dimethyl carbonate in water, are stabilized against coalescence in the presence of very small amounts of double hydrophilic block copolymers (DHBCs) composed of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blocks. Under optimized conditions, spherical particles of ACC with diameters less than 100 nm and narrow size distribution are obtained at a concentration of only 3 ppm of PEO-b-PAA as additive. Equivalent triblock or star DHBCs are compared to diblock copolymers. The results are interpreted assuming an interaction of the PAA blocks with the surface of the liquid droplets of the concentrated CaCO3 phase, formed by phase separation from the initially homogeneous reaction mixture. The adsorption layer of the block copolymer protects the liquid precursor of ACC from coalescence and/or coagulation.

Tribological Behavior of Aqueous Copolymer Lubricant in Mixed Lubrication Regime.

PubMed

Ta, Thi D; Tieu, A Kiet; Zhu, Hongtao; Zhu, Qiang; Kosasih, Prabouno B; Zhang, Jie; Deng, Guanyu

2016-03-02

Although a number of experiments have been attempted to investigate the lubrication of aqueous copolymer lubricant, which is applied widely in metalworking operations, a comprehensive theoretical investigation at atomistic level is still lacking. This study addresses the influence of loading pressure and copolymer concentration on the structural properties and tribological performance of aqueous copolymer solution of poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO) at mixed lubrication using a molecular dynamic (MD) simulation. An effective interfacial potential, which has been derived from density functional theory (DFT) calculations, was employed for the interactions between the fluid's molecules and iron surface. The simulation results have indicated that the triblock copolymer is physisorption on iron surface. Under confinement by iron surfaces, the copolymer molecules form lamellar structure in aqueous solution and behave differently from its bulk state. The lubrication performance of aqueous copolymer lubricant increases with concentration, but the friction reduction is insignificant at high loading pressure. Additionally, the plastic deformation of asperity is dependent on both copolymer concentration and loading pressure, and the wear behavior shows a linear dependence of friction force on the number of transferred atoms between contacting asperities.

PLA-PEG-PLA copolymer-based polymersomes as nanocarriers for delivery of hydrophilic and hydrophobic drugs: preparation and evaluation with atorvastatin and lisinopril.

PubMed

Danafar, H; Rostamizadeh, K; Davaran, S; Hamidi, M

2014-10-01

Tri-block poly(lactide)-poly(ethylene glycol)-poly(lactide) (PLA-PEG-PLA) copolymers were synthesized and used to prepare polymersomes loaded separately by the hydrophobic and hydrophilic model drugs, atorvastatin and lisinopril, respectively. The resulting nanostructures were characterized by various techniques such as FTIR, DSC, PCS and AFM. The polymersomes exhibited high encapsulation efficiencies of almost 78% and 70.8% for atorvastatin and lisinopril, respectively. Investigation on FTIR and DSC results revealed that such a high encapsulation efficiency is due to strong interaction between atorvastatin and the copolymer. The impact of drug/copolymer ratio and copolymer composition on drug-loading efficiency and drug release behavior were also studied. The results showed that in case of lisinopril, polymersomes exhibited a triphasic drug release, while for atorvastatin a biphasic release profile was obtained. Overall, the results indicated that PLA-PEG-PLA polymersomes can be considered as a promising carrier for both hydrophilic and hydrophobic drugs.

Selective molecular annealing: in situ small angle X-ray scattering study of microwave-assisted annealing of block copolymers.

PubMed

Toolan, Daniel T W; Adlington, Kevin; Isakova, Anna; Kalamiotis, Alexis; Mokarian-Tabari, Parvaneh; Dimitrakis, Georgios; Dodds, Christopher; Arnold, Thomas; Terrill, Nick J; Bras, Wim; Hermida Merino, Daniel; Topham, Paul D; Irvine, Derek J; Howse, Jonathan R

2017-08-09

Microwave annealing has emerged as an alternative to traditional thermal annealing approaches for optimising block copolymer self-assembly. A novel sample environment enabling small angle X-ray scattering to be performed in situ during microwave annealing is demonstrated, which has enabled, for the first time, the direct study of the effects of microwave annealing upon the self-assembly behavior of a model, commercial triblock copolymer system [polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene]. Results show that the block copolymer is a poor microwave absorber, resulting in no change in the block copolymer morphology upon application of microwave energy. The block copolymer species may only indirectly interact with the microwave energy when a small molecule microwave-interactive species [diethylene glycol dibenzoate (DEGDB)] is incorporated directly into the polymer matrix. Then significant morphological development is observed at DEGDB loadings ≥6 wt%. Through spatial localisation of the microwave-interactive species, we demonstrate targeted annealing of specific regions of a multi-component system, opening routes for the development of "smart" manufacturing methodologies.

Controlling block copolymer phase behavior using ionic surfactant

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

Ray, D.; Aswal, V. K.

2016-05-23

The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO{sub 26}PO{sub 39}EO{sub 26})] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle–surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at highermore » temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.« less

Temperature-responsive in situ nanoparticle hydrogels based on hydrophilic pendant cyclic ether modified PEG-PCL-PEG.

PubMed

Feng, Zujian; Zhao, Junqiang; Li, Yin; Xu, Shuxin; Zhou, Junhui; Zhang, Jianhua; Deng, Liandong; Dong, Anjie

2016-10-20

Thermo-sensitive injectable hydrogels based on poly(ε-caprolactone)/poly(ethylene glycol) (PCL/PEG) block copolymers have attracted considerable attention for sustained drug release and tissue engineering applications. Previously, we have reported a thermo-sensitive hydrogel of P(CL-co-TOSUO)-PEG-P(CL-co-TOSUO) (PECT) triblock copolymers modified by hydrophilic cyclic ether pendant groups 1,4,8-trioxa-[4.6]spiro-9-undecanone (TOSUO). Unfortunately, the low gel modulus of PECT (only 50-70 Pa) may limit its applications. Herein, another kind of thermogelling triblock copolymer of a pendant cyclic ether-modified caprolactonic poloxamer analog, PEG-P(CL-co-TOSUO)-PEG (PECTE), was successfully prepared by control of the hydrophilicity/hydrophobicity balance and chemical compositions of the copolymers. PECTE powder could directly disperse in water to form a stable nanoparticle (NP) aqueous dispersion and underwent sol-gel-sol transition behavior at a higher concentration with the temperature increasing from ambient or lower temperatures. Significantly, the microstructure parameters (e.g., different chemical compositions of the hydrophobic block and topology) played a critical role in the phase transition behavior. Furthermore, comparison studies on PECTE and PEG-PCL-PEG (PECE) showed that the introduction of pendant cyclic ether groups into PCL blocks could avoid unexpected ahead-of-time gelling of the PECE aqueous solution. In addition, the rheological analysis of PECTE and PECT indicated that the storage modulus of the PECTE hydrogel could be 100 times greater than that of the PECT hydrogel under the same mole ratios of TOSUO/CL and lower molecular weight. Consequently, PECTE thermal hydrogel systems are believed to be promising as in situ gel-forming biomaterials for drug delivery and tissue engineering.

Thermo-responsive triblock copolymer phase transition behaviour in imidazolium-based ionic liquids: Role of the effect of alkyl chain length of cations.

PubMed

Umapathi, Reddicherla; Venkatesu, Pannuru

2017-01-01

Different biophysical techniques such as fluorescence spectroscopy, dynamic light scattering (DLS), viscosity (η) and Fourier transform infrared (FTIR) spectroscopy have been carried out to characterize the effect of imidazolium-based ionic liquids (ILs) on the thermo-responsive triblock copolymer, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly-(ethylene glycol) (PEG-PPG-PEG). In addition, to demonstrate the distinct morphological changes of various self-assembled morphologies, we further employed field emission scanning electron microscope (FESEM). To investigate the effect of alkyl chain length of the cation, concentration of the ILs and the related Hofmeister series on the phase behaviour of PEG-PPG-PEG, we used a series of ILs possessing same Cl - anion and a set of cation [C n mim] + with increasing alkyl chain length of cation such as 1-ethyl-3-methylimidazolium chloride ([Emim][Cl]), 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]), 1-hexyl-3-methylimidazolium chloride ([Hmim][Cl]) and 1-decyl-3-methylimidazolium chloride ([Dmim][Cl]). The critical micellization temperature (CMT) of the copolymer in the presence of well hydrated cations is directly correlated to their hydration. The overall specific ranking of ILs in decreasing the CMT of PEG-PPG-PEG in aqueous solution was [Emim][Cl]>[Bmim][Cl]>[Hmim][Cl]>[Dmim][Cl]. The trend of these ILs followed the well-known Hofmeister series of cations of ILs. The present study provides important information about the solution properties that can be helpful to tune the IL or temperature-sensitive copolymer CMT and micelle shapes which are crucial for understanding the drug delivery mechanisms. Copyright © 2016 Elsevier Inc. All rights reserved.

Thermoresponsive complex amphiphilic block copolymer micelles investigated by laser light scattering.

PubMed

Zhao, Fang; Xie, Dinghai; Zhang, Guangzhao; Pispas, Stergios

2008-05-22

Poly(isoprene)-block-poly(ethylene oxide) (PI-b-PEO) diblock copolymers form micelles in water. The introduction of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-b-PPO-b-PEO) triblock copolymer leads to the formation of mixed micelles through hydrophobic interaction. The dimension of the mixed micelles varies with the weight ratio (r) of PEO-b-PPO-b-PEO to PI-b-PEO. By use of laser light scattering, we have investigated the temperature dependence of the structural evolution of the micelles at different r. At r<10, the size of the mixed micelles decreases with temperature. At r>10, due to the excessive PEO-b-PPO-b-PEO chains in solution, as temperature increases, the mixed micelles aggregate into larger micelle clusters.

Phase structure and properties of poly(ethylene terephthalate)/polyethylene based on recycled materials

Treesearch

Yong Lei; Qinglin Wu; Craig M. Clemons; Weihong Guo

2009-01-01

Blends based on recycled high density polyethylene (R-HDPE) and recycled poly(ethylene terephthalate) (R-PET) were made through reactive extrusion. The effects of maleated polyethylene (PE-g-MA), triblock copolymer of styrene and ethylene/butylene (SEBS), and 4,40-methylenedi(phenyl isocyanate) (MDI) on blend properties were studied. The 2% PE-g-MA improved the...

pH-Responsive Triblock Copolymeric Micelles Decorated with a Cell-Penetrating Peptide Provide Efficient Doxorubicin Delivery

NASA Astrophysics Data System (ADS)

Ng, Khen Eng; Amin, Mohd Cairul Iqbal Mohd; Katas, Haliza; Amjad, Muhammad Wahab; Butt, Adeel Masood; Kesharwani, Prashant; Iyer, Arun K.

2016-12-01

This study developed novel triblock pH-responsive polymeric micelles (PMs) using cholic acid-polyethyleneimine-poly- l-arginine (CA-PEI-pArg) copolymers. PEI provided pH sensitivity, while the hydrophilic cell-penetrating pArg peptide promoted cellular PM internalization. The copolymers self-assembled into PMs in aqueous solution at above the critical micelle concentration (2.98 × 10-7 M) and encapsulated doxorubicin in the core region, with a 34.2% ( w/ w) entrapment efficiency. PMs showed pH-dependent swelling, increasing in size by almost sevenfold from pH 7.4 to 5.0. Doxorubicin release was pH-dependent, with about 65% released at pH 5.0, and 32% at pH 7.4. Cellular uptake, assessed by confocal microscopy and flow cytometry, was enhanced by using doxorubicin-loaded CA-PEI-pArg PMs, as compared to free doxorubicin and DOX-loaded CA-PEI PMs. Moreover, 24-h incubation of these PMs with a human breast cancer cell line produced greater cytotoxicity than free doxorubicin. These results indicate that pH-responsive CA-PEI-pArg micelles could provide a versatile delivery system for targeted cancer therapy using hydrophobic drugs.

Fluorination of phthalocyanine substituents: Improved photoproperties and enhanced photodynamic efficacy after optimal micellar formulations.

PubMed

Pucelik, Barbara; Gürol, Ilke; Ahsen, Vefa; Dumoulin, Fabienne; Dąbrowski, Janusz M

2016-11-29

A fluorinated phthalocyanine and its non-fluorinated analogue were selected to evaluate the potential enhancement of fluorination on photophysical, photochemical and redox properties as well as on biological activity in cellular and animal models. Due to the pharmacological relevance, the affinity of these phthalocyanines towards biological membranes (logP ow ) as well as their primary interaction with human serum albumin (HSA) or low-density lipoprotein (LDL) were determined. Water-dispersible drug formulation of phthalocyanines via Pluronic ® -based triblock copolymer micelles was prepared to avoid self-aggregation effects and to improve their delivery. The obtained results demonstrate that phthalocyanines incorporation into tunable-polymeric micelles significantly enhanced their cellular uptake and their photocytotoxicity. The improved biodistribution and photodynamic efficacy of the phthalocyanines-triblock copolymer conjugates was also confirmed in vivo in CT26 bearing BALB/c mice. PDT with both compounds led to tumor growth inhibition in all treated animals. Fluorinated phthalocyanine 2 turned out to be the most effective anticancer agent as the tumors of 20% of mice treated regressed completely and did not appear for over one year after treatment. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Kinetics of Phase Transition from Lamellar to Hexagonally Packed Cylinders for a Triblock Copolymer in a Selective Solvent

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

Liu,Y.; Li, M.; Bansil, R.

2007-01-01

We examined the kinetics of the transformation from the lamellar (LAM) to the hexagonally packed cylinder (HEX) phase for the triblock copolymer, polystyrene-b-poly (ethylene-co-butylene)-b-polystyrene (SEBS) in dibutyl phthalate (DBP), a selective solvent for polystyrene (PS), using time-resolved small-angle X-ray scattering (SAXS). We observe the HEX phase with the EB block in the cores at a lower temperature than that observed for the LAM phase due to the solvent selectivity of DBP for the PS block. Analysis of the SAXS data for a deep temperature quench well below the LAM-HEX transition shows that the transformation occurs in a one-step process. Wemore » calculate the scattering using a geometric model of rippled layers with adjacent layers totally out of phase during the transformation. The agreement of the calculations with the data further supports the continuous transformation mechanism from the LAM to HEX for a deep quench. In contrast, for a shallow quench close to the order-order transition, we find agreement with a two-step nucleation and growth mechanism.« less

Improving proton conduction pathways in di- and triblock copolymer membranes: Branched versus linear side chains

NASA Astrophysics Data System (ADS)

Dorenbos, G.

2017-06-01

Phase separation within a series of polymer membranes in the presence of water is studied by dissipative particle dynamics. Each polymer contains hydrophobic A beads and hydrophilic C beads. Three parent architectures are constructed from a backbone composed of connected hydrophobic A beads to which short ([C]), long ([A3C]), or symmetrically branched A5[AC][AC] side chains spring off. Three di-block copolymer derivatives are constructed by covalently bonding an A30 block to each parent architecture. Also three tri-blocks with A15 blocks attached to both ends of each parent architecture are modeled. Monte Carlo tracer diffusion calculations through the water containing pores for 1226 morphologies reveal that water diffusion for parent architectures is slowest and diffusion through the di-blocks is fastest. Furthermore, diffusion increases with side chain length and is highest for branched side chains. This is explained by the increase of water pore size with , which is the average number of bonds that A beads are separated from a nearest C bead. Optimization of within the amphiphilic parent architecture is expected to be essential in improving proton conduction in polymer electrolyte membranes.

Surface modification of paclitaxel-loaded tri-block copolymer PLGA- b-PEG- b-PLGA nanoparticles with protamine for liver cancer therapy

NASA Astrophysics Data System (ADS)

Gao, Nansha; Chen, Zhihong; Xiao, Xiaojun; Ruan, Changshun; Mei, Lin; Liu, Zhigang; Zeng, Xiaowei

2015-08-01

In order to enhance the therapeutic effect of chemotherapy on liver cancer, a biodegradable formulation of protamine-modified paclitaxel-loaded poly(lactide- co-glycolide)- b-poly(ethylene glycol)- b-poly(lactide- co-glycolide) (PLGA- b-PEG- b-PLGA) nanoparticles (PTX-loaded/protamine NPs) was prepared. Tri-block copolymer PLGA- b-PEG- b-PLGA was synthesized by ring-opening polymerization and characterized by 1H NMR spectroscopy and gel permeation chromatography. PTX-loaded and PTX-loaded/protamine NPs were characterized in terms of size, size distribution, zeta potential, surface morphology, drug encapsulation efficiency, and drug release. Confocal laser scanning microscopy showed that coumarin 6-loaded/protamine NPs were internalized by hepatocellular carcinoma cell line HepG2. The cellular uptake efficiency of NPs was obviously elevated after protamine modification. With commercial formulation Taxol® as the reference, HepG2 cells were also used to study the cytotoxicity of the NPs. PTX-loaded/protamine NPs exhibited significantly higher cytotoxicity than PTX-loaded NPs and Taxol® did. All the results suggested that surface modification of PTX-loaded PLGA- b-PEG- b-PLGA NPs with protamine boosted the therapeutic efficacy on liver cancer.

Importance of crystallinity of anchoring block of semi-solid amphiphilic triblock copolymers in stabilization of silicone nanoemulsions.

PubMed

Le Kim, Trang Huyen; Jun, Hwiseok; Nam, Yoon Sung

2017-10-01

Polymer emulsifiers solidified at the interface between oil and water can provide exceptional dispersion stability to emulsions due to the formation of unique semi-solid interphase. Our recent works showed that the structural stability of paraffin-in-water emulsions highly depends on the oil wettability of hydrophobic block of methoxy poly(ethylene glycol)-block-poly(ε-caprolactone) (mPEG-b-PCL). Here we investigate the effects of the crystallinity of hydrophobic block of triblock copolymer-based emulsifiers, PCLL-b-PEG-b-PCLL, on the colloidal properties of silicone oil-in-water nanoemulsions. The increased ratio of l-lactide to ε-caprolactone decreases the crystallinity of the hydrophobic block, which in turn reduces the droplet size of silicone oil nanoemulsions due to the increased chain mobility at the interface. All of the prepared nanoemulsions are very stable for a month at 37°C. However, the exposure to repeated freeze-thaw cycles quickly destabilizes the nanoemulsions prepared using the polymer with the reduced crystallinity. This work demonstrates that the anchoring chain crystallization in the semi-solid interphase is critically important for the structural robustness of nanoemulsions under harsh physical stresses. Copyright © 2017 Elsevier Inc. All rights reserved.

ABC Triblock Copolymer Worms: Synthesis, Characterization, and Evaluation as Pickering Emulsifiers for Millimeter-Sized Droplets

PubMed Central

2016-01-01

Polymerization-induced self-assembly (PISA) is used to prepare linear poly(glycerol monomethacrylate)–poly(2-hydroxypropyl methacrylate)–poly(benzyl methacrylate) [PGMA–PHPMA–PBzMA] triblock copolymer nano-objects in the form of a concentrated aqueous dispersion via a three-step synthesis based on reversible addition–fragmentation chain transfer (RAFT) polymerization. First, GMA is polymerized via RAFT solution polymerization in ethanol, then HPMA is polymerized via RAFT aqueous solution polymerization, and finally BzMA is polymerized via “seeded” RAFT aqueous emulsion polymerization. For certain block compositions, highly anisotropic worm-like particles are obtained, which are characterized by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The design rules for accessing higher order morphologies (i.e., worms or vesicles) are briefly explored. Surprisingly, vesicular morphologies cannot be accessed by targeting longer PBzMA blocks—instead, only spherical nanoparticles are formed. SAXS is used to rationalize these counterintuitive observations, which are best explained by considering subtle changes in the relative enthalpic incompatibilities between the three blocks during the growth of the PBzMA block. Finally, the PGMA–PHPMA–PBzMA worms are evaluated as Pickering emulsifiers for the stabilization of oil-in-water emulsions. Millimeter-sized oil droplets can be obtained using low-shear homogenization (hand-shaking) in the presence of 20 vol % n-dodecane. In contrast, control experiments performed using PGMA–PHPMA diblock copolymer worms indicate that these more delicate nanostructures do not survive even these mild conditions. PMID:27795581

The self-assembly of particles with isotropic interactions: Using DNA coated colloids to create designer nanomaterials

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

Thompson, R. B.; Dion, S.; Konigslow, K. von

Self-consistent field theory equations are presented that are suitable for use as a coarse-grained model for DNA coated colloids, polymer-grafted nanoparticles and other systems with approximately isotropic interactions. The equations are generalized for arbitrary numbers of chemically distinct colloids. The advantages and limitations of such a coarse-grained approach for DNA coated colloids are discussed, as are similarities with block copolymer self-assembly. In particular, preliminary results for three species self-assembly are presented that parallel results from a two dimensional ABC triblock copolymer phase. The possibility of incorporating crystallization, dynamics, inverse statistical mechanics and multiscale modelling techniques are discussed.

Fiber lubrication: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Liu, Hongyi

Molecular and mesoscopic level description of friction and lubrication remains a challenge because of difficulties in the phenomenological understanding of to the behaviors of solid-liquid interfaces during sliding. Fortunately, there is the computational simulation approach opens an opportunity to predict and analyze interfacial phenomena, which were studied with molecular dynamics (MD) and mesoscopic dynamics (MesoDyn) simulations. Polypropylene (PP) and cellulose are two of most common polymers in textile fibers. Confined amorphous surface layers of PP and cellulose were built successfully with xenon crystals which were used to compact the polymers. The physical and surface properties of the PP and cellulose surface layers were investigated by MD simulations, including the density, cohesive energy, volumetric thermal expansion, and contact angle with water. The topology method was employed to predict the properties of poly(alkylene glycol) (PAG) diblock copolymers and Pluronic triblock copolymers used as lubricants on surfaces. Density, zero shear viscosity, shear module, cohesive energy and solubility parameter were predicted with each block copolymer. Molecular dynamics simulations were used to study the interaction energy per unit contact area of block copolymer melts with PP and cellulose surfaces. The interaction energy is defined as the ratio of interfacial interaction energy to the contact area. Both poly(proplene oxide) (PPO) and poly(ethylene oxide) (PEO) segments provided a lipophilic character to both PP and cellulose surfaces. The PPO/PEO ratio and the molecular weight were found to impact the interaction energy on both PP and cellulose surfaces. In aqueous solutions, the interaction energy is complicated due to the presence of water and the cross interactions between the multiple molecular components. The polymer-water-surface (PWS) calculation method was proposed to calculate such complex systems. In a contrast with a vacuum condition, the presence of water increases the attractive interaction energy of the diblock copolymer on the cellulose surface, compared with that on the PP surface. Water decreases the interaction energy of the triblock copolymer on the cellulose surface, compared with that on the PP surface. MesoDyn was adopted to investigate the self-assembled morphology of the triblock copolymer, in aqueous solution, confined and sheared at solid-liquid interfaces. In a bulk aqueous solution, when the polymer concentration reached 10% v/v, micelles were observed with PPO blocks in the core and PEO blocks in the shell of the micelles. At the concentrations of 25% and 50%, worm-like micelles and irregular cylinders were observed in solutions, respectively. The micelles were formed faster in aqueous solutions confined by cellulose surfaces than that in the bulk. The formed micelles were broken under shearing, which led to a depletion of polymers at the interfaces. During the shearing on the PP surfaces, the polymers were adsorbed on the surfaces protecting the PP surfaces. This simulation study in the fiber lubrication was in good agreement with the experimental results and so provided an approach to visualize the polymer configuration at the liquid-solid interface, predict the lubricant-surface systems, and theoretically guide the experiments of designing new/efficient lubricants for fibers.

Polydispersity effects in poly(isoprene-b-styrene-b-ethylene oxide) triblock terpolymers

NASA Astrophysics Data System (ADS)

Meuler, Adam J.; Ellison, Christopher J.; Qin, Jian; Evans, Christopher M.; Hillmyer, Marc A.; Bates, Frank S.

2009-06-01

Four hydroxyl-terminated poly(isoprene-b-styrene) diblock copolymers with comparable molecular weights and compositions (equivalent volume fractions of polyisoprene and polystyrene) but different polystyrene block polydispersity indices (Mw/Mn=1.06,1.16,1.31,1.44) were synthesized by anionic polymerization using either sec-butyllithium or the functional organolithium 3-triisopropylsilyloxy-1-propyllithium. Poly(ethylene oxide) (PEO) blocks were grown from the end of each of these parent diblocks to yield four series of poly(isoprene-b-styrene-b-ethylene oxide) (ISO) triblock terpolymers that were used to interrogate the effects of varying the polydispersity of the middle bridged polystyrene block. In addition to the neat triblock samples, 13 multicomponent blends were prepared at four different compositions from the ISO materials containing a polystyrene segment with Mw/Mn=1.06; these blends were used to probe the effects of increasing the polydispersity of the terminal PEO block. The melt-phase behavior of all samples was characterized using small-angle X-ray scattering and dynamic mechanical spectroscopy. Numerous polydispersity-driven morphological transitions are reported, including transitions from lamellae to core-shell gyroid, from core-shell gyroid to hexagonally packed cylinders, and from network morphologies [either O70 (the orthorhombic Fddd network) or core-shell gyroid] to lamellae. Domain periodicities and order-disorder transition temperatures also vary with block polydispersities. Self-consistent field theory calculations were performed to supplement the experimental investigations and help elucidate the molecular factors underlying the polydispersity effects. The consequences of varying the polydispersity of the terminal PEO block are comparable to the polydispersity effects previously reported in AB diblock copolymers. Namely, domain periodicities increase with increasing polydispersity and domain interfaces tend to curve toward polydisperse blocks. The changes in phase behavior that are associated with variations in the polydispersity of the middle bridged polystyrene block, however, are not analogous to those reported in AB diblock copolymers, as increases in this middle block polydispersity are not always accompanied by (i) increased domain periodicities and (ii) a tendency for domain interfaces to curve toward the polydisperse domain. These results highlight the utility of polydispersity as a tool to tune the phase behavior of ABC block terpolymers.

Square and Rectangular Arrays from Directed Assembly of Sphere-forming Diblock Copolymers in Thin Films

NASA Astrophysics Data System (ADS)

Ji, Shengxiang; Nagpal, Umang; Liao, Wen; de Pablo, Juan; Nealey, Paul

2010-03-01

Patterns of square and rectangular arrays with nanoscale dimensions are scientifically and technologically important. Fabrication of square array patterns in thin films has been demonstrated by directed assembly of cylinder-forming diblock copolymers on chemically patterned substrates, supramolecular assembly of diblock copolymers, and self-assembly of triblock terpolymers. However, a macroscopic area of square array patterns with long-range order has not been achieved, and the fabrication of rectangular arrays has not been reported so far. Here we report a facile approach for fabricating patterns of square and rectangular arrays by directing the assembly of sphere-forming diblock copolymers on chemically patterned substrates. On stripe patterns, a square arrangement of half spheres, corresponding to the (100) plane of the body-centred cubic (BCC) lattice, formed on film surfaces. When the underlying pattern periods mismatched with the copolymer period, the square pattern could be stretched (up to ˜60%) or compressed (˜15%) to form rectangular arrays. Monte Carlo simulations have been further used to verify the experimental results and the 3-dimensional arrangements of spheres.

Directed Self-Assembly of Triblock Copolymer on Chemical Patterns for Sub-10-nm Nanofabrication via Solvent Annealing.

PubMed

Xiong, Shisheng; Wan, Lei; Ishida, Yoshihito; Chapuis, Yves-Andre; Craig, Gordon S W; Ruiz, Ricardo; Nealey, Paul F

2016-08-23

Directed self-assembly (DSA) of block copolymers (BCPs) is a leading strategy to pattern at sublithographic resolution in the technology roadmap for semiconductors and is the only known solution to fabricate nanoimprint templates for the production of bit pattern media. While great progress has been made to implement block copolymer lithography with features in the range of 10-20 nm, patterning solutions below 10 nm are still not mature. Many BCP systems self-assemble at this length scale, but challenges remain in simultaneously tuning the interfacial energy atop the film to control the orientation of BCP domains, designing materials, templates, and processes for ultra-high-density DSA, and establishing a robust pattern transfer strategy. Among the various solutions to achieve domains that are perpendicular to the substrate, solvent annealing is advantageous because it is a versatile method that can be applied to a diversity of materials. Here we report a DSA process based on chemical contrast templates and solvent annealing to fabricate 8 nm features on a 16 nm pitch. To make this possible, a number of innovations were brought in concert with a common platform: (1) assembling the BCP in the phase-separated, solvated state, (2) identifying a larger process window for solvated triblock vs diblock BCPs as a function of solvent volume fraction, (3) employing templates for sub-10-nm BCP systems accessible by lithography, and (4) integrating a robust pattern transfer strategy by vapor infiltration of organometallic precursors for selective metal oxide synthesis to prepare an inorganic hard mask.

Anomalistic Self-Assembled Phase Behavior of Block Copolymer Blended with Organic Derivative Depending on Temperature

DOE PAGES

Kim, Tae-Hwan; Kim, Eunhye; Do, Changwoo; ...

2016-08-16

Amphiphilic Pluronic block copolymers have attracted great attention in a broad spectrum of potential applications due to the excellent phase behaviors in an aqueous solution, and many efforts have been made to investigate their phase behaviors under various external conditions. With a variety of external conditions, however, the closed looplike phase behaviors of a Pluronic block copolymer in an aqueous solution have not been reported yet. Herein, we report the closed looplike (CLL) phase behavior of a Pluronic P65 triblock copolymer blended with an organic derivative, 5-methylsalicylic acid (5mS), in aqueous solution, which is very unique for block copolymers. Asmore » the 5mS concentration increases, the isotropic to ordered phase or back to isotropic phase transition temperature is decreased while the number of closed loops is increased to two. To the best of our knowledge, this is the first demonstration of a CLL phase transition of a Pluronic block copolymer in an aqueous solution, which is readily applicable to optical devices such as optical sensors or optoelectronics, and nanotemplates for a highly ordered superlattice. Additionally, this provides new insight into the understanding on the phase behavior of a Pluronic block copolymer blended with additives.« less

Drug-conjugated PLA-PEG-PLA copolymers: a novel approach for controlled delivery of hydrophilic drugs by micelle formation.

PubMed

Danafar, H; Rostamizadeh, K; Davaran, S; Hamidi, M

2017-12-01

A conjugate of the antihypertensive drug, lisinopril, with triblock poly(lactic acid)-poly(ethylene glycol)-poly(lactic acid) (PLA-PEG-PLA) copolymer was synthesized by the reaction of PLA-PEG-PLA copolymer with lisinopril in the presence of dicyclohexylcarbodiimide and dimethylaminopyridine. The conjugated copolymer was characterized in vitro by hydrogen nuclear magnetic resonance (HNMR), Fourier transform infrared (FTIR), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) techniques. Then, the lisinopril conjugated PLA-PEG-PLA were self-assembled into micelles in aqueous solution. The resulting micelles were characterized further by various techniques such as dynamic light scattering (DLS) and atomic force microscopy (AFM). The results revealed that the micelles formed by the lisinopril-conjugated PLA-PEG-PLA have spherical structure with the average size of 162 nm. The release behavior of conjugated copolymer, micelles and micelles physically loaded by lisinopril were compared in different media. In vitro release study showed that in contrast to physically loaded micelles, the release rate of micelles consisted of the conjugated copolymer was dependent on pH of media where it was higher at lower pH compared to the neutral medium. Another feature of the conjugated micelles was their more sustained release profile compared to the lisinopril-conjugated copolymer and physically loaded micelles.

Evaluation of molecular volume change of block copolymer depending on temperature: A SANS study

DOE PAGES

Kim, Tae-Hwan; Do, Changwoo; Han, Young-Soo

2017-12-24

Amphiphilic Pluronic triblock copolymers form various self-assembled structures such as sphere, cylinder, lamellae and so on, depending on temperature, leading to the increase of hydrophobicity of block copolymers. However, the effective molecular volume change of the block copolymer has not been fully exploited yet, when temperature increases. Here in this paper, we have investigated the effective molecular volume change of the block copolymer upon heating by using the contrast variation small angle neutron scattering. The scattering length densities (SLDs) of the block copolymer were experimentally obtained from the neutron scattering contrast variation method between the solvent and the block copolymermore » at varying temperature. Even though the SLD, which is the intrinsic property of the material, should not be changed by temperature elevation, it was dependent on temperature, indicating that the molecular volume is changed. Therefore, we obtained the increase rate of the molecular volume change of the block copolymer (the effective molecular volume change) from the comparison of the calculated SLD and the standard SLD, which is evaluated by plotting the SANS intensity at the first order Bragg peak as the function of temperature at each volume fraction of D 2O and H 2O that is about 25.5%–51.3% depending on temperature.« less

Evaluation of molecular volume change of block copolymer depending on temperature: A SANS study

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

Kim, Tae-Hwan; Do, Changwoo; Han, Young-Soo

Amphiphilic Pluronic triblock copolymers form various self-assembled structures such as sphere, cylinder, lamellae and so on, depending on temperature, leading to the increase of hydrophobicity of block copolymers. However, the effective molecular volume change of the block copolymer has not been fully exploited yet, when temperature increases. Here in this paper, we have investigated the effective molecular volume change of the block copolymer upon heating by using the contrast variation small angle neutron scattering. The scattering length densities (SLDs) of the block copolymer were experimentally obtained from the neutron scattering contrast variation method between the solvent and the block copolymermore » at varying temperature. Even though the SLD, which is the intrinsic property of the material, should not be changed by temperature elevation, it was dependent on temperature, indicating that the molecular volume is changed. Therefore, we obtained the increase rate of the molecular volume change of the block copolymer (the effective molecular volume change) from the comparison of the calculated SLD and the standard SLD, which is evaluated by plotting the SANS intensity at the first order Bragg peak as the function of temperature at each volume fraction of D 2O and H 2O that is about 25.5%–51.3% depending on temperature.« less

Anomalistic Self-Assembled Phase Behavior of Block Copolymer Blended with Organic Derivative Depending on Temperature

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

Kim, Tae-Hwan; Kim, Eunhye; Do, Changwoo

Amphiphilic Pluronic block copolymers have attracted great attention in a broad spectrum of potential applications due to the excellent phase behaviors in an aqueous solution, and many efforts have been made to investigate their phase behaviors under various external conditions. With a variety of external conditions, however, the closed looplike phase behaviors of a Pluronic block copolymer in an aqueous solution have not been reported yet. Herein, we report the closed looplike (CLL) phase behavior of a Pluronic P65 triblock copolymer blended with an organic derivative, 5-methylsalicylic acid (5mS), in aqueous solution, which is very unique for block copolymers. Asmore » the 5mS concentration increases, the isotropic to ordered phase or back to isotropic phase transition temperature is decreased while the number of closed loops is increased to two. To the best of our knowledge, this is the first demonstration of a CLL phase transition of a Pluronic block copolymer in an aqueous solution, which is readily applicable to optical devices such as optical sensors or optoelectronics, and nanotemplates for a highly ordered superlattice. Additionally, this provides new insight into the understanding on the phase behavior of a Pluronic block copolymer blended with additives.« less

Controlled Synthesis of Polyenes by Catalytic Methods. Progress Report, December 1, 1992 -- November 30, 1993

DOE R&D Accomplishments Database

Schrock, R. R.

1993-12-01

Four studies are reported: living cyclopolymerization of diethyl dipropargylmalonate by Mo(CH-t-Bu)(NAr)[OCMe(CF{sub 3}){sub 2}]{sub 2} in dimethoxyethane, effect of chain length on conductivity of polyacetylene, nonlinear optical analysis of a series of triblock copolymers containing model polyenes, and synthesis of bifunctional hexafluoro-t-butoxide Mo species and their use as initiators in ROMP reactions.

Experimental and theoretical studies on inhibition of mild steel corrosion by some synthesized polyurethane tri-block co-polymers

PubMed Central

Kumar, Sudershan; Vashisht, Hemlata; Olasunkanmi, Lukman O.; Bahadur, Indra; Verma, Hemant; Singh, Gurmeet; Obot, Ime B.; Ebenso, Eno E.

2016-01-01

Polyurethane based tri-block copolymers namely poly(N-vinylpyrrolidone)-b-polyurethane-b-poly(N-vinylpyrrolidone) (PNVP-PU) and poly(dimethylaminoethylmethacrylate)-b-polyurethane-b-poly(dimethylaminoethylmethacrylate) (PDMAEMA-PU) were synthesized through atom transfer radical polymerization (ATRP) mechanism. The synthesized polymers were characterized using nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC) methods. The corrosion inhibition performances of the compounds were investigated on mild steel (MS) in 0.5 M H2SO4 medium using electrochemical measurements, surface analysis, quantum chemical calculations and molecular dynamic simulations (MDS). Potentiodynamic polarization (PDP) measurements revealed that the polymers are mixed-type corrosion inhibitors. Electrochemical impedance spectroscopy (EIS) measurements showed that the polymers inhibit MS corrosion by adsorbing on MS surface to form pseudo-capacitive interface. The inhibitive effects of the polymers increase with increasing concentration and decrease with increasing temperature. The adsorption of both the polymers on MS surface obey the Langmuir adsorption isotherm and involves both physisorption and chemisorption mechanisms. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses showed that the polymers formed protective film on MS surface and shield it from direct acid attack. Quantum chemical calculations and molecular dynamic simulations studies corroborate experimental results. PMID:27515383

Chemical Modification and Structure-property Relationships of Acrylic and Ionomeric Thermoplastic Elastomer Gels

NASA Astrophysics Data System (ADS)

Vargantwar, Pruthesh Hariharrao

Block copolymers (BCs) have remained at the forefront of materials research due to their versatility in applications ranging from hot-melt/pressure-sensitive adhesives and impact modifiers to compatibilizing agents and vibration-dampening/nanotemplating media. Of particular interest are macromolecules composed of two or more chemically dissimilar blocks covalently linked together to form triblock or pentablock copolymers. If the blocks are sufficiently incompatible and the copolymer behaves as a thermoplastic elastomer, the molecules can spontaneously self-assemble to form nanostructured materials that exhibit shape memory due to the formation of a supramolecular network. The BCs of these types are termed as conventional. When BCs contain blocks having ionic moieties such as sulfonic acid groups, they are termed as block ionomers. Designing new systems based on either conventional or ionic BCs, characterizing their structure-property relationships and later using them as electroacive polymers form the essential objectives of this work. Electroactive polymers (EAPs) exhibit electromechanical actuation when stimulated by an external electric field. In the first part of this work, it is shown that BCs resolve some of the outstanding problems presently encountered in the design of two different classes of EAP actuators: dielectric elastomers (DEs) and ionic polymer metal composites (IPMCs). All-acrylic triblock copolymer gels used as DEs actuate with high efficacy without any requirement of mechanical prestrain and, thus, eliminate the need for bulky and heavy hardware essential with prestrained dielectric actuators, as well as material problems associated with stress relaxation. The dependence of actuation behavior on gel morphology as evaluated from mechanical and microstructure studies is observed. In the case of IPMCs, ionic BCs employed in this study greatly facilitate processing compared to other contenders such as NafionRTM, which is commonly used in this class of EAPs. The unique copolymer investigated here (i) retains its mechanical integrity when highly solvated by polar solvents, (ii) demonstrates a high degree of actuation when tested in a cantilever configuration, and (iii) avoids the shortcomings of back-relaxation/overshoot within the testing conditions when used in combination with an appropriate solvent. In the second part of this work, two chemical strategies to design midblock sulfonated block ionomers are explored. In one case, selective sulfonation of the midblocks in triblock copolymers is achieved via a dioxane:sulfur trioxide chemistry, while in the other acetyl sulfate is used for the same purpose. Excellent control on the degree of sulfonation (DOS) is achieved. The block ionomers swell in different solvents while retaining their mechanical integrity. They show disorder-order, order-order, and order-reduced order morphological transitions as DOS varies. These transitions in morphologies are reflected in their thermal behavior as well. The microstructures show periodicity, which is, again, a function of DOS. The transitions are explained in terms of the molar volume expansion and volume densification of the blocks on sulfonation. The ionic levels, morphology and periodicity in microstructure are important for applications such as actuators, sensors and fuel cell membranes. The ability to tune these aspects in the ionomers designed in this work make them potential candidates for these applications.

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

Lee, Li -Chen; Lu, Jie; Weck, Marcus

In shell cross-linked micelles (SCMs) containing acid sites in the shell and base sites in the core are prepared from amphiphilic poly(2-oxazoline) triblock copolymers. These materials are utilized as two-chamber nanoreactors for a prototypical acid-base bifunctional tandem deacetalization-nitroaldol reaction. Furthermore, the acid and base sites are localized in different regions of the micelle, allowing the two steps in the reaction sequence to largely proceed in separate compartments, akin to the compartmentalization that occurs in biological systems.

Controlled Thermoresponsive Hydrogels by Stereocomplexed PLA-PEG-PLA Prepared via Hybrid Micelles of Pre-Mixed Copolymers with Different PEG Lengths

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

Abebe, Daniel G.; Fujiwara, Tomoko

2012-09-05

The stereocomplexed hydrogels derived from the micelle mixture of two enantiomeric triblock copolymers, PLLA-PEG-PLLA and PDLA-PEG-PDLA, reported in 2001 exhibited sol-to-gel transition at approximately body temperature upon heating. However, the showed poor storage modulus (ca. 1000 Pa) determined their insufficiency as injectable implant biomaterials for many applications. In this study, the mechanical property of these hydrogels was significantly improved by the modifications of molecular weights and micelle structure. Co-micelles composed of block copolymers with two sizes of PEG block length were shown to possess unique and dissimilar properties from the micelles composed of single-sized block copolymers. The stereomixture of PLA-PEG-PLAmore » comicelles showed a controllable sol-to-gel transition at a wide temperature range of 4 and 80 C. The sol-gel phase diagram displays a linear relationship of temperature versus copolymer composition; hence, a transition at body temperature can be readily achieved by adjusting the mixed copolymer ratio. The resulting thermoresponsive hydrogels exhibit a storage modulus notably higher (ca. 6000 Pa) than that of previously reported hydrogels. As a physical network solely governed by self-reorganization of micelles, followed by stereocomplexation, this unique system offers practical, safe, and simple implantable biomaterials.« less

Formation of ordered microphase-separated pattern during spin coating of ABC triblock copolymer.

PubMed

Huang, Weihuan; Luo, Chunxia; Zhang, Jilin; Han, Yanchun

2007-03-14

In this paper, the authors have systematically studied the microphase separation and crystallization during spin coating of an ABC triblock copolymer, polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO). The microphase separation of PS-b-P2VP-b-PEO and the crystallization of PEO blocks can be modulated by the types of the solvent and the substrate, the spinning speed, and the copolymer concentration. Ordered microphase-separated pattern, where PEO and P2VP blocks adsorbed to the substrate and PS blocks protrusions formed hexagonal dots above the P2VP domains, can only be obtained when PS-b-P2VP-b-PEO is dissolved in N,N-dimethylformamide and the films are spin coated onto the polar substrate, silicon wafers or mica. The mechanism of the formation of regular pattern by microphase separation is found to be mainly related to the inducement of the substrate (middle block P2VP wetting the polar substrate), the quick vanishment of the solvent during the early stage of the spin coating, and the slow evaporation of the remaining solvent during the subsequent stage. On the other hand, the probability of the crystallization of PEO blocks during spin coating decreases with the reduced film thickness. When the film thickness reaches a certain value (3.0 nm), the extensive crystallization of PEO is effectively prohibited and ordered microphase-separated pattern over large areas can be routinely prepared. When the film thickness exceeds another definite value (12.0 nm), the crystallization of PEO dominates the surface morphology. For films with thickness between these two values, microphase separation and crystallization can simultaneously occur.

Beyond Simple AB Diblock Copolymers: Application of Bifunctional and Trifunctional RAFT Agents to PISA in Water.

PubMed

Mellot, Gaëlle; Beaunier, Patricia; Guigner, Jean-Michel; Bouteiller, Laurent; Rieger, Jutta; Stoffelbach, François

2018-06-20

The influence of the macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agent architecture on the morphology of the self-assemblies obtained by aqueous RAFT dispersion polymerization in polymerization-induced self-assembly (PISA) is studied by comparing amphiphilic AB diblock, (AB) 2 triblock, and triarm star-shaped (AB) 3 copolymers, constituted of N,N-dimethylacrylamide (DMAc = A) and diacetone acrylamide (DAAm = B). Symmetrical triarm (AB) 3 copolymers could be synthesized for the first time in a PISA process. Spheres and higher order morphologies, such as worms or vesicles, could be obtained for all types of architectures and the parameters that determine their formation have been studied. In particular, we found that the total DP n of the PDMAc and the PDAAm segments, i.e., the same overall molar mass, at the same M n (PDMAc)/M n (PDAAm) ratio, rather than the individual length of the arms determined the morphologies for the linear (AB) 2 and star shaped (AB) 3 copolymers obtained by using the bi- and trifunctional macro-RAFT agents. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fatigue crack propagation in self-assembling nanocomposites

NASA Astrophysics Data System (ADS)

Klingler, Andreas; Wetzel, Bernd

2016-05-01

Self-assembling block-copolymers allow the easy manufacturing of nanocomposites due to the thermodynamically driven in situ formation of nanosized phases in thermosetting resins during the curing process. Complex mechanical dispersion processes can be avoided. The current study investigates the effect of a block-copolymer on the fatigue crack propagation resistance of a cycloaliphatic amine cured epoxy resin. It was found that a small amount of MAM triblock-copolymer significantly increases the resistance to fatigue crack propagation of epoxy. Crack growth rate and the Paris law exponent for fatigue-crack growth were considerably reduced from m=15.5 of the neat epoxy to m=8.1 of the nanocomposite. To identify the related reinforcing and fracture mechanisms structural analyses of the fractured surfaces were performed by scanning electron microscope. Characteristic features were identified to be deformation, debonding and fracture of the nano-phases as well as crack pinning. However, the highest resistance against fatigue crack propagation was achieved in a bi-continuous microstructure that consisted of an epoxy-rich phase with embedded submicron sized MAM inclusions, and which was surrounded by a block-copolymer-rich phase that showed rupture and plastic deformation.

PLGA-PEG-PLGA hydrogel for ocular drug delivery of dexamethasone acetate.

PubMed

Gao, Yuan; Sun, Yan; Ren, Fuzheng; Gao, Shen

2010-10-01

This study aims to investigate the suitability of thermosensitive triblock polymer poly-(DL-lactic acid-co-glycolic acid) (PLGA)-polyethylene glycol (PEG)-PLGA as a matrix material for ocular delivery of dexamethasone acetate (DXA). The copolymer was synthesized and evaluated for its thermosensitive and gelation properties. DXA in situ gel-forming solution based on PLGA-PEG-PLGA copolymer of 20% (w/w) was prepared and evaluated for ocular pharmacokinetics in rabbit according to the microdialysis method, which was compared to the normal eye drop. The copolymer with 20% (w/w) had a low critical solution temperature of 32 degrees C, which is close to the surface temperature of the eye. The C(max) of DXA in the anterior chamber for the PLGA-PEG-PLGA solution was 125.2 microg/mL, which is sevenfold higher than that of the eye drop, along with greater area under the concentration-time curves (AUC). These results suggest that the PLGA-PEG-PLGA copolymer is potential thermosensitive in situ gel-forming material for ocular drug delivery, and it may improve the bioavailability, efficacy of some eye drugs.

Two-dimensional phase separated structures of block copolymers on solids

NASA Astrophysics Data System (ADS)

Sen, Mani; Jiang, Naisheng; Endoh, Maya; Koga, Tadanori; Ribbe, Alexander

The fundamental, yet unsolved question in block copolymer (BCP) thin films is the self-organization process of BCPs at the solid-polymer melt interface. We here focus on the self-organization processes of cylinder-forming polystyrene-block-poly (4-vinylpyridine) diblock copolymer and lamellar-forming poly (styrene-block-butadiene-block-styrene) triblock copolymer on Si substrates as model systems. In order to reveal the buried interfacial structures, the following experimental protocols were utilized: the BCP monolayer films were annealed under vacuum at T>Tg of the blocks (to equilibrate the melts); vitrification of the annealed BCP films via rapid quench to room temperature; subsequent intensive solvent leaching (to remove unadsorbed chains) with chloroform, a non-selective good solvent for the blocks. The strongly bound BCP layers were then characterized by using atomic force microscopy, scanning electron microscopy, grazing incidence small angle X-ray scattering, and X-ray reflectivity. The results showed that both blocks lie flat on the substrate, forming the two-dimensional, randomly phase-separated structure irrespective of their microdomain structures and interfacial energetics. Acknowledgement of financial support from NSF Grant (CMMI -1332499).

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

Schmitt, Adam K.; Mahanthappa, Mahesh K.

Using a combination of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), we document the composition-dependent morphologies of 39 new poly(lactide-block-1,4-butadiene-block-lactide) (LBL) block polymers, comprising a broad dispersity B segment (Mn = 4.5–17.7 kg/mol;more » $$\\def\\eth{{\\specialfont\\char238}}$$ = Mw/Mn = 1.72–1.88) and narrow dispersity L end blocks (Mn = 0.6–15.3 kg/mol; $$\\def\\eth{{\\specialfont\\char238}}$$ = 1.10–1.21) with volume fractions 0.26 ≤ fB ≤ 0.95. A subset of these samples undergo melt self-assembly into cylindrical, lamellar, and apparently bicontinuous morphologies. By assessing the states of order and disorder in these triblock polymer melts using temperature-dependent SAXS, we find that broad B segment dispersity increases the minimum segregation strength χN ≳ 27 required for LBL triblock self-assembly relative to the self-consistent mean-field theory prediction χN ≥ 17.9 for narrow dispersity analogues. While B segment dispersity has previously been shown to thermodynamically stabilize the self-assembled morphologies of low χ/high N ABA triblocks, the present study indicates that broad B block dispersity in related high χ/low N systems destabilizes the microphase-separated melt. These observations are rationalized in terms of recent theories that suggest that broad segmental dispersity substantially enhances fluctuation effects at low N, thus disfavoring melt segregation.« less

Imparting large macroscopic changes with small changes in polypeptide composition

NASA Astrophysics Data System (ADS)

Sing, Michelle; McKinley, Gareth; Olsen, Bradley

Block copolymers composed of polypeptides provide an excellent platform for exploring the underlying physics surrounding macroscopic associative network behavior. Previous work in our group has elucidated a difference in the mechanical properties of two nearly identical elastin-like polypeptide (ELP) endblocks. In poly(ELP)s, this substitution is known to result in tighter beta turns. These beta turns exhibit slower responses to changes in temperature within the material. Under shear, the modulus for the alanine-containing ELP triblock is almost three times higher than the glycine-containing ELP. Additionally, preliminary tensile tests show higher stress and strain at break for the alanine ELP triblock. We are able to explain the reasons for this behavior using a variety of spectroscopic and analytical techniques. Small angle neutron and x-ray scattering indicate differences in ordering between the alanine and glycine containing ELP materials both in shear and in stagnant flow.

Photoluminescence and solid state properties of rigid pi- conjugated polymers with applications to LED: Alkyl- substituted p-phenyleneethynylene polymers and triblock copolymers

NASA Astrophysics Data System (ADS)

Huang, Wen-Yao

A series of substituted poly(p-phenyleneethynylene)s, PPE, were synthesized by alkyne metathesis. The substituents dibutyl (a), dioctyl (b), ditetradecyl (c), di-2-ethylhexyl (d) and di-2-cyclohexylethyl; (e)were placed on the 2,5 positions of the phenyl rings. X-ray diffraction studies indicated that the main chains of each polymer were arranged in regular, layered arrays. Liquid crystalline structures were observed by polarized optical microscopy in PPE 4b, 4c and 4d. The temperatures of isotropization of the liquid crystalline structures coincided with the disordering temperatures determined by differential scanning calorimetry. The UV absorption spectra showed a gradual blue shift of the λmax for all these polymers, suggesting a decrease in the electronic delocalization along the chain as the size and geometry of the side group changed. The photoluminescence spectra in dilute toluene solutions are consistent with vibronic coupling and emission from localized excited states. The emission spectra of thin films show characteristics typical of excimer or aggregate formation in the solid state. Lastly, an improved method of molecular weight determination by end group analysis was devised. Molecular organization and orientation in thin films (~100 nm) of a triblock copolymer, PPEPEG, was studied. The morphology of the thin film can be visualized as consisting of PMMA as the major phase in which domains of vertically oriented triblock copolymers are dispersed with PEG groups facing the air-film interface. The molecular and supramolecular structure of a series of well-defined fully conjugated poly(2,5- diakyl-p-phenyleneethynylene)s, PPE, in toluene has been studied in the sol state and in the gel state by surface tension and photoluminescence measurements. Poly (2,6[4- phenyl quinoline]), I, and poly (2,6[p-phenylene] 4- phenyl quinoline), II, were synthesized by the self- condensation of 5-acetyl-2-aminobezophenone and 4-amino- 4 '-acetyl-3-benzoyl biphenyl, respectively. They were soluble in acidic solvents. The fluorescent properties of I and II were investigated as a function of concentration in HCOOH, CCl2HCOOH, and CH 3SO3H solutions. Silica sol was used as nanoscale glue to prepare composite gels. (Abstract shortened by UMI.)

Effects of nanoparticles on the compatibility of PEO-PMMA block copolymers.

PubMed

Mu, Dan; Li, Jian-Quan; Li, Wei-Dong; Wang, Song

2011-12-01

The compatibility of six kinds of designed poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) copolymers was studied at 270, 298 and 400 K via mesoscopic modeling. The values of the order parameters depended on both the structures of the block copolymers and the simulation temperature, while the values of the order parameters of the long chains were higher than those of the short ones; temperature had a more obvious effect on long chains than on the short ones. Plain copolymers doped with poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA) homopolymer showed different order parameter values. When a triblock copolymer had the same component at both ends and was doped with one of its component polymers as a homopolymer (such as A5B6A5 doped with B6 or A5 homopolymer), the value of its order parameter depended on the simulation temperature. The highest order parameter values were observed for A5B6A5 doped with B6 at 400 K and for A5B6A5 doped with A5 at 270 K. A study of copolymers doped with nanoparticles showed that the mesoscopic phase was influenced by not only the properties of the nanoparticles, such as the size and density, but also the compositions of the copolymers. Increasing the size of the nanoparticles used as a dopant had the most significant effect on the phase morphologies of the copolymers.

Tailored biodegradable triblock copolymer coatings obtained by MAPLE: a parametric study

NASA Astrophysics Data System (ADS)

Brajnicov, S.; Neacsu, P.; Moldovan, A.; Marascu, V.; Bonciu, A.; Ion, R.; Dinca, V.; Cimpean, A.; Dinescu, M.

2017-11-01

Biocompatible and biodegradable coatings with controllable and tailored chemical and physical characteristics (i.e. morphology and roughness) are of great interest in bone related research applications. Within this research direction, in this work, a series of novel biodegradable coatings based on triblock copolymers poly(lactide- co-caprolactone)-block-poly(ethylene-glycol)-block-poly(lactide- co-caprolactone) (PLCL-PEG-PLCL) were obtained by matrix-assisted pulsed laser evaporation (MAPLE) and their morphological characteristics and roughness were modulated by varying target composition and laser fluence. The coatings were used for preliminary in vitro testing with MC3T3-E1 pre-osteoblasts. It was found that for a specific range of fluences, the main functional groups in the MAPLE-deposited thin films, as determined by Fourier transform infrared spectroscopy, are similar to the molecular structures of the initial material. Depending on the deposition parameters, significant changes in morphologies, i.e. material accumulation in the form of droplets, wrinkles, or carpet-like structures were revealed by atomic force microscopy (AFM) and scanning electron microscopy. The optimized coating characteristics were further correlated to MC3T3-E1 pre-osteoblasts response. The ability to control the morphology and to maintain unaltered the chemistry of the deposited material through MAPLE is an important step in creating functional bio-interfaces in the field of biomedical research and tissue engineering.

Self-Assembled CNT-Polymer Hybrids in Single-Walled Carbon Nanotubes Dispersed Aqueous Triblock Copolymer Solutions

NASA Astrophysics Data System (ADS)

Vijayaraghavan, D.; Manjunatha, A. S.; Poojitha, C. G.

2018-04-01

We have carried out scanning electron microscopy (SEM), differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS), electrical conductivity, and 1H NMR studies as a function of temperature on single-walled carbon nanotubes (SWCNTs) dispersed aqueous triblock copolymer (P123) solutions. The single-walled carbon nanotubes in this system aggregate to form bundles, and the bundles aggregate to form net-like structures. Depending on the temperature and phases of the polymer, this system exhibits three different self-assembled CNT-polymer hybrids. We find CNT-unimer hybrid at low temperatures, CNT-micelle hybrid at intermediate temperatures wherein the polymer micelles are adsorbed in the pores of the CNT nets, and another type of CNT-micelle hybrid at high temperatures wherein the polymer micelles are adsorbed on the surface of the CNT bundles. Our DSC thermogram showed two peaks related to these structural changes in the CNT-polymer hybrids. Temperature dependence of the 1H NMR chemical shifts of the molecular groups of the polymer and the AC electrical conductivity of the composite also showed discontinuous changes at the temperatures at which the CNT-polymer hybrid's structural changes are seen. Interestingly, for a higher CNT concentration (0.5 wt.%) in the system, the aggregated polymer micelles adsorbed on the CNTs exhibit cone-like and cube-like morphologies at the intermediate and at high temperatures respectively.

Polydispersity-Driven Block Copolymer Amphiphile Self-Assembly into Prolate-Spheroid Micelles

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

Schmitt, Andrew L.; Repollet-Pedrosa, Milton H.; Mahanthappa, Mahesh K.

The aqueous self-assembly behavior of polydisperse poly(ethylene oxide-b-1,4-butadiene-b-ethylene oxide) (OBO) macromolecular triblock amphiphiles is examined to discern the implications of continuous polydispersity in the hydrophobic block on the resulting aqueous micellar morphologies of otherwise monodisperse polymer surfactants. The chain length polydispersity and implicit composition polydispersity of these samples furnishes a distribution of preferred interfacial curvatures, resulting in dilute aqueous block copolymer dispersions exhibiting coexisting spherical and rod-like micelles with vesicles in a single sample with a O weight fraction, w{sub O}, of 0.18. At higher w{sub O} = 0.51-0.68, the peak in the interfacial curvature distribution shifts and we observemore » the formation of only American football-shaped micelles. We rationalize the formation of these anisotropically shaped aggregates based on the intrinsic distribution of preferred curvatures adopted by the polydisperse copolymer amphiphiles and on the relief of core block chain stretching by chain-length-dependent intramicellar segregation.« less

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

Ertem, S. Piril; Caire, Benjamin R.; Tsai, Tsung-Han

Anion exchange membranes (AEMs) are a promising class of materials for applications that require selective ion transport, such as fuel cells, water purification, and electrolysis devices. Studies of structure–morphology–property relationships of ion-exchange membranes revealed that block copolymers exhibit improved ion conductivity and mechanical properties due to their microphase-separated morphologies with well-defined ionic domains. While most studies focused on symmetric diblock or triblock copolymers, here, the first example of a midblock quaternized pentablock AEM is presented. A symmetric ABCBA pentablock copolymer was functionalized to obtain a midblock brominated polymer. Solution cast films were then quaternized to obtain AEMs with resulting ionmore » exchange capacities (IEC) ranging from 0.4 to 0.9 mmol/g. Despite the relatively low IEC, the polymers were highly conductive (up to 60 mS/cm Br2 at 90 8C and 95%RH) with low water absorption (<25 wt %) and maintained adequate mechanical properties in both dry and hydrated conditions. Xray scattering and transmission electron microscopy (TEM) revealed formation of cylindrical non-ionic domains in a connected ionic phase.« less

Anomalous Micellization of Pluronic Block Copolymers

NASA Astrophysics Data System (ADS)

Leonardi, Amanda; Ryu, Chang Y.

2014-03-01

Poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, commercially known as Pluronics, are a unique family of amphiphilic triblock polymers, which self-assemble into micelles in aqueous solution. These copolymers have shown promise in therapeutic, biomedical, cosmetic, and nanotech applications. As-received samples of Pluronics contain low molecular weight impurities (introduced during the manufacturing and processing), that are ignored in most applications. It has been observed, however, that in semi-dilute aqueous solutions, at concentrations above 1 wt%, the temperature dependent micellization behavior of the Pluronics is altered. Anomalous behavior includes a shift of the critical micellization temperature and formation of large aggregates at intermediate temperatures before stable sized micelles form. We attribute this behavior to the low molecular weight impurities that are inherent to the Pluronics which interfere with the micellization process. Through the use of Dynamic Light Scattering and HPLC, we compared the anomalous behavior of different Pluronics of different impurity levels to their purified counterparts.

Onion-like microspheres with tricomponent from gelable triblock copolymers.

PubMed

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

2010-06-01

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

Adjustable bridge blocks make huge difference to the self-assembly of multiblock copolymers

NASA Astrophysics Data System (ADS)

Li, Weihua

We present theoretical studies on two types of multiblock copolymers, whose self-assemblies lead to a lot of novel ordered nanostructures. The first example is BABCB multiblock terpolymer, where A- and C-blocks separately aggregate into isolated domains and the three B-blocks with adjustable lengths form the matrix. As a result, the middle B-block forms a natural bridge connecting A- and C-domains. In contrast to ABC, the BABCB can form many binary spherical and cylindrical phases with tunable coordination numbers. In addition, the ABCB solution can form a lot of planet-satellite micellar superstructures with tunable number of satellites that varies from 3 to 20. The another system is AB-type multiblock copolymers. In contrast to the above system, there is no natural bridge. Accordingly, we introduce multiple arms into the architecture which tend to partition themselves into different domains to maximize their configurational entropy, thus forming effective bridges. Furthermore, each arm is devised as BAB triblock to enable adjustable length of bridges. With this copolymer, we predict a few non-classical ordered phases, including a square array cylinder. Our study opens the possibilities of fabricating desired nanostructures using designed block copolymers. National Natural Science Foundation of China (No. 21322407, 21574026).

Acid–base bifunctional shell cross-linked micelle nanoreactor for one-pot tandem reaction

DOE PAGES

Lee, Li -Chen; Lu, Jie; Weck, Marcus; ...

2015-12-29

In shell cross-linked micelles (SCMs) containing acid sites in the shell and base sites in the core are prepared from amphiphilic poly(2-oxazoline) triblock copolymers. These materials are utilized as two-chamber nanoreactors for a prototypical acid-base bifunctional tandem deacetalization-nitroaldol reaction. Furthermore, the acid and base sites are localized in different regions of the micelle, allowing the two steps in the reaction sequence to largely proceed in separate compartments, akin to the compartmentalization that occurs in biological systems.

Synthesis and studies of polypeptide materials: Self-assembled block copolypeptide amphiphiles, DNA-condensing block copolypeptides and membrane-interactive random copolypeptides

NASA Astrophysics Data System (ADS)

Wyrsta, Michael Dmytro

A new class of transition metal initiators for the controlled polymerization of alpha-aminoacid-N-carboxyanhydrides (alpha-NCAs), has been developed by Deming et al. This discovery has allowed for the synthesis of well-defined "protein-like" polymers. Using this chemistry we have made distinct block/random copolypeptides for biomedical applications. Drug delivery, gene delivery, and antimicrobial polymers were the focus of our research efforts. The motivation for the synthesis and study of synthetic polypeptide based materials comes from proteins. Natural proteins are able to adopt a staggeringly large amount of uniquely well-defined folded structures. These structures account for the diversity in properties of proteins. As catalysts (enzymes) natural proteins perform some of the most difficult chemistry with ease and precision at ambient pressures and temperatures. They also exhibit incredible structural properties that directly result from formation of complex hierarchical assemblies. Self-assembling block copolymers were synthesized with various compositions and architectures. In general, di- and tri-block amphiphiles were studied for their self-assembling properties. Both spherical and tubular vesicles were found to assemble from di- and tri-block amphiphiles, respectively. In addition to self-assembly, pH responsiveness was engineered into these amphiphiles by the incorporation of basic residues (lysine) into the hydrophobic block. Another form of self-assembly studied was the condensation of DNA using cationic block copolymers. It was found that cationic block copolymers could condense DNA into compact, ordered, water-soluble aggregates on the nanoscale. These aggregates sufficiently protected DNA from nucleases and yet were susceptible to proteases. These studies form the basis of a gene delivery platform. The ease with which NCAs are polymerized renders them completely amenable to parallel synthetic methods. We have employed this technique to discover new antimicrobial polypeptides. The polymers studied were themselves the antimicrobial agent, not a self-assembled aggregate that contained antibiotics. It was found that powerful antibacterial polymers could be readily prepared with simple binary compositions. Antibacterial activity was sensitive to copolymer composition, bacterial cell-wall type, and insensitive to chain length (within reason).

Fatigue crack propagation in self-assembling nanocomposites

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

Klingler, Andreas; Wetzel, Bernd

Self-assembling block-copolymers allow the easy manufacturing of nanocomposites due to the thermodynamically driven in situ formation of nanosized phases in thermosetting resins during the curing process. Complex mechanical dispersion processes can be avoided. The current study investigates the effect of a block-copolymer on the fatigue crack propagation resistance of a cycloaliphatic amine cured epoxy resin. It was found that a small amount of MAM triblock-copolymer significantly increases the resistance to fatigue crack propagation of epoxy. Crack growth rate and the Paris law exponent for fatigue-crack growth were considerably reduced from m=15.5 of the neat epoxy to m=8.1 of the nanocomposite.more » To identify the related reinforcing and fracture mechanisms structural analyses of the fractured surfaces were performed by scanning electron microscope. Characteristic features were identified to be deformation, debonding and fracture of the nano-phases as well as crack pinning. However, the highest resistance against fatigue crack propagation was achieved in a bi-continuous microstructure that consisted of an epoxy-rich phase with embedded submicron sized MAM inclusions, and which was surrounded by a block-copolymer-rich phase that showed rupture and plastic deformation.« less

(Electro)Mechanical Properties of Olefinic Block Copolymers

NASA Astrophysics Data System (ADS)

Spontak, Richard

2014-03-01

Conventional styrenic triblock copolymers (SBCs) swollen with a midblock-selective oil have been previously shown to exhibit excellent electromechanical properties as dielectric elastomers. In this class of electroactive polymers, compliant electrodes applied as active areas to opposing surfaces of an elastomer attract each other, and thus compress the elastomer due to the onset of a Maxwell stress, upon application of an external electric field. This isochoric process is accompanied by an increase in lateral area, which yields the electroactuation strain (measuring beyond 300% in SBC systems). Performance parameters such as the Maxwell stress, transverse strain, dielectric breakdown, energy density and electromechanical efficiency are determined directly from the applied electric field and resulting electroactuation strain. In this study, the same principle used to evaluate SBC systems is extended to olefinic block copolymers (OBCs), which can be described as randomly-coupled multiblock copolymers that consist of crystallizable polyethylene hard segments and rubbery poly(ethylene-co-octene) soft segments. Considerations governing the development of a methodology to fabricate electroresponsive OBC systems are first discussed for several OBCs differing in composition and bulk properties. Evidence of electroactuation in selectively-solvated OBC systems is presented and performance metrics measured therefrom are quantitatively compared with dielectric elastomers derived from SBC and related materials.

Influence of water-insoluble nonionic copolymer E(6)P(39)E(6) on the microstructure and self-aggregation dynamics of aqueous SDS solution-NMR and SANS investigations.

PubMed

Prameela, G K S; Phani Kumar, B V N; Aswal, V K; Mandal, Asit Baran

2013-10-28

The influence of water-insoluble nonionic triblock copolymer PEO-PPO-PEO [poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)] i.e., E6P39E6 with molecular weight 2800, on the microstructure and self-aggregation dynamics of anionic surfactant sodium dodecylsulfate (SDS) in aqueous solution (D2O) were investigated using high resolution nuclear magnetic resonance (NMR) and small-angle neutron scattering (SANS) measurements. Variable concentration and temperature proton ((1)H), carbon ((13)C) NMR chemical shifts, (1)H self-diffusion coefficients, (1)H spin-lattice and spin-spin relaxation rates data indicate that the higher hydrophobic nature of copolymer significantly influenced aggregation characteristics of SDS. The salient features of the NMR investigations include (i) the onset of mixed micelles at lower SDS concentrations (<3 mM) relative to the copolymer-free case and their evolution into SDS free micelles at higher SDS concentrations (~30 mM), (ii) disintegration of copolymer-SDS mixed aggregate at moderate SDS concentrations (~10 mM) and still binding of a copolymer with SDS and (iii) preferential localization of the copolymer occurred at the SDS micelle surface. SANS investigations indicate prolate ellipsoidal shaped mixed aggregates with an increase in SDS aggregation number, while a contrasting behavior in the copolymer aggregation is observed. The aggregation features of SDS and the copolymer, the sizes of mixed aggregates and the degree of counterion dissociation (α) extracted from SANS data analysis corroborate reasonably well with those of (1)H NMR self-diffusion and sodium ((23)Na) spin-lattice relaxation data.

The effect of poloxamer 188 on nanoparticle morphology, size, cancer cell uptake, and cytotoxicity.

PubMed

Yan, Fei; Zhang, Chao; Zheng, Yi; Mei, Lin; Tang, Lina; Song, Cunxian; Sun, Hongfan; Huang, Laiqiang

2010-02-01

The aim of this work was to investigate the effect of triblock copolymer poloxamer 188 on nanoparticle morphology, size, cancer cell uptake, and cytotoxicity. Docetaxel-loaded nanoparticles were prepared by oil-in-water emulsion/solvent evaporation technique using biodegradable poly(lactic-co-glycolic acid) (PLGA) with or without addition of poloxamer 188, respectively. The resulting nanoparticles were found to be spherical with a rough and porous surface. The nanoparticles had an average size of around 200 nm with a narrow size distribution. The in vitro drug-release profile of both nanoparticle formulations showed a biphasic release pattern. An increased level of uptake of PLGA/poloxamer 188 nanoparticles in the docetaxel-resistant MCF-7 TAX30 human breast cancer cell line could be found in comparison with that of PLGA nanoparticles. In addition, the docetaxel-loaded PLGA/poloxamer 188 nanoparticles achieved a significantly higher level of cytotoxicity than that of docetaxel-loaded PLGA nanoparticles and Taxotere (P < .05). In conclusion, the results showed advantages of docetaxel-loaded PLGA nanoparticles incorporated with poloxamer 188 compared with the nanoparticles without incorporation of poloxamer 188 in terms of sustainable release and efficacy in breast cancer chemotherapy. The effects of poloxamer 188, a triblock copolymer were studied on nanoparticle morphology, size, cancer cell uptake and cytotoxicity. An increased level of uptake of PLGA/poloxamer 188 nanoparticles in resistant human breast cancer cell line was demonstrated, resulting in a significantly higher level of cytotoxicity. Copyright 2010 Elsevier Inc. All rights reserved.

Magnetic solid-phase extraction of phthalate esters (PAEs) in apparel textile by core-shell structured Fe3O4@silica@triblock-copolymer magnetic microspheres.

PubMed

Xu, Mei; Liu, Minhua; Sun, Meirong; Chen, Kun; Cao, Xiujun; Hu, Yaoming

2016-04-01

In this paper, novel core-shell structured magnetic Fe3O4/silica nanocomposites with triblock-copolymer grafted on their surface (Fe3O4@SiO2@MDN) were successfully fabricated by combining a sol-gel method with a seeded aqueous-phase radical copolymerization approach. Owing to the excellent characteristics of the strong magnetic responsivity, outstanding hydrophilicity and abundant π-electron system, the obtained core-shell structured microspheres showed great potential as a magnetic solid phase extraction (MSPE) adsorbent. Several kinds of phthalate esters (PAEs) were selected as model analytes to systematically evaluate the applicability of adsorbents for extraction followed by gas chromatography-mass spectrometry (GC-MS) analyses. Various parameters, including adsorbents amounts, adsorption time, species of eluent, and desorption time were optimized. Under the optimized conditions, Validation experiments such as recovery, reproducibility, and limit of detection were carried on and showed satisfactory results. The analysis method showed excellent linearity with a wide range of 0.2-10mg/kg (R(2)>0.9974) and low limits of detection (LOD) of 0.02-0.09 mg/kg (S/N=3). Ultimately, the novel magnetic adsorbents were successfully employed to detect the PAEs in apparel textile samples. And the results indicated that this novel approach brought forward in the present work offered an attractive alternative for rapid, efficient and sensitive MSPE for PAEs compounds. Copyright © 2015 Elsevier B.V. All rights reserved.

Hydration of cations: a key to understanding of specific cation effects on aggregation behaviors of PEO-PPO-PEO triblock copolymers.

PubMed

Lutter, Jacob C; Wu, Tsung-yu; Zhang, Yanjie

2013-09-05

This work reports results from the interactions of a series of monovalent and divalent cations with a triblock copolymer, poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO). Phase transition temperatures of the polymer in the presence of chloride salts with six monovalent and eight divalent cations were measured using an automated melting point apparatus. The polymer undergoes a two-step phase transition, consisting of micellization of the polymer followed by aggregation of the micelles, in the presence of all the salts studied herein. The results suggest that hydration of cations plays a key role in determining the interactions between the cations and the polymer. The modulation of the phase transition temperature of the polymer by cations can be explained as a balance between three interactions: direct binding of cations to the oxygen in the polymer chains, cations sharing one water molecule with the polymer in their hydration layer, and cations interacting with the polymer via two water molecules. Monovalent cations Na(+), K(+), Rb(+), and Cs(+) do not bind to the polymer, while Li(+) and NH4(+) and all the divalent cations investigated including Mg(2+), Ca(2+), Sr(2+), Ba(2+), Co(2+), Ni(2+), Cu(2+), and Cd(2+) bind to the polymer. The effects of the cations correlate well with their hydration thermodynamic properties. Mechanisms for cation-polymer interactions are discussed.

Rheological study of the effect of polyethylene oxide (PEO) homopolymer on the gelation of PEO-PPO-PEO triblock copolymer in aqueous solution

NASA Astrophysics Data System (ADS)

Li, Xiaolei; Hyun, Kyu

2018-05-01

The effects of polyethylene oxide (PEO) homopolymer on the gelation behavior of a PEO100-PPO65-PEO100 triblock copolymer (Pluronic F127) were explored in aqueous solution under non-isothermal and isothermal conditions. Under non-isothermal conditions (temperature sweep test), two transition points were observed on increasing temperature, that is, at lower and upper gelation temperatures (LTgel and UTgel, respectively). Between LTgel and UTgel, F127 aqueous solutions maintained a hard gel state. Both molecular weight (MW) and PEO concentration affected these two gelation temperatures. In particular, relative molecular weight (MWrel ≡ molecular weight of PEO homopolymer/PEO segment of F127) affected LTgel. LTgel decreased on increasing PEO concentration at MWrel values of <1, but increased on increasing PEO concentration at MWrel values of >1. On the other hand, UTgel decreased with increasing PEO concentration regardless of MWrel. Under isothermal conditions (fixed temperature between LTgel and UTgel), the effects of PEO homopolymer on the mechanical properties of F127 hard gel were systemically investigated using small and large amplitude oscillatory shear tests. In the linear viscoelastic regime, total intra-cycle stress and elastic intra-cycle stress were similar, and viscous response increased on increasing PEO concentration. However, at large strain amplitudes, hard gels showed intra-cycle stiffening but inter-cycle softening behavior. In addition, on increasing PEO concentrations, viscous nonlinearities underwent strain-rate thickening followed by strain-rate thinning.

Stealth properties of poly(ethylene oxide)-based triblock copolymer micelles: a prerequisite for a pH-triggered targeting system.

PubMed

Van Butsele, K; Morille, M; Passirani, C; Legras, P; Benoit, J P; Varshney, S K; Jérôme, R; Jérôme, C

2011-10-01

Evaluation of the biocompatibility of pH-triggered targeting micelles was performed with the goal of studying the effect of a poly(ethylene oxide) (PEO) coating on micelle stealth properties. Upon protonation under acidic conditions, pH-sensitive poly(2-vinylpyridine) (P2VP) blocks were stretched, exhibiting positive charges at the periphery of the micelles as well as being a model targeting unit. The polymer micelles were based on two different macromolecular architectures, an ABC miktoarm star terpolymer and an ABC linear triblock copolymer, which combined three different polymer blocks, i.e. hydrophobic poly(ε-caprolactone), PEO and P2VP. Neutral polymer micelles were formed at physiological pH. These systems were tested for their ability to avoid macrophage uptake, their complement activation and their pharmacological behavior after systemic injection in mice, as a function of their conformation (neutral or protonated). After protonation, complement activation and macrophage uptake were up to twofold higher than for neutral systems. By contrast, when P2VP blocks and the targeting unit were buried by the PEO shell at physiological pH, micelle stealth properties were improved, allowing their future systemic injection with an expected long circulation in blood. Smart systems responsive to pH were thus developed which therefore hold great promise for targeted drug delivery to an acidic tumoral environment. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Order-Order Transition of C → sdG → sL → S in ABC Triblock Copolymer Thin Film Induced by Solvent Vapor.

PubMed

Luo, Chunxia; Huang, Weihuan; Han, Yanchun

2009-04-01

The morphology transition of polystyrene-block-poly(butadiene)-block-poly(2-vinylpyridine) (SBV) triblock thin film induced in benzene vapor showing weak selectivity for PS is investigated. The order-order transitions (OOT) in the sequence of core-shell cylinders (C), sphere in 'diblock gyroid' (sdG), sphere in lamella (sL) and sphere (S) are observed. The projection along (111) direction in Gyroid phase (sdG(111)) is found to epitaxially grow from C(001) in the film. Instead of sdG(111), sdG(110)(0.1875) develops to the phase of sL. Consequently, the film experiences the transition sequence of sdG(111) → sdG(211) → sdG(110)(0.25)  → sdG(110)(0.1875) between C and sL. The mechanism is analyzed from the total surface area of the blocks. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Manipulating the ABCs of self-assembly via low-χ block polymer design

PubMed Central

Chang, Alice B.; Lee, Byeongdu; Garland, Carol M.; Jones, Simon C.; Matsen, Mark W.

2017-01-01

Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χij). In this article, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χAC ≲ 0), promotes organization into a unique mixed-domain lamellar morphology, which we designate LAMP. Transmission electron microscopy indicates that LAMP exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM3) with ABCB periods. Complementary small-angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations and predicts that LAMP is thermodynamically stable below a critical χAC, above which LAM3 emerges. Both experiments and theory expose close analogies to ABA′ triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. These conclusions provide fresh opportunities for block polymer design with potential consequences spanning all self-assembling soft materials. PMID:28588139

Synthesis and Characterization of Stimuli Responsive Block Copolymers, Self-Assembly Behavior and Applications

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

Determan, Michael Duane

The central theme of this thesis work is to develop new block copolymer materials for biomedical applications. While there are many reports of stimuli-responsive amphiphilic [19-21] and crosslinked hydrogel materials [22], the development of an in situ gel forming, pH responsive pentablock copolymer is a novel contribution to the field, Figure 1.1 is a sketch of an ABCBA pentablock copolymer. The A blocks are cationic tertiary amine methacrylates blocked to a central Pluronic F127 triblock copolymer. In addition to the prerequisite synthetic and macromolecular characterization of these new materials, the self-assembled supramolecular structures formed by the pentablock were experimentally evaluated.more » This synthesis and characterization process serves to elucidate the important structure property relationships of these novel materials, The pH and temperature responsive behavior of the pentablock copolymer were explored especially with consideration towards injectable drug delivery applications. Future synthesis work will focus on enhancing and tuning the cell specific targeting of DNA/pentablock copolymer polyplexes. The specific goals of this research are: (1) Develop a synthetic route for gel forming pentablock block copolymers with pH and temperature sensitive properties. Synthesis of these novel copolymers is accomplished with ATRP, yielding low polydispersity and control of the block copolymer architecture. Well defined macromolecular characteristics are required to tailor the phase behavior of these materials. (2) Characterize relationship between the size and shape of pentablock copolymer micelles and gel structure and the pH and temperature of the copolymer solutions with SAXS, SANS and CryoTEM. (3) Evaluate the temperature and pH induced phase separation and macroscopic self-assembly phenomenon of the pentablock copolymer. (4) Utilize the knowledge gained from first three goals to design and formulate drug delivery formulations based on the multi-responsive properties of the pentablock copolymer. Demonstrate potential biomedical applications of these materials with in vitro drug release studies from pentablock copolymer hydrogels. The intent of this work is to contribute to the knowledge necessary for further tailoring of these, and other functional block copolymer materials for biomedical applications.« less

PCL-PDMS-PCL copolymer-based microspheres mediate cardiovascular differentiation from embryonic stem cells

NASA Astrophysics Data System (ADS)

Song, Liqing

Poly-epsilon-caprolactone (PCL) based copolymers have received much attention as drug or growth factor delivery carriers and tissue engineering scaffolds due to their biocompatibility, biodegradability, and tunable biophysical properties. Copolymers of PCL and polydimethylsiloxane (PDMS) also have shape memory behaviors and can be made into thermoresponsive shape memory polymers for various biomedical applications such as smart sutures and vascular stents. However, the influence of biophysical properties of PCL-PDMS-PCL copolymers on stem cell lineage commitment is not well understood. In this study, PDMS was used as soft segments of varying length to tailor the biophysical properties of PCL-based co-polymers. While low elastic modulus (<10 kPa) of the tri-block copolymer PCL-PDMS-PCL affected cardiovascular differentiation of embryonic stem cells, the range of 60-100 MPa PCL-PDMS-PCL showed little influence on the differentiation. Then different size (30-140 mum) of microspheres were fabricated from PCL-PDMS-PCL copolymers and incorporated within embryoid bodies (EBs). Mesoderm differentiation was induced using bone morphogenetic protein (BMP)-4 for cardiovascular differentiation. Differential expressions of mesoderm progenitor marker KDR and vascular markers CD31 and VE-cadherin were observed for the cells differentiated from EBs incorporated with microspheres of different size, while little difference was observed for cardiac marker alpha-actinin expression. Small size of microspheres (30 mum) resulted in higher expression of KDR while medium size of microspheres (94 mum) resulted in higher CD31 and VE-cadherin expression. This study indicated that the biophysical properties of PCL-based copolymers impacted stem cell lineage commitment, which should be considered for drug delivery and tissue engineering applications.

Injectable biodegradable temperature-responsive PLGA-PEG-PLGA copolymers: synthesis and effect of copolymer composition on the drug release from the copolymer-based hydrogels.

PubMed

Qiao, Mingxi; Chen, Dawei; Ma, Xichen; Liu, Yanjun

2005-04-27

Injectable biodegradable temperature-responsive poly(DL-lactide-co-glycolide-b-ethylene glycol-b-DL-lactide-co-glycolide) (PLGA-PEG-PLGA) triblock copolymers with DL-lactide/glycolide molar ratio ranging from 6/1 to 15/l were synthesized from monomers of DL-lactide, glycolide and polyethylene glycol and characterized by 1H NMR. The resulting copolymers are soluble in water to form free flowing fluid at room temperature but become hydrogels at body temperature. The hydrophobicity of the copolymer increased with the increasing of DL-lactide/glycolide molar ratio. In vitro dissolution studies with two different hydrophobic drugs (5-fluorouracil and indomethacin) were performed to study the effect of DL-lactide/glycolide molar ratio on drug release and to elucidate drug release mechanism. The release mechanism for hydrophilic 5-fluorouracil was diffusion-controlled, while hydrophobic indomethacin showed an biphasic profile comprising of an initial diffusion-controlled stage followed by the hydrogel erosion-dominated stage. The effect of DL-lactide/glycolide molar ratio on drug release seemed to be dependent on the drug release mechanism. It has less effect on the drug release during the diffusion-controlled stage, but significantly affected drug release during the hydrogel erosion-controlled stage. Compared with ReGel system, the synthesized copolymers showed a higher gelation temperature and longer period of drug release. The copolymers can solubilize the hydrophobic indomethacin and the solubility (13.7 mg/ml) was increased 3425-fold compared to that in water (4 microg/ml, 25 degrees C). Two methods of physical mixing method and solvent evaporation method were used for drug solubilization and the latter method showed higher solubilization efficiency.

Thinking Outside the 'Block': Alternative Polymer Compositions for Micellar Drug Delivery.

PubMed

Jones, Marie-Christine

2015-01-01

With a number of formulations currently in clinical trials, the interest in polymer micelles as drug carriers in unlikely to subside. Historically, linear diblock copolymers have been used as the building blocks for micelle preparation. Yet, recent advances in polymer chemistry have meant that a wider variety of polymer architectures and compositions have become available and been trialed for pharmaceutical applications. This mini-review aims to provide an overview of recent, exciting developments in triblock, graft and hyperbranched polymer chemistries that may change the way polymeric micelles drug formulations are prepared.

Multicomponent Nanomaterials with Complex Networked Architectures from Orthogonal Degradation and Binary Metal Backfilling in ABC Triblock Terpolymers

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

Cowman, Christina D.; Padgett, Elliot; Tan, Kwan Wee

2015-05-13

Selective degradation of block copolymer templates and backfilling the open mesopores is an effective strategy for the synthesis of nanostructured hybrid and inorganic materials. Incorporation of more than one type of inorganic material in orthogonal ways enables the synthesis of multicomponent nanomaterials with complex yet well-controlled architectures; however, developments in this field have been limited by the availability of appropriate orthogonally degradable block copolymers for use as templates. We report the synthesis and self-assembly into cocontinuous network structures of polyisoprene-block-polystyrene-block-poly(propylene carbonate) where the polyisoprene and poly(propylene carbonate) blocks can be orthogonally removed from the polymer film. Through sequential block etchingmore » and backfilling the resulting mesopores with different metals, we demonstrate first steps toward the preparation of three-component polymer–inorganic hybrid materials with two distinct metal networks. Multiblock copolymers in which two blocks can be degraded and backfilled independently of each other, without interference from the other, may be used in a wide range of applications requiring periodically ordered complex multicomponent nanoarchitectures.« less

Filamentous, mixed micelles of triblock copolymers enhance tumor localization of indocyanine green in a murine xenograft model

PubMed Central

Kim, Tae Hee; Mount, Christopher W; Dulken, Benjamin W; Ramos, Jenelyn; Fu, Caroline J; Khant, Htet A; Chiu, Wah; Gombotz, Wayne R; Pun, Suzie H

2012-01-01

Polymeric micelles formed by the self-assembly of amphiphilic block copolymers can be used to encapsulate hydrophobic drugs for tumor-delivery applications. Filamentous carriers with high aspect ratios offer potential advantages over spherical carriers, including prolonged circulation times. In this work, mixed micelles comprised of poly (ethylene oxide)-poly-[(R)-3-hydroxybutyrate]-poly (ethylene oxide) (PEO-PHB-PEO) and Pluronic F-127 (PF-127) were used to encapsulate a near-infrared fluorophore. The micelle formulations were assessed for tumor accumulation after tail vein injection to xenograft tumor-bearing mice by non-invasive optical imaging. The mixed micelle formulation that facilitated the highest tumor accumulation was shown by cryo-electron microscopy to be filamentous in structure compared to spherical structures of pure PF-127 micelles. In addition, increased dye loading efficiency and dye stability was attained in this mixed micelle formulation compared to pure PEO-PHB-PEO micelles. Therefore, the optimized PEO-PHB-PEO/PF-127 mixed micelle formulation offers advantages for cancer delivery over micelles formed from the individual copolymer components. PMID:22118658

Block copolymer lithography of rhodium nanoparticles for high temperature electrocatalysis.

PubMed

Boyd, David A; Hao, Yong; Li, Changyi; Goodwin, David G; Haile, Sossina M

2013-06-25

We present a method for forming ordered rhodium nanostructures on a solid support. The approach makes use of a block copolymer to create and assemble rhodium chloride nanoparticles from solution onto a surface; subsequent plasma and thermal processing are employed to remove the polymer and fully convert the nanostructures to metallic rhodium. Films cast from a solution of the triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) dissolved in toluene with rhodium(III) chloride hydrate were capable of producing a monolayer of rhodium nanoparticles of uniform size and interparticle spacing. The nanostructures were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The electrocatalytic performance of the nanoparticles was investigated with AC impedance spectroscopy. We observed that the addition of the particles to a model solid oxide fuel cell anode provided up to a 14-fold improvement in the anode activity as evidenced by a decrease in the AC impedance resistance. Examination of the anode after electrochemical measurement revealed that the basic morphology and distribution of the particles were preserved.

Multicomponent nanomaterials with complex networked architectures from orthogonal degradation and binary metal backfilling in ABC triblock terpolymers

DOE PAGES

Cowman, Christina D.; Padgett, Elliot; Tan, Kwan Wee; ...

2015-04-02

Selective degradation of block copolymer templates and backfilling the open mesopores is an effective strategy for the synthesis of nanostructured hybrid and inorganic materials. Incorporation of more than one type of inorganic material in orthogonal ways enables the synthesis of multicomponent nanomaterials with complex yet well-controlled architectures; however, developments in this field have been limited by the availability of appropriate orthogonally degradable block copolymers for use as templates. We report the synthesis and self-assembly into cocontinuous network structures of polyisoprene-block-polystyrene-block-poly(propylene carbonate) where the polyisoprene and poly(propylene carbonate) blocks can be orthogonally removed from the polymer film. Through sequential block etchingmore » and backfilling the resulting mesopores with different metals, we demonstrate first steps toward the preparation of three-component polymer–inorganic hybrid materials with two distinct metal networks. Lastly, multiblock copolymers in which two blocks can be degraded and backfilled independently of each other, without interference from the other, may be used in a wide range of applications requiring periodically ordered complex multicomponent nanoarchitectures.« less

Dye-sensitized PS-b-P2VP-templated nickel oxide films for photoelectrochemical applications

PubMed Central

Massin, Julien; Bräutigam, Maximilian; Kaeffer, Nicolas; Queyriaux, Nicolas; Field, Martin J.; Schacher, Felix H.; Popp, Jürgen; Chavarot-Kerlidou, Murielle; Dietzek, Benjamin; Artero, Vincent

2015-01-01

Moving from homogeneous water-splitting photocatalytic systems to photoelectrochemical devices requires the preparation and evaluation of novel p-type transparent conductive photoelectrode substrates. We report here on the sensitization of polystyrene-block-poly-(2-vinylpyridine) (PS-b-P2VP) diblock copolymer-templated NiO films with an organic push–pull dye. The potential of these new templated NiO film preparations for photoelectrochemical applications is compared with NiO material templated by F108 triblock copolymers. We conclude that NiO films are promising materials for the construction of dye-sensitized photocathodes to be inserted into photoelectrochemical (PEC) cells. However, a combined effort at the interface between materials science and molecular chemistry, ideally funded within a Global Artificial Photosynthesis Project, is still needed to improve the overall performance of the photoelectrodes and progress towards economically viable PEC devices. PMID:26052420

Dye-sensitized PS-b-P2VP-templated nickel oxide films for photoelectrochemical applications.

PubMed

Massin, Julien; Bräutigam, Maximilian; Kaeffer, Nicolas; Queyriaux, Nicolas; Field, Martin J; Schacher, Felix H; Popp, Jürgen; Chavarot-Kerlidou, Murielle; Dietzek, Benjamin; Artero, Vincent

2015-06-06

Moving from homogeneous water-splitting photocatalytic systems to photoelectrochemical devices requires the preparation and evaluation of novel p-type transparent conductive photoelectrode substrates. We report here on the sensitization of polystyrene-block-poly-(2-vinylpyridine) (PS-b-P2VP) diblock copolymer-templated NiO films with an organic push-pull dye. The potential of these new templated NiO film preparations for photoelectrochemical applications is compared with NiO material templated by F108 triblock copolymers. We conclude that NiO films are promising materials for the construction of dye-sensitized photocathodes to be inserted into photoelectrochemical (PEC) cells. However, a combined effort at the interface between materials science and molecular chemistry, ideally funded within a Global Artificial Photosynthesis Project, is still needed to improve the overall performance of the photoelectrodes and progress towards economically viable PEC devices.

Block copolymer self-assembly–directed synthesis of mesoporous gyroidal superconductors

PubMed Central

Robbins, Spencer W.; Beaucage, Peter A.; Sai, Hiroaki; Tan, Kwan Wee; Werner, Jörg G.; Sethna, James P.; DiSalvo, Francis J.; Gruner, Sol M.; Van Dover, Robert B.; Wiesner, Ulrich

2016-01-01

Superconductors with periodically ordered mesoporous structures are expected to have properties very different from those of their bulk counterparts. Systematic studies of such phenomena to date are sparse, however, because of a lack of versatile synthetic approaches to such materials. We demonstrate the formation of three-dimensionally continuous gyroidal mesoporous niobium nitride (NbN) superconductors from chiral ABC triblock terpolymer self-assembly–directed sol-gel–derived niobium oxide with subsequent thermal processing in air and ammonia gas. Superconducting materials exhibit a critical temperature (Tc) of about 7 to 8 K, a flux exclusion of about 5% compared to a dense NbN solid, and an estimated critical current density (Jc) of 440 A cm−2 at 100 Oe and 2.5 K. We expect block copolymer self-assembly–directed mesoporous superconductors to provide interesting subjects for mesostructure-superconductivity correlation studies. PMID:27152327

Block copolymer self-assembly-directed synthesis of mesoporous gyroidal superconductors.

PubMed

Robbins, Spencer W; Beaucage, Peter A; Sai, Hiroaki; Tan, Kwan Wee; Werner, Jörg G; Sethna, James P; DiSalvo, Francis J; Gruner, Sol M; Van Dover, Robert B; Wiesner, Ulrich

2016-01-01

Superconductors with periodically ordered mesoporous structures are expected to have properties very different from those of their bulk counterparts. Systematic studies of such phenomena to date are sparse, however, because of a lack of versatile synthetic approaches to such materials. We demonstrate the formation of three-dimensionally continuous gyroidal mesoporous niobium nitride (NbN) superconductors from chiral ABC triblock terpolymer self-assembly-directed sol-gel-derived niobium oxide with subsequent thermal processing in air and ammonia gas. Superconducting materials exhibit a critical temperature (T c) of about 7 to 8 K, a flux exclusion of about 5% compared to a dense NbN solid, and an estimated critical current density (J c) of 440 A cm(-2) at 100 Oe and 2.5 K. We expect block copolymer self-assembly-directed mesoporous superconductors to provide interesting subjects for mesostructure-superconductivity correlation studies.

Charged triblock copolymer self-assembly into charged micelles

NASA Astrophysics Data System (ADS)

Chen, Yingchao; Zhang, Ke; Zhu, Jiahua; Wooley, Karen; Pochan, Darrin; Department of Material Science; Engineering University of Delaware Team; Department of Chemistry Texas A&M University Collaboration

2011-03-01

Micelles were formed through the self-assembly of amphiphlic block copolymer poly(acrylic acid)-block-poly(methyl acrylate)-block-polystyrene (PAA-PMA-PS). ~Importantly, the polymer is complexed with diamine molecules in pure THF solution prior to water titration solvent processing-a critical aspect in the control of final micelle geometry. The addition of diamine triggers acid-base complexation ~between the carboxylic acid PAA side chains and amines. ~Remarkably uniform spheres were found to form close-packed patterns when forced into dried films and thin, solvated films when an excess of amine was used in the polymer assembly process. Surface properties and structural features of these hexagonal-packed spherical micelles with charged corona have been explored by various characterization methods including Transmission Electron Microscopy (TEM), cryogenic TEM, z-potential analysis and Dynamic Light Scattering. The forming mechanism for this pattern and morphology changes against external stimulate such as salt will be discussed.

Micellar and analytical implications of a new potentiometric PVC sensor based on neutral ion-pair complexes of dodecylmethylimidazolium bromide-sodium dodecylsulfate.

PubMed

Sanan, Reshu; Mahajan, Rakesh Kumar

2013-03-15

With an aim to characterize the micellar aggregates of imidazolium based ionic liquids, a new potentiometric PVC sensor based on neutral ion-pair complexes of dodecylmethylimidazolium bromide-sodium dodecylsulfate (C12MeIm(+)DS(-)) has been developed. The electrode exhibited a linear response for the concentration range of 7.9×10(-5)-9.8×10(-3) M with a super-Nernstian slope of 92.94 mV/decade, a response time of 5 s and critical micellar concentration (cmc) of 10.09 mM for C12MeImBr. The performance of the electrode in investigating the cmc of C12MeImBr in the presence of two drugs [promazine hydrochloride (PMZ) and promethazine hydrochloride (PMT)] and three triblock copolymers (P123, L64 and F68) has been found to be satisfactory on comparison with conductivity measurements. Various micellar parameters have been evaluated for the binary mixtures of C12MeImBr with drugs and triblock copolymers using Clint's, Rubingh's, and Motomura's approach. Thus the electrode offers a simple, straightforward and relatively fast technique for the characterization of micellar aggregates of C12MeImBr, complementing existing conventional techniques. Further, the analytical importance of proposed C12MeIm(+)-ISE as end point indicator in potentiometric titrations and for direct determination of cationic surfactants [cetylpyridinium chloride (CPC), tetradecyltrimethylammonium bromide (TTAB), benzalkonium chloride (BC)] in some commercial products was judged by comparing statistically with classical two-phase titration methods. Copyright © 2013 Elsevier Inc. All rights reserved.

TiO2 Nanostructure Synthesized by Sol-Gel for Dye Sensitized Solar Cells as Renewable Energy Source

NASA Astrophysics Data System (ADS)

Ramelan, A. H.; Wahyuningsih, S.; Saputro, S.; Supriyanto, E.; Hanif, Q. A.

2017-02-01

The use of renewable materials as a constituent of a smart alternative energy such as the use of natural dyes for light harvesting needs to be developed. Synthesis of anatase titanium dioxide (TiO2) and fabrication Dye-Sensitized Solar Cell (DSSC) using dye-based of anthocyanin from purple sweet potato (Ipomoea batatas L.) as a photosensitizer had been done. Synthesis TiO2 through sol-gel process with the addition of triblock copolymer Pluronic F127 template was controlled at pH 3 whereas calcination was carried out at a temperature of 500 °C, 550 °C and 600 °C. The obtained TiO2 were analyzed by XRD, SAA, and SEM. The conclusion is anatase TiO2 obtained until annealing up to 600 °C. Self-assembly Pluronic F127 triblock copolymer capable of restraining the growth of TiO2 crystals. Retention growth of TiO2 mesoporous produces material character that can be used as builders photoanode DSSC with natural sensitizer anthocyanin from purple sweet potatoes. Based on the analysis of X-ray diffraction patterns and surface area analyser, the higher the calcination temperature the greater the size of the anatase crystals is obtained, however, the smaller its surface area. Purple sweet potato anthocyanin’s dyed on to TiO2 was obtained a good enough performance for DSSC’s and gain the optimum performance from DSSC’s system built with mesoporous TiO2 annealed 550 °C using flavylium form anthocyanin.

Use of the Flory-Huggins theory to predict the solubility of nifedipine and sulfamethoxazole in the triblock, graft copolymer Soluplus.

PubMed

Altamimi, Mohammad A; Neau, Steven H

2016-01-01

Drug dispersed in a polymer can improve bioavailability; dispersed amorphous drug undergoes recrystallization. Solid solutions eliminate amorphous regions, but require a measure of the solubility. Use the Flory-Huggins Theory to predict crystalline drugs solubility in the triblock, graft copolymer Soluplus® to provide a solid solution. Physical mixtures of the two drugs with similar melting points but different glass forming ability, sulfamethoxazole and nifedipine, were prepared with Soluplus® using a quick technique. Drug melting point depression (MPD) was measured using differential scanning calorimetry. The Flory-Huggins Theory allowed: (1) interaction parameter, χ, calculation using MPD data to provide a measure of drug-polymer interaction strength and (2) estimation of the free energy of mixing. A phase diagram was constructed with the MPD data and glass transition temperature (Tg) curves. The interaction parameters with Soluplus® and the free energy of mixing were estimated. Drug solubility was calculated by the intersection of solubility equations and that of MPD and Tg curves in the phase diagram. Negative interaction parameters indicated strong drug-polymer interactions. The phase diagram and solubility equations provided comparable solubility estimates for each drug in Soluplus®. Results using the onset of melting rather than the end of melting support the use of the onset of melting. The Flory-Huggins Theory indicates that Soluplus® interacts effectively with each drug, making solid solution formation feasible. The predicted solubility of the drugs in Soluplus® compared favorably across the methods and supports the use of the onset of melting.

Use of the Flory-Huggins theory to predict the solubility of nifedipine and sulfamethoxazole in the triblock, graft copolymer Soluplus.

PubMed

Altamimi, Mohammad A; Neau, Steven H

2016-03-01

Drug dispersed in a polymer can improve bioavailability; dispersed amorphous drug undergoes recrystallization. Solid solutions eliminate amorphous regions, but require a measure of the solubility. Use the Flory-Huggins Theory to predict crystalline drugs solubility in the triblock, graft copolymer Soluplus® to provide a solid solution. Physical mixtures of the two drugs with similar melting points but different glass forming ability, sulfamethoxazole and nifedipine, were prepared with Soluplus® using a quick technique. Drug melting point depression (MPD) was measured using differential scanning calorimetry. The Flory-Huggins Theory allowed: (1) interaction parameter, χ, calculation using MPD data to provide a measure of drug-polymer interaction strength and (2) estimation of the free energy of mixing. A phase diagram was constructed with the MPD data and glass transition temperature (T g ) curves. The interaction parameters with Soluplus® and the free energy of mixing were estimated. Drug solubility was calculated by the intersection of solubility equations and that of MPD and T g curves in the phase diagram. Negative interaction parameters indicated strong drug-polymer interactions. The phase diagram and solubility equations provided comparable solubility estimates for each drug in Soluplus®. Results using the onset of melting rather than the end of melting support the use of the onset of melting. The Flory-Huggins Theory indicates that Soluplus® interacts effectively with each drug, making solid solution formation feasible. The predicted solubility of the drugs in Soluplus® compared favorably across the methods and supports the use of the onset of melting.

Uniaxial Extensional Behavior of A--B--A Thermoplastic Elastomers: Structure-Properties Relationship and Modeling

NASA Astrophysics Data System (ADS)

Martinetti, Luca

At service temperatures, A--B--A thermoplastic elastomers (TPEs) behave similarly to filled (and often entangled) B-rich rubbers since B block ends are anchored on rigid A domains. Therefore, their viscoelastic behavior is largely dictated by chain mobility of the B block rather than by microstructural order. Relating the small- and large-strain response of undiluted A--B--A triblocks to molecular parameters is a prerequisite for designing associated TPE-based systems that can meet the desired linear and nonlinear rheological criteria. This dissertation was aimed at connecting the chemical and topological structure of A--B--A TPEs with their viscoelastic properties, both in the linear and in the nonlinear regime. Since extensional deformations are relevant for the processing and often the end-use applications of thermoplastic elastomers, the behavior was investigated predominantly in uniaxial extension. The unperturbed size of polymer coils is one of the most fundamental properties in polymer physics, affecting both the thermodynamics of macromolecules and their viscoelastic properties. Literature results on poly(D,L-lactide) (PLA) unperturbed chain dimensions, plateau modulus, and critical molar mass for entanglement effect in viscosity were reviewed and discussed in the framework of the coil packing model. Self-consistency between experimental estimates of melt chain dimensions and viscoelastic properties was discussed, and the scaling behaviors predicted by the coil packing model were identified. Contrary to the widespread belief that amorphous polylactide must be intrinsically stiff, the coil packing model and accurate experimental measurements undoubtedly support the flexible nature of PLA. The apparent brittleness of PLA in mechanical testing was attributed to a potentially severe physical aging occurring at room temperature and to the limited extensibility of the PLA tube statistical segment. The linear viscoelastic response of A--B--A TPEs was first examined at temperatures where the A domains are glassy. Characteristic length scales and tube model parameters were determined, and the role of the glassy A domains on the entangled rubbery B network was assessed. Thermo-rheological complexity, observed near and below Tg,A, was attributed to augmented motional freedom of the B block ends at the corresponding A/B interfaces, in harmony with the theoretical treatment of thermo-rheological complexity for two-phase materials developed by Fesko and Tschoegl. When the magnitude of the steepness index was taken into account, the shift behavior was analogous to the response measured for pure B melts. Building upon the procedure proposed by Ferry and co-workers for entangled and unfilled polymer melts, a new method was developed to extract the matrix monomeric friction coefficient zeta0 from the linear response behavior of a filled system in the rubber-glass transition region, and to estimate the size of Gaussian submolecules. Stress relaxation beyond the path equilibration time was found qualitatively and quantitatively compatible with dynamically undiluted arm retraction dynamics of entangled dangling structures (originating either from a fraction of triblock chains having one end residing outside A domains or from diblock impurities). By employing tube models and rubber elasticity theories, suitably modified to account for microphase-segregation, the linear elastic behavior across the rubbery plateau and up to the entanglement time was modeled, and a simple analytical expression relating the Langley trapping factor with the fraction of entangled and unentangled dangling structures of the material was obtained. The critical-gel-like behavior typical of A--B--A TPEs at service temperatures approaching Tg,A was analyzed in terms of a power-law distribution of relaxation times derived from the wedge distribution, shown to be equivalent to Chambon--Winter's critical gel model and to the mechanical behavior of a fractional element. A relation between the observed power-law exponent and molecular structure was established. The measured low-frequency response, originating from the incipient glass transition of the A domains, was exploited and extrapolated to lower frequencies via a sequential application of the fractional Maxwell model and the fractional Zener model. With only a few, physically meaningful material parameters a realistic description of the A--B--A self-similar relaxation was obtained over a frequency range much broader than the experimental window and not accessible via time-temperature superposition. The relationship between large-strain response and network structure of A--B--A triblocks was investigated, by examining (1) the effect of linear relaxation mechanisms on the tensile behavior, (2) the sources of elastic and viscoelastic nonlinearities, and (3) the strain rate dependence of the ultimate properties. For the first time in the literature, the complex high-dimensional rheological signature of chewing gum was analyzed, especially in response to nonlinear and unsteady deformations in both shear and extension. A unique rheological fingerprint was obtained that is sufficient to provide a new robust definition of chewing gum that is independent of specific molecular composition. (Abstract shortened by ProQuest.).

Preparation of curcumin-loaded PCL-PEG-PCL triblock copolymeric nanoparticles by a microchannel technology.

PubMed

Guo, Fangyuan; Guo, Dingjia; Zhang, Wei; Yan, Qinying; Yang, Yan; Hong, Weiyong; Yang, Gensheng

2017-03-01

Biodegradable polymeric nanoparticles (NPs) have potential therapeutic applications; however, preparing NPs of a specific diameter and uniform size distribution is a challenge. In this work, we fabricated a microchannel system for the preparation of curcumin (Cur)-loaded NPs by the interfacial precipitation method, which rapidly and consistently generated stable NPs with a relatively smaller diameter, narrow size distribution, and higher drug-loading capacity and entrapment efficiency. Poly(ε-caprolactone)-poly(ethylene glycol)-poly (ε-caprolactone) triblock copolymers(PCEC) used as the carrier material was synthesized and characterized. Cur-loaded PCEC NPs had an average size of 167.2nm with a zeta potential of -29.23mV, and showed a loading capacity and drug entrapment efficiency of 15.28%±0.23% and 96.11%±0.13%, respectively. Meanwhile, the NPs demonstrated good biocompatibility and bioavailability, efficient cellular uptake, and long circulation time and a possible liver targeting effect in vivo. These results indicate that the Cur-loaded PCEC NPs can be used as drug carriers in controlled delivery systems and other biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Core-Shell-Corona Micelles with a Responsive Shell.

PubMed

Gohy, Jean-François; Willet, Nicolas; Varshney, Sunil; Zhang, Jian-Xin; Jérôme, Robert

2001-09-03

A reactor for the synthesis of gold nanoparticles is one of the uses of a poly(styrene)-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) triblock copolymer (PS-b-P2VP-b-PEO) which forms core-shell-corona micelles in water. Very low polydispersity spherical micelles are observed that consist of a PS core surrounded by a pH-sensitive P2VP shell and a corona of PEO chains end-capped by a hydroxyl group. The corona can act as a site for attaching responsive or sensing molecules. © 2001 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

A Laterally-Mobile Mixed Polymer/Polyelectrolyte Brush Undergoes a Macroscopic Phase Separation

NASA Astrophysics Data System (ADS)

Lee, Hoyoung; Park, Hae-Woong; Tsouris, Vasilios; Choi, Je; Mustafa, Rafid; Lim, Yunho; Meron, Mati; Lin, Binhua; Won, You-Yeon

2013-03-01

We studied mixed PEO and PDMAEMA brushes. The question we attempted to answer was: When the chain grafting points are laterally mobile, how will this lateral mobility influence the structure and phase behavior of the mixed brush? Two different model mixed PEO/PDMAEMA brush systems were prepared: a mobile mixed brush by spreading a mixture of two diblock copolymers, PEO-PnBA and PDMAEMA-PnBA, onto the air-water interface, and an inseparable mixed brush using a PEO-PnBA-PDMAEMA triblock copolymer having respective brush molecular weights matched to those of the diblock copolymers. These two systems were investigated by surface pressure-area isotherm, X-ray reflectivity and AFM imaging measurements. The results suggest that the mobile mixed brush undergoes a lateral macroscopic phase separation at high chain grafting densities, whereas the inseparable system is only microscopically phase separated under comparable brush density conditions. We also conducted an SCF analysis of the phase behavior of the mixed brush system. This analysis further supported the experimental findings. The macroscopic phase separation observed in the mobile system is in contrast to the microphase separation behavior commonly observed in two-dimensional laterally-mobile small molecule mixtures.

Substrate effect on nanoporous structure of silica wires by channel-confined self-assembly of block-copolymer and sol-gel precursors

DOE PAGES

Hu, Michael Z.; Lai, Peng

2015-09-22

Nanoporous silica wires of various wire diameters were developed by space-confined molecular self-assembly of triblock copolymer ethylene/propylene/ethylene (P123) and silica alkoxide precursor (tetraethylorthosilicate, TEOS). Two distinctive hard-templating substrates, anodized aluminum oxide (AAO) and track-etched polycarbonate (EPC), with channel diameters in the range between 10 nm and 200 nm were employed for space-confinement of soft molecular self-assembly driven by the block-copolymer microphase separation. It was observed in the scanning and transmission electron microscope (STEM) studies that the substrate geometry and material characteristics had pronounced effects on the structure and morphology of the silica nanowires. A substrate wall effect was proposed tomore » explain the ordering and orientation of the intra-wire mesostructure. Circular and spiral nanostructures were found only in wires formed in AAO substrate, not in EPC. Pore-size differences and distinctive wall morphologies of the nanowires relating to the substrates were discussed. It was shown that the material and channel wall characteristics of different substrates play key roles in the ordering and morphology of the intra-wire nanostructures.« less

Lithium Storage Performance of Zinc Ferrite Nanoparticle Synthesized with the Assistance of Triblock Copolymer P123.

PubMed

Yao, J H; Li, Y W; Song, X B; Zhang, Y F; Yan, J

2018-05-01

The ZnFe2O4 samples with the triblock copolymer P123 (P123) additive quantity of 0 wt.%, 2 wt.%, 5 wt.%, 8 wt.% and 10 wt.% were prepared by a very facile homogeneous precipitation method followed by high temperature sintering. The microstructures of the prepared samples were analyzed by X-ray diffraction (XRD) and Field emission scanning electron microscopy (FESEM). The results revealed that the five prepared samples are all normal spinel zinc ferrite (ZnFe2O4); the sample with the P123 additive quantity of 8 wt.% has the smallest particle size among the five samples. The lithium storage performances of the prepared samples are characterized by cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and charge-discharge tests. The results demonstrated that adding proper amount of P123 can obviously improve the lithium storage performances of zinc ferrite spinel powder. But excessive P123 can induce the particle agglomerates so that the lithium storage performance of sample decays significantly. The ZnFe2O4 sample with the P123 additive quantity of 8 wt.% exhibited the highest electrochemical activity, the best rate performance, and superior cycling stability. For example, after 50 charge/discharge cycles under a current density of 120 mA g-1, the ZnFe2O4 sample with the P123 additive quantity of 8 wt.% can retain a specific discharge capacity of 468 mAh g-1, much higher than that of for the ZnFe2O4 sample with the P123 additive quantity of 0 wt.% (224 mAh g-1).

Preparation of Chitin Nanofibers-Gold Metallic Nanocomposite by Phase Transfer Method

NASA Astrophysics Data System (ADS)

Shervani, Zameer; Taisuke, Yukawa; Ifuku, Shinsuke; Saimoto, Hiroyuki; Morimoto, Minoru

2012-10-01

Chitin nanofibers (CNFs)-Au(0) nanoparticles (Au NPs) blends in dispersion, flakes and thin film or sheet forms were first prepared by mixing pre-organized Au NPs prepared in triblock copolymer with diluted CNFs suspension. Water soluble polymer triblock copolymer poly (methyl vinyl ether, PMVE) in the amount 0.6 wt.% was used to prepare NPs and 0.12 wt.% net chitin content was used as CNFs suspension to prepare the blended composite. Au NPs of size 4.4 nm (σ = 1.2) were obtained when Au salt (HAuCl4ṡ3H2O (hydrogen tetrachloroaurate (III) trihydrate) was reduced by 5 equivalents of NaBH4. PMVE polymer acted as a stabilizing or capping agent for pre-organized NPs. Completion of reaction was fast, all salt reduced to metallic form in just 15 min after the addition of NaBH4. CNFs (1 wt.% chitin) which was used to prepare CNFs-Au NPs blend composite were prepared from crab shell in never dried acidic condition by established combination of chemical and mechanical processes that gave 25-40 nm width and high aspect ratio CNFs. When polymer capped Au NPs mixed with CNF suspension, all Au NPs and 56% polymer were mass transferred from water phase to entangle with more polar moieties of CNFs-water suspension as no trace of Au NPs were noticed in water-polymer mother liquor after blending with CNFs suspension. Particles size of CNFs-Au NPs composite was measured by employing TEM, SAXS and SEM techniques. CNFs-Au NPs composite were characterized in solution and compressed dried sheet form by recording digital images, UV-vis and XRD spectroscopies. CNFs-Au NPs suspension had antibacterial activity against gram positive bacteria S. aureus.

Protein hydrogels with engineered biomolecular recognition

NASA Astrophysics Data System (ADS)

Mi, Lixin

Extracellular matrices (ECMs) are the hydrated macromolecular gels in which cells migrate and proliferate and organize into tissues in vivo . The development of artificial ECM with the required mechanical, physico-chemical, and biological properties has long been a challenge in the biomaterial research field. In this dissertation, a novel set of bioactive protein hydrogels has been synthesized and characterized at both molecular and materials levels. The self-recognized and self-assembled protein copolymers have the ability to provide engineered biofunctionality through the controlled arrangement of bioactive domains on the nanoscale. Genetic engineering methods have been employed to synthesize these protein copolymers. Plasmid DNA carrying genes to express both di- and tri-block proteins have been constructed using molecular cloning techniques. These genes were expressed in bacterial E. coli to ensure homogeneous protein length and anticipated structure. Three diblock protein sequences having a leucine zipper construct on one end and polyelectrolyte (AGAGAGPEG)10 on the other, have been studied by circular dichroism, size-exclusion chromatography, analytical ultracentrifugation, and static light scattering to characterize their secondary structure, structural stability, and oligomeric state. The results show that ABC diblock mixtures form very stable heterotrimer aggregates via self-recognition and self-assembly of the coiled coil end domains. Tri-block proteins with two leucine zipper motif ends flanking the polyelectrolyte random coil in the middle have been investigated by circular dichroism and fluorescence spectroscopy, and the hydrogels formed by self-assembly of these tri-blocks have been studied using transmission electronic microscopy and diffusing wave spectroscopy. The reversible gelation behavior is the result of heterotrimeric aggregation of helices to form the physical crosslinks in the gel, with the polyelectrolyte region center block retaining water soluble and swelling. The RGD cell adhesion tripeptide has been inserted into the polyelectrolyte region by site-directed mutagenesis. Two dimensional human foreskin fibroblast cultures have shown that the RGD-containing protein surface is bioactive in promoting cell attachment, cell signaling, and cytoskeleton organization. The protein and the cell recognize and interact at molecular level. Collectively, these findings indicate that this bioactive protein hydrogel system is a promising biomaterial for mammalian cell culture. This research may provide insights for the rational development of bioactive ECM for specific cell and tissue engineering applications.

Macroscopic Electrical Wires from Vapor Deposited Poly(3,4-ethylenedioxythiophene).

PubMed

Koch, Lukas; Polek, Anna; Rudd, Sam; Evans, Drew

2017-01-11

Conducting polymers represent a field of materials innovation that bridges the properties of metals (electrical conduction) with those of traditional polymers (mechanical flexibility). Although electronic properties have been studied, minimal attention is given to their mechanical properties such as tensile strength. This study presents macroscopic wires made from the vapor phase polymerization of poly(3,4-ethylenedioxythiophene) using triblock copolymers as a molecular template. These macroscopic wires are conductive (up to 5 × 10 4 S/m), and possess tensile properties (Young's modulus ∼1.1 GPa; tensile strength ∼90 MPa) comparable to commercially available polymers (Nylon-6 and poly(methyl methacrylate)), without need for nonconductive mechanical fillers.

Thermodynamic and kinetic control of charged, amphiphilic triblock copolymer assembly via interaction with organic counterions in solvent mixtures

NASA Astrophysics Data System (ADS)

Cui, Honggang

2007-12-01

Amphiphilic block copolymers, consisting of at least two types of monomers with different affinity to the dissolving solvent(s), have been recognized as a molecular building unit for their chemical tunability and design flexibility. Amphiphilic block copolymers with a chargeable block have structural features of polyelectrolytes, block copolymers and surfactants. The combination of these different features offers great flexibility for developing novel assembled morphologies at the nanoscale and outstanding ability to control and manipulate those morphologies. The nanostructures, formed from the spontaneous association of amphiphilic block copolymer in selective solvents, show promise for applications in nanotechnology and pharmaceuticals, including drug delivery, tissue engineering and bio-imaging. A basic knowledge of their modes of self-assembly and their correspondence to application-related properties is just now being developed and poses a considerable scientific challenge. The goal of this dissertation is to investigate the associative behavior of charged, amphiphilic block copolymers in solvent mixtures while in the presence of organic counterions. Self-assembly of poly (acrylic acid)- block-poly (methyl acrylate)-block-polystyrene (PAA- b-PMA-b-PS) triblock copolymers produces nanodomains in THF/water solution specifically through the interaction with organic counterions (polyamines). These assembled structures can include classic micelles (spheres, cylinders and vesicles), but, more importantly, include non-classic micelles (disks, toroids, branched micelles and segmented micelles). Each micelle structure is stable and reproducible at different assembly conditions. The assembled micellar structures depend on not only solution components (thermodynamics) but also mixing procedure and consequent self-assembly pathway (kinetics). The key factors that determine the thermodynamic interactions that partially define the assembled structures and the kinetic assembly process include THF/water ratio, PS block length, the type and amount of organic counterions, and the mixing pathway. Their formation mechanism has been investigated from three aspects: (i) the chain structure of organic counterions, including spacer length, chain hydrophobicity between ionizable groups and the number of ionizable groups (amine group); (ii) molecular structure of the triblock copolymer, including block length of polystyrene and chain architecture; (iii) relative variation of the components, such as different ratios of THF to water and the different ratios of amine groups to acid groups. The first example of a novel micelle formed was the toroidal micelle. The toroidal micelle morphology, which is theoretically predicted but rarely observed, has been produced by the self assembly of PAA99- b-PMA73-b-PS66 in combination with 2,2-(ethylenedioxy)diethylamine (EDDA) and mixed THF/H2O solvent. It was found that toroids can be constructed by two mechanisms: elimination of energetically unfavored cylindrical micelle endcaps or perforation of disk-like micelles. Three-fold junctions were formed as intermediate structures to facilitate toroidal formation from cylindrical micelles. In order to construct toroids from cylindrical micelles, three requirements must be met: lower bending modulus (flexibility of cylinders), selfattraction between cylinders, and extra endcapping energy originating from chain packing frustration. Extremely high energy spheres can also fuse into toroids. Disk-like micelles can transform into a toroidal morphology when cylindrical packing geometry was initiated along the rims of disk-like micelles via solvent mixing that eventually perforated the disk center. The toroidal morphology can be kinetically trapped by either ridding the system of organic solvent or chemically crosslinking the PAA corona with EDDA via addition of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methiodide (DPEM). The interaction of positively-charged, multivalent organic amines with the negatively-charged PAA corona plays a decisive role in the formation of these micelles. Inter-chain binding from the interaction of the two amine end groups of diamines with acid groups from different PAA corona blocks governs the final assembled structures. Diamines with hydrophilic spacers induced the formation of micelles with larger interfacial curvature as the spacer length increased. Disk-like micelles, cylindrical micelles or spherical micelles were observed with the gradual increase of hydrophilic spacer length. Diamines with variable hydrophobic spacers showed a similar effect when the spacer length was less than six methylene units. Application of longer hydrophobic diamines had a reverse effect on the interfacial curvature. This effect was attributed to the interaction of hydrophobic diamine hydrocarbon linking chains with the PMA-b-PS hydrophobic core. These findings indicate an easy method to tune micelle structure with multivalent organic counterions. (Abstract shortened by UMI.)

Mixed micellization between natural and synthetic block copolymers: β-casein and Lutrol F-127.

PubMed

Portnaya, Irina; Khalfin, Rafail; Kesselman, Ellina; Ramon, Ory; Cogan, Uri; Danino, Dganit

2011-02-28

Amphiphilic block copolymers and mixtures of amphiphiles find broad applications in numerous technologies, including pharma, food, cosmetic and detergency. Here we report on the interactions between a biological charged diblock copolymer, β-casein, and a synthetic uncharged triblock copolymer, Lutrol F-127 (EO(101)PO(56)EO(101)), on their mixed micellization characteristics and the micelles' structure and morphology. Isothermal titration calorimetry (ITC) experiments indicate that mixed micelles form when Lutrol is added to monomeric as well as to assembled β-casein. The main driving force for the mixed micellization is the hydrophobic interactions. Above β-casein CMC, strong perturbations caused by penetration of the hydrophobic oxypropylene sections of Lutrol into the protein micellar core lead to disintegration of the micelles and reformation of mixed Lutrol/β-casein micelles. The negative enthalpy of micelle formation (ΔH) and cooperativity increase with raising β-casein concentration in solution. ζ-potential measurements show that Lutrol interacts with the protein micelles to form mixed micelles even below its critical micellization temperature (CMT). They further indicate that Lutrol effectively masks the protein charges, probably by forming a coating layer of the ethyleneoxide rich chains. Small-angle X-ray scattering (SAXS) and cryogenic-transmission electron microscopy (cryo-TEM) indicate relatively small changes in the oblate micellar shape, but do show swelling along the small axis of β-casein micelles in the presence of Lutrol, thereby confirming the formation of mixed micelles.

Self-assembled micelles based on pH-sensitive PAE-g-MPEG-cholesterol block copolymer for anticancer drug delivery.

PubMed

Zhang, Can Yang; Xiong, Di; Sun, Yao; Zhao, Bin; Lin, Wen Jing; Zhang, Li Juan

2014-01-01

A novel amphiphilic triblock pH-sensitive poly(β-amino ester)-g-poly(ethylene glycol) methyl ether-cholesterol (PAE-g-MPEG-Chol) was designed and synthesized via the Michael-type step polymerization and esterification condensation method. The synthesized copolymer was determined with proton nuclear magnetic resonance and gel permeation chromatography. The grafting percentages of MPEG and cholesterol were determined as 10.93% and 62.02%, calculated from the area of the characteristic peaks, respectively. The amphiphilic copolymer was confirmed to self-assemble into core/shell micelles in aqueous solution at low concentrations. The critical micelle concentrations were 6.92 and 15.14 mg/L at pH of 7.4 and 6.0, respectively, obviously influenced by the changes of pH values. The solubility of pH-responsive PAE segment could be transformed depending on the different values of pH because of protonation-deprotonation of the amino groups, resulting in pH sensitivity of the copolymer. The average particle size of micelles increased from 125 nm to 165 nm with the pH decreasing, and the zeta potential was also significantly changed. Doxorubicin (DOX) was entrapped into the polymeric micelles with a high drug loading level. The in vitro DOX release from the micelles was distinctly enhanced with the pH decreasing from 7.4 to 6.0. Toxicity testing proved that the DOX-loaded micelles exhibited high cytotoxicity in HepG2 cells, whereas the copolymer showed low toxicity. The results demonstrated how pH-sensitive PAE-g-MPEG-Chol micelles were proved to be a potential vector in hydrophobic drug delivery for tumor therapy.

PEGylated Biodegradable Polyesters for PGSS Microparticles Formulation: Processability, Physical and Release Properties.

PubMed

Perinelli, D R; Cespi, M; Bonacucina, G; Naylor, A; Whitaker, M; Lam, J K W; Howdle, S M; Casettari, L; Palmieri, G F

2016-01-01

Particles from Gas Saturated Solution (PGSS) is an emergent method that employs supercritical carbon dioxide (scCO2) to produce microparticles. It is suitable for encapsulating biologically active compounds including therapeutic peptides and proteins. Poly(lactide acid) (PLA) and/or poly(lactic-coglycolic acid) (PLGA) are the most commonly used materials in PGSS, due to their good processability in scCO2. Previous studies demonstrated that the properties of the microparticles can be modulated by adding polyethylene glycol (PEG) or tri-block PEGylated copolymers. In the present work, the effect of the addition of biodegradable PEGylated di-block copolymers on the physical properties and drug release performance of microparticles prepared by PGSS technique was evaluated. mPEG5kDa-P(L)LA and mPEG5kDa-P(L)LGA with similar molecular weights were synthesized and their behaviour, when exposed to supercritical CO2, was investigated. Different microparticle formulations, composed of a high (81%) or low (9%) percentage of the synthesized copolymers were prepared and compared in terms of particle size distribution, morphology, yield and protein release. Drug release studies were performed using bovine serum albumin (BSA) as a model protein. PEGylated copolymers showed good processability in PGSS without significant changes to the physical properties of the microparticles. However, the addition of PEG exerted a modulating effect on the microparticle drug dissolution behaviour, increasing the rate of BSA release as a function of its content in the formulation. This study demonstrated the feasibility of producing microparticles by using PEGylated di-block copolymers through a PGSS technique at mild operating conditions (low operating pressure and temperature).

Self-assembled micelles based on pH-sensitive PAE-g-MPEG-cholesterol block copolymer for anticancer drug delivery

PubMed Central

Zhang, Can Yang; Xiong, Di; Sun, Yao; Zhao, Bin; Lin, Wen Jing; Zhang, Li Juan

2014-01-01

A novel amphiphilic triblock pH-sensitive poly(β-amino ester)-g-poly(ethylene glycol) methyl ether-cholesterol (PAE-g-MPEG-Chol) was designed and synthesized via the Michael-type step polymerization and esterification condensation method. The synthesized copolymer was determined with proton nuclear magnetic resonance and gel permeation chromatography. The grafting percentages of MPEG and cholesterol were determined as 10.93% and 62.02%, calculated from the area of the characteristic peaks, respectively. The amphiphilic copolymer was confirmed to self-assemble into core/shell micelles in aqueous solution at low concentrations. The critical micelle concentrations were 6.92 and 15.14 mg/L at pH of 7.4 and 6.0, respectively, obviously influenced by the changes of pH values. The solubility of pH-responsive PAE segment could be transformed depending on the different values of pH because of protonation–deprotonation of the amino groups, resulting in pH sensitivity of the copolymer. The average particle size of micelles increased from 125 nm to 165 nm with the pH decreasing, and the zeta potential was also significantly changed. Doxorubicin (DOX) was entrapped into the polymeric micelles with a high drug loading level. The in vitro DOX release from the micelles was distinctly enhanced with the pH decreasing from 7.4 to 6.0. Toxicity testing proved that the DOX-loaded micelles exhibited high cytotoxicity in HepG2 cells, whereas the copolymer showed low toxicity. The results demonstrated how pH-sensitive PAE-g-MPEG-Chol micelles were proved to be a potential vector in hydrophobic drug delivery for tumor therapy. PMID:25364250

Bioresorbable polypeptide-based comb-polymers efficiently improves the stability and pharmacokinetics of proteins in vivo.

PubMed

Turabee, Md Hasan; Thambi, Thavasyappan; Lym, Jae Seung; Lee, Doo Sung

2017-03-28

Stimuli-responsive polypeptides are a promising class of biomaterials due to their tunable physicochemical and biological properties. Herein, a series of novel pH- and thermo-responsive block copolymers based on polypeptides were synthesized by ring-opening polymerization of γ-benzyl-l-glutamate-N-carboxyanhydride in the presence of poly(ethylene glycol)-diamine macroinitiator followed by aminolysis. The resulting polypeptide-based triblock copolymer, poly[(2-(dibutylamino)ethyl-l-glutamate)-co-(γ-benzyl-l-glutamate)]-poly(ethylene glycol)-b-poly[(2-(dibutylamino)ethyl-l-glutamate)-co-(γ-benzyl-l-glutamate)] (PNLG-co-PBLG-b-PEG-b-PBLG-co-PNLG), exists as a low viscous sol at low pH and temperature (≤pH 6.4, 25 °C) but it transforms to a soft gel under physiological conditions (pH 7.4 and 37 °C). The physical properties of the polypeptide gel can be tuned by controlling the ratio between hydrophobic PBLG and pH-sensitive PNLG blocks. The polypeptide-based copolymer did not show any noticeable cytotoxicity to fibroblast cells in vitro. It was found that subcutaneous injection of the polypeptide copolymer solution into the dorsal region of Sprague-Dawley (SD) rats formed a gel instantly without major inflammation. The gels were completely biodegraded in six weeks and found to be bioresorbable. Human growth hormone (hGH)-loaded polypeptide-based biodegradable copolymer sols readily formed a viscoelastic gel that inhibited an initial burst and prolonged the hGH release for one week. Overall, due to their bioresorbable and sustained release protein characteristics, polypeptide hydrogels may serve as viable platforms for therapeutic protein delivery and the surface tunable properties of polypeptide hydrogels can be exploited for other potential therapeutic proteins.

Dissipative particle dynamics simulation on the self-assembly and disassembly of pH-sensitive polymeric micelle with coating repair agent

NASA Astrophysics Data System (ADS)

Wang, Xiumin; Gao, Jianbang; Wang, Zhikun; Xu, Jianchang; Li, Chunling; Sun, Shuangqing; Hu, Songqing

2017-10-01

Dissipative particle dynamics (DPD) simulations were applied to investigate the coating repair agent dicyclopentadience (DCPD) in pH-sensitive micelles. The results show micelles self-assembled from triblock copolymers with strong hydrophobic interaction are not conducive to loading DCPD, and only micelles with weak interaction parameter can encapsulate DCPD well. After protonation, the structure of micelle was disassembled and DCPD beads have a stronger ability to shrink polymer chains and exposed to water. This work provides mesoscopic insight into self-assembly and disassembly of desired agent-loaded micelle, and might be useful for the design of new materials for agent delivery.

Novel Hydrogels from Telechelic Polymers

NASA Astrophysics Data System (ADS)

Taribagil, Rajiv R.

The last two decades have seen telechelic polymers support an increasing number of applications as stabilizers and flow modifiers in fields as varied as pharmaceutics, paints and oil recovery. Mainly consisting of a long hydrophilic block end-capped with hydrophobic blocks, these polymers form gels at modest concentrations, comprising hydrophobic junctions with hydrophilic blocks bridging these junctions. This thesis examines two different types of telechelic polymer hydrogels: concentrated dispersions of telechelic triblock copolymers and dilute solutions of wormlike micelles cross-linked by hydrophobically end-capped polymers. Aqueous gels of telechelic poly(ethylene oxide) (PEO)-based triblock polymers, with homo and hetero combinations of 1,2-polybutadiene (PB) and poly(perfluoropropylene oxide) (PFPO) as hydrophobic end-blocks, were investigated using a combination of cryogenic scanning electron microscopy and small-angle neutron scattering. The PB-b-PEO-b-PB copolymers formed networks of spherical micelles at all concentrations as expected, albeit with significant spatial heterogeneity that diminished with increasing concentration. The PFPO-b-PEO-b-PFPO copolymers also formed networks by aggregation of the end-blocks, but the PFPO blocks tended to adopt disk-like or even sheet-like structures. This is attributed to the extremely high interfacial tension of PFPO with water and is consistent with the "super-strong" segregation regime behavior. The heterotelechelic PB-b-PEO- b-PFPO terpolymers adopted a quite different structure, namely an intricate bicontinuous open-cell foam, with cells on the order of 500 nm in size and cell walls composed of PFPO disks embedded in PB sheets. These various network structures illustrate the potential of using end-block chemistry to manipulate both the morphology and the physical properties of polymer gels. Dilute aqueous solutions containing 1 wt% cetyltrimethylammonium tosylate, a surfactant well recognized to form wormlike micelles, and low concentrations of hydrophobically end-capped poly(ethylene oxide), were investigated using dynamic mechanical spectroscopy and small-angle neutron scattering. The detailed examination shows that addition of as little as 0.1 wt% of the polymer to the dilute wormlike micelle solution leads to a massive enhancement in its viscoelastic response. This phenomenon raises the possibility of significantly reducing the amount of additive required to achieve a desired rheological profile, with concomitant advantages in both cost and environmental impact.

Integrated method of thermosensitive triblock copolymer-salt aqueous two phase extraction and dialysis membrane separation for purification of lycium barbarum polysaccharide.

PubMed

Wang, Yun; Hu, Xiaowei; Han, Juan; Ni, Liang; Tang, Xu; Hu, Yutao; Chen, Tong

2016-03-01

A polymer-salt aqueous two-phase system (ATPS) consisting of thermosensitive copolymer ethylene-oxide-b-propylene-oxide-b-ethylene-oxide (EOPOEO) and NaH2PO4 was employed in deproteinization for lycium barbarum polysaccharide (LBP). The effects of salt type and concentration, EOPOEO concentration, amount of crude LBP solution and temperature were studied. In the primary extraction process, LBP was preferentially partitioned to the bottom (salt-rich) phase with high recovery ratio of 96.3%, while 94.4% of impurity protein was removed to the top (EOPOEO-rich) phase. Moreover, the majority of pigments could be discarded to top phase. After phase-separation, the LBP in the bottom phase was further purified by dialysis membrane to remove salt and other small molecular impurities. The purity of LBP was enhanced to 64%. Additionally, the FT-IR spectrum was used to identify LBP. EOPOEO was recovered by a temperature-induced separation, and reused in a new ATPS. An ideal extraction and recycle result were achieved. Copyright © 2015 Elsevier Ltd. All rights reserved.

Self-assembly of block copolymers into sieve-like particles with arrayed switchable channels and as scaffolds to guide the arrangement of gold nanoparticles.

PubMed

He, Yun; Zhang, Yan; Yan, Nan; Zhu, Yutian; Jiang, Wei; Shi, Dean

2017-10-12

Well-defined polymeric particles with not only a controllable shape and internal nanostructures but also stimuli-responsive functions have attracted intensive attention because of their great potential in various fields. Herein, we created unique sieve-like particles with lattice arrayed switchable channels via the confined self-assembly of poly(4-vinylpyridine)-b-polystyrene-b-poly(4-vinylpyridine) (P4VP-b-PS-b-P4VP) triblock copolymers within the emulsion droplets and the subsequent swelling treatment in ethanol. It is worth noting that the hexagonally packed P4VP channels in the sieve-like particles are switched on and off by changing the solvent type, i.e., P4VP channels are switched on in ethanol and switched off in water, which can operate as a solvent-controlled chemical gate. Moreover, the well-defined sieve-like particles can be further used as scaffolds to guide the spatial arrangement of gold nanoparticles, which generates hybrid nanomaterials with controllable morphology and ordered spatial arrangement of AuNPs.

Multilayer nanoparticles with a magnetite core and a polycation inner shell as pH-responsive carriers for drug delivery

NASA Astrophysics Data System (ADS)

Guo, Miao; Yan, Yu; Liu, Xiaozhou; Yan, Husheng; Liu, Keliang; Zhang, Hongkai; Cao, Youjia

2010-03-01

Nanocarriers with multilayer core-shell architecture were prepared by coating a superparamagnetic Fe3O4 core with a triblock copolymer. The first block of the copolymer formed the biocompatible outermost shell of the nanocarrier. The second block that contains amino groups and hydrophobic moiety formed the inner shell. The third block bound tightly onto the Fe3O4 core. Chlorambucil (an anticancer agent) and indomethacin (an anti-inflammation agent), each containing a carboxyl group and a hydrophobic moiety, were loaded into the amino-group-containing inner shell by a combination of ionic and hydrophobic interactions. The release rate of the loaded drugs was slow at pH 7.4, mimicking the blood environment, whereas the release rate increased significantly at acidic pH, mimicking the intracellular conditions in the endosome/lysosome. This can be attributed to the disruption of the ionic bond caused by protonation of the carboxylate anion of the drugs and the swelling of the inner shell caused by protonation of the amino groups.

Role of monomer sequence and backbone chemistry in polypeptoid copolymers for marine antifouling coatings

NASA Astrophysics Data System (ADS)

Patterson, Anastasia; Wenning, Brandon; Rizis, Georgios; Calabrese, David; Finlay, John; Franco, Sofia; Clare, Anthony; Kramer, Edward; Ober, Christopher; Segalman, Rachel

The design rules elucidated in this work suggest that antifouling coatings bearing pendant peptoid side chains perform better overall in marine fouling tests than those with peptide side chains, with extremely low attachment of N. incerta and high removal of U. linza. This difference in performance is likely due to the lack of a hydrogen bond donor in the peptoid backbone. Furthermore, we show that the bulk polymer material of these hierarchical coatings (based on PEO or PDMS) plays a key role in determining both surface presentation and fouling release performance. We demonstrate these trends utilizing a modular coating based on a triblock copolymer consisting of polystyrene and a vinyl-containing midblock, to which sequence-defined pendant oligomers (peptides or peptoids with sequences of oligo-PEO and fluoroalkyl groups) are attached via thiol-ene ``click'' chemistry. Surface presentation was analyzed with X-ray photoelectron spectroscopy and captive bubble water contact angle, and antifouling performance was evaluated with attachment and removal bioassays of the marine macroalga U. linza and diatom N. incerta. NSF GRFP and ONR PECASE.

Preparation of end-grafted polymer brushes by nitroxide-mediated free radical polymerization of vaporized vinyl monomers.

PubMed

Li, Jun; Chen, Xiaoru; Chang, Ying-Chih

2005-10-11

In this work, we report a gas-phase polymerization approach to create end-grafted vinyl based polymer films on silicon oxide based substrates. The "surface-initiated vapor deposition polymerization" (SI-VDP) of vaporized vinyl monomers, via the nitroxide-mediated free radical polymerization mechanism, was developed to fabricate various homo- and block copolymer brushes from surface-bound initiators, 1-(4'-oxa-2'-phenyl-12'-trimethoxysilyldodecyloxy)-2,2,6,6-tetra-methylpiperidine ("TEMPO"). The resulting polymer thin films were characterized by the Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ellipsometry, and contact angle goniometry, respectively, to identify the surface composition, film thickness, surface coverage, and water contact angles. Through the SI-VDP, end-grafted polymer films of polystyrene (PSt), poly(acrylic acid) (PAAc), poly(N-(2-hydroxypropyl) methacrylamide) (PHPMA), and poly(N-isopropylacrylamide) (PNIPAAm) with 10-200 nm thicknesses were fabricated. Furthermore, the block copolymer films of PAAc (1st block)-b-PSt (2nd block), PSt (1st block)-b-PAAc (2nd block), and a triblock copolymer film of PAAc (1st)-b-PSt (2nd)-b-PHPMA (3rd), were also fabricated, suggesting the "renewability" of the TEMPO-initiated polymerization in the SI-VDP scheme. It is also noticed that the SI-VDP is more efficient than the conventional solution phase polymerization in producing functional polymer brushes such as PNIPAAm, PAAc, or PAAc-b-PSt end-grafted films. In summary, our studies have shown clear advantages of the SI-VDP setup for the nitroxide-mediated polymerization scheme in controlling synthesis of end-grafted homo- and copolymer thin films.

NMR investigations of self-aggregation characteristics of SDS in a model assembled tri-block copolymer solution.

PubMed

Kumar, B V N Phani; Priyadharsini, S Umayal; Prameela, G K S; Mandal, Asit Baran

2011-08-01

The present work was undertaken with a view to understand the influence of a model non-ionic tri-block copolymer PEO-PPO-PEO (poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)) with molecular weight 5800 i.e., P123 [(EO)(20)-(PO)(70)-(EO)(20)] on the self-aggregation characteristics of the anionic surfactant sodium dodecylsulfate (SDS) in aqueous solution (D(2)O) using NMR chemical shift, self-diffusion and nuclear spin-relaxation as suitable experimental probes. In addition, polymer diffusion has been monitored as a function of SDS concentration. The concentration-dependent chemical shift, diffusion data and relaxation data indicated the significant interaction of polymeric micelles with SDS monomers and micelles at lower and intermediate concentrations of SDS, whereas the weak interaction of the polymer with SDS micelles at higher concentrations of SDS. It has been observed that SDS starts aggregating on the polymer at a lower concentration i.e., critical aggregation concentration (cac=1.94 mM) compared to polymer-free situation, and the onset of secondary micelle concentration (C(2)=27.16 mM) points out the saturation of the 0.2 wt% polymer or free SDS monomers/micelles at higher concentrations of SDS. It has also been observed that the parameter cac is almost independent in the polymer concentrations of study. The TMS (tetramethylsilane) has been used as a solubilizate to measure the bound diffusion coefficient of SDS-polymer mixed system. The self-diffusion data were analyzed using two-site exchange model and the obtained information on aggregation dynamics was commensurate with that inferred from chemical shift and relaxation data. The information on slow motions of polymer-SDS system was also extracted using spin-spin and spin-lattice relaxation rate measurements. The relaxation data points out the disintegration of polymer network at higher concentrations of SDS. The present NMR investigations have been well corroborated by surface tension and conductivity measurements. Copyright © 2011 Elsevier Inc. All rights reserved.

The impact of microfluidic mixing of triblock micelleplexes on in vitro / in vivo gene silencing and intracellular trafficking

NASA Astrophysics Data System (ADS)

Feldmann, Daniel P.; Xie, Yuran; Jones, Steven K.; Yu, Dongyue; Moszczynska, Anna; Merkel, Olivia M.

2017-06-01

The triblock copolymer polyethylenimine-polycaprolactone-polyethylene glycol (PEI-PCL-PEG) has been shown to spontaneously assemble into nano-sized particulate carriers capable of complexing with nucleic acids for gene delivery. The objective of this study was to investigate micelleplex characteristics, their in vitro and in vivo fate following microfluidic preparation of siRNA nanoparticles compared to the routinely used batch reactor mixing technique. Herein, PEI-PCL-PEG nanoparticles were prepared with batch reactor or microfluidic mixing techniques and characterized by various biochemical assays and in cell culture. Microfluidic nanoparticles showed a reduction of overall particle size as well as a more uniform size distribution when compared to batch reactor pipette mixing. Confocal microscopy, flow cytometry and qRT-PCR displayed the subcellular delivery of the microfluidic formulation and confirmed the ability to achieve mRNA knockdown. Intratracheal instillation of microfluidic formulation resulted in a significantly more efficient (p < 0.05) knockdown of GAPDH compared to treatment with the batch reactor formulation. The use of microfluidic mixing techniques yields an overall smaller and more uniform PEG-PCL-PEI nanoparticle that is able to more efficiently deliver siRNA in vivo. This preparation method may prove to be useful when a scaled up production of well-defined polyplexes is required.

Development of a robust pH-sensitive polyelectrolyte ionomer complex for anticancer nanocarriers

PubMed Central

Lim, Chaemin; Youn, Yu Seok; Lee, Kyung Soo; Hoang, Ngoc Ha; Sim, Taehoon; Lee, Eun Seong; Oh, Kyung Taek

2016-01-01

A polyelectrolyte ionomer complex (PIC) composed of cationic and anionic polymers was developed for nanomedical applications. Here, a poly(ethylene glycol)–poly(lactic acid)–poly(ethylene imine) triblock copolymer (PEG–PLA–PEI) and a poly(aspartic acid) (P[Asp]) homopolymer were synthesized. These polyelectrolytes formed stable aggregates through electrostatic interactions between the cationic PEI and the anionic P(Asp) blocks. In particular, the addition of a hydrophobic PLA and a hydrophilic PEG to triblock copolyelectrolytes provided colloidal aggregation stability by forming a tight hydrophobic core and steric hindrance on the surface of PIC, respectively. The PIC showed different particle sizes and zeta potentials depending on the ratio of cationic PEI and anionic P(Asp) blocks (C/A ratio). The doxorubicin (dox)-loaded PIC, prepared with a C/A ratio of 8, demonstrated pH-dependent behavior by the deprotonation/protonation of polyelectrolyte blocks. The drug release and the cytotoxicity of the dox-loaded PIC (C/A ratio: 8) increased under acidic conditions compared with physiological pH, due to the destabilization of the formation of the electrostatic core. In vivo animal imaging revealed that the prepared PIC accumulated at the targeted tumor site for 24 hours. Therefore, the prepared pH-sensitive PIC could have considerable potential as a nanomedicinal platform for anticancer therapy. PMID:26955270

Role of hydration and water coordination in micellization of Pluronic block copolymers.

PubMed

Šturcová, Adriana; Schmidt, Pavel; Dybal, Jiří

2010-12-15

Raman, attenuated total reflectance FTIR, near-infrared spectroscopy, and DFT calculations have been used in a study of aqueous solutions of three tri-block copolymers poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) or PEO-PPO-PEO with commercial names Pluronic PE6200, PE6400 and F68. It is shown that the process of micellization as a response to increased temperature is reflected in the hydroxyl stretching region of infrared and Raman spectra, which contains information both about restructuring of water and changes of polymer chains in polymer/water aggregates. Raman spectra exhibit differences between individual Pluronics even at temperatures below the critical micellization temperature (CMT). According to the attenuated total reflection (ATR) FTIR spectra, the same five water coordination types defined by the number of donated/accepted hydrogen bonds are present in interacting water as in bulk water. It indicates that models considering mixed states of water with different hydrogen bonding environments provide appropriate descriptions of bound water both below and above the CMT. Above the CMT, aggregate hydration increases in the order PE6400 < PE6200 < F68, although that does not fully correspond to the EO/PO ratio, and points to the differences in microstructure of aggregates formed by each copolymer. This study relates nanoscale phenomena (hydrophobic and hydrophilic hydration) with the mesoscale phenomenon of micellization. Copyright © 2010 Elsevier Inc. All rights reserved.

Molecular arrangement of symmetric and non-symmetric triblock copolymers of poly(ethylene oxide) and poly(isobutylene) at the air/water interface.

PubMed

Fuchs, Christian; Hussain, Hazrat; Schwieger, Christian; Schulz, Matthias; Binder, Wolfgang H; Kressler, Jörg

2015-01-01

The behavior of a series of amphiphilic triblock copolymers of poly(ethylene oxide) (PEO) and poly(isobutylene) (PIB); including both symmetric (same degree of polymerization (DP) of the terminal PEO blocks) PEOm-b-PIBn-b-PEOm and non-symmetric (different DP of the terminal PEO blocks) PEOm-b-PIBn-b-PEOz, is investigated at the air/water interface by measuring surface pressure vs mean molecular area isotherms (π vs mmA), Langmuir-Blodgett (LB) technique, and infrared reflection-absorption spectroscopy (IRRAS). The block copolymer (PEO32-b-PIB160-b-PEO32) with longer PEO segments forms a stable monolayer and the isotherm reveals a pseudo-plateau starting at π∼5.7 mN/m, also observed in the IRRAS, which is assigned to the pancake-to-brush transition related to the PEO dissolution into the subphase and subsequent PEO brush dehydration. Another plateau is observed at π∼40 mN/m, which is attributed to the film collapse due to multilayer formation. The pancake-to-brush transition could not be observed for samples with smaller PEO chains. The isotherms for block copolymers, with short PEO chains, both symmetric (PEO3-b-PIBn-b-PEO3) and non-symmetric (PEO12-b-PIBn-b-PEO3), reveal another transition at π∼20-25 mN/m. This is interpreted to be due to the conformational transition from a folded state where the middle PIB block is anchored to the water surface at both ends by the terminal hydrophilic segments to an unfolded state with PIB anchored to the water surface at one end. It is assumed that this transition involves the removal of PEO3 chains from the water surface in case of non-symmetric PEO12-b-PIB85-b-PEO3 and in case of symmetric, probably one PEO3 of each PEO3-b-PIB85-b-PEO3 chain. Because of the weaker interaction of the short PEO3 chains with the water surface as compared with the relatively longer PEO12 chains, the film of PEO3-b-PIB85-b-PEO3 collapses at much lower surface pressure after the transition as compared with the PEO12-b-PIB85-b-PEO3. The AFM images reveal the formation of microdomains of almost uniform height (6-7 nm) in LB films of PEO3-b-PIB85-b-PEO3 and PEO12-b-PIB85-b-PEO3 after transferring onto silicon surfaces. These domains are assumed to be the mesomorphic domains of ordered and folded PIB chains. Copyright © 2014 Elsevier Inc. All rights reserved.

Precision synthesis of functional materials via RAFT polymerization and click-type chemical reactions

NASA Astrophysics Data System (ADS)

Flores, Joel Diez

2011-12-01

The need to tailor polymeric architectures with specific physico-chemical properties via the simplest, cleanest, and most efficient synthetic route possible has become the ultimate goal in polymer synthesis. Recent progress in macromolecular science, such as the discoveries of controlled/"living" free radical polymerization (CRP) methods, has brought about synthetic capabilities to prepare (co)polymers with advanced topologies, predetermined molecular weights, narrow molecular weight distributions, and precisely located functional groups. In addition, the establishment of click chemistry has redefined the selected few highly efficient chemical reactions that become highly useful in post-polymerization modification strategies. Hence, the ability to make well-defined topologies afforded by controlled polymerization techniques and the facile incorporation of functionalities along the chain via click-type reactions have yielded complex architectures, allowing the investigation of physical phenomena which otherwise could not be studied with systems prepared via conventional methods. The overarching theme of the research work described in this dissertation is the fusion of the excellent attributes of reversible addition-fragmentation chain transfer (RAFT) polymerization method, which is one of the CRP techniques, and click-type chemical reactions in the precision of synthesis of advanced functional materials. Chapter IV is divided into three sections. In Section I, the direct RAFT homopolymerization of 2-(acryloyloxy)ethyl isocyanate (AOI) and subsequent post-polymerization modifications are described. The polymerization conditions were optimized in terms of the choice of RAFT chain transfer agent (CTA), polymerization temperature and the reaction medium. Direct RAFT polymerization of AOI requires a neutral CTA, and relatively low reaction temperature to yield AOI homopolymers with low polydispersities. Efficient side-chain functionalization of PAOI homopolymers was achieved via reaction with model amine, thiol and alcohol compounds yielding urea, thiourethane and urethane derivatives, respectively. Reactions with amines and thiols (in the presence of base) were rapid, quantitative and efficient. However, the reaction with alcohols catalyzed by dibutyltin dilaurate (DBTDL) was relatively slow but proceeded to completion. Selective reaction pathways for the addition of difunctional ethanolamine and mercaptoethanol were also investigated. A related strategy is described in Section II wherein a hydroxyl-containing diblock copolymer precursor was transformed into a library of functional copolymers via two sequential post-polymerization modification reactions. A diblock copolymer scaffold, poly[(N,N-dimethylacrylamide)-b-( N-(2-hydroxyethyl)acrylamide] (PDMA-b-PHEA) was first prepared. The hydroxyl groups of the HEA block were then reacted with 2-(acryloyloxy)ethylisocyanate (AOI) and allylisocyanate (AI) resulting in acrylate- and allyl-functionalized copolymer precursors, respectively. The efficiencies of Michael-type and free radical thiol addition reactions were investigated using selected thiols having alkyl, aryl, hydroxyl, carboxylic acid, amine and amino acid functionalities. The steps of RAFT polymerization, isocyanate-hydroxyl coupling and thiol-ene addition are accomplished under mild conditions, thus offering facile and modular routes to synthesize functional copolymers. The synthesis and solution studies of pH- and salt-responsive triblock copolymer are described in Section III. This system is capable of forming self-locked micellar structures which may be controlled by changing solution pH as well as ionic strength. A triblock copolymer containing a permanently hydrophilic poly(N,N-dimethylacrylamide) (PDMA) outer block, a salt-sensitive zwitterionic poly(3[2-(N-methylacrylamido)ethyl dimethylammonio]propanesulfonate) (PMAEDAPS) middle block and a pH-responsive 3-acrylamido-3-methylbutanoic acid (PAMBA) core block was synthesized using aqueous RAFT polymerization. A facile formation of "self-locking" shell cross-linked micelles is achieved by changing solution pH and salt concentration. The reversible "self-locking" is attained from the interactions of zwitterionic groups in the middle block that constitutes the shell of the micelles. The structure slowly dissociates into unimers in 2-3 days at pH above the pKa of the PAMBA block.

Growth and shrinkage of pluronic micelles by uptake and release of flurbiprofen: variation of pH.

PubMed

Alexander, Shirin; de Vos, Wiebe M; Castle, Thomas C; Cosgrove, Terence; Prescott, Stuart W

2012-04-24

The micellization of Pluronic triblock copolymers (P103, P123, and L43) in the presence of flurbiprofen at different pH was studied by small-angle neutron scattering (SANS), pulsed-field gradient stimulated-echo nuclear magnetic resonance (PFGSE-NMR), and surface tension measurements. Addition of flurbiprofen to the Pluronic at low pH leads to an increase in the fraction of micellization, aggregation number, and the core radius of the micelles. However, changing the pH to above the pKa of flurbiprofen in an ethanol/water mixture (∼6.5) reduces the fraction of micellization and results in a weaker interaction between the drug and micelles due to the increased drug solubility in aqueous solution.

Research on the Ordered Mesoporous Silica for Tobacco Harm Reduction

NASA Astrophysics Data System (ADS)

Wang, Y.; Y Li, Z.; Ding, J. X.; Hu, Z. J.; Liu, Z.; Zhou, G.; Huang, T. H.

2017-12-01

For reducting tobacco harm, this paper prepared an ordered mesoporous silica by using triblock copolymer Pluronic P123 as template. The property of this material was characterized by the X-ray scattering spectrum(XRD), Transmission electron microscopy(TEM), Scanning electron microscopy (SEM) and Nitrogen adsorption/desorption. Then this ordered mesoporous silica was added into the cigarette filter in order to researching its effect of cigarette harm index. The result shows that the feature of SBA-15 was grain morphology, ordered arrangement, tubular porous 2-D hexagonal structure. The application of SBA-15 in cigarette filter can selectively reduce harmful components in cigarette smoke such as crotonaldehyde, hydrogen cyanide, benzo pyrene and tar. The synthesized SBA-15 could properly reduce cigarette harm index.

Surfactant-assisted Nanocasting Route for Synthesis of Highly Ordered Mesoporous Graphitic Carbon and Its Application in CO2 Adsorption

NASA Astrophysics Data System (ADS)

Wang, Yangang; Bai, Xia; Wang, Fei; Qin, Hengfei; Yin, Chaochuang; Kang, Shifei; Li, Xi; Zuo, Yuanhui; Cui, Lifeng

2016-05-01

Highly ordered mesoporous graphitic carbon was synthesized from a simple surfactant-assisted nanocasting route, in which ordered mesoporous silica SBA-15 maintaining its triblock copolymer surfactant was used as a hard template and natural soybean oil (SBO) as a carbon precursor. The hydrophobic domain of the surfactant assisted SBO in infiltration into the template’s mesoporous channels. After the silica template was carbonized and removed, a higher yield of highly-ordered graphitic mesoporous carbon with rod-like morphology was obtained. Because of the improved structural ordering, the mesoporous carbon after amine modification could adsorb more CO2 compared with the amine-functionalized carbon prepared without the assistance of surfactant.

Synthesis and structural characterization of ZnO-and CuO-NPs supported mesoporous silica materials (hexagonal SBA-15 and lamellar-SiO2)

NASA Astrophysics Data System (ADS)

El-Nahhal, Issa M.; Salem, Jamil K.; Tabasi, Nihal S.; Hempelmann, Rolf; Kodeh, Fawzi S.

2018-01-01

Two different mesoporous silica structures (hexagonal and lamellar) were synthesized via sol-gel method using a series of triblock copolymer (Pluronic) surfactants. L81, L61 & L31 surfactants form lamellar structure whereas P123 surfactant forms a hexagonal structure. CuO and ZnO nanoparticles (NPs) supported mesoporous silica were synthesized using impregnation method. The structural properties of these materials were investigated using several characterization techniques such as FTIR, XRD, SAXS, TEM and TGA. SAXS and TEM confirmed that the obtained mesoporous silica is based on the EO/PO ratio of Pluronic surfactants. They proved that the mesoporosity of silica is well maintained even after they loaded with metal oxide nanoparticles.

Aqueous-Based Fabrication of Low-VOC Nanostructured Block Copolymer Films as Potential Marine Antifouling Coatings.

PubMed

Kim, Kris S; Gunari, Nikhil; MacNeil, Drew; Finlay, John; Callow, Maureen; Callow, James; Walker, Gilbert C

2016-08-10

The ability to fabricate nanostructured films by exploiting the phenomenon of microphase separation has made block copolymers an invaluable tool for a wide array of coating applications. Standard approaches to engineering nanodomains commonly involve the application of organic solvents, either through dissolution or annealing protocols, resulting in the release of volatile organic compounds (VOCs). In this paper, an aqueous-based method of fabricating low-VOC nanostructured block copolymer films is presented. The reported procedure allows for the phase transfer of water insoluble triblock copolymer, poly(styrene-block-2 vinylpyridine-block-ethylene oxide) (PS-b-P2VP-b-PEO), from a water immiscible phase to an aqueous environment with the assistance of a diblock copolymeric phase transfer agent, poly(styrene-block-ethylene oxide) (PS-b-PEO). Phase transfer into the aqueous phase results in self-assembly of PS-b-P2VP-b-PEO into core-shell-corona micelles, which are characterized by dynamic light scattering techniques. The films that result from coating the micellar solution onto Si/SiO2 surfaces exhibit nanoscale features that disrupt the ability of a model foulant, a zoospore of Ulva linza, to settle. The multilayered architecture consists of a pH-responsive P2VP-"shell" which can be stimulated to control the size of these features. The ability of these nanostructured thin films to resist protein adsorption and serve as potential marine antifouling coatings is supported through atomic force microscopy (AFM) and analysis of the settlement of Ulva linza zoospore. Field trials of the surfaces in a natural environment show the inhibition of macrofoulants for 1 month.

Multifunctional triblock co-polymer mP3/4HB-b-PEG-b-lPEI for efficient intracellular siRNA delivery and gene silencing.

PubMed

Zhou, Li; Chen, Zhifei; Wang, Feifei; Yang, Xiuqun; Zhang, Biliang

2013-04-01

A non-viral siRNA carrier composed of mono-methoxy-poly (3-hydroxybutyrate-co-4-hydroxybutyrate)-block-polyethylene glycol-block-linear polyethyleneimine (mP3/4HB-b-PEG-b-lPEI) was synthesized using 1800 Da linear polyethyleneimine and evaluated for siRNA delivery. Our study demonstrated that siRNA could be efficiently combined with mP3/4HB-b-PEG-b-lPEI (mAG) co-polymer and was protected from nuclease degradation. The combined siRNA were released from the complexes easily under heparin competition. The particle size of the mAG/siRNA complexes was 158 nm, with a ζ-potential of around 28 mV. Atomic force microscopy images displayed spherical and homogeneously distributed complexes. The mAG block co-polymer displayed low cytotoxicity and efficient cellular uptake of Cy3-siRNA in A549 cells by flow cytometry and confocal microscopy. In vitro transfection efficiency of the block co-polymer was assessed using siRNA against luciferase in cultured A549-Luc, HeLa-Luc, HLF-Luc, A375-Luc and MCF-7-Luc cells. A higher transfection efficiency and lower cytotoxicity was obtained by mAG block co-polymer in five cell lines. Furthermore, a remarkable improvement in luciferase gene silencing efficiency of the mAG complex (up to 90-95%) over that of Lipofectamine™ 2000 (70-82%) was observed in HLF-Luc and A375-Luc cells. Additionally, a mAG/p65-siRNA complex also showed a better capability than Lipofectamine™ 2000/p65-siRNA complex to drastically reduce the p65 mRNA level down to 10-16% in HeLa, U251 and HUVEC cells at an N/P ratio of 70. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Self-assembly concepts for multicompartment nanostructures

NASA Astrophysics Data System (ADS)

Gröschel, André H.; Müller, Axel H. E.

2015-07-01

Compartmentalization is ubiquitous to many biological and artificial systems, be it for the separate storage of incompatible matter or to isolate transport processes. Advancements in the synthesis of sequential block copolymers offer a variety of tools to replicate natural design principles with tailor-made soft matter for the precise spatial separation of functionalities on multiple length scales. Here, we review recent trends in the self-assembly of amphiphilic block copolymers to multicompartment nanostructures (MCNs) under (semi-)dilute conditions, with special emphasis on ABC triblock terpolymers. The intrinsic immiscibility of connected blocks induces short-range repulsion into discrete nano-domains stabilized by a third, soluble block or molecular additive. Polymer blocks can be synthesized from an arsenal of functional monomers directing self-assembly through packing frustration or response to various fields. The mobility in solution further allows the manipulation of self-assembly processes into specific directions by clever choice of environmental conditions. This review focuses on practical concepts that direct self-assembly into predictable nanostructures, while narrowing particle dispersity with respect to size, shape and internal morphology. The growing understanding of underlying self-assembly mechanisms expands the number of experimental concepts providing the means to target and manipulate progressively complex superstructures.

Polymeric micelle assembly for the smart synthesis of mesoporous platinum nanospheres with tunable pore sizes.

PubMed

Li, Yunqi; Bastakoti, Bishnu Prasad; Malgras, Victor; Li, Cuiling; Tang, Jing; Kim, Jung Ho; Yamauchi, Yusuke

2015-09-14

A facile method for the fabrication of well-dispersed mesoporous Pt nanospheres involves the use of a polymeric micelle assembly. A core-shell-corona type triblock copolymer [poly(styrene-b-2-vinylpyridine-b-ethylene oxide), PS-b-P2VP-b-PEO] is employed as the pore-directing agent. Negatively charged PtCl4 (2-) ions preferably interact with the protonated P2VP(+) blocks while the free PEO chains prevent the aggregation of the Pt nanospheres. The size of the mesopores can be finely tuned by varying the length of the PS chain. Furthermore, it is demonstrated that the metallic mesoporous nanospheres thus obtained are promising candidates for applications in electrochemistry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Easy and General Synthesis of Large-Sized Mesoporous Rare-Earth Oxide Thin Films by 'Micelle Assembly'.

PubMed

Li, Yunqi; Bastakoti, Bishnu Prasad; Imura, Masataka; Dai, Pengcheng; Yamauchi, Yusuke

2015-12-01

Large-sized (ca. 40 nm) mesoporous Er2O3 thin films are synthesized by using a triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) as a pore directing agent. Each block makes different contributions and the molar ratio of PVP/Er(3+) is crucial to guide the resultant mesoporous structure. An easy and general method is proposed and used to prepare a series of mesoporous rare-earth oxide (Sm2O3, Dy2O3, Tb2O3, Ho2O3, Yb2O3, and Lu2O3) thin films with potential uses in electronics and optical devices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chameleon-like elastomers with molecularly encoded strain-adaptive stiffening and coloration

NASA Astrophysics Data System (ADS)

Vatankhah-Varnosfaderani, Mohammad; Keith, Andrew N.; Cong, Yidan; Liang, Heyi; Rosenthal, Martin; Sztucki, Michael; Clair, Charles; Magonov, Sergei; Ivanov, Dimitri A.; Dobrynin, Andrey V.; Sheiko, Sergei S.

2018-03-01

Active camouflage is widely recognized as a soft-tissue feature, and yet the ability to integrate adaptive coloration and tissuelike mechanical properties into synthetic materials remains elusive. We provide a solution to this problem by uniting these functions in moldable elastomers through the self-assembly of linear-bottlebrush-linear triblock copolymers. Microphase separation of the architecturally distinct blocks results in physically cross-linked networks that display vibrant color, extreme softness, and intense strain stiffening on par with that of skin tissue. Each of these functional properties is regulated by the structure of one macromolecule, without the need for chemical cross-linking or additives. These materials remain stable under conditions characteristic of internal bodily environments and under ambient conditions, neither swelling in bodily fluids nor drying when exposed to air.

Sulfonated Styrene-(ethylene-co-butylene)-styrene/Montmorillonite Clay Nanocomposites: Synthesis, Morphology, and Properties

PubMed Central

2008-01-01

Sulfonated styrene-(ethylene-butylene)-styrene triblock copolymer (SSEBS) was synthesized by reaction of acetyl sulfate with SEBS. SSESB-clay nanocomposites were then prepared from hydrophilic Na-montmorillonite (MT) and organically (quaternary amine) modified hydrophobic nanoclay (OMT) at very low loading. SEBS did not show improvement in properties with MT-based nanocomposites. On sulfonation (3 and 6 weight%) of SEBS, hydrophilic MT clay-based nanocomposites exhibited better mechanical, dynamic mechanical, and thermal properties, and also controlled water–methanol mixture uptake and permeation and AC resistance. Microstructure determined by X-ray diffraction, atomic force microscopy, and transmission electron microscopy due to better dispersion of MT nanoclay particles and interaction of MT with SSEBS matrix was responsible for this effect. The resulting nanocomposites have potential as proton transfer membranes for Fuel Cell applications.

Flexible, cathodoluminescent and free standing mesoporous silica films with entrapped quasi-2D perovskites

NASA Astrophysics Data System (ADS)

Vassilakopoulou, Anastasia; Papadatos, Dionysios; Koutselas, Ioannis

2017-04-01

The effective entrapment of hybrid organic-inorganic semiconductors (HOIS) into mesoporous polymer-silica hybrid matrices, formed as free standing flexible films, is presented for the first time. A blend of quasi-2D HOIS, simply synthesized by mixing two-dimensional (2D) and three dimensional (3D) HOIS, exhibiting strong photoluminescence, is embedded into porous silica matrices during the sol-gel synthesis, using tetraethylorthosilicate as precursor and Pluronic F-127 triblock copolymer as structure directing agent, under acidic conditions. The final nanostructure hybrid forms flexible, free standing films, presenting high cathodoluminescence and long stable excitonic luminescence, indicating the protective character of the hybrid matrix towards the entrapped perovskite. A significant result is that the photoluminescence of the entrapped HOIS is not affected even after films' prolonged exposure to water.

Direct synthesis and application of bridged diamino-functionalized periodic mesoporous organosilicas with high nitrogen contents

NASA Astrophysics Data System (ADS)

Zhu, Feng-Xia; Zhao, Pu-Su; Sun, Xiao-Jun; An, Li-Tao; Deng, Yong; Wu, Jia-Min

2017-11-01

Bridged diamino-functionalized periodic mesoporous organosilicas [BD-PMO(Et), Et = ethyl] materials were synthesized directly by co-condensation of 2-bis (triethoxysilyl)ethane (BTEE) and 1,4-bis[3-(tirmethoxysilyl)-propyl]ethylenediamino (BTMSEN) under acidic conditions with pluronic triblock copolymer P123 as a template. The nitrogen content in BD-PMO(Et) could be adjusted up to 40% without disturbing the ordered mesoporous structure. These materials were proved to be effective heterogeneous catalysts for the liquid-phase reactions such as Knoevenagel and Henry condensations as well as in the intermolecular cross-double-Michael addition reaction between α-methyl-β-nitrostyrene and α, β-unsaturated ketone. They exhibited comparable catalytic activities with homogeneous catalyst piperazine and can be reused for several times without any negative environmental impact.

Block Copolymer Adhesion Measured by Contact Mechanics Methods

NASA Astrophysics Data System (ADS)

Falsafi, A.; Bates, S.; Tirrell, M.; Pocius, A. V.

1997-03-01

Adhesion measurements for a series of polyolefin diblocks and triblocks are presented. These materials have poly(ethylene-propylene) or poly(ethyl-ethylene) rubbery block, and semicrystalline polyethylene block as physical crosslinker. The experiments consist of compression and decompression profiles of contact area between the samples as a function of normal load, analyzed by the JKR Theory. The samples are prepared either by formation of caps from the bulk material in melting and subsequent cooling, and/or coating them in thin films on surface modified elastic foundations of polydimethylsiloxane caps. The latter minimizes the viscoelastic losses which are dominant in the bulk of material. The effect of molecular architecture and microstructure on adhesion energy and dynamics of separation, obtained from decompression experiments, is discussed in view of their influence on molecular arrangements at the contacting surfaces.

PCL-PDMS-PCL Copolymer-Based Microspheres Mediate Cardiovascular Differentiation from Embryonic Stem Cells.

PubMed

Song, Liqing; Ahmed, Mohammad Faisel; Li, Yan; Bejoy, Julie; Zeng, Changchun; Li, Yan

2017-10-01

Poly-ɛ-caprolactone (PCL) based microspheres have received much attention as drug or growth factor delivery carriers and tissue engineering scaffolds due to their biocompatibility, biodegradability, and tunable biophysical properties. In addition, PCL and polydimethylsiloxane (PDMS) can be fabricated into thermoresponsive shape memory polymers for various biomedical applications (e.g., smart sutures and vascular stents). However, the influence of biophysical properties of PCL-PDMS based microspheres on stem cell lineage commitment has not been well understood. In this study, PDMS was used as soft segments of varying length to tailor the elastic modulus of PCL-based copolymers. It was found that lower elastic modulus (<10 kPa) of the tri-block copolymer PCL-PDMS-PCL promoted vascular differentiation of embryonic stem cells, but the range of 60-100 MPa PCL-PDMS-PCL had little influence on cardiovascular differentiation. Then different sizes (30-140 μm) of PCL-PDMS-PCL microspheres were fabricated and incorporated with embryoid bodies (EBs). Differential expression of KDR, CD31, and VE-cadherin was observed for the EBs containing microspheres of different sizes. Higher expression of KDR was observed for the condition with small size of microspheres (32 μm), while higher CD31 and VE-cadherin expression was observed for the group of medium size of microspheres (94 μm). Little difference in cardiac marker α-actinin was observed for different microspheres. This study indicates that the biophysical properties of PCL-PDMS-PCL microspheres impact vascular lineage commitment and have implications for drug delivery and tissue engineering.

Thermoreversible networks for moldable photo-responsive elastomers (Presentation Recording)

NASA Astrophysics Data System (ADS)

Kornfield, Julia A.; Kurji, Zuleikha

2015-10-01

Soft-solids that retain the responsive optical anisotropy of liquid crystals (LC) can be used as mechano-optical, electro-optical and electro-mechanical elements. We use self-assembly of block copolymers to create reversible LC gels and elastomers that flow at elevated temperatures and physically cross link upon cooling. In the melt, they can be spun, coated or molded. Segregation of the end-blocks forms uniform and uniformly spaced crosslinks. Matched sets of block copolymers are synthesized from a single "prepolymer." Specifically, we begin with polymers having polystyrene (PS) end blocks and a poly(1,2-butadiene) midblock. The pendant vinyl groups along the backbone of the midblock are used to graft mesogens, converting it to a side-group LC polymer (SGLCP). In the present case, cyanobiphenyl groups are used as the nonphotoresponsive mesogens and azobenzene groups are used as photoresponsive mesogens. Here we show that matched pairs of block copolymers, with and without photo-responsive mesogens, provide model systems in which the optical density can be adjusted while holding other properties fixed (cross-link density, modulus, birefringence, isotropic-nematic transition temperature). For example, a triblock in which the SGLCP block has 95% cyanobiphenyl and 5% azo side groups is miscible with one having 100% cyanobiphenyl side groups. Simply blending the two gives a series of LC elastomers that have from 0 to 5% azo, while having all other physical properties matched. Results will be presented that show the outcomesof this approach to systematic and largely independent control of optical density and photo-mechanical sensitivity.

Molecular Velcro constructed from polymer loop brushes showing enhanced adhesion force

NASA Astrophysics Data System (ADS)

Zhou, Tian; Han, Biao; Han, Lin; Li, Christopher; Department of Materials Science; Engineering Team; School of Biomedical Engineering, Science; Health Systems Team

2015-03-01

Molecular Velcro is commonly seen in biological systems as the formation of strong physical entanglement at molecular scale could induce strong adhesion, which is crucial to many biological processes. To mimic this structure, we designed, and fabricated polymer loop brushes using polymer single crystals with desired surface functionality and controlled chain folding. Compared with reported loop brushes fabricated using triblock copolymers, the present loop bushes have precise loop sizes, loop grafting density, and well controlled tethering locations on the solid surface. Atomic force microscopy-based force spectroscopy measurements using a polymer chain coated probe reveal that the adhesion force are significantly enhanced on the loop brush surface as compared with its single-strand counterpart. This study directly shows the effect of polymer brush conformation on their properties, and suggests a promising strategy for advanced polymer surface design.

All-solid-state flexible supercapacitors fabricated with bacterial nanocellulose papers, carbon nanotubes, and triblock-copolymer ion gels.

PubMed

Kang, Yu Jin; Chun, Sang-Jin; Lee, Sung-Suk; Kim, Bo-Yeong; Kim, Jung Hyeun; Chung, Haegeun; Lee, Sun-Young; Kim, Woong

2012-07-24

We demonstrate all-solid-state flexible supercapacitors with high physical flexibility, desirable electrochemical properties, and excellent mechanical integrity, which were realized by rationally exploiting unique properties of bacterial nanocellulose, carbon nanotubes, and ionic liquid based polymer gel electrolytes. This deliberate choice and design of main components led to excellent supercapacitor performance such as high tolerance against bending cycles and high capacitance retention over charge/discharge cycles. More specifically, the performance of our supercapacitors was highly retained through 200 bending cycles to a radius of 3 mm. In addition, the supercapacitors showed excellent cyclability with C(sp) (~20 mF/cm(2)) reduction of only <0.5% over 5000 charge/discharge cycles at the current density of 10 A/g. Our demonstration could be an important basis for material design and development of flexible supercapacitors.

Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in- situ formed lanthanide complexes

NASA Astrophysics Data System (ADS)

Wang, Yige; Wang, Li; Li, Huanrong; Liu, Peng; Qin, Dashan; Liu, Binyuan; Zhang, Wenjun; Deng, Ruiping; Zhang, Hongjie

2008-03-01

Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film. TEM image shows that the in-situ formed lanthanide complexes were homogeneously distributed throughout the whole thin film. The quantum yield and the number of water coordinated to lanthanide metal center have been theoretically determined based on the luminescence data.

Bending and Force Recovery in Polymer Films and Microgel Formation

NASA Astrophysics Data System (ADS)

Elder, Theresa Marie

To determine correlation between geometry and material three different model films: polymethylsiloxane (PDMS), polystyrene (PS), and polycarbonate (PC), were singly bent and doubly bent (forming D-cones). Bends were chosen as they are fundamental in larger complex geometries such as origami and crumples. Bending was carried out between two plates taking force and displacement measurements. Processing of data using moment equations yielded values for bending moduli for studied films that were close to accepted values. Force recovery showed logarithmic trends for PDMS and stretched exponential trends for PS and PC. In a separate experiment a triblock copolymer of polystyrene-polyacrylic acid-polystyrene was subjected to different good and bad solvent mixing with any resulting particle morphology examined. Particles formed more uniformly with high water concentration, particles formed with high toluene concentration and agitation yielded three separate morphologies.

Fabrication of a stretchable solid-state micro-supercapacitor array.

PubMed

Kim, Daeil; Shin, Gunchul; Kang, Yu Jin; Kim, Woong; Ha, Jeong Sook

2013-09-24

We fabricated a stretchable micro-supercapacitor array with planar SWCNT electrodes and an ionic liquid-based triblock copolymer electrolyte. The mechanical stability of the entire supercapacitor array upon stretching was obtained by adopting strategic design concepts. First, the narrow and long serpentine metallic interconnections were encapsulated with polyimide thin film to ensure that they were within the mechanical neutral plane. Second, an array of two-dimensional planar micro-supercapacitor with SWCNT electrodes and an ion-gel-type electrolyte was made to achieve all-solid-state energy storage devices. The formed micro-supercapacitor array showed excellent performances which were stable over stretching up to 30% without any noticeable degradation. This work shows the strong potential of a stretchable micro-supercapacitor array in applications such as wearable computers, power dressing, electronic newspapers, paper-like mobile phones, and other easily collapsible gadgets.

Role of Monomer Sequence, Hydrogen Bonding and Mesoscale Architecture in Marine Antifouling Coatings

NASA Astrophysics Data System (ADS)

Segalman, Rachel

Polypeptoids are non-natural, sequence specific polymers that offer the opportunity to probe the effect of monomer sequence, chirality, and chain shape on self-assembly and surface properties. Additionally, polypeptoid synthesis is more scaleable than traditional polypeptides suggesting their utility in large area applications. We have designed efficient marine anti-fouling coatings by using triblock copolymer scaffolds to which polypeptoids are tethered in order to tune both the modulus and surface energies with great precision. Surprisingly, when short sequences are tethered to a polymer backbone, polypeptoids consistently outperform analogous polypeptides in antifouling properties. We hypothesize that the hydrogen bonding inherent to the polypeptide backbone drives the observed differences in performance. We also find that the polymer scaffold housing the polypeptoids also plays a crucial role in directing surface presentation and therefore the overall coating properties.

RAFT polymerization and some of its applications.

PubMed

Moad, Graeme; Rizzardo, Ezio; Thang, San H

2013-08-01

Reversible addition-fragmentation chain transfer (RAFT) is one of the most robust and versatile methods for controlling radical polymerization. With appropriate selection of the RAFT agent for the monomers and reaction conditions, it is applicable to the majority of monomers subject to radical polymerization. The process can be used in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, which include microgels and polymer brushes. In this Focus Review we describe how the development of RAFT and RAFT application has been facilitated by the adoption of continuous flow techniques using tubular reactors and through the use of high-throughput methodology. Applications described include the use of RAFT in the preparation of polymers for optoelectronics, block copolymer therapeutics, and star polymer rheology control agents. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of the nonionic block copolymer pluronic P85 on gene expression in mouse muscle and antigen-presenting cells.

PubMed

Gaymalov, Zagit Z; Yang, Zhihui; Pisarev, Vladimir M; Alakhov, Valery Yu; Kabanov, Alexander V

2009-02-01

DNA vaccines can be greatly improved by polymer agents that simultaneously increase transgene expression and activate immunity. We describe here Pluronic P85 (P85), a triblock copolymer of ethylene oxide (EO) and propylene oxide (PO) EO(26)-PO(40)-EO(26). Using a mouse model we demonstrate that co-administration of a bacterial plasmid DNA with P85 in a skeletal muscle greatly increases gene expression in the injection site and distant organs, especially the draining lymph nodes and spleen. The reporter expression colocalizes with the specific markers of myocytes and keratinocytes in the muscle, as well as dendritic cells (DCs) and macrophages in the muscle, lymph nodes and spleen. Furthermore, DNA/P85 and P85 alone increase the systemic expansion of CD11c+ (DC), and local expansion of CD11c+, CD14+ (macrophages) and CD49b+ (natural killer) cell populations. DNA/P85 (but not P85) also increases maturation of local DC (CD11c+ CD86+, CD11c+ CD80 +, and CD11c+ CD40+. We suggest that DNA/P85 promotes the activation and recruitment of the antigen-presenting cells, which further incorporate, express and carry the transgene to the immune system organs.

Repair of full-thickness articular cartilage defect using stem cell-encapsulated thermogel.

PubMed

Zhang, Yanbo; Zhang, Jin; Chang, Fei; Xu, Weiguo; Ding, Jianxun

2018-07-01

Cartilage defect repair by hydrogel-based tissue engineering is becoming one of the most potential treatment strategies. In this work, a thermogel of triblock copolymer poly(lactide-co-glycolide)-block-poly(ethylene glycol)-block-poly(lactide-co-glycolide) (PLGA-PEG-PLGA) was prepared as scaffold of bone marrow mesenchymal stem cells (BMMSCs) for repair of full-thickness articular cartilage defect. At first, the copolymer solution showed a reversible sol-gel transition at physiological temperature range, and the mechanical properties of such thermogel were high enough to support the repair of cartilage. Additionally, excellent biodegradability and biocompatibility of the thermogel were demonstrated. By implanting the BMMSC-encapsulated thermogel into the full-thickness articular cartilage defect (5.0 mm in diameter and 4.0 mm in depth) in the rabbit, it was found that the regenerated cartilage integrated well with the surrounding normal cartilage and subchondral bone at 12 weeks post-surgery. The upregulated expression of glycosaminoglycan and type II collagen in the repaired cartilage, and the comparable biomechanical properties with normal cartilage suggested that the cell-encapsulated PLGA-PEG-PLGA thermogel had great potential in serving as the promising scaffold for cartilage regeneration. Copyright © 2018 Elsevier B.V. All rights reserved.

Preparation of uniform-sized PELA microspheres with high encapsulation efficiency of antigen by premix membrane emulsification.

PubMed

Wei, Qiang; Wei, Wei; Tian, Rui; Wang, Lian-Yan; Su, Zhi-Guo; Ma, Guang-Hui

2008-07-15

Relatively uniform-sized poly(lactide-co-ethylene glycol) (PELA) microspheres with high encapsulation efficiency were prepared rapidly by a novel method combining emulsion-solvent extraction and premix membrane emulsification. Briefly, preparation of coarse double emulsions was followed by additional premix membrane emulsification, and antigen-loaded microspheres were obtained by further solidification. Under the optimum condition, the particle size was about 1 mum and the coefficient of variation (CV) value was 18.9%. Confocal laser scanning microscope and flow cytometer analysis showed that the inner droplets were small and evenly dispersed and the antigen was loaded uniformly in each microsphere when sonication technique was occupied to prepare primary emulsion. Distribution pattern of PEG segment played important role on the properties of microspheres. Compared with triblock copolymer PLA-PEG-PLA, the diblock copolymer PLA-mPEG yielded a more stable interfacial layer at the interface of oil and water phase, and thus was more suitable to stabilize primary emulsion and protect coalescence of inner droplets and external water phase, resulting in high encapsulation efficiency (90.4%). On the other hand, solidification rate determined the time for coalescence during microspheres fabrication, and thus affected encapsulation efficiency. Taken together, improving the polymer properties and solidification rate are considered as two effective strategies to yield high encapsulation.

Thermodynamic Interactions between Polystyrene and Long-Chain Poly(n-Alkyl Acrylates) Derived from Plant Oils.

PubMed

Wang, Shu; Robertson, Megan L

2015-06-10

Vegetable oils and their fatty acids are promising sources for the derivation of polymers. Long-chain poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) are readily derived from fatty acids through conversion of the carboxylic acid end-group to an acrylate or methacrylate group. The resulting polymers contain long alkyl side-chains with around 10-22 carbon atoms. Regardless of the monomer source, the presence of alkyl side-chains in poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) provides a convenient mechanism for tuning their physical properties. The development of structured multicomponent materials, including block copolymers and blends, containing poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) requires knowledge of the thermodynamic interactions governing their self-assembly, typically described by the Flory-Huggins interaction parameter χ. We have investigated the χ parameter between polystyrene and long-chain poly(n-alkyl acrylate) homopolymers and copolymers: specifically we have included poly(stearyl acrylate), poly(lauryl acrylate), and their random copolymers. Lauryl and stearyl acrylate were chosen as model alkyl acrylates derived from vegetable oils and have alkyl side-chain lengths of 12 and 18 carbon atoms, respectively. Polystyrene is included in this study as a model petroleum-sourced polymer, which has wide applicability in commercially relevant multicomponent polymeric materials. Two independent methods were employed to measure the χ parameter: cloud point measurements on binary blends and characterization of the order-disorder transition of triblock copolymers, which were in relatively good agreement with one another. The χ parameter was found to be independent of the alkyl side-chain length (n) for large values of n (i.e., n > 10). This behavior is in stark contrast to the n-dependence of the χ parameter predicted from solubility parameter theory. Our study complements prior work investigating the interactions between polystyrene and short-chain polyacrylates (n ≤ 10). To our knowledge, this is the first study to explore the thermodynamic interactions between polystyrene and long-chain poly(n-alkyl acrylates) with n > 10. This work lays the groundwork for the development of multicomponent structured systems (i.e., blends and copolymers) in this class of sustainable materials.

Molecular Dynamics Simulations of Cubic Phases in Pluronics Systems and Their Role in Templating Nanoparticles

NASA Astrophysics Data System (ADS)

Anderson, Joshua; Travesset, Alex; Lorenz, Chris

2007-03-01

We discuss molecular dynamics simulations aimed at predicting phase diagrams in Pluronic systems. Crystalline phases with cubic symmetries are particularly challenging to simulate. A general method that is able to obtain these phases is presented. As an example, we show our results for a system of ABA triblock polymers where each hydrophilic A block contains 10 beads and the hydrophobic block B contains 7 beads. These values match the ratio of PEO to PPO in Pluronic F127. Numerous simulation runs are carried out with differing initial conditions, which consistently produce textbook bcc and fcc lattices of micelles along with two other distorted bcc lattices. We find that the formation of a lattice is sensitive to the system's preparation and depends mainly on the kinetic temperature and equilibration time. Examination of the distorted lattices shows that they are related to the finite size of the simulation box. We conclude with some discussion on using these crystals as a template for nanoparticles or biomineralization.

Block Copolymers and Ionic Liquids: A New Class of Functional Nanocomposites

NASA Astrophysics Data System (ADS)

Lodge, Timothy

2009-03-01

Block copolymers provide a remarkably versatile platform for achieving desired nanostructures by self-assembly, with lengthscales varying from a few nanometers up to several hundred nanometers. Ionic liquids are an emerging class of solvents, with an appealing set of physical attributes. These include negligible vapor pressure, high chemical and thermal stability, tunable solvation properties, high ionic conductivity, and wide electrochemical windows. For various applications it will be necessary to solidify the ionic liquid into particular spatial arrangements, such as membranes or gels, or to partition the ionic liquid in coexisting phases, such as microemulsions and micelles. One example includes formation of spherical, cylindrical, and vesicular micelles by poly(butadiene-b-ethylene oxide) and poly(styrene-b-methylmethacrylate) in the common hydrophobic ionic liquids [BMI][PF6] and [EMI][TFSI]. This work has been extended to the formation of reversible micelle shuttles between ionic liquids and water, whereby entire micelles transfer from one phase to the other, reversibly, depending on temperature and solvent quality. Formation of ion gels has been achieved by self-assembly of poly(styrene-b-ethylene oxide-b-styrene) triblocks in ionic liquids, and by the thermoreversible system poly(N-isopropylacrylamide-b-ethylene oxide-b-N-isopropylacrylamide), using as little as 4% copolymer. Further, these gels have been shown to be remarkably effective as gate dielectrics in organic thin film transistors. The remarkably high capacitance of the ion gels (> 10 μF/cm^2) supports a very high carrier density in an organic semiconductor such as poly(3-hexylthiophene), leading to milliamp currents for low applied voltages. Furthermore, the rapid mobility of the ions enables switching speeds approaching 10 kHz, orders of magnitude higher than achievable with other polymer-based dielectrics such as PEO/LiClO4. Finally, we have shown that ordered nanostructures of block copolymers plus ionic liquids show the characteristic self-assembly properties of strongly-segregated systems. Prospects for anisotropic ionic conductivity are also being explored.

Influence of electrolytes on the microenvironment of F127 triblock copolymer micelles: a solvation and rotational dynamics study of coumarin dyes.

PubMed

Kumbhakar, Manoj; Ganguly, Rajib

2007-04-19

Dynamic Stokes' shift and fluorescence anisotropy measurements of coumarin 153 (C153) and coumarin 151 (C151) as fluorescence probes have been carried out to understand the influence of electrolytes (NaCl and LiCl) on the hydration behavior of aqueous (ethylene oxide)100-(propylene oxide)70-(ethylene oxide)100 (EO100-PO70-EO100, F127) block copolymer micelles. A small blue shift in the fluorescence spectra of C153 has been observed in presence of electrolytes due to the dehydration of the oxyethylene chains in the PEO-PPO region, although fluorescence spectra of C151 remain unaltered. The close vicinity of bulk water for C151 probably negates the effect of dehydration in the PEO region. Fluorescence anisotropy measurements indicate a gradual increase in microviscosity with electrolyte concentrations. The partial collapse of copolymer blocks in the presence of electrolytes has been suggested as a reason for the increase in microviscosity along with the strong hydration of ions in the corona region. The interplay between the ion hydration and the mechanically trapped water content, and specific interaction of ions, such as complexation of Li+ ions with the copolymer block, is found to control solvation dynamics in the corona region. In addition to that, it has been established that Na+ ions reside deep into the corona region whereas Li+ ions prefer to reside closer to the surface. Owing to its higher lyotropicity, LiCl influences the corona hydration to a greater extent than NaCl and sets in micelle-micelle interaction above the 2 M LiCl concentration, as reflected in the saturation of solvation time constants. The formation of larger clusters of F127 micelles above 2 M LiCl has been confirmed by dynamic light scattering measurements; however, such cluster formation is not evident with NaCl.

Antibacterial modification of an injectable, biodegradable, non-cytotoxic block copolymer-based physical gel with body temperature-stimulated sol-gel transition and controlled drug release.

PubMed

Wang, Xiaowen; Hu, Huawen; Wang, Wenyi; Lee, Ka I; Gao, Chang; He, Liang; Wang, Yuanfeng; Lai, Chuilin; Fei, Bin; Xin, John H

2016-07-01

Biomaterials are being extensively used in various biomedical fields; however, they are readily infected with microorganisms, thus posing a serious threat to the public health care. We herein presented a facile route to the antibacterial modification of an important A-B-A type biomaterial using poly (ethylene glycol) methyl ether (mPEG)- poly(ε-caprolactone) (PCL)-mPEG as a typical model. Inexpensive, commercial bis(2-hydroxyethyl) methylammonium chloride (DMA) was adopted as an antibacterial unit. The effective synthesis of the antibacterial copolymer mPEG-PCL-∼∼∼-PCL-mPEG (where ∼∼∼ denotes the segment with DMA units) was well confirmed by FTIR and (1)H NMR spectra. At an appropriate modification extent, the DMA unit could render the copolymer mPEG-PCL-∼∼∼-PCL-mPEG highly antibacterial, but did not largely alter its fascinating intrinsic properties including the thermosensitivity (e.g., the body temperature-induced sol-gel transition), non-cytotoxicity, and controlled drug release. A detailed study on the sol-gel-sol transition behavior of different copolymers showed that an appropriate extent of modification with DMA retained a sol-gel-sol transition, despite the fact that a too high extent caused a loss of sol-gel-sol transition. The hydrophilic and hydrophobic balance between mPEG and PCL was most likely broken upon a high extent of quaternization due to a large disturbance effect of DMA units at a large quantity (as evidenced by the heavily depressed PCL segment crystallinity), and thus the micelle aggregation mechanism for the gel formation could not work anymore, along with the loss of the thermosensitivity. The work presented here is highly expected to be generalized for synthesis of various block copolymers with immunity to microorganisms. Light may also be shed on understanding the phase transition behavior of various multiblock copolymers. Copyright © 2016 Elsevier B.V. All rights reserved.

Facile Control of the Porous Structure of Larch-Derived Mesoporous Carbons via Self-Assembly for Supercapacitors

PubMed Central

Zhao, Xin; Li, Wei; Chen, Honglei; Wang, Shoujuan; Kong, Fangong; Liu, Shouxin

2017-01-01

Mesoporous carbons have been successfully synthesized via self-assembly using larch-based resins as precursors and triblock copolymers as soft templates. The porous structure of mesoporous carbons can be tailored by adjusting the ratio of hydrophilic/hydrophobic (EO/PO) units owing to interfacial curvature. Interestingly, the porous structures show a distinct change from vortex-like to worm-like pores, to stripe-like pores, and to ordered two-dimensional hexagonal pores as the ratio of hydrophilic/hydrophobic units increases, indicating the significant effect of EO/PO ratio on the porous structure. The mesoporous carbons as supercapacitor electrodes exhibit superior electrochemical capacitive performance and a high degree of reversibility after 2000 cycles for supercapacitors due to the well-defined mesoporosity of the carbon materials. Meanwhile, the superior carbon has a high specific capacitance of 107 F·g−1 in 6 M KOH at a current density of 10 A·g−1. PMID:29156641

Facile Control of the Porous Structure of Larch-Derived Mesoporous Carbons via Self-Assembly for Supercapacitors.

PubMed

Zhao, Xin; Li, Wei; Chen, Honglei; Wang, Shoujuan; Kong, Fangong; Liu, Shouxin

2017-11-20

Mesoporous carbons have been successfully synthesized via self-assembly using larch-based resins as precursors and triblock copolymers as soft templates. The porous structure of mesoporous carbons can be tailored by adjusting the ratio of hydrophilic/hydrophobic (EO/PO) units owing to interfacial curvature. Interestingly, the porous structures show a distinct change from vortex-like to worm-like pores, to stripe-like pores, and to ordered two-dimensional hexagonal pores as the ratio of hydrophilic/hydrophobic units increases, indicating the significant effect of EO/PO ratio on the porous structure. The mesoporous carbons as supercapacitor electrodes exhibit superior electrochemical capacitive performance and a high degree of reversibility after 2000 cycles for supercapacitors due to the well-defined mesoporosity of the carbon materials. Meanwhile, the superior carbon has a high specific capacitance of 107 F·g -1 in 6 M KOH at a current density of 10 A·g -1 .

Monodisperse Carbon Nanospheres with Hierarchical Porous Structure as Electrode Material for Supercapacitor

NASA Astrophysics Data System (ADS)

Yang, Xiutao; Xia, Hui; Liang, Zhongguan; Li, Haiyan; Yu, Hongwen

2017-09-01

Carbon nanospheres with distinguishable microstructure were prepared by carbonization and subsequent KOH activation of F108/resorcinol-formaldehyde composites. The dosage of triblock copolymer Pluronic F108 is crucial to the microstructure differences. With the adding of F108, the polydisperse carbon nanospheres (PCNS) with microporous structure, monodisperse carbon nanospheres (MCNS) with hierarchical porous structure, and agglomerated carbon nanospheres (ACNS) were obtained. Their microstructure and capacitance properties were carefully compared. As a result of the synergetic effect of mono-dispersion spheres and hierarchical porous structures, the MCNS sample shows improved electrochemical performance, i.e., the highest specific capacitance of 224 F g-1 (0.2 A g-1), the best rate capability (73% retention at 20 A g-1), and the most excellent capacitance retention of 93% over 10,000 cycles, making it to be the promising electrode material for high-performance supercapacitors.

Synthesis of a large-sized mesoporous phosphosilicate thin film through evaporation-induced polymeric micelle assembly.

PubMed

Li, Yunqi; Bastakoti, Bishnu Prasad; Imura, Masataka; Suzuki, Norihiro; Jiang, Xiangfen; Ohki, Shinobu; Deguchi, Kenzo; Suzuki, Madoka; Arai, Satoshi; Yamauchi, Yusuke

2015-01-01

A triblock copolymer, poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) was used as a soft template to synthesize large-sized mesoporous phosphosilicate thin films. The kinetically frozen PS core stabilizes the micelles. The strong interaction of the inorganic precursors with the P2VP shell enables the fabrication of highly robust walls of phosphosilicate and the PEO helps orderly packing of the micelles during solvent evaporation. The molar ratio of phosphoric acid and tetraethyl orthosilicate is crucial to achieve the final mesostructure. The insertion of phosphorus species into the siloxane network is studied by (29) Si and (31) P MAS NMR spectra. The mesoporous phosphosilicate films exhibit steady cell adhesion properties and show great promise as excellent materials in bone-growth engineering applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Versatile magnetometer assembly for characterizing magnetic properties of nanoparticles.

PubMed

Araujo, J F D F; Bruno, A C; Louro, S R W

2015-10-01

We constructed a versatile magnetometer assembly for characterizing iron oxide nanoparticles. The magnetometer can be operated at room temperature or inside a cryocooler at temperatures as low as 6 K. The magnetometer's sensor can be easily exchanged and different detection electronics can be used. We tested the assembly with a non-cryogenic commercial Hall sensor and a benchtop multimeter in a four-wire resistance measurement scheme. A magnetic moment sensitivity of 8.5 × 10(-8) Am(2) was obtained with this configuration. To illustrate the capability of the assembly, we synthesized iron oxide nanoparticles coated with different amounts of a triblock copolymer, Pluronic F-127, and characterized their magnetic properties. We determined that the polymer coating does not affect the magnetization of the particles at room temperature and demonstrates that it is possible to estimate the average size of coating layers from measurements of the magnetic field of the sample.

Versatile magnetometer assembly for characterizing magnetic properties of nanoparticles

NASA Astrophysics Data System (ADS)

Araujo, J. F. D. F.; Bruno, A. C.; Louro, S. R. W.

2015-10-01

We constructed a versatile magnetometer assembly for characterizing iron oxide nanoparticles. The magnetometer can be operated at room temperature or inside a cryocooler at temperatures as low as 6 K. The magnetometer's sensor can be easily exchanged and different detection electronics can be used. We tested the assembly with a non-cryogenic commercial Hall sensor and a benchtop multimeter in a four-wire resistance measurement scheme. A magnetic moment sensitivity of 8.5 × 10-8 Am2 was obtained with this configuration. To illustrate the capability of the assembly, we synthesized iron oxide nanoparticles coated with different amounts of a triblock copolymer, Pluronic F-127, and characterized their magnetic properties. We determined that the polymer coating does not affect the magnetization of the particles at room temperature and demonstrates that it is possible to estimate the average size of coating layers from measurements of the magnetic field of the sample.

Physicochemical properties of micelles of poly(styrene-b-[3-(methacryloylamino)propyl]trimethylammonium chloride-b-ethylene oxide) in aqueous solutions.

PubMed

Liu, Jingjing; Liu, Dian; Yokoyama, Yuuichi; Yusa, Shin-Ichi; Nakashima, Kenichi

2009-01-20

Polymeric micelles from a new triblock copolymer, polystyrene-block-poly[(3-(methacryloylamino)propyl)trimethylammonium chloride]-block-poly(ethylene oxide) (PS-b-PMAPTAC-b-PEO), were prepared in aqueous solutions and characterized by various techniques including dynamic light scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and fluorescence spectroscopy. The micelle consists of a PS core, PMAPTAC shell, and PEO corona. It was revealed by SEM and DLS measurements that the micelles have a spherical structure with a hydrodynamic diameter about 75 nm. The addition of tungstate to the micellar solution caused a morphological change in the micelles from extended to shrunken spheres, which can be attributed to the fact that electrostatic repulsion among the cationic PMAPTAC blocks is canceled by the negative charge of the bound tungstate ions. Effective incorporation of tungstate ions into the micelles were confirmed by TEM and zeta-potential measurements.

The research and preparation of a novel nano biodegradable polymer external reinforcement

NASA Astrophysics Data System (ADS)

Zhang, Xiangman; Chen, Bin; Fu, Weiguo; Fang, Zhengdong; Liu, Zhenjie; Lu, Weifeng; Shi, Zhengyu; Chen, Lili; Chen, Tao

2011-10-01

The use of current drug-loaded vascular scaffolds is limited in sustained drug release and stability studies in clinical and preclinical trials. We found that poly( L-glutamic acid)-b-poly(propylene oxide)-b-poly( L-glutamic acid) (PLGA-b-PPO-b-PLGA) triblock copolymers can deliver multiple poorly water-soluble drugs (e.g., Paclitaxel) at clinically relevant doses. In this study, we synthesized a new drug-loaded vascular external graft with electrospun nanofibrous scaffolds [poly( L-lactide-co-ɛ-caprolactone) (PLCL):fibrinogen; 2:1 (w/w)] and drug-loaded PLGA-b-PPO-b-PLGA micelles. Cell proliferation and viability assay results showed that beagle smooth muscle cells grew well on the surface of vascular graft-coated micelles at a percentages of 10% (w/w) GPG:PLCL-fibrinogen. This study demonstrates that micelle-coated electrospun PLCL-fibrinogen vascular scaffolds have potential applications in vascular tissue engineering.

Mesoporous CeO2 nanoparticles synthesized by an inverse miniemulsion technique and their catalytic properties in methane oxidation

NASA Astrophysics Data System (ADS)

Nabih, Nermeen; Schiller, Renate; Lieberwirth, Ingo; Kockrick, Emanuel; Frind, Robert; Kaskel, Stefan; Weiss, Clemens K.; Landfester, Katharina

2011-04-01

Cerium(IV) oxide nanoparticles were synthesized using an inverse miniemulsion technique with cerium nitrate hexahydrate as precursor. The resulting nanocrystallites are as small as 5 nm with a specific surface area of 158 m2 g - 1 after calcination at 400 °C. With the addition of cetyltrimethylammonium bromide (CTAB) or (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)) triblock copolymers (PEO-PPO-PEO) as template in the miniemulsion droplets, the specific surface area can be increased up to 255 m2 g - 1. The miniemulsions were characterized by dynamic light scattering (DLS) and the obtained oxides were examined by x-ray diffraction (XRD), nitrogen sorption (BET and BJH), and transmission electron microscopy (TEM). The catalytic activity of the resulting ceria was investigated for the temperature-programmed oxidation (TPO) of methane.

Fracture behavior of nano-scale rubber-modified epoxies

NASA Astrophysics Data System (ADS)

Bacigalupo, Lauren N.

The primary focus of the first portion of this study is to compare physical and mechanical properties of a model epoxy that has been toughened with one of three different types of rubber-based modifier: a traditional telechelic oligomer (phase separates into micro-size particles), a core-shell latex particle (preformed nano-scale particles) and a triblock copolymer (self-assembles into nano-scale particles). The effect of modifier content on the physical properties of the matrix was determined using several thermal analysis methods, which provided insight into any inherent alterations of the epoxy matrix. Although the primary objective is to study the role of particle size on the fracture toughness, stiffness and strength were also determined since these properties are often reduced in rubber-toughened epoxies. It was found that since the CSR- and SBM-modified epoxies are composed of less rubber, thermal and mechanical properties of the epoxy were better maintained. In order to better understand the fracture behavior and mechanisms of the three types of rubber particles utilized in this study, extensive microscopy analysis was conducted. Scanning transmission electron microscopy (STEM) was used to quantify the volume fraction of particles, transmission optical microscopy (TOM) was used to determine plastic damage zone size, and scanning electron microscopy (SEM) was used to assess void growth in the plastic zone after fracture. By quantifying these characteristics, it was then possible to model the plastic damage zone size as well as the fracture toughness to elucidate the behavior of the rubber-modified epoxies. It was found that localized shear yielding and matrix void growth are the active toughening mechanisms in all rubber-modified epoxies in this study, however, matrix void growth was more prevalent. The second portion of this study investigated the use of three acrylate-based triblocks and four acrylate-based diblocks to modify a model epoxy system. By varying block lengths and the polarity of the epoxy-miscible blocks, a variety of morphologies were generated (such as spherical micelles, layer particles and worm-like micelles). It was found that in some cases, the epoxy-miscible block did not yield domains substantial enough to facilitate increases in toughness. Overall, the thermal and mechanical properties of the acrylate-based triblock- and diblock-modified epoxies were found to be similar to CTBN-modified epoxy, which was used as a control. However, there were properties that were improved with the acrylate-based diblock-modified epoxies when compared to the acrylate-based triblock modified epoxies. Specifically, the viscosity penalty of the diblock-modified epoxies was shown to be a marked improvement over the triblock-modified epoxies, especially given that the fracture toughness values are similar. This reduction in the viscosity penalty becomes an important criterion when considering processing procedures and applications. Additionally, comparing the morphology of the resulting modified-epoxies utilizing atomic force microscopy (AFM) and scanning electron microscopy (SEM) led to a better understanding of the relationship between the particle morphology obtained and the physical properties of the acrylate-based rubber-modified epoxy systems in this research.

Transport properties of proton-exchange membranes: Effect of supercritical-fluid processing and chemical functionality

NASA Astrophysics Data System (ADS)

Pulido Ayazo

NafionRTM membranes commonly used in direct methanol fuel cells (DMFC), are tipically limited by high methanol permeability (also known as the cross-over limitation). These membranes have phase segregated sulfonated ionic domains in a perfluorinated backbone, which makes processing challenging and limited by phase equilibria considerations. This study used supercritical fluids (SCFs) as a processing alternative, since the gas-like mass transport properties of SCFs allow a better penetration into the membranes and the use of polar co-solvents influenced their morphology, fine-tuning the physical and transport properties in the membrane. Measurements of methanol permeability and proton conductivity were performed to the NafionRTM membranes processed with SCFs at 40ºC and 200 bar and the co-solvents as: acetone, tetrahydrofuran (THF), isopropyl alcohol, HPLC-grade water, acetic acid, cyclohexanone. The results obtained for the permeability data were of the order of 10 -8-10-9 cm2/s, two orders of magnitude lower than unprocessed Nafion. Proton conductivity results obtained using AC impedance electrochemical spectroscopy was between 0.02 and 0.09 S/cm, very similar to the unprocessed Nafion. SCF processing with ethanol as co-solvent reduced the methanol permeability by two orders of magnitude, while the proton conductivity was only reduced by 4%. XRD analysis made to the treated samples exhibited a decreasing pattern in the crystallinity, which affects the transport properties of the membrane. Also, SAXS profiles of the Nafion membranes processed were obtained with the goal of determining changes produced by the SCF processing in the hydrophilic domains of the polymer. With the goal of searching for new alternatives in proton exchange membranes (PEMs) triblock copolymer of poly(styrene-isobutylene-styrene) (SIBS) and poly(styrene-isobutylene-styrene) SEBS were studied. These sulfonated tri-block copolymers had lower methanol permeabilities, but also lower proton conductivity, even with blends of these and blends with Nafion membranes. Other alternative studied was the functionalization of the membranes SIBS with metallic cations, which decreased the methanol permeability in the membranes containing the cations Mg2+, Zn2+ and Al 3+, while the proton conductivity was maintained more or less constant. The permeation of methanol vapor was investigated and the behavior through the membranes studied followed a pattern of Fick's Law, while the pattern shown by the permeation in liquid phase was non-Fickian.

Synthesis and characterization of injectable, thermosensitive, and biocompatible acellular bone matrix/poly(ethylene glycol)-poly (ε-caprolactone)-poly(ethylene glycol) hydrogel composite.

PubMed

Ni, Pei-Yan; Fan, Min; Qian, Zhi-Yong; Luo, Jing-Cong; Gong, Chang-Yang; Fu, Shao-Zhi; Shi, Shuai; Luo, Feng; Yang, Zhi-Ming

2012-01-01

In orthopedic tissue engineering, the extensively applied acellular bone matrix (ABM) can seldom be prefabricated just right to mold the cavity of the diverse defects, might induce severe inflammation on account of the migration of small granules and usually bring the patients great pain in the treatment. In this study, a new injectable thermosensitive ABM/PECE composite with good biocompatibility was designed and prepared by adding the ABM granules into the triblock copolymer poly(ethylene eglycol)-poly(ε-caprolactone)-poly(ethylene eglycol) (PEG-PCL-PEG, PECE). The PECE was synthesized by ring-opening copolymerization and characterized by ¹H NMR. The ABM was prepared by acellular treatment of natural bone and ground to fine granules. The obtained ABM/PECE composite showed the most important absorption bands of ABM and PECE copolymer in FT-IR spectroscopy and underwent sol-gel phage transition from solution to nonflowing hydrogel at 37°C. SEM results indicated that the ABM/PECE composite with different ABM contents all presented similar porous 3D structure. ABM/PECE composite presented mild cytotoxicity to rat MSCs in vitro and good biocompatibility in the BALB/c mice subcutis up to 4 weeks. In conclusion, all the results confirmed that the injectable thermosensitive ABM/PECE composite was a promising candidate for orthopedic tissue engineering in a minimally-invasive way. Copyright © 2011 Wiley Periodicals, Inc.

Bilateral PLA/alginate membranes for the prevention of postsurgical adhesions.

PubMed

Kessler, Martina; Esser, Eva; Groll, Jürgen; Tessmar, Jörg

2016-11-01

A bilateral barrier membrane for the prevention of postsurgical adhesions was developed. Thereby, a smooth PLA side was supposed to keep the affected tissues glidingly separated, while a mucoadhesive side made of alginate was meant to keep the barrier resident on the site of injury so that suturing becomes redundant or at least the membrane stays long enough to facilitate surgical handling. Because hydrophilic alginate and lipophilic PLA films show only low cohesion, solution electrospun meshes of PLA and PLA-PEG-PLA triblock copolymers with varying poly(ethylene glycol) [PEG] content were investigated as cohesion promoter to avoid an easy separation of the functionally different layers. Using direct electrospinning onto the PLA film, a modified contact surface of the mesh was created, which allowed the tested alginate solutions (3%, 5%) to infiltrate to different extents. Thereby, an increasing content of hydrophilic PEG within the mesh copolymer and a lower alginate concentration facilitated the infiltration. As a result, the PLA film with a PLA35k-PEG10k-PLA35k (racemic PLA chains) mesh and an alginate layer cast from a 3% alginate solution appeared to be the most effective combination as examined by means of a t peel test, a mucoadhesion test, a tensile test and optical evaluations. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1563-1570, 2016. © 2015 Wiley Periodicals, Inc.

Effect of poly(ethylene oxide) homopolymer and two different poly(ethylene oxide-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymers on morphological, optical, and mechanical properties of nanostructured unsaturated polyester.

PubMed

Builes, Daniel H; Hernández-Ortiz, Juan P; Corcuera, Ma Angeles; Mondragon, Iñaki; Tercjak, Agnieszka

2014-01-22

Novel nanostructured unsaturated polyester resin-based thermosets, modified with poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and two poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) block copolymers (BCP), were developed and analyzed. The effects of molecular weights, blocks ratio, and curing temperatures on the final morphological, optical, and mechanical properties were reported. The block influence on the BCP miscibility was studied through uncured and cured mixtures of unsaturated polyester (UP) resins with PEO and PPO homopolymers having molecular weights similar to molecular weights of the blocks of BCP. The final morphology of the nanostructured thermosetting systems, containing BCP or homopolymers, was investigated, and multiple mechanisms of nanostructuration were listed and explained. By considering the miscibility of each block before and after curing, it was determined that the formation of the nanostructured matrices followed a self-assembly mechanism or a polymerization-induced phase separation mechanism. The miscibility between PEO or PPO blocks with one of two phases of UP matrix was highlighted due to its importance in the final thermoset properties. Relationships between the final morphology and thermoset optical and mechanical properties were examined. The mechanisms and physics behind the morphologies lead toward the design of highly transparent, nanostructured, and toughened thermosetting UP systems.

2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization

DOE PAGES

Feng, Hongbo; Changez, Mohammad; Hong, Kunlun; ...

2016-12-23

Poly(2-isopropenyl-2-oxazoline) (PIPOx) has drawn significant attention for numerous applications. However, the successful living anionic polymerization of 2-isopropenyl-2-oxazoline has not been reported previously. In this paper, we describe how well-defined PIPOx with quantitative yields, controlled molecular weights from 6800 to over 100 000 g/mol and low polydispersity indices (PDI ≤ 1.17) were synthesized successfully via living anionic polymerization using diphenylmethylpotassium/diethylzinc (DPM-K/Et 2Zn) in tetrahydrofuran (THF) at 0 °C. In particular, we report the precise synthesis of well-defined PIPOx with the highest molecular weight ever reported (over 100 000 g/mol) and low PDI of 1.17. The resulting polymers were characterized by 1Hmore » and 13C nuclear magnetic resonance spectroscopy (NMR) along with size exclusion chromatography (SEC). Additionally, the reactivity of living PIPOx was investigated by crossover block copolymerization with styrene (St), 2-vinylpyridine (2VP), and methyl methacrylate (MMA). It was found that the nucleophilicity of living PIPOx is of this order: living PS > living P2VP > living PMMA > living PIPOx. The self-assembly behavior in bulk of PIPOx-b-PS-b-PIPOx triblock copolymers having different block ratios of 10:80:10 and 25:50:25 was studied using transmission electron microscopy (TEM). Finally, the formation of spherical and lamellar nanostructures, respectively, was observed.« less

2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization

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

Feng, Hongbo; Changez, Mohammad; Hong, Kunlun

Poly(2-isopropenyl-2-oxazoline) (PIPOx) has drawn significant attention for numerous applications. However, the successful living anionic polymerization of 2-isopropenyl-2-oxazoline has not been reported previously. In this paper, we describe how well-defined PIPOx with quantitative yields, controlled molecular weights from 6800 to over 100 000 g/mol and low polydispersity indices (PDI ≤ 1.17) were synthesized successfully via living anionic polymerization using diphenylmethylpotassium/diethylzinc (DPM-K/Et 2Zn) in tetrahydrofuran (THF) at 0 °C. In particular, we report the precise synthesis of well-defined PIPOx with the highest molecular weight ever reported (over 100 000 g/mol) and low PDI of 1.17. The resulting polymers were characterized by 1Hmore » and 13C nuclear magnetic resonance spectroscopy (NMR) along with size exclusion chromatography (SEC). Additionally, the reactivity of living PIPOx was investigated by crossover block copolymerization with styrene (St), 2-vinylpyridine (2VP), and methyl methacrylate (MMA). It was found that the nucleophilicity of living PIPOx is of this order: living PS > living P2VP > living PMMA > living PIPOx. The self-assembly behavior in bulk of PIPOx-b-PS-b-PIPOx triblock copolymers having different block ratios of 10:80:10 and 25:50:25 was studied using transmission electron microscopy (TEM). Finally, the formation of spherical and lamellar nanostructures, respectively, was observed.« less

Macroscopic lateral heterogeneity observed in a laterally mobile immiscible mixed polyelectrolyte-neutral polymer brush

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

Lee, Hoyoung; Tsouris, Vasilios; Lim, Yunho

We studied mixed poly(ethylene oxide) (PEO) and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes. The question we attempted to answer was: when the chain grafting points are laterally mobile, how will this lateral mobility influence the structure and phase behavior of the mixed brush? Three different model mixed PEO/PDMAEMA brush systems were prepared: (1) a laterally mobile mixed brush by spreading onto the air–water interface a mixture of poly(ethylene oxide)–poly(n-butyl acrylate) (PEO–PnBA) and poly(2-(dimethylamino)ethyl methacrylate)–poly(n-butyl acrylate) (PDMAEMA–PnBA) diblock copolymers (the specific diblock copolymers used will be denoted as PEO 113–PnBA 100 and PDMAEMA 118–PnBA 100, where the subscripts refer to the number-average degreesmore » of polymerization of the individual blocks), (2) a mobility-restricted (inseparable) version of the above mixed brush prepared using a PEO–PnBA–PDMAEMA triblock copolymer (denoted as PEO 113–PnBA 89–PDMAEMA 120) having respective brush molecular weights matched with those of the diblock copolymers, and (3) a different laterally mobile mixed PEO and PDMAEMA brush prepared from a PEO 113–PnBA 100 and PDMAEMA 200–PnBA 103 diblock copolymer combination, which represents a further more height-mismatched mixed brush situation than described in (1). These three mixed brush systems were investigated by surface pressure–area isotherm and X-ray (XR) reflectivity measurements. These experimental data were analyzed within the theoretical framework of a continuum self-consistent field (SCF) polymer brush model. The combined experimental and theoretical results suggest that the mobile mixed brush derived using the PEO 113–PnBA 100 and PDMAEMA 118–PnBA 100 combination (i.e., mixed brush System #1) undergoes a lateral macroscopic phase separation at high chain grafting densities, whereas the more height-mismatched system (System #3) is only microscopically phase separated under comparable brush density conditions even though the lateral mobility of the grafted chains is unrestricted. The macroscopic phase separation observed in the laterally mobile mixed brush system is in contrast with the microphase separation behavior commonly observed in two-dimensional laterally mobile charged small molecule mixtures. Further study is needed to determine the detailed morphologies of the macro- and microphase-separated mixed PEO/PDMAEMA brushes.« less

Formation of cage-like particles by poly(amino acid)-based block copolymers in aqueous solution.

PubMed Central

Cudd, A; Bhogal, M; O'Mullane, J; Goddard, P

1991-01-01

When dissolved in N,N-dimethylformamide and then dialyzed against phosphate-buffered saline, A-B-A block copolymers composed of poly [N5-(2-hydroxyethyl)-L-glutamine]-block-poly(gamma-benzyl-L-glutamate)- block-poly [N5-(2-hydroxyethyl)-L-glutamine] form particles. The particles are cage-like structures with average diameters of 300 nm (average polydispersity, 0.3-0.5). They are stable in aqueous solution at 4 degrees C for up to 3 weeks, at which time flocculation becomes apparent. Negative staining and freeze-fracture electron microscopy suggest that cage-like particles are formed by selective association of segregated micelle populations. A model of particle formation is presented in which B blocks form micelles in dimethylformamide. On dialysis against an aqueous solution, the extended A blocks then associate intermolecularly to form rod-shaped micelles, which connect the B block micelles. The result is a meshed cage-like particle. The implications of these observations on the aggregation behavior of polymeric surfactants in dilute solution are discussed. Images PMID:11607245

Fracture behavior of block copolymer and graphene nanoplatelet modified epoxy and fiber reinforced/epoxy polymer composites

NASA Astrophysics Data System (ADS)

Kamar, Nicholas T.

Glass and carbon fiber reinforced/epoxy polymer composites (GFRPs and CFRPs) have high strength-to-weight and stiffness-to-weight ratios. Thus, GFRPs and CFRPs are used to lightweight aircraft, marine and ground vehicles to reduce transportation energy utilization and cost. However, GFRP and CFRP matrices have a low resistance to crack initiation and propagation; i.e. they have low fracture toughness. Current methods to increase fracture toughness of epoxy and corresponding GFRP and CFRPs often reduce composite mechanical and thermomechanical properties. With the advent of nanotechnology, new methods to improve the fracture toughness and impact properties of composites are now available. The goal of this research is to identify the fracture behavior and toughening mechanisms of nanoparticle modified epoxy, GFRPs and CFRPs utilizing the triblock copolymer poly(styrene)-block-poly(butadiene)-block-poly(methylmethacrylate) (SBM) and graphene nanoplatelets (GnPs) as toughening agents. The triblock copolymer SBM was used to toughen the diglycidyl ether of bisphenol-A (DGEBA) resin cured with m-phenylenediamine (mPDA) and corresponding AS4-12k CFRPs. SBM self assembled in epoxy to form nanostructured domains leading to larger increases in fracture toughness, KQ (MPa*m 1/2) than the traditional, phase separating carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber. Additionally, SBM increased the mode-I fracture toughness, GIc (J/m2) of CFRPs without corresponding reductions in composite three-point flexural properties and glass transition temperature (Tg). Fractography of SBM modified epoxy and CFRPs via scanning electron microscopy (SEM) showed that sub 100 nm spherical micelles cavitated to induce void growth and matrix shear yielding toughening mechanisms. Furthermore, SBM did not suppress epoxy Tg, while CTBN decreased Tg with both increasing concentration and acrylonitrile content. Graphene nanoplatelets (GnPs) consist of a few layers of graphene sheets, which are a single atomic layer of sp2 hybridized carbon atoms arranged in a honeycomb lattice. GnPs have excellent thermal, electrical and mechanical properties and are thus attractive fillers for composite materials. GnPs with a basal plane diameter of 5 microm were incorporated between lamina in GFRPs made via vacuum assisted resin transfer molding (VARTM). At only 0.25 wt%, GnPs improved GFRP flexural strength and GIc by 29 and 25%, respectively. GnPs also improved the low velocity drop weight impact properties of the GFRP laminates. Ultrasonic C-scans and dye penetration experiments on impacted laminates showed that the impact-side damage area decreased with increasing concentration of GnPs, while the back-side damage area increased. The addition of GnPs improved absorption and dissipation of impact energy throughout GFRP laminates. Additionally, GnPs were investigated as toughening agents in epoxy and corresponding AS4-12k CFRPs. In epoxy and CFRPs, GnPs activate a crack deflection toughening mechanism, resulting in increased fracture surface area and fracture energy. Hybrid GnP/SBM modified epoxy and CFRPs were also investigated.

Self assembly and shear induced morphologies of asymmetric block copolymers with spherical domains

NASA Astrophysics Data System (ADS)

Mandare, Prashant N.

2007-12-01

Microphase separated block copolymers have been subject of investigation for past two decades. While most of the work is focused on classical phases of lamellae or cylinders, spherical phases have received less attention. The present study deals with the self-assembly in spherical phases of block copolymers that results into formation of a three-dimensional cubic lattice. A model triblock copolymer with several transition temperatures is chosen. Solidification in this model system results from either the arrangement of nanospheres of minor block on a BCC lattice or by formation of physical network where the nanospheres act as crosslinks. The solid-like behavior is characterized by extremely slow relaxation modes. Long time stress relaxation of the model material was examined to distinguish between the solid and liquid behavior. Stress relaxation data from a conventional rheometer was extended to very long times by using a newly built instrument, Relaxometer. The BCC lattice structure of the material behaves as liquid over long time except at low temperatures where an equilibrium modulus is observed. This long time behavior was extended to low shear rate behavior using steady shear rheology. The zero shear viscosity observed at extremely low shear rates has a very high value that is close to the viscosity calculated from stress relaxation experiments. The steady shear viscosity decreases by several orders of magnitude over a small range of shear rates. SAXS experiments on samples sheared even at very low rates indicated loss of the BCC order that was present in the annealed samples before shearing. In the second part, response of the BCC microstructure to large stress was explored. Shearing at constant rate and with LAOS at low frequencies lead to destruction of BCC lattice. The structure recovers upon cessation of the shear with kinetics similar to the one following thermal quench. Under certain conditions, LAOS leads to formation of monodomain textures. At low frequencies, there exists an upper and lower bound on strain amplitude where mono-domain textures can be obtained. Upon alignment, the modulus drops by about 30%. Measurement of rheological properties offers an indirect method to distinguish between polycrystalline structure and monodomain texture.

Thermal properties of poly(urethane-ester-siloxane)s based on hyperbranched polyester

NASA Astrophysics Data System (ADS)

Pergal, M. V.; Džunuzović, J. V.; Kićanović, M.; Vodnik, V.; Pergal, M. M.; Jovanović, S.

2011-12-01

Novel polyurethanes (PUs) were synthesized using hydroxy-terminated hyperbranched polyester (BH-20) and 4,4'-methylenediphenyl diisocyanate (MDI) as hard segments and hydroxy-terminated ethylene oxide-poly(dimethylsiloxane)-ethylene oxide triblock copolymer (PDMS-EO) as soft segment, with soft segment content ranging from 30 to 60 wt %. The PUs were synthesized by two-step solution polymerization method. The influence of the soft segment content on the structure, swelling behavior and thermal properties of PUs was investigated. According to the results obtained by swelling measurements, the increase of the hard segment content resulted in the increase of the crosslinking density of synthesized samples. DSC results showed that the glass transition temperatures increase from 36 to 65°C with increasing hard segment content. It was demonstrated using thermogravimetric analysis (TGA) that thermal stability of investigated PUs increases with increase of the soft PDMS-EO content. This was concluded from the temperatures corresponding to the 10 wt % loss, which represents the beginning of thermal degradation of samples.

Visual tracing of diffusion and biodistribution for amphiphilic cationic nanoparticles using photoacoustic imaging after ex vivo intravitreal injections

PubMed Central

Xu, Xu; Xu, Zhaokang; Liu, Junyi; Zhang, Zhaoliang; Chen, Hao; Li, Xingyi; Shi, Shuai

2016-01-01

To visually trace the diffusion and biodistribution of amphiphilic cation micelles after vitreous injection, various triblock copolymers of monomethoxy poly(ethylene glycol)–poly(ε-caprolactone)–polyethylenimine were synthesized with different structures of hydrophilic and hydrophobic segments, followed by labeling with near-infrared fluorescent dye Cyanine5 or Cyanine7. The micellar size, polydispersity index, and surface charge were measured by dynamic light scattering. The diffusion was monitored using photoacoustic imaging in real time after intravitreal injections. Moreover, the labeled nanoparticle distribution in the posterior segment of the eye was imaged histologically by confocal microscopy. The results showed that the hydrophilic segment increased vitreous diffusion, while a positive charge on the particle surface hindered diffusion. In addition, the particles diffused through the retinal layers and were enriched in the retinal pigment epithelial layer. This work tried to study the diffusion rate via a simple method by using visible images, and then provided basic data for the development of intraocular drug carriers. PMID:27785015

Membranes with artificial free-volume for biofuel production

PubMed Central

Petzetakis, Nikos; Doherty, Cara M.; Thornton, Aaron W.; Chen, X. Chelsea; Cotanda, Pepa; Hill, Anita J.; Balsara, Nitash P.

2015-01-01

Free-volume of polymers governs transport of penetrants through polymeric films. Control over free-volume is thus important for the development of better membranes for a wide variety of applications such as gas separations, pharmaceutical purifications and energy storage. To date, methodologies used to create materials with different amounts of free-volume are based primarily on chemical synthesis of new polymers. Here we report a simple methodology for generating free-volume based on the self-assembly of polyethylene-b-polydimethylsiloxane-b-polyethylene triblock copolymers. We have used this method to fabricate a series of membranes with identical compositions but with different amounts of free-volume. We use the term artificial free-volume to refer to the additional free-volume created by self-assembly. The effect of artificial free-volume on selective transport through the membranes was tested using butanol/water and ethanol/water mixtures due to their importance in biofuel production. We found that the introduction of artificial free-volume improves both alcohol permeability and selectivity. PMID:26104672

Membranes with artificial free-volume for biofuel production

NASA Astrophysics Data System (ADS)

Petzetakis, Nikos; Doherty, Cara M.; Thornton, Aaron W.; Chen, X. Chelsea; Cotanda, Pepa; Hill, Anita J.; Balsara, Nitash P.

2015-06-01

Free-volume of polymers governs transport of penetrants through polymeric films. Control over free-volume is thus important for the development of better membranes for a wide variety of applications such as gas separations, pharmaceutical purifications and energy storage. To date, methodologies used to create materials with different amounts of free-volume are based primarily on chemical synthesis of new polymers. Here we report a simple methodology for generating free-volume based on the self-assembly of polyethylene-b-polydimethylsiloxane-b-polyethylene triblock copolymers. We have used this method to fabricate a series of membranes with identical compositions but with different amounts of free-volume. We use the term artificial free-volume to refer to the additional free-volume created by self-assembly. The effect of artificial free-volume on selective transport through the membranes was tested using butanol/water and ethanol/water mixtures due to their importance in biofuel production. We found that the introduction of artificial free-volume improves both alcohol permeability and selectivity.

Low-Temperature Fluorination of Soft-Templated Mesoporous Carbons for a High-Power Lithium/Carbon Fluoride Battery

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

Fulvio, Pasquale F.; Brown, Suree S.; Adcock, Jamie

Soft-templated mesoporous carbons and activated mesoporous carbons were fluorinated using elemental fluorine between room temperature and 235 °C. The mesoporous carbons were prepared via self-assembly synthesis of phloroglucinol–formaldehyde as a carbon precursor in the presence of triblock ethylene oxide–propylene oxide–ethylene oxide copolymer BASF Pluronic F127 as the template. The F/C ratios ranged from ~0.15 to 0.75 according to gravimetric, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis. Materials have mesopore diameters up to 11 nm and specific surface areas as high as 850 m² g⁻¹ after fluorination as calculated from nitrogen adsorption isotherms at -196 °C. Furthermore, the materialsmore » exhibit higher discharge potentials and energy and power densities as well as faster reaction kinetics under high current densities than commercial carbon fluorides with similar fluorine contents when tested as cathodes for Li/CF x batteries.« less

Low-Temperature Fluorination of Soft-Templated Mesoporous Carbons for a High-Power Lithium/Carbon Fluoride Battery

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

Fulvio, Pasquale F; Dai, Sheng; Guo, Bingkun

Soft-templated mesoporous carbons and activated mesoporous carbons were fluorinated using elemental fluorine between room temperature and 235 C. The mesoporous carbons were prepared via self-assembly synthesis of phloroglucinol formaldehyde as a carbon precursor in the presence of triblock ethylene oxide propylene oxide ethylene oxide copolymer BASF Pluronic F127 as the template. The F/C ratios ranged from 0.15 to 0.75 according to gravimetric, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis. Materials have mesopore diameters up to 11 nm and specific surface areas as high as 850 m2 g 1 after fluorination as calculated from nitrogen adsorption isotherms at 196more » C. Furthermore, the materials exhibit higher discharge potentials and energy and power densities as well as faster reaction kinetics under high current densities than commercial carbon fluorides with similar fluorine contents when tested as cathodes for Li/CFx batteries.« less

Shear rheological characterization of gel healing response and construction of rheo-PIV system

NASA Astrophysics Data System (ADS)

Bawiskar, Abhishek D.

Thermo-reversible gels are solvent-filled 3D networks of polymer chains interconnected by physical (transient) crosslinks. On applying a high shear stress, the crosslinks are broken and these gels show a typical stress-strain behavior due to cohesive fracture of the gel. When heated above a critical temperature and cooled back to room temperature, all the crosslinks are re-formed. Interestingly, partial to full recovery of broken crosslinks is also observed by simply letting the gel stand at room temperature. In this study, the fracture and healing behavior of a model acrylic triblock copolymer gel has been characterized by shear rheometry. A mathematical model has also been proposed to better understand the mechanics at the molecular level and predict the healing time of a system. A rheo-PIV system was built as part of the project, to observe and confirm the bulk healing process in situ. Spontaneous self-healing behavior has immense potential in controlled drug delivery systems, coatings, food and various other applications.

Microwave-assisted synthesis of porous carbon-titania and highly crystalline titania nanostructures.

PubMed

Parker, Alison; Marszewski, Michal; Jaroniec, Mietek

2013-03-01

Porous carbon-titania and highly crystalline titania nanostructured materials were obtained through a microwave-assisted one-pot synthesis. Resorcinol and formaldehyde were used as carbon precursors, triblock copolymer Pluronic F127 as a stabilizing agent, and titanium isopropoxide as a titania precursor. This microwave-assisted one-pot synthesis involved formation of carbon spheres according to the recently modified Stöber method followed by hydrolysis and condensation of titania precursor. This method afforded carbon-titania composite materials containing anatase phase with specific surface areas as high as 390 m(2) g(-1). The pure nanostructured titania, obtained after removal of carbon through calcination of the composite material in air, was shown to be the anatase phase with considerably higher degree of crystallinity and the specific surface area as high as 130 m(2) g(-1). The resulting titania, because of its high surface area, well-developed porosity, and high crystallinity, is of great interest for catalysis, water treatment, lithium batteries, and other energy-related applications.

Metal Ion-Induced Self-Assembly of a Multi-Responsive Block Copolypeptide into Well-Defined Nanocapsules.

PubMed

van Eldijk, Mark B; Schoonen, Lise; Cornelissen, Jeroen J L M; Nolte, Roeland J M; van Hest, Jan C M

2016-05-01

Protein cages are an interesting class of biomaterials with potential applications in bionanotechnology. Therefore, substantial effort is spent on the development of capsule-forming designer polypeptides with a tailor-made assembly profile. The expanded assembly profile of a triblock copolypeptide consisting of a metal ion chelating hexahistidine-tag, a stimulus-responsive elastin-like polypeptide block, and a pH-responsive morphology-controlling viral capsid protein is presented. The self-assembly of this multi-responsive protein-based block copolymer is triggered by the addition of divalent metal ions. This assembly process yields monodisperse nanocapsules with a 20 nm diameter composed of 60 polypeptides. The well-defined nanoparticles are the result of the emergent properties of all the blocks of the polypeptide. These results demonstrate the feasibility of hexahistidine-tags to function as supramolecular cross-linkers. Furthermore, their potential for the metal ion-mediated encapsulation of hexahistidine-tagged proteins is shown. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combinatorial Optimization of Heterogeneous Catalysts Used in the Growth of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Cassell, Alan M.; Verma, Sunita; Delzeit, Lance; Meyyappan, M.; Han, Jie

2000-01-01

Libraries of liquid-phase catalyst precursor solutions were printed onto iridium-coated silicon substrates and evaluated for their effectiveness in catalyzing the growth of multi-walled carbon nanotubes (MWNTs) by chemical vapor deposition (CVD). The catalyst precursor solutions were composed of inorganic salts and a removable tri-block copolymer (EO)20(PO)70(EO)20 (EO = ethylene oxide, PO = propylene oxide) structure-directing agent (SDA), dissolved in ethanol/methanol mixtures. Sample libraries were quickly assayed using scanning electron microscopy after CVD growth to identify active catalysts and CVD conditions. Composition libraries and focus libraries were then constructed around the active spots identified in the discovery libraries to understand how catalyst precursor composition affects the yield, density, and quality of the nanotubes. Successful implementation of combinatorial optimization methods in the development of highly active, carbon nanotube catalysts is demonstrated, as well as the identification of catalyst formulations that lead to varying densities and shapes of aligned nanotube towers.

The synthesis of novel hybrid thiol-functionalized nano-structured SBA-15

NASA Astrophysics Data System (ADS)

Hoang, Van Duc; Phuong Dang, Tuyet; Khieu Dinh, Quang; Phu Nguyen, Huu; Vu, Anh Tuan

2010-09-01

Mesoporous thiol-functionalized SBA-15 has been directly synthesized by co-condensation of tetraethyl orthosilicate (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) with triblock copolymer P123 as-structure-directing agent under hydrothermal conditions. Surfactant removal was performed by Soxhlet ethanol extraction. These materials have been characterized by powder x-ray diffraction (XRD), nitrogen adsorption/desorption (BET model), transmission electron microscopy (TEM), thermal analysis, infrared spectroscopy (IR) and energy-dispersive x-ray spectroscopy (EDX). The main parameters, such as the initial molar ratio of MPTMS to TEOS, the time of adding MPTMS to synthesized gel and the Soxhlet ethanol extraction on the thiol functionalized SBA-15 with high thiol content and highly ordered hexagonal mesostructure, were investigated and evaluated. The adsorption capacity of the thiol-functionalized and non-functionalized SBA-15 materials for Pb2+ ion from aqueous solution was tested. It was found that the Pb2+ adsorption capacity of the thiol functionalized SBA-15 is three times higher than that of non-functionalized SBA-15.

Water-Soluble Spinel Ferrites by a Modified Polyol Process as Contrast Agents in MRI

NASA Astrophysics Data System (ADS)

Basina, Georgia; Tzitzios, Vasilis; Niarchos, Dimitris; Li, Wanfeng; Khurshid, Hafsa; Mao, Hui; Hadjipanayis, Costas; Hadjipanayis, George

2010-12-01

Magnetic nanoparticles have recently been very attractive for biomedical applications. In this study, we have synthesized ferrite nanoparticles for application as contrast agents in MRI experiments. Fe3O4 and MnFe2O4 spinel ferrites with a mean size of 11-12 nm, were prepared by a modified polyol route in commercially available polyethylene glycol with molecular weight 600 (PEG-600). The reaction takes place in the presence of water soluble and non-toxic tri-block copolymer known as Pluronic® F-127 (PEO100-PPO65-PEO100). The nanoparticles have saturation magnetization values of 52 and 68 emu/g for MnFe2O4 and Fe3O4, respectively. Both the Fe3O4, and MnFe2O4 nanoparticles make stable solutions in water known as ferrofluids. Preliminary data demonstrated the capability of these nanoparticles to induce imaging contrast in T2 weighted MRI experiments, making these materials suitable for biomedical applications such as medical MRI.

Visual tracing of diffusion and biodistribution for amphiphilic cationic nanoparticles using photoacoustic imaging after ex vivo intravitreal injections.

PubMed

Xu, Xu; Xu, Zhaokang; Liu, Junyi; Zhang, Zhaoliang; Chen, Hao; Li, Xingyi; Shi, Shuai

To visually trace the diffusion and biodistribution of amphiphilic cation micelles after vitreous injection, various triblock copolymers of monomethoxy poly(ethylene glycol)-poly(ε-caprolactone)-polyethylenimine were synthesized with different structures of hydrophilic and hydrophobic segments, followed by labeling with near-infrared fluorescent dye Cyanine5 or Cyanine7. The micellar size, polydispersity index, and surface charge were measured by dynamic light scattering. The diffusion was monitored using photoacoustic imaging in real time after intravitreal injections. Moreover, the labeled nanoparticle distribution in the posterior segment of the eye was imaged histologically by confocal microscopy. The results showed that the hydrophilic segment increased vitreous diffusion, while a positive charge on the particle surface hindered diffusion. In addition, the particles diffused through the retinal layers and were enriched in the retinal pigment epithelial layer. This work tried to study the diffusion rate via a simple method by using visible images, and then provided basic data for the development of intraocular drug carriers.

Triblock copolymer-mediated synthesis of catalytically active gold nanostructures

NASA Astrophysics Data System (ADS)

Santos, Douglas C.; de Souza, Viviane C.; Vasconcelos, Diego A.; Andrade, George R. S.; Gimenez, Iara F.; Teixeira, Zaine

2018-04-01

The design of nanostructures based on poly(ethylene oxide)-poly(propylene)-poly(ethylene oxide) (PEO-PPO-PEO) and metal nanoparticles is becoming an important research topic due to their multiple functionalities in different fields, including nanomedicine and catalysis. In this work, water-soluble gold nanoparticles have been prepared through a green aqueous synthesis method using Pluronic F127 as both reducing and stabilizing agents. The size dependence (varying from 2 to 70 nm) and stability of gold nanoparticles were systematically studied by varying some parameters of synthesis, which were the polymer concentration, temperature, and exposure to UV-A light, being monitored by UV-Vis spectroscopy and TEM. Also, an elaborated study regarding to the kinetic of formation (nucleation and growth) was presented. Finally, the as-prepared Pluronic-capped gold nanoparticles have shown excellent catalytic activity towards the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride, in which a higher catalytic performance was exhibited when compared with gold nanoparticles prepared by classical reduction method using sodium citrate. [Figure not available: see fulltext.

Interface-mediated fabrication of bowl-like and deflated ballon-like hollow carbon nanospheres.

PubMed

Zhang, Haijiao; Li, Xia

2015-08-15

In our work, two kinds of hollow carbon nanospheres with controlled morphologies have been successfully prepared from low-cost and nontoxic glucose as the sole carbon precursor under neutral aqueous medium via a simple hydrothermal route. During the process, sodium dodecylbenzene sulfonate (SDBS) and triblock copolymer P123 ((EO)20(PO)70(EO)20) was skillfully selected as the structure-directing agent, respectively. SEM, TEM and AFM results revealed that the two products showed bowl-like and deflated-balloon-like morphology with uniform particle sizes, respectively. Based on the experimental observations, a possible formation mechanism was also discussed, in which the growth of the carbon nanospheres involved an interface-medicated assembly process. The present method was easy, green and mild. Apart from the unique nanostructure, the obtained bowl-like hollow carbon nanospheres exhibited excellent biocompatibility. In particular, it should be mentioned that the open window formed by the bowl-like morphology can facilitate ion transport, thus improving their performances. Copyright © 2015 Elsevier Inc. All rights reserved.

Membranes with artificial free-volume for biofuel production

DOE PAGES

Petzetakis, Nikos; Doherty, Cara M.; Thornton, Aaron W.; ...

2015-06-24

Free-volume of polymers governs transport of penetrants through polymeric films. Control over free-volume is thus important for the development of better membranes for a wide variety of applications such as gas separations, pharmaceutical purifications and energy storage. To date, methodologies used to create materials with different amounts of free-volume are based primarily on chemical synthesis of new polymers. Here we report a simple methodology for generating free-volume based on the self-assembly of polyethylene-b-polydimethylsiloxane-b-polyethylene triblock copolymers. Here, we have used this method to fabricate a series of membranes with identical compositions but with different amounts of free-volume. We use the termmore » artificial free-volume to refer to the additional free-volume created by self-assembly. The effect of artificial free-volume on selective transport through the membranes was tested using butanol/water and ethanol/water mixtures due to their importance in biofuel production. Moreover, we found that the introduction of artificial free-volume improves both alcohol permeability and selectivity.« less

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

PubMed

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

2015-04-20

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

Pluronic®-bile salt mixed micelles.

PubMed

Patel, Vijay; Ray, Debes; Bahadur, Anita; Ma, Junhe; Aswal, V K; Bahadur, Pratap

2018-06-01

The present study was aimed to examine the interaction of two bile salts viz. sodium cholate (NaC) and sodium deoxycholate (NaDC) with three ethylene polyoxide-polypropylene polyoxide (PEO-PPO-PEO) triblock copolymers with similar PPO but varying PEO micelles with a focus on the effect of pH on mixed micelles. Mixed micelles of moderately hydrophobic Pluronic ® P123 were examined in the presence of two bile salts and compared with those from very hydrophobic L121 and very hydrophilic F127. Both the bile salts increase the cloud point (CP) of copolymer solution and decreased apparent micelle hydrodynamic diameter (D h ). SANS study revealed that P123 forms small spherical micelles showing a decrease in size on progressive addition of bile salts. The negatively charged mixed micelles contained fewer P123 molecules but progressively rich in bile salt. NaDC being more hydrophobic displays more pronounced effect than NaC. Interestingly, NaC shows micellar growth in acidic media which has been attributed to the formation of bile acids by protonation of carboxylate ion and subsequent solubilization. In contrast, NaDC showed phase separation at higher concentration. Nuclear Overhauser effect spectroscopy (NOESY) experiments provided information on interaction and location of bile salts in micelles. Results are discussed in terms of hydrophobicity of bile salts and Pluronics ® and the site of bile salt in polymer micelles. Proposed molecular interactions are useful to understand more about bile salts which play important role in physiological processes. Copyright © 2018 Elsevier B.V. All rights reserved.

Nanocomposites based on hierarchical porous carbon fiber@vanadium nitride nanoparticles as supercapacitor electrodes.

PubMed

Ran, Fen; Wu, Yage; Jiang, Minghuan; Tan, Yongtao; Liu, Ying; Kong, Lingbin; Kang, Long; Chen, Shaowei

2018-03-28

In this study, a hybrid electrode material for supercapacitors based on hierarchical porous carbon fiber@vanadium nitride nanoparticles is fabricated using the method of phase-separation mediated by the PAA-b-PAN-b-PAA tri-block copolymer. In the phase-separation procedure, the ionic block copolymer self-assembled on the surface of carbon nanofibers, and is used to adsorb NH 4 VO 3 . Thermal treatment at controlled temperatures under an NH 3  : N 2 atmosphere led to the formation of vanadium nitride nanoparticles that are distributed uniformly on the nanofiber surface. By changing the PAN to PAA-b-PAN-b-PAA ratio in the casting solution, a maximum specific capacitance of 240.5 F g -1 is achieved at the current density of 0.5 A g -1 with good rate capability at a capacitance retention of 72.1% at 5.0 A g -1 in an aqueous electrolyte of 6 mol L -1 KOH within the potential range of -1.10 to 0 V (rN/A = 1.5/1.0). Moreover, an asymmetric supercapacitor is assembled by using the hierarchical porous carbon fiber@vanadium nitride as the negative electrode and Ni(OH) 2 as the positive electrode. Remarkably, at the power density of 400 W kg -1 , the supercapacitor device delivers a better energy density of 39.3 W h kg -1 . It also shows excellent electrochemical stability, and thus might be used as a promising energy-storage device.

Long time response of soft magnetorheological gels.

PubMed

An, Hai-Ning; Sun, Bin; Picken, Stephen J; Mendes, Eduardo

2012-04-19

Swollen physical magnetorheological (MR) gels were obtained by self-assembling of triblock copolymers containing dispersed soft magnetic particles. The transient rheological responses of these systems were investigated experimentally. Upon sudden application of a homogeneous magnetic field step change, the storage modulus of MR gels continued to increase with time. Such increase trend of the storage modulus could be expressed by a double-exponential function with two distinct modes, a fast and a slow one. The result was compared with the transient rheological response of equivalent MR fluids (paraffin oil without copolymer) and a MR elastomer (PDMS) and interpreted as the consequence of strong rearrangement of the original particle network under magnetic field. Similar to the structure evolution of MR fluids, the ensemble of results suggests that "chaining" and "clustering" processes are also happening inside the gel and are responsible for the rheological behavior, provided they are happening on a smaller length scale (long chains and clusters are hindered). We show that response times of several minutes are typical for the slow response of MR gels. The characteristic time t(2) for the slow process is significantly dependent on the magnetic flux density, the matrix viscoelastic property, particle volume fraction, and sample's initial particle distribution. In order to validate our results, the role of dynamic strain history was clarified. We show that, in the linear viscoelastic region, the particle rearrangement of MR gels was not hindered or accelerated by the dynamic strain history.

Preparation of biocompatible copolymeric micelles as a carrier of atorvastatin and rosuvastatin for potential anticancer activity study.

PubMed

Hamidreza Kheiri, Manjili; Alimohammadi, Niusha; Danafar, Hossein

2018-05-18

Statins are widely used for the treatment of hypercholesterolemia. However, their inhibitory action on HMG-CoA reductase also results in the depletion of intermediate biosynthetic products, which importantly contribute to cell proliferation. The aim of the present study was to compare the effects of the individual commercially available statins on investigational breast cancer. Thus, in this study, biodegradable polymeric micelles as carrier of statins were prepared using biodegradable copolymers (PCL-PEG-PCL). These nanoparticles were prepared with two statins (atorvastatin and rosuvastatin) and drug loading, release, kinetic release, and anti-cancer activity of these drugs were studied. The triblock copolymer PCL-PEG-PCL was synthesized by a ring opening polymerization of e-caprolactone in the presence of PEG as the initiator and Sn(oct) 2 as the catalyst. The synthesized copolymers and nanoparticles were characterized by FTIR, HNMR, GPC, DLS, and AFM analyses. The drug loading and release of drugs were studied by UV-Vis. Additionally, MTT assays on HFF-2 cell lines were performed for determination of biocompatibility of micelles. Finally, the anticancer activity of micelles was studied on MCF-7 breast cancer cell lines. The results showed that the average diameter of nanoparticles was less than 45 nm. The loading capacity of atorvastatin and rosuvastatin was 20.0 ± 1.01% and 13.21 ± 1.18%, respectively, and encapsulation efficiency of atorvastatin and rosuvastatin was 88.19 ± 1.11% and 69.32 ± 0.23%, respectively. The results showed strong and dose-dependent inhibition of cell (MCF-7line) growth by the nanoparticles compared with statins. The result of cell viability assay on the MCF-7 cell line verified that the bare nanoparticles showed little inherent cytotoxicity whereas the statins-loaded nanoparticles were cytotoxic.

Engineering of the E. coli outer membrane protein FhuA to overcome the hydrophobic mismatch in thick polymeric membranes.

PubMed

Muhammad, Noor; Dworeck, Tamara; Fioroni, Marco; Schwaneberg, Ulrich

2011-03-17

Channel proteins like the engineered FhuA Δ1-159 often cannot insert into thick polymeric membranes due to a mismatch between the hydrophobic surface of the protein and the hydrophobic surface of the polymer membrane. To address this problem usually specific block copolymers are synthesized to facilitate protein insertion. Within this study in a reverse approach we match the protein to the polymer instead of matching the polymer to the protein. To increase the FhuA Δ1-159 hydrophobic surface by 1 nm, the last 5 amino acids of each of the 22 β-sheets, prior to the more regular periplasmatic β-turns, were doubled leading to an extended FhuA Δ1-159 (FhuA Δ1-159 Ext). The secondary structure prediction and CD spectroscopy indicate the β-barrel folding of FhuA Δ1-159 Ext. The FhuA Δ1-159 Ext insertion and functionality within a nanocontainer polymeric membrane based on the triblock copolymer PIB(1000)-PEG(6000)-PIB(1000) (PIB = polyisobutylene, PEG = polyethyleneglycol) has been proven by kinetic analysis using the HRP-TMB assay (HRP = Horse Radish Peroxidase, TMB = 3,3',5,5'-tetramethylbenzidine). Identical experiments with the unmodified FhuA Δ1-159 report no kinetics and presumably no insertion into the PIB(1000)-PEG(6000)-PIB(1000) membrane. Furthermore labeling of the Lys-NH(2) groups present in the FhuA Δ1-159 Ext channel, leads to controllability of in/out flux of substrates and products from the nanocontainer. Using a simple "semi rational" approach the protein's hydrophobic transmembrane region was increased by 1 nm, leading to a predicted lower hydrophobic mismatch between the protein and polymer membrane, minimizing the insertion energy penalty. The strategy of adding amino acids to the FhuA Δ1-159 Ext hydrophobic part can be further expanded to increase the protein's hydrophobicity, promoting the efficient embedding into thicker/more hydrophobic block copolymer membranes.

Giant surfactants of poly(ethylene oxide)- b-polystyrene-(molecular nanoparticle): nanoparticle-driven self-assembly with sub-10-nm nanostructures in thin films

NASA Astrophysics Data System (ADS)

Hsu, Chih-Hao; Lin, Zhiwei; Dong, Xue-Hui; Hsieh, I.-Fan; Cheng, Stephen Z. D.

2014-03-01

Giant surfactants are built upon precisely attaching shape- and volume-persistent molecular nanoparticles (MNP) to polymeric flexible tails. The unique class of self-assembling materials, giant surfactants, has been demonstrated to form self-assembled ordered nanostructures, and their self-assembly behaviors are remarkably sensitive to primary chemical structures. In this work, two sets of giant surfactants with functionalized MNP attached to diblock copolymer tails were studied in thin films. Carboxylic acid-functionalized [60]fullerene (AC60) tethered with PEO- b-PS (PEO-PS-AC60) represents an ABA' (hydrophilic-hydrophobic-hydrophilic) giant surfactant, and fluoro-functionalized polyhedral oligomeric silsesquioxane (FPOSS) tethered with PEO- b-PS (PEO-PS-FPOSS) represents an ABC (hydrophilic-hydrophobic-omniphobic) one. The dissimilar chemical natures of the MNPs result in different arrangement of MNPs in self-assembled structures, the dispersion of AC60 in PEO domain and the single domain of FPOSS. Moreover, the chemically bonded MNPs could induce the originally disordered small molecular PEO- b-PS to form ordered cylindrical and lamellar structure, as evidenced by TEM and GISAXS, leading to sub-10-nm nanostructures of copolymer in the thin film state.

Understanding the interaction of block copolymers with DMPC lipid bilayer using coarse-grained molecular dynamics simulations.

PubMed

Hezaveh, Samira; Samanta, Susruta; De Nicola, Antonio; Milano, Giuseppe; Roccatano, Danilo

2012-12-13

In this paper, we present a computational model of the adsorption and percolation mechanism of poloxamers (poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) triblock copolymers) across a 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayer. A coarse-grained model was used to cope with the long time scale of the percolation process. The simulations have provided details of the interaction mechanism of Pluronics with lipid bilayer. In particular, the results have shown that polymer chains containing a PPO block with a length comparable to the DMPC bilayer thickness, such as P85, tends to percolate across the lipid bilayer. On the contrary, Pluronics with a shorter PPO chain, such as L64 and F38, insert partially into the membrane with the PPO block part while the PEO blocks remain in water on one side of the lipid bilayer. The percolation of the polymers into the lipid tail groups reduces the membrane thickness and increases the area per lipid. These effects are more evident for P85 than L64 or F38. Our findings are qualitatively in good agreement with published small-angle X-ray scattering experiments that have evidenced a thinning effect of Pluronics on the lipid bilayer as well as the role of the length of the PPO block on the permeation process of the polymer through the lipid bilayer. Our theoretical results complement the experimental data with a detailed structural and dynamic model of poloxamers at the interface and inside the lipid bilayer.

Solid-state synthesis of ordered mesoporous carbon catalysts via a mechanochemical assembly through coordination cross-linking

PubMed Central

Zhang, Pengfei; Wang, Li; Yang, Shize; Schott, Jennifer A.; Liu, Xiaofei; Mahurin, Shannon M.; Huang, Caili; Zhang, Yu; Fulvio, Pasquale F.; Chisholm, Matthew F.; Dai, Sheng

2017-01-01

Ordered mesoporous carbons (OMCs) have demonstrated great potential in catalysis, and as supercapacitors and adsorbents. Since the introduction of the organic–organic self-assembly approach in 2004/2005 until now, the direct synthesis of OMCs is still limited to the wet processing of phenol-formaldehyde polycondensation, which involves soluble toxic precursors, and acid or alkali catalysts, and requires multiple synthesis steps, thus restricting the widespread application of OMCs. Herein, we report a simple, general, scalable and sustainable solid-state synthesis of OMCs and nickel OMCs with uniform and tunable mesopores (∼4–10 nm), large pore volumes (up to 0.96 cm3 g−1) and high-surface areas exceeding 1,000 m2 g−1, based on a mechanochemical assembly between polyphenol-metal complexes and triblock co-polymers. Nickel nanoparticles (∼5.40 nm) confined in the cylindrical nanochannels show great thermal stability at 600 °C. Moreover, the nickel OMCs offer exceptional activity in the hydrogenation of bulky molecules (∼2 nm). PMID:28452357

Multi-shape memory polymers achieved by the spatio-assembly of 3D printable thermoplastic building blocks.

PubMed

Li, Hongze; Gao, Xiang; Luo, Yingwu

2016-04-07

Multi-shape memory polymers were prepared by the macroscale spatio-assembly of building blocks in this work. The building blocks were methyl acrylate-co-styrene (MA-co-St) copolymers, which have the St-block-(St-random-MA)-block-St tri-block chain sequence. This design ensures that their transition temperatures can be adjusted over a wide range by varying the composition of the middle block. The two St blocks at the chain ends can generate a crosslink network in the final device to achieve strong bonding force between building blocks and the shape memory capacity. Due to their thermoplastic properties, 3D printing was employed for the spatio-assembly to build devices. This method is capable of introducing many transition phases into one device and preparing complicated shapes via 3D printing. The device can perform a complex action via a series of shape changes. Besides, this method can avoid the difficult programing of a series of temporary shapes. The control of intermediate temporary shapes was realized via programing the shapes and locations of building blocks in the final device.

Fabrication of perforated isoporous membranes via a transfer-free strategy: enabling high-resolution separation of cells.

PubMed

Ou, Yang; Lv, Chang-Jiang; Yu, Wei; Mao, Zheng-Wei; Wan, Ling-Shu; Xu, Zhi-Kang

2014-12-24

Thin perforated membranes with ordered pores are ideal barriers for high-resolution and high-efficiency selective transport and separation of biological species. However, for self-assembled thin membranes with a thickness less than several micrometers, an additional step of transferring the membranes onto porous supports is generally required. In this article, we present a facile transfer-free strategy for fabrication of robust perforated composite membranes via the breath figure process, and for the first time, demonstrate the application of the membranes in high-resolution cell separation of yeasts and lactobacilli without external pressure, achieving almost 100% rejection of yeasts and more than 70% recovery of lactobacilli with excellent viability. The avoidance of the transfer step simplifies the fabrication procedure of composite membranes and greatly improves the membrane homogeneity. Moreover, the introduction of an elastic triblock copolymer increases the interfacial strength between the membrane and the support, and allows the preservation of composite membranes in a dry state. Such perforated ordered membranes can also be applied in other size-based separation systems, enabling new opportunities in bioseparation and biosensors.

Distinct Tensile Response of Model Semi-flexible Elastomer Networks

NASA Astrophysics Data System (ADS)

Aguilera-Mercado, Bernardo M.; Cohen, Claude; Escobedo, Fernando A.

2011-03-01

Through coarse-grained molecular modeling, we study how the elastic response strongly depends upon nanostructural heterogeneities in model networks made of semi-flexible chains exhibiting both regular and realistic connectivity. Idealized regular polymer networks have been shown to display a peculiar elastic response similar to that of super-tough natural materials (e.g., organic adhesives inside abalone shells). We investigate the impact of chain stiffness, and the effect of including tri-block copolymer chains, on the network's topology and elastic response. We find in some systems a dual tensile response: a liquid-like behavior at small deformations, and a distinct saw-tooth shaped stress-strain curve at moderate to large deformations. Additionally, stiffer regular networks exhibit a marked hysteresis over loading-unloading cycles that can be deleted by heating-cooling cycles or by performing deformations along different axes. Furthermore, small variations of chain stiffness may entirely change the nature of the network's tensile response from an entropic to an enthalpic elastic regime, and micro-phase separation of different blocks within elastomer networks may significantly enhance their mechanical strength. This work was supported by the American Chemical Society.

A thermoreversible hydrogel as a biosynthetic bandage for corneal wound repair.

PubMed

Pratoomsoot, Chayanin; Tanioka, Hidetoshi; Hori, Kuniko; Kawasaki, Satoshi; Kinoshita, Shigeru; Tighe, Patrick J; Dua, Harminder; Shakesheff, Kevin M; Rose, Felicity Rosamari A J

2008-01-01

Ocular trauma and disorders that lead to corneal blindness account for over 2 million new cases of monocular blindness every year. A popular ocular surface reconstruction therapy, amniotic membrane transplantation, has been shown to aid corneal wound repair. However, the success rates of the procedure are variable. Here, we proposed to bioengineer a novel synthetic material that would serve as a biomimetic corneal bandage. The PLGA-PEG-PLGA triblock copolymer was synthesised via ring-opening polymerisation. Thermoreversible gelation behaviour was investigated at different polymer concentrations (23%, 30%, 35%, 40%, 45%, w/v) at temperatures ranging between 5 and 60 degrees C. Viscoelastic properties were studied in dynamic mechanical analysis with 1 degrees C/min temperature ramp. Cryo-SEM revealed a porous hydrogel with interconnecting networks. No adverse cytotoxicity was observed with an in vitro scratch-wound assay and in in vivo biocompatibility tests. We have demonstrated that the PLGA-PEG-PLGA hydrogel possessed a suitable gelling profile and, for the first time, the biocompatibility properties for this application as a potential bandage for corneal wound repair.

Effect of Pluronic F-127 on the photosensitizing activity of tetraphenylporphyrins in organic and aqueous phases

NASA Astrophysics Data System (ADS)

Savko, M. A.; Aksenova, N. A.; Akishina, A. K.; Khasanova, O. V.; Glagolev, N. N.; Rumyantseva, V. D.; Zhdanova, K. A.; Spokoinyi, A. L.; Solov'eva, A. B.

2017-11-01

The solubilization of hydrophobic porphyrin photosensitizers (PPSes) to obtain corresponding water-soluble forms is an important line of modern antimicrobial photodynamic therapy. It is shown that a triblock copolymer of ethylene and propylene oxides, Pluronic F-127, one of the most nontoxic and effective polymer surface active substances (SASes), can be used for the conversion of hydrophobic tetraphenylporphyrin (TPP) and monosubstituted and tetrasubstituted hydroxy, amino, and nitro TPPs into water-soluble forms. It is found that Pluronic has a substantially higher solubilizing affinity (defined as the minimum molar concentration of an SAS required for the complete migration of porphyrin with a specific molar concentration to the aqueous phase) toward monosubstituted TPPs than to corresponding tetrasubstituted porphyrins. It is shown that with Pluronic in the organic phase, the activity of tetraphenylporphyrin in a test reaction of the oxidation of anthracene is higher than that of its monosubstituted and tetrasubstituted derivatives. In an aqueous medium, the activity of solubilized mono derivatives of TPP is comparable to that of unsubstituted TPP and is higher than the activity of the corresponding tetra derivatives of TPP.

Long-Term Biostability of Self-Assembling Protein Polymers in the Absence of Covalent Crosslinking

PubMed Central

Sallach, Rory E.; Cui, Wanxing; Balderrama, Fanor; Martinez, Adam W.; Wen, Jing; Haller, Carolyn A.; Taylor, Jeannette V.; Wright, Elizabeth R.; Long, Robert C.; Chaikof, Elliot L.

2009-01-01

Unless chemically crosslinked, matrix proteins, such as collagen or silk, display a limited lifetime in vivo with significant degradation observed over a period of weeks. Likewise, amphiphilic peptides, lipopeptides, or glycolipids that self-assemble through hydrophobic interactions to form thin films, fiber networks, or vesicles do not demonstrate in vivo biostability beyond a few days. We report herein that a self-assembling, recombinant elastin-mimetic triblock copolymer elicited minimal inflammatory response and displayed robust in vivo stability for periods exceeding 1 year, in the absence of either chemical or ionic crosslinking. Specifically, neither a significant inflammatory response nor calcification was observed upon implantation of test materials into the peritoneal cavity or subcutaneous space of a mouse model. Moreover, serial quantitative magnetic resonance imaging, evaluation of pre- and post-explant ultrastructure by cryo-high resolution scanning electron microscopy, and an examination of implant mechanical responses revealed substantial preservation of form, material architecture, and biomechanical properties, providing convincing evidence of a non-chemically or ionically crosslinked protein polymer system that exhibits long-term stability in vivo. PMID:19854505

Structure-Property Relationships in Tough, Superabsorbent Thermoplastic Elastomers for Hemorrhage Control

NASA Astrophysics Data System (ADS)

Beyer, Frederick; Bain, Erich; Long, Tyler; Mrozek, Randy; Savage, Alice; Martin, Halie; Dadmun, Mark; Lenhart, Joseph

Between 2001 and 2009, uncontrolled hemorrhaging from major trauma accounted for the deaths of roughly 80% of wounded soldiers with potentially survivable injuries. Modern hemostatic materials are limited in their ability to deliver therapeutic agents, causing tissue damage themselves, or being difficult to remove intact. The goal of this study is to create a mechanically robust polymer that takes up as much as 1000 wt% water in seconds while maintaining sufficient toughness to be removed intact from the wound intact. A thermoplastic elastomer scaffold in which physical crosslinks provide mechanical toughness might provide an appropriate combination of fast swelling and excellent toughness if the matrix material can be engineered to be strongly hydrophilic and swell rapidly. In this work, a commercial SBS triblock copolymer has been modified with poly(acrylic acid) side chains, resulting in materials that are superabsorbent but retain good mechanical properties when saturated. Although SAXS experiments failed to show any significant changes in morphology, even with 800 wt% water uptake, preliminary SANS experiments using selectively deuterated materials and swelling with D2O show significant changes in morphology. Our most recent findings will be presented.

Investigation of Molecular Structure and Thermal Properties of Thermo-Oxidative Aged SBS in Blends and Their Relations

PubMed Central

Xu, Xiong; Yu, Jianying; Xue, Lihui; Zhang, Canlin; Zha, Yagang; Gu, Yi

2017-01-01

Tri-block copolymer styrene–butadiene (SBS) is extensively applied in bituminous highway construction due to its high elasticity and excellent weather resistance. With the extension of time, tri-block structural SBS automatically degrades into bi-block structural SB- with some terminal oxygen-containing groups under the comprehensive effects of light, heat, oxygen, etc. In this paper, the effects of aging temperature, aging time and oxygen concentration on the molecular structure of thermo-oxidative aged SBS were mainly investigated using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), and the correlation between oxygen-containing groups and thermal properties (TG–DTG) was further discussed. The FTIR and XPS results show that rapid decomposition of SBS will occur with increments of aging temperature, aging time and oxygen concentration, and a large number of oxygen-containing groups such as –OH, C=O, –COOH, etc. will be formed during thermo-oxidative aging. In short-term aging, changes in aging temperature and oxygen concentration have a significant impact on the structural damage of SBS. However, in long-term aging, it has no further effect on the molecular structure of SBS or on increasing oxygen concentration. The TG and DTG results indicate that the concentration of substances with low molecular weight gradually increases with the improvement of the degree of aging of the SBS, while the initial decomposition rate increases at the beginning of thermal weightlessness and the decomposition rate slows down in comparison with neat SBS. From the relation between the XPS and TG results, it can be seen that the initial thermal stability of SBS rapidly reduces as the relative concentration of the oxygen-containing groups accumulates around 3%, while the maximum decomposition temperature slowly decreases when the relative concentration of the oxygen-containing groups is more than 3%, due to the difficult damage to strong bonds on the molecular structure of aged SBS. PMID:28773124

Investigation of Molecular Structure and Thermal Properties of Thermo-Oxidative Aged SBS in Blends and Their Relations.

PubMed

Xu, Xiong; Yu, Jianying; Xue, Lihui; Zhang, Canlin; Zha, Yagang; Gu, Yi

2017-07-07

Tri-block copolymer styrene-butadiene (SBS) is extensively applied in bituminous highway construction due to its high elasticity and excellent weather resistance. With the extension of time, tri-block structural SBS automatically degrades into bi-block structural SB- with some terminal oxygen-containing groups under the comprehensive effects of light, heat, oxygen, etc. In this paper, the effects of aging temperature, aging time and oxygen concentration on the molecular structure of thermo-oxidative aged SBS were mainly investigated using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), and the correlation between oxygen-containing groups and thermal properties (TG-DTG) was further discussed. The FTIR and XPS results show that rapid decomposition of SBS will occur with increments of aging temperature, aging time and oxygen concentration, and a large number of oxygen-containing groups such as -OH, C=O, -COOH, etc. will be formed during thermo-oxidative aging. In short-term aging, changes in aging temperature and oxygen concentration have a significant impact on the structural damage of SBS. However, in long-term aging, it has no further effect on the molecular structure of SBS or on increasing oxygen concentration. The TG and DTG results indicate that the concentration of substances with low molecular weight gradually increases with the improvement of the degree of aging of the SBS, while the initial decomposition rate increases at the beginning of thermal weightlessness and the decomposition rate slows down in comparison with neat SBS. From the relation between the XPS and TG results, it can be seen that the initial thermal stability of SBS rapidly reduces as the relative concentration of the oxygen-containing groups accumulates around 3%, while the maximum decomposition temperature slowly decreases when the relative concentration of the oxygen-containing groups is more than 3%, due to the difficult damage to strong bonds on the molecular structure of aged SBS.

The effect of the triblock properties on the morphologies and photophysical properties of nanoparticle loaded with carboxylic dendrimer phthalocyanine

NASA Astrophysics Data System (ADS)

Lv, Huafei; Chen, Zhe; Yu, Xinxin; Pan, Sujuan; Zhang, Tiantian; Xie, Shusen; Yang, Hongqin; Peng, Yiru

2016-09-01

Photodynamic therapy (PDT) is an emerging alternative treatment for various cancers and age-related macular degeneration. Phthalocyanines (Pcs) and their substituted derivatives are under intensive investigation as the second generation photosensitizers. A big challenge for the application of Pcs is poor solubility and limited accumulation in the tumor tissues, which severely reduced its PDT efficacy. Nano-delivery systems such as polymeric micelles are promising tools for increasing the solubility and improving delivery efficiency of Pcs for PDT application. In this paper, nanoparticles of amphiphilic triblock copolymer poly(L-lysine)-b-poly (ethylene glycol)-b-poly(L-lysine) were developed to encapsulate 1-2 generation carboxylic poly (benzyl aryl ether) dendrimer. The morphologies and photophysical properties of polymeric nanoparticles loaded with 1-2 generation dendritic phthalocyanines (G1-ZnPc(COOH)8/m and G2-ZnPc(COOH)16/m) were studied by AFM, UV/Vis and fluorescent spectroscopic method. The morphologies of self-assembled PLL-PEG-PLL aggregates exhibited concentration dependence. Its morphologies changed from cocoon-like to spheral. The diameters of G1-ZnPc(COOH)8/m and G2-ZnPc(COOH)16/m were in the range of 33-147 nm, increasing with the increase of the concentration of PLL-PEG-PLL. The morphologies of G2-ZnPc(COOH)16/m also changed from cocoon-like to sphere with the increase of the concentration of PLL-PEG-PLL. It was found that, the no obviously Q change was observed between the free phthalocyanines and nanoparticles. The fluorescence intensity of polymer nanoparticles were higher enhanced compared with free dendritic phthalocyanines. The dendrimer phthalocyanine loaded with poly(L-lysine)-b-poly (ethylene glycol)-b-poly(L-lysine) presented suitable physical stability, improved photophysical properties suggesting it may be considered as a promising formulation for PDT.

Multifunctional Triblock Nanocarrier (PAMAM-PEG-PLL) for the Efficient Intracellular siRNA Delivery and Gene Silencing

PubMed Central

2011-01-01

A novel triblock poly(amido amine)-poly(ethylene glycol)-poly-l-lysine (PAMAM-PEG-PLL) nanocarrier was designed, synthesized, and evaluated for the delivery of siRNA. The design of the nanocarrier is unique and provides a solution to most of the common problems associated with the delivery and therapeutic applications of siRNA. Every component in the triblock nanocarrier plays a significant role and performs multiple functions: (1) tertiary amine groups in the PAMAM dendrimer work as a proton sponge and play a vital role in the endosomal escape and cytoplasmic delivery of siRNA; (2) PEG, a linker connecting PLL and PAMAM dendrimers renders nuclease stability and protects siRNA in human plasma; (3) PLL provides primary amines to form polyplexes with siRNA through electrostatic interaction and also acts as penetration enhancer; and (4) conjugation to PEG and PAMAM reduced toxicity of PLL and the entire triblock nanocarrier PAMAM-PEG-PLL. The data obtained show that the polyplexes resulted from the conjugation of siRNA, and the proposed nanocarriers were effectively taken up by cancer cells and induced the knock down of the target BCL2 gene. In addition, triblock nanocarrier/siRNA polyplexes showed excellent stability in human plasma. PMID:21322531

Biosolar energy generation and harvesting from biomolecule-copolymer hybrid systems

NASA Astrophysics Data System (ADS)

Chu, Bong-Chieh Benjamin

Alternative energy sources have become an increasingly important topic as energy needs outpace supply. Furthermore, as the world moves into the digital age of portable electronics, highly efficient and lightweight energy sources will need to be developed. Current technology, such as lithium ion batteries, provide enough power to run portable electronics for hours or days, but can still allow for improvement in their power density (W/kg). Utilizing energy-transducing membrane proteins, which are by nature highly efficient, it is possible to engineer biological-based energy sources with energy densities far greater than any solid-state systems. Furthermore, solar powered membrane proteins have the added benefit of a virtually unlimited supply of energy. This work has developed protein-polymer hybrid films and nanoscale vesicles for a variety of applications from fuel-cell technology to biological-based photovoltaics. Bacteriorhodopsin (BR), a light-activated proton pump, and Cytochrome C Oxidase (COX), a protein involved in the electron transport chain in mitochondria, were reconstituted into biomimetic triblock copolymer membranes. Block copolymer membranes mimic the amphiphilic nature of a natural lipid bilayer but exhibit greater mechanical stability due to UV-polymerizable endgroups. In BR/COX functionalized nanovesicles, proton gradients generated by the light-activated proton pumping of BR are used to drive COX in reverse to generate electrons, providing a hybrid biologically-active polymer to convert solar energy to chemical energy, and finally to electrical energy. This work has found protein activity in planar membranes through the photoelectric current generation by BR and the proton pumping activity of BR-functionalized polymer membranes deposited onto proton exchange membranes, as well as the coupled functionality of BR and COX through current generation in cyclic voltammetry and direct current measurements. Current switching between light and dark environments of composite BR/COX polymer vesicles show a light-dependent current generation with current changes as high as 10muA. Furthermore, electrode modifications were made using polymer and polymer/carbon nanotube (CNT) coatings as anti-absorbent and conductive anti-absorbent layers for the purpose of a more robust electrode. These findings have shown that biological functionality can be engineered into synthetic polymers to make hybrid devices.

Evaluating structure in thin block copolymer films with soft x-rays (Conference Presentation)

NASA Astrophysics Data System (ADS)

Sunday, Daniel; Liman, Christopher; Hannon, Adam F.; Ren, Jiaxing; Chen, Xuanxuan; Suh, Hyo Seon; de Pablo, Juan J.; Nealey, Paul F.; Kline, R. Joseph

2017-03-01

The semiconductor industry is evaluating a variety of approaches for the cost efficient production of future processing and memory generations. Amongst the technologies being explored are multiple patterning steps, extreme ultraviolet (EUV) lithography, multiple-beam electron beam lithography and the directed self-assembly (DSA) of block copolymers (BCPs). BCP DSA utilizes a chemical or topographical template to induce long range order in a thin film of BCP which enhances the resolution of the original pattern. The characterization of buried structure within a DSA BCP film is challenging due to the lack of contrast between the organic materials. Critical-dimension small angle x-ray scattering (CDSAXS) measurements were performed on DSA BCP films, using soft X-rays to tune the contrast, in order to understand the relationship between template structure and film morphology.1 The results of these measurements show that as the width of the guiding stripe widens the arrangement of the BCP on the guiding stripe inverts, shifting from the A block being centered on the guiding stripe to the B block being centered on the guiding stripe. The initial results of integration of mean field simulations into the analysis of scattering data will also be discussed. In addition to examining the BCP structure with CDSAXS, soft X-ray reflectivity2 measurements were performed on BCP to better understand the relationship between interface width for systems with alternative architectures (triblocks) and additives (polymers/ionic liquids). The addition of a selectively associating additive increases the interaction parameter between the two blocks, resulting in the reduction of the interface width and access to smaller pitches. The use of soft X-ray reflectivity allows the evaluation of the distribution of the additive. (1) Sunday, D. F.; Hammond, M. R.; Wang, C.; Wu, W.; Delongchamp, D. M.; Tjio, M.; Cheng, J. Y.; Kline, R. J.; Pitera, J. W. Determination of the Internal Morphology of Nanostructures Patterned by Directed Self Assembly. ACS Nano 2014, 8, 8426-8437. (2) Sunday, D. F.; Kline, R. J. Reducing Block Copolymer Interfacial Widths through Polymer Additives. Macromolecules 2015, 48, 679-686.

Novel polymeric micelles for insect pest control: encapsulation of essential oil monoterpenes inside a triblock copolymer shell for head lice control.

PubMed

Lucia, Alejandro; Toloza, Ariel Ceferino; Guzmán, Eduardo; Ortega, Francisco; Rubio, Ramón G

2017-01-01

Essential oil components (EOCs) are molecules with interesting application in pest control, these have been evaluated against different insect pest from more than 100 years, but their practical use is rather limited. Thus, the enhancement of their bioavailability and manageability due to their dispersion in water can open new perspective for the preparation of formulations for the control of insect pest. In this work, we studied the encapsulation of different monoterpenes in a poloxamer shell in order to prepare aqueous formulations that can be used for the development of platforms used in pest control. Micellar systems containing a 5 wt% of poloxamer 407 and 1.25 wt% of the different monoterpenes were prepared. Dynamic Light Scattering (DLS) experiments were carried out to characterize the dispersion of the EOCs in water. The pediculicidal activity of these micellar systems was tested on head lice using an ex vivo immersion test. The poloxamers allowed the dispersion of EOCs in water due to their encapsulation inside the hydrophobic core of the copolymer micelles. From this study, we concluded that it is possible to make stable micellar systems containing water (>90 wt%), 1.25 wt% of different monoterpenes and a highly safe polymer (5wt% Poloxamer 407). These formulations were effective against head lice with mortality ranging from 30 to 60%, being the most effective emulsions those containing linalool, 1,8-cineole, α -terpineol, thymol, eugenol, geraniol and nonyl alcohol which lead to mortalities above 50%. Since these systems showed good pediculicidal activity and high physicochemical stability, they could be a new route for the green fabrication of biocompatible and biosustainable insecticide formulations.

Mitochondrial mechanisms of neuronal rescue by F-68, a hydrophilic Pluronic block co-polymer, following acute substrate deprivation.

PubMed

Wang, Janice C; Bindokas, Vytautas P; Skinner, Matthew; Emrick, Todd; Marks, Jeremy D

2017-10-01

Global brain ischemia can lead to widespread neuronal death and poor neurologic outcomes in patients. Despite detailed understanding of the cellular and molecular mechanisms mediating neuronal death following focal and global brain hypoxia-ischemia, treatments to reduce ischemia-induced brain injury remain elusive. One pathway central to neuronal death following global brain ischemia is mitochondrial dysfunction, one consequence of which is the cascade of intracellular events leading to mitochondrial outer membrane permeabilization. A novel approach to rescuing injured neurons from death involves targeting cellular membranes using a class of synthetic molecules called Pluronics. Pluronics are triblock copolymers of hydrophilic poly[ethylene oxide] (PEO) and hydrophobic poly[propylene oxide] (PPO). Evidence is accumulating to suggest that hydrophilic Pluronics rescue injured neurons from death following substrate deprivation by preventing mitochondrial dysfunction. Here, we will review current understanding of the nature of interaction of Pluronic molecules with biological membranes and the efficacy of F-68, an 80% hydrophilic Pluronic, in rescuing neurons from injury. We will review data indicating that F-68 reduces mitochondrial dysfunction and mitochondria-dependent death pathways in a model of neuronal injury in vitro, and present new evidence that F-68 acts directly on mitochondria to inhibit mitochondrial outer membrane permeabilization. Finally, we will present results of a pilot, proof-of-principle study suggesting that F-68 is effective in reducing hippocampal injury induced by transient global ischemia in vivo. By targeting mitochondrial dysfunction, F-68 and other Pluronic molecules constitute an exciting new approach to rescuing neurons from acute injury. Copyright © 2017 Elsevier Ltd. All rights reserved.

Component effect of stem cell-loaded thermosensitive polypeptide hydrogels on cartilage repair.

PubMed

Liu, He; Cheng, Yilong; Chen, Jinjin; Chang, Fei; Wang, Jincheng; Ding, Jianxun; Chen, Xuesi

2018-06-01

Biophysical properties of the desired biomimetic scaffolds, such as porosity and elasticity, have been proven associated with the efficacy of cartilage regeneration. In this work, the copolymers of poly(l-alanine)-block-poly(ethylene glycol)-block-poly(l-alanine) (PA-PEG-PA) and poly(l-alanine-co-l-phenylalanine)-block-poly(ethylene glycol)-block-poly(l-alanine-co-l-phenylalanine) (PAF-PEG-PAF) with different ratios of alanine to phenylalanine were synthesized. The introduction of a hydrophobic amino acid, i.e., phenylalanine, into polyalanine-based thermosensitive hydrogel led to the enhanced gelation behaviors and upregulated mechanical properties. Moreover, the increase of phenylalanine content resulted in the enlarged pore size and enhanced mechanical strength of PAF-PEG-PAF thermogel, followed by the regeneration of hyaline-like cartilage with reduced fibrous tissue formation in vivo. The findings indicated the great potential of thermosensitive polypeptide hydrogels in cartilage tissue engineering. Articular cartilage defect has limited self-repair ability due to the lack of blood supply and innervation, which may lead to knee osteoarthritis afterwards. Injectable hydrogels are demonstrated possessing outstanding properties as biomimetic scaffolds in cartilage tissue engineering, while the effect of biophysical properties on the efficacy of cartilage regeneration has not been revealed. Herein, the poly(ethylene glycol)-polypeptide triblock copolymers with different ratios of alanine to phenylalanine were synthesized. The sol-to-gel transition temperature and the critical gelation concentration decreased as the increased amount of phenylalanine unit, resulting in the enlarged pore size and enhanced mechanical strength. These features lead to better regeneration of hyaline-like cartilage with reduced fibrous tissue formation, indicating great potential of thermosensitive polypeptide hydrogels for efficient cartilage repair. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Poloxamer 188 (p188) as a membrane resealing reagent in biomedical applications.

PubMed

Moloughney, Joseph G; Weisleder, Noah

2012-12-01

Maintenance of the integrity of the plasma membrane is essential for maintenance of cellular function and prevention of cell death. Since the plasma membrane is frequently exposed to a variety of mechanical and chemical insults the cell has evolved active processes to defend against these injuries by resealing disruptions in the plasma membrane. Cell membrane repair is a conserved process observed in nearly every cell type where intracellular vesicles are recruited to sites of membrane disruption where they can fuse with themselves or the plasma membrane to create a repair patch. When disruptions are extensive or there is an underlying pathology that reduces the membrane repair capacity of a cell this defense mechanism may prove insufficient and the cell could die due to breakdown of the plasma membrane. Extensive loss of cells can compromise the integrity and function of tissues and leading to disease. Thus, methods to increase membrane resealing capacity could have broad utility in a number of disease states. Efforts to find reagents that can modulate plasma membrane reseal found that specific tri-block copolymers, such as poloxamer 188 (P188, or Pluronic F68), can increase the structural stability and resealing of the plasma membrane. Here we review several current patents and patent applications that present inventions making use of P188 and other copolymers to treat specific disease states such as muscular dystrophy, heart failure, neurodegenerative disorders and electrical injuries, or to facilitate biomedical applications such as transplantation. There appears to be promise for the application of poloxamers in the treatment of various diseases, however there are potential concerns with toxicity with long term application and bioavailability in some cases.

Novel polymeric micelles for insect pest control: encapsulation of essential oil monoterpenes inside a triblock copolymer shell for head lice control

PubMed Central

Guzmán, Eduardo; Ortega, Francisco; Rubio, Ramón G.

2017-01-01

Background Essential oil components (EOCs) are molecules with interesting application in pest control, these have been evaluated against different insect pest from more than 100 years, but their practical use is rather limited. Thus, the enhancement of their bioavailability and manageability due to their dispersion in water can open new perspective for the preparation of formulations for the control of insect pest. In this work, we studied the encapsulation of different monoterpenes in a poloxamer shell in order to prepare aqueous formulations that can be used for the development of platforms used in pest control. Methods Micellar systems containing a 5 wt% of poloxamer 407 and 1.25 wt% of the different monoterpenes were prepared. Dynamic Light Scattering (DLS) experiments were carried out to characterize the dispersion of the EOCs in water. The pediculicidal activity of these micellar systems was tested on head lice using an ex vivo immersion test. Results The poloxamers allowed the dispersion of EOCs in water due to their encapsulation inside the hydrophobic core of the copolymer micelles. From this study, we concluded that it is possible to make stable micellar systems containing water (>90 wt%), 1.25 wt% of different monoterpenes and a highly safe polymer (5wt% Poloxamer 407). These formulations were effective against head lice with mortality ranging from 30 to 60%, being the most effective emulsions those containing linalool, 1,8-cineole, α-terpineol, thymol, eugenol, geraniol and nonyl alcohol which lead to mortalities above 50%. Discussion Since these systems showed good pediculicidal activity and high physicochemical stability, they could be a new route for the green fabrication of biocompatible and biosustainable insecticide formulations. PMID:28439460

A functionalizable reverse thermal gel based on a polyurethane/PEG block copolymer

PubMed Central

Park, Daewon; Wu, Wei; Wang, Yadong

2010-01-01

Injectable reverse thermal gels have great potentials as biomaterials for tissue engineering and drug delivery. However, most existing gels lack functional groups that can be modified with biomolecules that can guide cell/material interactions. We created an amine-functionalized ABA block copolymer, poly(ethylene glycol)-poly(serinol hexamethylene urethane), or ESHU. This reverse thermal gel consists of a hydrophobic block (B): poly(serinol hexamethylene urethane) and a hydrophilic block (A): poly(ethylene glycol). The polymer was characterized by GPC, FTIR and 1H FTNMR. Rheological study demonstrated that ESHU solution in phosphate-buffered saline initiated phase transition at 32°C and reached maximum elastic modulus at 37°C. The in vitro degradation tests performed in PBS and cholesterol esterase solutions revealed that the polymer was hydrolyzable and the presence of cholesterol esterase greatly accelerated the hydrolysis. The in vitro cytotoxicity tests carried out using baboon smooth muscle cells demonstrated that ESHU had good cytocompatibility with cell viability indistinguishable from tissue culture treated polystyrene. Subcutaneous implantation in rats revealed well tolerated accurate inflammatory response with moderate ED-1 positive macrophages in the early stages, which largely resolved 4 weeks post-implantation. We functionalized ESHU with a hexapeptide, Ile-Lys-Val-Ala-Val-Ser (IKVAVS), which gelled rapidly at body temperature. We expect this new platform of functionalizable reverse thermal gels to provide versatile biomaterials in tissue engineering and regenerative medicine. PMID:20937526

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

Rock, C.D.; Zeevaart, J.A.D.

Previous {sup 18}O labeling studies of abscisic acid (ABA) have shown that apple (Malus domestica Borkh. cv Granny Smith) fruits synthesize a majority of ({sup 18}O)ABA with the label incorporated in the 1{prime}-hydroxyl position and unlabeled in the carboxyl group (JAD Zeevaart, TG Heath, DA Gage (1989) Plant Physiol 91: 1594-1601). It was proposed that exchange of {sup 18}O in the side chain with the medium occurred at an aldehyde intermediate stage of ABA biosynthesis. We have isolated ABA-aldehyde and 1{prime}-4{prime}-trans-ABA-diol (ABA-trans-diol) from {sup 18}O-labeled apple fruit tissue and measured the extent and position of {sup 18}O incorporation by tandemmore » mass spectrometry. {sup 18}O-Labeling patterns of ABA-aldehyde, ABA-trans-diol, and ABA indicate that ABA-aldehyde is a precursor to, and ABA-trans-diol a catabolite of, ABA. Exchange of {sup 18}O in the carbonyl of ABA-aldehyde can be the cause of loss of {sup 18}O from the side chain of ({sup 18}O)ABA. Results of feeding experiments with deuterated substrates provide further support for the precursor-product relationship of ABA-aldehyde {yields} ABA {yields} ABA-trans-diol. The ABA-aldehyde and ABA-trans-diol contents of fruits and leaves were low, approximately 1 and 0.02 nanograms per gram fresh weight for ABA-aldehyde and ABA-trans-diol, respectively, while ABA levels in fruits ranged from 10 to 200 nanograms per gram fresh weight. ABA biosynthesis was about 10-fold lower in fruits than in leaves. In fruits, the majority of ABA was conjugated to {beta}-D-glucopyranosyl abscisate, whereas in leaves ABA was mainly hydroxylated to phaseic acid. Parallel pathways for ABA and trans-ABA biosynthesis and conjugation in fruits and leaves are proposed.« less

Electrodeposited Ni-Based Magnetic Mesoporous Films as Smart Surfaces for Atomic Layer Deposition: An "All-Chemical" Deposition Approach toward 3D Nanoengineered Composite Layers.

PubMed

Zhang, Jin; Quintana, Alberto; Menéndez, Enric; Coll, Mariona; Pellicer, Eva; Sort, Jordi

2018-05-02

Mesoporous Ni and Cu-Ni (Cu 20 Ni 80 and Cu 45 Ni 55 in at. %) films, showing a three-dimensional (3D) porous structure and tunable magnetic properties, are prepared by electrodeposition from aqueous surfactant solutions using micelles of P-123 triblock copolymer as structure-directing entities. Pores between 5 and 30 nm and dissimilar space arrangements (continuous interconnected networks, circular pores, corrugated mesophases) are obtained depending on the synthetic conditions. X-ray diffraction studies reveal that the Cu-Ni films have crystallized in the face-centered cubic structure, are textured, and exhibit certain degree of phase separation, particularly those with a higher Cu content. Atomic layer deposition (ALD) is used to conformally coat the mesopores of Cu 20 Ni 80 film with amorphous Al 2 O 3 , rendering multiphase "nano-in-meso" metal-ceramic composites without compromising the ferromagnetic response of the metallic scaffold. From a technological viewpoint, these 3D nanoengineered composite films could be appealing for applications like magnetically actuated micro/nanoelectromechanical systems (MEMS/NEMS), voltage-driven magneto-electric devices, capacitors, or as protective coatings with superior strength and tribological performance.

Structural and Luminescence Properties of Lu2O3:Eu3+ F127 Tri-Block Copolymer Modified Thin Films Prepared by Sol-Gel Method

PubMed Central

de Jesus Morales Ramírez, Angel; Hernández, Margarita García; Murillo, Antonieta García; de Jesús Carrillo Romo, Felipe; Palmerin, Joel Moreno; Velazquez, Dulce Yolotzin Medina; Jota, María Luz Carrera

2013-01-01

Lu2O3:Eu3+ transparent, high density, and optical quality thin films were prepared using the sol-gel dip-coating technique, starting with lutetium and europium nitrates as precursors and followed by hydrolysis in an ethanol-ethylene glycol solution. Acetic acid and acetylacetonate were incorporated in order to adjust pH and as a sol stabilizer. In order to increment the thickness of the films and orient the structure, F127 Pluronic acid was incorporated during the sol formation. Structural, morphological, and optical properties of the films were investigated for different F127/Lu molar ratios (0–5) in order to obtain high optical quality films with enhanced thickness compared with the traditional method. X-ray diffraction (XRD) shows that the films present a highly oriented cubic structure <111> beyond 1073 K for a 3-layer film, on silica glass substrates. The thickness, density, porosity, and refractive index evolution of the films were investigated by means of m-lines microscopy along with the morphology by scanning electron microscope (SEM) and luminescent properties. PMID:28809336

Preparation of ordered mesoporous alumina-doped titania films with high thermal stability and their application to high-speed passive-matrix electrochromic displays.

PubMed

Jiang, Xiangfen; Bastakoti, Bishnu Prasad; Weng, Wu; Higuchi, Tetsuya; Oveisi, Hamid; Suzuki, Norihiro; Chen, Wei-Jung; Huang, Yu-Tzu; Yamauchi, Yusuke

2013-08-12

Ordered mesoporous alumina-doped titania thin films with anatase crystalline structure were prepared by using triblock copolymer Pluronic P123 as structure-directing agent. Uniform Al doping was realized by using aluminum isopropoxide as a dopant source which can be hydrolyzed together with titanium tetraisopropoxide. Aluminum doping into the titania framework can prevent rapid crystallization to the anatase phase, thereby drastically increasing thermal stability. With increasing Al content, the crystallization temperatures tend to increase gradually. Even when the Al content doped into the framework was increased to 15 mol %, a well-ordered mesoporous structure was obtained, and the mesostructural ordering was still maintained after calcination at 550 °C. During the calcination process, large uniaxial shrinkage occurred along the direction perpendicular to the substrate with retention of the horizontal mesoscale periodicity, whereby vertically oriented nanopillars were formed in the film. The resulting vertical porosity was successfully exploited to fabricate a high-speed and high-quality passive-matrix electrochromic display by using a leuco dye. The vertical nanospace in the films can effectively prevent drifting of the leuco dye. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rare-earth metal oxide doped transparent mesoporous silica plates under non-aqueous condition as a potential UV sensor.

PubMed

Lee, Sang-Joon; Park, Sung Soo; Lee, Sang Hyun; Hong, Sang-Hyun; Ha, Chang-Sik

2013-11-01

Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide.

New mesostructured organosilica with chiral sugar derived structures: nice host for gold nanoparticles stabilisation.

PubMed

Hérault, Damien; Cerveau, Geneviève; Corriu, Robert J P; Mehdi, Ahmad

2011-01-14

In this paper we describe the synthesis of functionalised mesoporous organosilicas containing a mannitol derivative in the framework. For this purpose, a bis-silylated precursor 3,4-Di-O-[3-(triethoxysilylpropyl)carbamate]-1,2:5,6-di-O-isopropylidene-D-mannitol was prepared by coupling of 1,2:5,6-di-O-isopropylidene-D-mannitol with 3-(triethoxysilylpropyl)isocyanate. The framework-functionalised materials were obtained in one step by the "direct synthesis" method which consists of a co-hydrolysis and polycondensation of a bis-silylated mannitol precursor with tetraethylorthosilicate (TEOS) in the presence of a non-ionic triblock co-polymer (P123) as structure-directing agent. Interestingly, deprotection of the 1,2,5,6 OH functional groups occurred during the material synthesis. The obtained solids were characterized by (13)C and (29)Si CP-MAS NMR, N(2) adsorption-desorption, powder X-ray diffraction, TEM and elemental analysis. We have shown that, the OH functional groups, which are released during the synthesis of the mesoporous silica, can be used for chelation of ions and stabilisation of nanoparticles. The subsequent growth of gold (0) nanoparticles in the wall has been investigated and evidenced.

Improving the visible light photocatalytic activity of mesoporous TiO2 via the synergetic effects of B doping and Ag loading

NASA Astrophysics Data System (ADS)

Tian, Baozhu; Shao, Zhimang; Ma, Yunfei; Zhang, Jinlong; Chen, Feng

2011-11-01

B-doped together with Ag-loaded mesoporous TiO2 (Ag/B-TiO2) was prepared by a two-step hydrothermal method in the presence of boric acid, triblock copolymer surfactant, and silver nitrate, followed by heat treatment. The obtained samples were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption. It was revealed that all samples consist of highly crystalline anatase with mesoporous structure. For Ag/B-TiO2, B was doped into TiO2 matrix in the form of both interstitial B and substitutional B while Ag was deposited on the surface of B-TiO2 in the form of metallic silver. Compared with the single B-doped or Ag-loaded TiO2 one, mesoporous Ag/B-TiO2 exhibits much higher visible light photocatalytic activity for the degradation of Rhodamine 6G, which can be ascribed to the synergistic effects of B doping and Ag loading by narrowing the band gap of the photocatalyst and preventing the fast recombination of the photogenerated charge carriers, respectively.

Development of Lipid-Shell and Polymer Core Nanoparticles with Water-Soluble Salidroside for Anti-Cancer Therapy

PubMed Central

Fang, Dai-Long; Chen, Yan; Xu, Bei; Ren, Ke; He, Zhi-Yao; He, Li-Li; Lei, Yi; Fan, Chun-Mei; Song, Xiang-Rong

2014-01-01

Salidroside (Sal) is a potent antitumor drug with high water-solubility. The clinic application of Sal in cancer therapy has been significantly restricted by poor oral absorption and low tumor cell uptake. To solve this problem, lipid-shell and polymer-core nanoparticles (Sal-LPNPs) loaded with Sal were developed by a double emulsification method. The processing parameters including the polymer types, organic phase, PVA types and amount were systemically investigated. The obtained optimal Sal-LPNPs, composed of PLGA-PEG-PLGA triblock copolymers and lipids, had high entrapment efficiency (65%), submicron size (150 nm) and negatively charged surface (−23 mV). DSC analysis demonstrated the successful encapsulation of Sal into LPNPs. The core-shell structure of Sal-LPNPs was verified by TEM. Sal released slowly from the LPNPs without apparent burst release. MTT assay revealed that 4T1 and PANC-1 cancer cell lines were sensitive to Sal treatment. Sal-LPNPs had significantly higher antitumor activities than free Sal in 4T1 and PANC-1 cells. The data indicate that LPNPs are a promising Sal vehicle for anti-cancer therapy and worthy of further investigation. PMID:24573250

Development of lipid-shell and polymer core nanoparticles with water-soluble salidroside for anti-cancer therapy.

PubMed

Fang, Dai-Long; Chen, Yan; Xu, Bei; Ren, Ke; He, Zhi-Yao; He, Li-Li; Lei, Yi; Fan, Chun-Mei; Song, Xiang-Rong

2014-02-25

Salidroside (Sal) is a potent antitumor drug with high water-solubility. The clinic application of Sal in cancer therapy has been significantly restricted by poor oral absorption and low tumor cell uptake. To solve this problem, lipid-shell and polymer-core nanoparticles (Sal-LPNPs) loaded with Sal were developed by a double emulsification method. The processing parameters including the polymer types, organic phase, PVA types and amount were systemically investigated. The obtained optimal Sal-LPNPs, composed of PLGA-PEG-PLGA triblock copolymers and lipids, had high entrapment efficiency (65%), submicron size (150 nm) and negatively charged surface (-23 mV). DSC analysis demonstrated the successful encapsulation of Sal into LPNPs. The core-shell structure of Sal-LPNPs was verified by TEM. Sal released slowly from the LPNPs without apparent burst release. MTT assay revealed that 4T1 and PANC-1 cancer cell lines were sensitive to Sal treatment. Sal-LPNPs had significantly higher antitumor activities than free Sal in 4T1 and PANC-1 cells. The data indicate that LPNPs are a promising Sal vehicle for anti-cancer therapy and worthy of further investigation.

Fabrication of hierarchical porous N-doping carbon membrane by using ;confined nanospace deposition; method for supercapacitor

NASA Astrophysics Data System (ADS)

Wang, Guoxu; Liu, Meng; Du, Juan; Liu, Lei; Yu, Yifeng; Sha, Jitong; Chen, Aibing

2018-03-01

The membrane carbon materials with hierarchical porous architecture are attractive because they can provide more channels for ion transport and shorten the ions transport path. Herein, we develop a facile way based on "confined nanospace deposition" to fabricate N-dopi-ng three dimensional hierarchical porous membrane carbon material (N-THPMC) via coating the nickel nitrate, silicate oligomers and triblock copolymer P123 on the branches of commercial polyamide membrane (PAM). During high temperature treatment, the mesoporous silica layer and Ni species serve as a "confined nanospace" and catalyst respectively, which are indispensable elements for formation of carbon framework, and the gas-phase carbon precursors which derive from the decomposition of PAM are deposited into the "confined nanospace" forming carbon framework. The N-THPMC with hierarchical macro/meso/microporous structure, N-doping (2.9%) and large specific surface area (994m2 g-1) well inherits the membrane morphology and hierarchical porous structure of PAM. The N-THPMC as electrode without binder exhibits a specific capacitance of 252 F g-1 at the current density of 1 A g-1 in 6 M KOH electrolyte and excellent cycling stability of 92.7% even after 5000 cycles.

Thioether-functionalized mesoporous fiber membranes: sol-gel combined electrospun fabrication and their applications for Hg2+ removal.

PubMed

Teng, Minmin; Wang, Hongtao; Li, Fengting; Zhang, Bingru

2011-03-01

Mesoporous polyvinylpyrrolidone (PVP)/SiO(2) composite nanofiber membranes functionalized with thioether groups have been fabricated by a combination method of sol-gel process and electrospinning. The precursor sol was synthesized by one-step co-condensation of tetraethyl orthosilicate (TEOS) and 1,4-bis(triethoxysilyl)propane tetrasulfide (BTESPTS, (CH(3)CH(2)O)(3)Si(CH(2))(3)S-S-S-S(CH(2))(3)Si-(OCH(2)CH(3))(3)), with the triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (P123, EO(20)PO(70)EO(20)) as template. After the addition of PVP, nanofiber membranes were prepared by electrospinning. The membranes were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) images, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), N(2) adsorption-desorption isotherms, and an Elementar Vario EL analyzer. The composites were used as highly selective adsorbents for Hg(2+) due to the modification with thioether groups (-S-), and were conveniently separated from the waste water. The composite could be regenerated through acidification. Copyright © 2010 Elsevier Inc. All rights reserved.

High performance sulfur, nitrogen and carbon doped mesoporous anatase-brookite TiO₂ photocatalyst for the removal of microcystin-LR under visible light irradiation.

PubMed

El-Sheikh, Said M; Zhang, Geshan; El-Hosainy, Hamza M; Ismail, Adel A; O'Shea, Kevin E; Falaras, Polycarpos; Kontos, Athanassios G; Dionysiou, Dionysios D

2014-09-15

Carbon, nitrogen and sulfur (C, N and S) doped mesoporous anatase-brookite nano-heterojunction titania photocatalysts have been synthesized through a simple sol-gel method in the presence of triblock copolymer Pluronic P123. XRD and Raman spectra revealed the formation of anatase and brookite mixed phases. XPS spectra indicated the presence of C, N and S dopants. The TEM images demonstrated the formation of almost monodisperse titania nanoparticles with particle sizes of approximately 10nm. N2 isotherm measurements confirmed that both doped and undoped titania anatase-brookite materials have mesoporous structure. The photocatalytic degradation of the cyanotoxin microcystin-LR (MC-LR) has been investigated using these novel nanomaterials under visible light illumination. The photocatalytic efficiency of the mesoporous titania anatase-brookite photocatalyst dramatically increased with the addition of the C, N and S non-metal, achieving complete degradation (∼ 100 %) of MC-LR. The results demonstrate the advantages of the synthetic approach and the great potential of the visible light activated C, N, and S doped titania photocatalysts for the treatment of organic micropollutants in contaminated waters under visible light. Copyright © 2014 Elsevier B.V. All rights reserved.

Novel chiral core-shell silica microspheres with trans-(1R,2R)-diaminocyclohexane bridged in the mesoporous shell: synthesis, characterization and application in high performance liquid chromatography.

PubMed

Wu, Xiabing; You, Linjun; Di, Bin; Hao, Weiqiang; Su, Mengxiang; Gu, Yu; Shen, Lingling

2013-07-19

Novel chiral core-shell silica microspheres with trans-(1R,2R)-diaminocyclohexane (DACH) moiety bridged in the mesoporous shell were synthesized using layer-by-layer method. The chiral mesoporous shell around the nonporous silica core was formed by the co-condensation of N,N'-bis-[(triethoxysilyl)propyl]-trans-(1R,2R)-bis-(ureido)-cyclohexane (DACH-BS) and tetraethoxysilane (TEOS) using octadecyltrimethylammonium chloride (C18TMACl) and triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (P123) as the templates. The functionalized core-shell silica microspheres were characterized and tested as chiral stationary phases for high performance liquid chromatography (HPLC). R/S-1,1'-bi-2,2'-naphthol, R/S-6,6'-dibromo-1,1'-bi-2-naphthol and R/S-1,1'-bi-2,2'-phenanthrol were enantioseparated rapidly on the column packed with the DACH core-shell silica particles. Moreover, the column packed with core-shell particles exhibited better performance than the column packed with the DACH functionalized periodic mesoporous organosilicas. Copyright © 2013 Elsevier B.V. All rights reserved.

Encapsulating Networks of Droplet Interface Bilayers in a Thermoreversible Organogel.

PubMed

Challita, Elio J; Najem, Joseph S; Monroe, Rachel; Leo, Donald J; Freeman, Eric C

2018-04-24

The development of membrane-based materials that exhibit the range and robustness of autonomic functions found in biological systems remains elusive. Droplet interface bilayers (DIBs) have been proposed as building blocks for such materials, owing to their simplicity, geometry, and capability for replicating cellular phenomena. Similar to how individual cells operate together to perform complex tasks and functions in tissues, networks of functionalized DIBs have been assembled in modular/scalable networks. Here we present the printing of different configurations of picoliter aqueous droplets in a bath of thermoreversible organogel consisting of hexadecane and SEBS triblock copolymers. The droplets are connected by means of lipid bilayers, creating a network of aqueous subcompartments capable of communicating and hosting various types of chemicals and biomolecules. Upon cooling, the encapsulating organogel solidifies to form self-supported liquid-in-gel, tissue-like materials that are robust and durable. To test the biomolecular networks, we functionalized the network with alamethicin peptides and alpha-hemolysin (αHL) channels. Both channels responded to external voltage inputs, indicating the assembly process does not damage the biomolecules. Moreover, we show that the membrane properties may be regulated through the deformation of the surrounding gel.

Effect of O/W process parameters on Crataegus azarolus L nanocapsule properties.

PubMed

Esmaeili, Akbar; Rahnamoun, Soraya; Sharifnia, Fariba

2013-05-29

Nanocapsules have many applications in the drug, cosmetic, fragrance, and food industries. In this study, Crataegus azarolus L. nanocapsules were prepared by a modified emulsion diffusion technique. In this technique a shell was first made from the polyester triblock copolymer poly(ethylene glycol)-poly(butylene adipate)-poly(ethylene glycol) (PEG-PBA-PEG) and then olive oil was set as the core of the nanocapsule by a method known as the polymer deposition solvent evaporation method. Varying amounts of C. azarolus extract, polymer, and olive oil were mixed in acetone and then added to water on a shaker. Finally, the acetone was removed by vacuuming. The size of the prepared nanocapsules were measured with a particle size analysis report (PSAR) and identified by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance (NMR). Our experiments showed that the size of the nanocapsules depends on the preparation conditions, i.e., the ratio of polymer to oil and concentrations of polymer and plant extract. A ratio of 1:0.25 polymer to oil was shown to be more suitable for the formation of smaller nanocapsules of C. azarolus.

Effect of O/W process parameters on Crataegus azarolus L nanocapsule properties

PubMed Central

2013-01-01

Background Nanocapsules have many applications in the drug, cosmetic, fragrance, and food industries. In this study, Crataegus azarolus L. nanocapsules were prepared by a modified emulsion diffusion technique. Methods In this technique a shell was first made from the polyester triblock copolymer poly(ethylene glycol)-poly(butylene adipate)-poly(ethylene glycol) (PEG-PBA-PEG) and then olive oil was set as the core of the nanocapsule by a method known as the polymer deposition solvent evaporation method. Varying amounts of C. azarolus extract, polymer, and olive oil were mixed in acetone and then added to water on a shaker. Finally, the acetone was removed by vacuuming. Results The size of the prepared nanocapsules were measured with a particle size analysis report (PSAR) and identified by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance (NMR). Conclusions Our experiments showed that the size of the nanocapsules depends on the preparation conditions, i.e., the ratio of polymer to oil and concentrations of polymer and plant extract. A ratio of 1:0.25 polymer to oil was shown to be more suitable for the formation of smaller nanocapsules of C. azarolus. PMID:23718829

Successful entrapment of carbon dots within flexible free-standing transparent mesoporous organic-inorganic silica hybrid films for photonic applications

NASA Astrophysics Data System (ADS)

Vassilakopoulou, Anastasia; Georgakilas, Vasilios; Vainos, Nikolaos; Koutselas, Ioannis

2017-04-01

The effective entrapment of Carbon dots (CDs) into a polymer-silica hybrid matrix, formed as free standing transparent flexible films, is presented. The composite's synthesis, characterization, device application and properties -mechanical, thermal and optical- are being provided and discussed. CDs of 3 nm mean size with strong photoluminescence are embedded into a silica matrix during the sol-gel procedure, using tetraethyl orthosilicate as the precursor and F127 triblock copolymer as the structure directing agent under acidic conditions. The final hybrid nanostructure forms free standing transparent films that show high flexibility and long term stable CDs luminescence indicating the protective character of the hybrid matrix. It is crucial that the photoluminescence of the hybrid's CDs is not seriously affected after thermal treatment at 550 °C for 30 min. Moreover, the herein reported hybrid is demonstrated to be suitable for the fabrication of advanced photonic structures using soft lithography processes due to its low shrinkage and distortion upon drying, both attributable to its porosity. Finally, it is reported that addition of F127 ethanolic solution in aqueous solution of CDs induces a blue-shift of their photoluminescence.

Glucose Synthesis in a Protein-Based Artificial Photosynthesis System.

PubMed

Lu, Hao; Yuan, Wenqiao; Zhou, Jack; Chong, Parkson Lee-Gau

2015-09-01

The objective of this study was to understand glucose synthesis of a protein-based artificial photosynthesis system affected by operating conditions, including the concentrations of reactants, reaction temperature, and illumination. Results from non-vesicle-based glyceraldehyde-3-phosphate (GAP) and glucose synthesis showed that the initial concentrations of ribulose-1,5-bisphosphate (RuBP) and adenosine triphosphate (ATP), lighting source, and temperature significantly affected glucose synthesis. Higher initial concentrations of RuBP and ATP significantly enhanced GAP synthesis, which was linearly correlated to glucose synthesis, confirming the proper functions of all catalyzing enzymes in the system. White fluorescent light inhibited artificial photosynthesis and reduced glucose synthesis by 79.2 % compared to in the dark. The reaction temperature of 40 °C was optimum, whereas lower or higher temperature reduced glucose synthesis. Glucose synthesis in the vesicle-based artificial photosynthesis system reconstituted with bacteriorhodopsin, F 0 F 1 ATP synthase, and polydimethylsiloxane-methyloxazoline-polydimethylsiloxane triblock copolymer was successfully demonstrated. This system efficiently utilized light-induced ATP to drive glucose synthesis, and 5.2 μg ml(-1) glucose was synthesized in 0.78-ml reaction buffer in 7 h. Light-dependent reactions were found to be the bottleneck of the studied artificial photosynthesis system.

Functionalized nanoporous silicas for the immobilization of penicillin acylase

NASA Astrophysics Data System (ADS)

Maria Chong, A. S.; Zhao, X. S.

2004-10-01

Nanoporous silica materials with uniform pore size and ordered structure have drawn growing interest of researchers since 1990s. A large-pore nanoporous material, SBA-15, was functionalized with organosilanes by co-condensation method in the presence of nonionic triblock copolymer P123 as a template under acidic conditions. The functionalization was demonstrated by using five organosilanes, namely 3-aminopropyltriethoxysilane (APTES), 3-mercaptopropyltrimethoxysilane (MPTMS), phenyltrimethoxysilane (PTMS), vinyltriethoxysilane (VTES), and 4-(triethoxysilyl)butyronitrile (TSBN), which modified the surface properties of the silica materials, enabling the materials to be a promising support for immobilization of biological molecules. The functionalized SBA-15 materials exhibited long-range ordering of two-dimensional hexagonal pore arrays of size ranging from 66 to 90 Å as demonstrated by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and physical adsorption techniques. A variety of organosilane density in the range of 0.5-2.6 mmol/g was achieved as revealed by elemental analysis and solid-state nuclear magnetic resonance (NMR) techniques. The functionalized materials displayed improved properties for immobilization of penicillin acylase (PA) in comparison with pure-silica SBA-15. Such improvement is believed to be due to the enhanced surface hydrophobicity and electrostatic interactions of the functional groups with the enzyme.

Synthesis of porous carbon/silica nanostructured microfiber with ultrahigh surface area

NASA Astrophysics Data System (ADS)

Zhou, Dan; Dong, Yan; Cui, Liru; Lin, Huiming; Qu, Fengyu

2014-12-01

Carbon/silica-nanostructured microfibers were synthesized via electrospinning method using phenol-formaldehyde resin and tetraethyl orthosilicate as carbon and silica precursor with triblock copolymer Pluronic P123 as soft template. The prepared samples show uniform microfiber structure with 1 μm in diameter and dozens of microns in length. Additionally, the mesopores in the material is about 2-6 nm. When the silica component was removed by HF, the porous carbon microfibers (PCMFs) were obtained. In addition, after the carbon/silica composites were calcined in air, the porous silica microfibers (PSiMFs) were obtained, revealing the converse porous nanostructure as PCMFs. It is a simple way to prepare PCMFs and PSiMFs with silica and carbon as the template to each other. Additionally, PCMFs possess an ultrahigh specific surface area (2,092 m2 g-1) and large pore volume. The electrochemical performance of the prepared PCMF material was investigated in 6.0 M KOH electrolyte. The PCMF electrode exhibits a high specific capacitance (252 F g-1 at 0.5 A g-1). Then, superior cycling stability (97 % retention after 4,000 cycles) mainly is due to its unique nanostructure.

Blending of diblock and triblock copolypeptide amphiphiles yields cell penetrating vesicles with low toxicity.

PubMed

Rodriguez, April R; Choe, Uh-Joo; Kamei, Daniel T; Deming, Timothy J

2015-01-01

We prepared dual hydrophilic triblock copolypeptide vesicles that form both micron and nanometer scale vesicles in aqueous media. The incorporation of terminal homoarginine segments into methionine sulfoxide-based vesicles was found to significantly enhance their cellular uptake compared to a non-ionic control. We also demonstrated that diblock and triblock copolypeptides with similar hydrophobic domains were found to mix well and form vesicle populations with uniform compositions. Blending of amphiphiles in vesicle nanocarriers was found to impart these materials with many advantageous properties, including good cellular uptake while maintaining minimal toxicity, as well as biological responsiveness to promote vesicle disruption and release of encapsulated cargos. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Soft-template construction of three-dimensionally ordered inverse opal structure from Li2FeSiO4/C composite nanofibers for high-rate lithium-ion batteries

NASA Astrophysics Data System (ADS)

Li, Donglin; Zhang, Wei; Sun, Ru; Yong, Hong-Tuan-Hua; Chen, Guangqi; Fan, Xiaoyong; Gou, Lei; Mao, Yiyang; Zhao, Kun; Tian, Miao

2016-06-01

Exploring a new method to fabricate small-sized nanofibers is essential to achieve superior performances for energy conversion and storage devices. Here, a novel soft-template strategy is developed to synthesize a three-dimensionally ordered macroporous (3DOM) architecture constructed from small-sized nanofibers. The effectiveness of a nanofiber-assembled three-dimensional inverse opal material as an electrode for high-rate lithium-ion batteries is demonstrated. The small-sized Li2FeSiO4/C composite nanofibers with a diameter of 20-30 nm are grown by employing a tri-block copolymer P123 as a structure directing agent. Accordingly, the macro-mesoporous hierarchical 3DOM architecture constructed from Li2FeSiO4/C nanofibers is further templated from P123 for the nanofibers and a polystyrene colloidal crystal array for the 3DOM architecture. We find that the thermal stability of the nanofiber morphology depends on the self-limited growth of Li2FeSiO4 nanocrystals in a crystalline-amorphous hybrid. As a cathode for a lithium-ion battery, the 3D hierarchical macro-mesoporous cathodes exhibit outstanding high-rate and ultralong-life performances with a capacity retention of 84% after 1500 cycles at 5 C in the voltage window of 1.5-4.5 V, which is greatly improved compared with a simple 3DOM Li2FeSiO4/C nanocomposite.Exploring a new method to fabricate small-sized nanofibers is essential to achieve superior performances for energy conversion and storage devices. Here, a novel soft-template strategy is developed to synthesize a three-dimensionally ordered macroporous (3DOM) architecture constructed from small-sized nanofibers. The effectiveness of a nanofiber-assembled three-dimensional inverse opal material as an electrode for high-rate lithium-ion batteries is demonstrated. The small-sized Li2FeSiO4/C composite nanofibers with a diameter of 20-30 nm are grown by employing a tri-block copolymer P123 as a structure directing agent. Accordingly, the macro-mesoporous hierarchical 3DOM architecture constructed from Li2FeSiO4/C nanofibers is further templated from P123 for the nanofibers and a polystyrene colloidal crystal array for the 3DOM architecture. We find that the thermal stability of the nanofiber morphology depends on the self-limited growth of Li2FeSiO4 nanocrystals in a crystalline-amorphous hybrid. As a cathode for a lithium-ion battery, the 3D hierarchical macro-mesoporous cathodes exhibit outstanding high-rate and ultralong-life performances with a capacity retention of 84% after 1500 cycles at 5 C in the voltage window of 1.5-4.5 V, which is greatly improved compared with a simple 3DOM Li2FeSiO4/C nanocomposite. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07783d

Synthesis, characterization, and property of biodegradable PEG-PCL-PLA terpolymers with miktoarm star and triblock architectures as drug carriers.

PubMed

Zhang, Yixin; Luo, Song; Liang, Yan; Zhang, Hai; Peng, Xinyu; He, Bin; Li, Sai

2018-03-01

A series of amphiphilic terpolymers with miktoarm star and triblock architectures of poly(ethylene glycol) (PEG), poly(ε-caprolactone) (PCL) and poly(l-lactide acid) (PLLA) or poly(DL-lactide acid) (PDLLA) terpolymers were synthesized as carriers for drug delivery. The architecture, molecular weight and crystallization behavior of the terpolymers were characterized. Anticancer drug doxorubicin was encapsulated in the micelles to investigate their drug loading properties. The miktoarm star terpolymers exhibited stronger crystallization capability, smaller size and better stability than that of triblock polymeric micelle, owing to the lower CMC values of miktoarm star polymeric micelle. Furthermore, the drug-loaded miktoarm star polymeric micelles showed the cumulative DOX release account of the micelles with PDLLA blocks was 65.3% while the release account of the corresponding micelles containing PLLA blocks was 45.2%. The IC 50 values of drug-loaded miktoarm star polymeric micelle were lower than triblock polymeric micelle. Meanwhile, Confocal laser scanning microscopy (CLSM) and Flow Cytometry results demonstrated that the miktoarm star micelles were more favorable for cellular internalization. The miktoarm star micelles with PDLLA blocks were promising carriers for anticancer drug delivery.

Increasing abscisic acid levels by immunomodulation in barley grains induces precocious maturation without changing grain composition.

PubMed

Staroske, Nicole; Conrad, Udo; Kumlehn, Jochen; Hensel, Götz; Radchuk, Ruslana; Erban, Alexander; Kopka, Joachim; Weschke, Winfriede; Weber, Hans

2016-04-01

Abscisic acid (ABA) accumulates in seeds during the transition to the seed filling phase. ABA triggers seed maturation, storage activity, and stress signalling and tolerance. Immunomodulation was used to alter the ABA status in barley grains, with the resulting transgenic caryopses responding to the anti-ABA antibody gene expression with increased accumulation of ABA. Calculation of free versus antibody-bound ABA reveals large excess of free ABA, increasing signficantly in caryopses from 10 days after fertilization. Metabolite and transcript profiling in anti-ABA grains expose triggered and enhanced ABA-functions such as transcriptional up-regulation of sucrose-to-starch metabolism, storage protein synthesis and ABA-related signal transduction. Thus, enhanced ABA during transition phases induces precocious maturation but negatively interferes with growth and development. Anti-ABA grains display broad constitutive gene induction related to biotic and abiotic stresses. Most of these genes are ABA- and/or stress-inducible, including alcohol and aldehyde dehydrogenases, peroxidases, chaperones, glutathione-S-transferase, drought- and salt-inducible proteins. Conclusively, ABA immunomodulation results in precocious ABA accumulation that generates an integrated response of stress and maturation. Repression of ABA signalling, occurring in anti-ABA grains, potentially antagonizes effects caused by overshooting production. Finally, mature grain weight and composition are unchanged in anti-ABA plants, although germination is somewhat delayed. This indicates that anti-ABA caryopses induce specific mechanisms to desensitize ABA signalling efficiently, which finally yields mature grains with nearly unchanged dry weight and composition. Such compensation implicates the enormous physiological and metabolic flexibilities of barley grains to adjust effects of unnaturally high ABA amounts in order to ensure and maintain proper grain development. © The Author 2016. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Increasing abscisic acid levels by immunomodulation in barley grains induces precocious maturation without changing grain composition

PubMed Central

Staroske, Nicole; Conrad, Udo; Kumlehn, Jochen; Hensel, Götz; Radchuk, Ruslana; Erban, Alexander; Kopka, Joachim; Weschke, Winfriede; Weber, Hans

2016-01-01

Abscisic acid (ABA) accumulates in seeds during the transition to the seed filling phase. ABA triggers seed maturation, storage activity, and stress signalling and tolerance. Immunomodulation was used to alter the ABA status in barley grains, with the resulting transgenic caryopses responding to the anti-ABA antibody gene expression with increased accumulation of ABA. Calculation of free versus antibody-bound ABA reveals large excess of free ABA, increasing signficantly in caryopses from 10 days after fertilization. Metabolite and transcript profiling in anti-ABA grains expose triggered and enhanced ABA-functions such as transcriptional up-regulation of sucrose-to-starch metabolism, storage protein synthesis and ABA-related signal transduction. Thus, enhanced ABA during transition phases induces precocious maturation but negatively interferes with growth and development. Anti-ABA grains display broad constitutive gene induction related to biotic and abiotic stresses. Most of these genes are ABA- and/or stress-inducible, including alcohol and aldehyde dehydrogenases, peroxidases, chaperones, glutathione-S-transferase, drought- and salt-inducible proteins. Conclusively, ABA immunomodulation results in precocious ABA accumulation that generates an integrated response of stress and maturation. Repression of ABA signalling, occurring in anti-ABA grains, potentially antagonizes effects caused by overshooting production. Finally, mature grain weight and composition are unchanged in anti-ABA plants, although germination is somewhat delayed. This indicates that anti-ABA caryopses induce specific mechanisms to desensitize ABA signalling efficiently, which finally yields mature grains with nearly unchanged dry weight and composition. Such compensation implicates the enormous physiological and metabolic flexibilities of barley grains to adjust effects of unnaturally high ABA amounts in order to ensure and maintain proper grain development. PMID:26951372

Effect of Ternary Solutes on the Evolution of Structure and Gel Formation in Amphiphilic Copolymer Solutions

NASA Astrophysics Data System (ADS)

Meznarich, Norman Anthony Kang

Aqueous solutions of polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) amphiphilic triblock copolymers (commercially known as Pluronic surfactants) undergo reversible and temperature-dependent micellization and arrangement into cubic ordered lattices known as "micelle gels". The macroscopic behavior of the ordering is a transition from a liquid to a gel. While the phase behavior and gel structure of pure Pluronic surfactant solutions have been well studied, less is known about the effects of added ternary solutes. In this dissertation, a comprehensive investigation into the effects of the added pharmaceutical methylparaben on solutions of F127 ranging from 10 to 30 wt% was conducted in order to better understand the behavior of F127 in multicomponent pharmaceutical formulations. The viscoelastic properties of F127 gel formation were studied using rheometry, where heating rates of 0.1, 1, and 10 degrees C/min were also used to probe the kinetics of the gel transition. In solutions containing methylparaben, F127 gelation occurred at up to 15 degrees C lower temperatures and was accelerated by a factor of three to four. Small angle x-ray scattering (SAXS) was used to characterize the structure of the ordered domains, and how they were affected by the presence of dissolved pharmaceuticals. It was found that ordered domain formation changed from heterogeneous nucleation and growth to possible homogeneous nucleation and growth. A roughly 2% reduction in the cubic lattice parameter was also observed for solutions containing methylparaben. Differential scanning calorimetry (DSC) experiments were performed on a series of different Pluronic surfactants in order to characterize the micellization behavior as a function of PPO center block length and PEO/PPO ratio. Added methylparaben suppressed the micellization endotherm, the degree of suppression depending linearly on the amount of added methylparaben, as well as the length of the PPO center block and PEO/PPO ratio. This dissertation yielded a thorough characterization of the changes in micellization and gelation behavior in F127 gels as a result of added pharmaceuticals. Previously unobserved behavior such as the onset of ordered domain formation in F127 gels was observed, and a greater understanding of the interactions between amphiphilic copolymer solutions and dissolved solutes was achieved.

Magnetic nanoparticles for bio-analytical applications

NASA Astrophysics Data System (ADS)

Yedlapalli, Sri Lakshmi

Magnetic nanoparticles are widely being used in various fields of medicine, biology and separations. This dissertation focuses on the synthesis and use of magnetic nanoparticles for targeted drug delivery and analytical separations. The goals of this research include synthesis of biocompatible surface modified monodisperse superparamagnetic iron oxide nanoparticles (SPIONs) by novel techniques for targeted drug delivery and use of SPIONs as analytical sensing tools. Surface modification of SPIONs was performed with two different co-polymers: tri block co-polymer Pluronics and octylamine modified polyacrylic acid. Samples of SPIONs were subsequently modified with 4 different commercially available, FDA approved tri-block copolymers (Pluronics), covering a wide range of molecular weights (5.75-14.6 kDa). A novel, technically simpler and faster phase transfer approach was developed to surface modify the SPIONs with Pluronics for drug delivery and other biomedical applications. The hydrodynamic diameter and aggregation properties of the Pluronic modified SPIONs were studied by dynamic light scattering (DLS). The coverage of SPIONs with Pluronics was supported with IR Spectroscopy and characterized by Thermo gravimetric Analysis (TGA). The drug entrapment capacity of SPIONs was studied by UV-VIS spectroscopy using a hydrophobic carbocyanine dye, which serves as a model for hydrophobic drugs. These studies resulted in a comparison of physical properties and their implications for drug loading capacities of the four types of Pluronic coated SPIONs for drug delivery assessment. These drug delivery systems could be used for passive drug targeting. However, Pluronics lack the functional group necessary for bioconjugation and hence cannot achieve active targeting. SPIONs were functionalized with octylamine modified polyacrylic acid-based copolymer, providing water solubility and facile biomolecular conjugation. Epirubicin was loaded onto SPIONs and the drug entrapment was studied by UVVIS spectrophotometry. In this study, the antisense oligonucleotide sequence to the anti-apoptopic protein survivin was coupled to SPIONs to provide molecular targeting and potential therapy for cancer cells. Successful coupling of antisense survivin to SPIONs was demonstrated by circular dichroism studies of the conjugate and its complementary sequence. Such multifunctional SPIONs can be used as active targeting agents for cancer cells, producing enhanced magnetic resonance imaging contrast and releasing chemotherapeutic agents to targeted cells. SPIONs also serve as an excellent platform for analytical sensing. Streptavidin modified SPIONs were used as substrates to immobilize biotinylated aptamers (single-stranded DNA). The binding affinity of such aptamers to its target was achieved by quantifying the amount of target released from the aptamer. This quantification was achieved using pH-mediated stacking capillary electrophoresis. SPIONs were shown to be more efficient compared to magnetic microbeads as the sensing elements. The binding affinity constant of the aptamer determined was almost 8-fold better than that obtained using magnetic microbeads.

Diversity and Evolution of AbaR Genomic Resistance Islands in Acinetobacter baumannii Strains of European Clone I▿†

PubMed Central

Krizova, Lenka; Dijkshoorn, Lenie; Nemec, Alexandr

2011-01-01

To assess the diversity of AbaR genomic resistance islands in Acinetobacter baumannii European clone I (MLST clonal complex 1), we investigated 26 multidrug-resistant strains of this major clone isolated from hospitals in 21 cities of 10 European countries between 1984 and 2005. Each strain harbored an AbaR structure integrated at the same position in the chromosomal ATPase gene. AbaR3, including four subtypes based on variations in class 1 integron cassettes, and AbaR10 were found in 15 and 2 strains, respectively, whereas a new, unique AbaR variant was discovered in each of the other 9 strains. These new variants, designated AbaR11 to AbaR19 (19.8 kb to 57.5 kb), seem to be truncated derivatives of AbaR3, likely resulting from the deletions of its internal parts mediated by either IS26 elements (AbaR12 to AbaR19) or homologous recombination (AbaR11). AbaR3 was detected in all 10 strains isolated in 1984 to 1991, while AbaR11 to AbaR19 were carried only by strains isolated since 1997. Our results and those from previous publications suggest that AbaR3 is the original form of AbaR in European clone I, which may have provided strains of the lineage with a selective advantage facilitating their spread in European hospitals in the 1980s or before. PMID:21537009

Mesophyll conductance decreases in the wild type but not in an ABA-deficient mutant (aba1) of Nicotiana plumbaginifolia under drought conditions.

PubMed

Mizokami, Yusuke; Noguchi, Ko; Kojima, Mikiko; Sakakibara, Hitoshi; Terashima, Ichiro

2015-03-01

Under drought conditions, leaf photosynthesis is limited by the supply of CO2 . Drought induces production of abscisic acid (ABA), and ABA decreases stomatal conductance (gs ). Previous papers reported that the drought stress also causes the decrease in mesophyll conductance (gm ). However, the relationships between ABA content and gm are unclear. We investigated the responses of gm to the leaf ABA content [(ABA)L ] using an ABA-deficient mutant, aba1, and the wild type (WT) of Nicotiana plumbaginifolia. We also measured leaf water potential (ΨL ) because leaf hydraulics may be related to gm . Under drought conditions, gm decreased with the increase in (ABA)L in WT, whereas both (ABA)L and gm were unchanged by the drought treatment in aba1. Exogenously applied ABA decreased gm in both WT and aba1 in a dose-dependent manner. ΨL in WT was decreased by the drought treatment to -0.7 MPa, whereas ΨL in aba1 was around -0.8 MPa even under the well-watered conditions and unchanged by the drought treatment. From these results, we conclude that the increase in (ABA)L is crucial for the decrease in gm under drought conditions. We discuss possible relationships between the decrease in gm and changes in the leaf hydraulics. © 2014 John Wiley & Sons Ltd.

ABA signaling in stress-response and seed development.

PubMed

Nakashima, Kazuo; Yamaguchi-Shinozaki, Kazuko

2013-07-01

KEY MESSAGE : We review the recent progress on ABA signaling, especially ABA signaling for ABA-dependent gene expression, including the AREB/ABF regulon, SnRK2 protein kinase, 2C-type protein phosphatases and ABA receptors. Drought negatively impacts plant growth and the productivity of crops. Drought causes osmotic stress to organisms, and the osmotic stress causes dehydration in plant cells. Abscisic acid (ABA) is produced under osmotic stress conditions, and it plays an important role in the stress response and tolerance of plants. ABA regulates many genes under osmotic stress conditions. It also regulates gene expression during seed development and germination. The ABA-responsive element (ABRE) is the major cis-element for ABA-responsive gene expression. ABRE-binding protein (AREB)/ABRE-binding factor (ABF) transcription factors (TFs) regulate ABRE-dependent gene expression. Other TFs are also involved in ABA-responsive gene expression. SNF1-related protein kinases 2 are the key regulators of ABA signaling including the AREB/ABF regulon. Recently, ABA receptors and group A 2C-type protein phosphatases were shown to govern the ABA signaling pathway. Moreover, recent studies have suggested that there are interactions between the major ABA signaling pathway and other signaling factors in stress-response and seed development. The control of the expression of ABA signaling factors may improve tolerance to environmental stresses.

Molecular identification of zeaxanthin epoxidase of Nicotiana plumbaginifolia, a gene involved in abscisic acid biosynthesis and corresponding to the ABA locus of Arabidopsis thaliana.

PubMed Central

Marin, E; Nussaume, L; Quesada, A; Gonneau, M; Sotta, B; Hugueney, P; Frey, A; Marion-Poll, A

1996-01-01

Abscisic acid (ABA) is a plant hormone which plays an important role in seed development and dormancy and in plant response to environmental stresses. An ABA-deficient mutant of Nicotiana plumbaginifolia, aba2, was isolated by transposon tagging using the maize Activator transposon. The aba2 mutant exhibits precocious seed germination and a severe wilty phenotype. The mutant is impaired in the first step of the ABA biosynthesis pathway, the zeaxanthin epoxidation reaction. ABA2 cDNA is able to complement N.plumbaginifolia aba2 and Arabidopsis thaliana aba mutations indicating that these mutants are homologous. ABA2 cDNA encodes a chloroplast-imported protein of 72.5 kDa, sharing similarities with different mono-oxigenases and oxidases of bacterial origin and having an ADP-binding fold and an FAD-binding domain. ABA2 protein, produced in Escherichia coli, exhibits in vitro zeaxanthin epoxidase activity. This is the first report of the isolation of a gene of the ABA biosynthetic pathway. The molecular identification of ABA2 opens the possibility to study the regulation of ABA biosynthesis and its cellular location. Images PMID:8665840

Molecular identification of zeaxanthin epoxidase of Nicotiana plumbaginifolia, a gene involved in abscisic acid biosynthesis and corresponding to the ABA locus of Arabidopsis thaliana.

PubMed

Marin, E; Nussaume, L; Quesada, A; Gonneau, M; Sotta, B; Hugueney, P; Frey, A; Marion-Poll, A

1996-05-15

Abscisic acid (ABA) is a plant hormone which plays an important role in seed development and dormancy and in plant response to environmental stresses. An ABA-deficient mutant of Nicotiana plumbaginifolia, aba2, was isolated by transposon tagging using the maize Activator transposon. The aba2 mutant exhibits precocious seed germination and a severe wilty phenotype. The mutant is impaired in the first step of the ABA biosynthesis pathway, the zeaxanthin epoxidation reaction. ABA2 cDNA is able to complement N.plumbaginifolia aba2 and Arabidopsis thaliana aba mutations indicating that these mutants are homologous. ABA2 cDNA encodes a chloroplast-imported protein of 72.5 kDa, sharing similarities with different mono-oxigenases and oxidases of bacterial origin and having an ADP-binding fold and an FAD-binding domain. ABA2 protein, produced in Escherichia coli, exhibits in vitro zeaxanthin epoxidase activity. This is the first report of the isolation of a gene of the ABA biosynthetic pathway. The molecular identification of ABA2 opens the possibility to study the regulation of ABA biosynthesis and its cellular location.

A new look at stress: abscisic acid patterns and dynamics at high-resolution.

PubMed

Jones, Alexander M

2016-04-01

Abscisic acid (ABA) is a key phytohormone promoting abiotic stress tolerance as well as developmental processes such as seed dormancy. A spatiotemporal map of ABA concentrations would greatly advance our understanding of the cell type and timing of ABA action. Organ and tissue-level ABA measurements, as well as indirect in vivo measurements such as cell-specific transcriptional analysis of ABA metabolic enzymes and ABA-responsive promoters, have all contributed to current views of the localization and timing of ABA accumulations. Recently developed Förster resonance energy transfer (FRET) biosensors for ABA that sense ABA levels directly promise to add unprecedented resolution to in vivo ABA spatiotemporal mapping and expand our knowledge of the mechanisms controlling ABA levels in space and time. © 2015 Carnegie Institution for Science New Phytologist © 2015 New Phytologist Trust.

Tetrahydroindazolone substituted 2-aminobenzamides as fluorescent probes: switching metal ion selectivity from zinc to cadmium by interchanging the amino and carbamoyl groups on the fluorophore.

PubMed

Jia, Jia; Xu, Qin-Chao; Li, Ri-chen; Tang, Xi; He, Ying-Fang; Zhang, Meng-Yu; Zhang, Yuan; Xing, Guo-Wen

2012-08-21

Three fluorescent probes CdABA', CdABA and ZnABA', which are structural isomers of ZnABA, have been designed with N,N-bis(2-pyridylmethyl) ethylenediamine (BPEA) as chelator and 2-aminobenzamide as fluorophore. These probes can be divided into two groups: CdABA, CdABA' for Cd(2+) and ZnABA, ZnABA' for Zn(2+). Although there is little difference in their chemical structures, the two groups of probes exhibit totally different fluorescence properties for preference of Zn(2+) or Cd(2+). In the group of Zn(2+) probes, ZnABA/ZnABA' distinguish Zn(2+) from Cd(2+) with F(Zn)(2+)-F(Cd)(2+) = 1.87-2.00. Upon interchanging the BPEA and carbamoyl groups on the aromatic ring of the fluorophore, the structures of ZnABA/ZnABA' are converted into CdABA/CdABA'. Interestingly, the metal ions selectivity of CdABA/CdABA' was switched to discriminate Cd(2+) from Zn(2+) with F(Cd)(2+)-F(Zn)(2+) = 2.27-2.36, indicating that a small structural modification could lead to a remarkable change of the metal ion selectivity. (1)H NMR titration and ESI mass experiments demonstrated that these fluorescent probers exhibited different coordination modes for Zn(2+) and Cd(2+). With CdABA' as an example, generally, upon addition of Cd(2+), the fluorescence response possesses PET pathway to display no obvious shift of maximum λ(em) in the absence or presence of Cd(2+). However, an ICT pathway could be employed after adding Zn(2+) into the CdABA' solution, resulting in a distinct red-shift of maximal λ(em).

Ectopic expression of ABSCISIC ACID 2/GLUCOSE INSENSITIVE 1 in Arabidopsis promotes seed dormancy and stress tolerance.

PubMed

Lin, Pei-Chi; Hwang, San-Gwang; Endo, Akira; Okamoto, Masanori; Koshiba, Tomokazu; Cheng, Wan-Hsing

2007-02-01

Abscisic acid (ABA) is an important phytohormone that plays a critical role in seed development, dormancy, and stress tolerance. 9-cis-Epoxycarotenoid dioxygenase is the key enzyme controlling ABA biosynthesis and stress tolerance. In this study, we investigated the effect of ectopic expression of another ABA biosynthesis gene, ABA2 (or GLUCOSE INSENSITIVE 1 [GIN1]) encoding a short-chain dehydrogenase/reductase in Arabidopsis (Arabidopsis thaliana). We show that ABA2-overexpressing transgenic plants with elevated ABA levels exhibited seed germination delay and more tolerance to salinity than wild type when grown on agar plates and/or in soil. However, the germination delay was abolished in transgenic plants showing ABA levels over 2-fold higher than that of wild type grown on 250 mm NaCl. The data suggest that there are distinct mechanisms underlying ABA-mediated inhibition of seed germination under diverse stress. The ABA-deficient mutant aba2, with a shorter primary root, can be restored to normal root growth by exogenous application of ABA, whereas transgenic plants overexpressing ABA2 showed normal root growth. The data reflect that the basal levels of ABA are essential for maintaining normal primary root elongation. Furthermore, analysis of ABA2 promoter activity with ABA2::beta-glucuronidase transgenic plants revealed that the promoter activity was enhanced by multiple prolonged stresses, such as drought, salinity, cold, and flooding, but not by short-term stress treatments. Coincidently, prolonged drought stress treatment led to the up-regulation of ABA biosynthetic and sugar-related genes. Thus, the data support ABA2 as a late expression gene that might have a fine-tuning function in mediating ABA biosynthesis through primary metabolic changes in response to stress.

Synthesis and Biological Activity of 2',3'-iso-Aryl-abscisic Acid Analogs.

PubMed

Wan, Chuan; Wang, Mingan; Yang, Dongyan; Han, Xiaoqiang; Che, Chuanliang; Ding, Shanshan; Xiao, Yumei; Qin, Zhaohai

2017-12-15

2',3'- iso -Benzoabscisic acid ( iso -PhABA), an excellent selective abscisic acid (ABA) analog, was developed in our previous work. In order to find its more structure-activity information, some structural modifications were completed in this paper, including the substitution of phenyl ring and replacing the ring with heterocycles. Thus, 16 novel analogs of iso -PhABA were synthesized and screened with three bioassays, Arabidopsis and lettuce seed germination and rice seedling elongation. Some of them, i.e., 2',3'- iso -pyridoabscisic acid ( iso -PyABA) and 2',3'- iso -franoabscisic acid ( iso -FrABA), displayed good bioactivities that closed to iso -PhABA and natural (+)-ABA. Some others, for instance, substituted- iso -PhABA, exhibited certain selectivity to different physiological process when compared to iso -PhABA or (+)-ABA. These analogs not only provided new candidates of ABA-like synthetic plant growth regulators (PGRs) for practical application, but also new potential selective agonist/antagonist for probing the specific function of ABA receptors.

Chemical inhibition of potato ABA 8'-hydroxylase activity alters in vitro and in vivo ABA metabolism and endogenous ABA levels but does not affect potato microtuber dormancy duration

USDA-ARS?s Scientific Manuscript database

The effects of azole-type P450 inhibitors and two metabolism-resistant ABA analogs on in vitro ABA 8'-hydroxylase activity, in planta ABA metabolism, endogenous ABA content, and tuber meristem dormancy duration were examined in potato (Solanum tuberosum L. cv. Russet Burbank). When functionally expr...

Enzyme immobilization and biocatalysis of polysiloxanes

NASA Astrophysics Data System (ADS)

Poojari, Yadagiri

Lipases have been proven to be versatile and efficient biocatalysts which can be used in a broad variety of esterification, transesterification, and ester hydrolysis reactions. Due to the high chemo-, regio-, and stereo-selectivity and the mild conditions of lipase-catalyzed reactions, the vast potential of these biocatalysts for use in industrial applications has been increasingly recognized. Polysiloxanes (silicones) are well known for their unique physico-chemical properties and can be prepared in the form of fluids, elastomers, gels and resins for a wide variety of applications. However, the enzymatic synthesis of silicone polyesters and copolymers is largely unexplored. In the present investigations, an immobilized Candida antarctica lipase B (CALB) on macroporous acrylic resin beads (Novozym-435 RTM) has been successfully employed as a catalyst to synthesize silicone polyesters and copolymers under mild reaction conditions. The silicone aliphatic polyesters and the poly(dimethylsiloxane)--poly(ethylene glycol) (PDMS-PEG) copolymers were synthesized in the bulk (without using a solvent), while the silicone aromatic polyesters, the silicone aromatic polyamides and the poly(epsilon-caprolactone)--poly(dimethylsiloxane)--poly(epsilon-caprolactone) (PCL-PDMS-PCL) triblock copolymers were synthesized in toluene. The synthesized silicone polyesters and copolymers were characterized by Gel Permeation Chromatography (GPC), Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC) and Wide Angle X-ray Diffraction (WAXD). This dissertation also describes a methodology for physical immobilization of the enzyme pepsin from Porcine stomach mucosa in silicone elastomers utilizing condensation-cure room temperature vulcanization (RTV) of silanol-terminated poly(dimethylsiloxane) (PDMS). The activity and the stability of free pepsin and pepsin immobilized in silicone elastomers were studied with respect to pH, temperature, cross-link density, organic solvents and storage time using a hemoglobin assay. A notable finding was that free pepsin had zero activity in neutral buffer solution (pH 7) after incubation for 5 hours, while pepsin immobilized in the silicone elastomers was found to retain more than 70% of its maximum normalized activity. These results demonstrate that cross-linked poly(dimethylsiloxane) (PDMS) is a promising support material for the physical entrapment of hydrolytic enzymes such as pepsin. The Novozym-435 has been widely employed as a biocatalyst for esterification and transesterification of a variety of organic compounds including synthesis of polyesters and polylactones due to its high catalytic-efficiency and high thermal stability in organic media. However, the Novozym-435 was found to have poor mechanical stability and the enzyme was found to leach out from the resin into the organic media. In the present research work, efforts were made to solve the above two problems by chemical immobilization of CALB on surface modified porous silica gel particles. The surface of the porous silica gel particles was silanized using (gamma-Aminopropyl)triethoxysilane and then the CALB was chemically crosslinked onto the surface of the silica gel particles using glutaraldehyde. Although the thermal stability of the CALB immobilized silica gel particles was found to be lower compared to that of Novozym-435. The CALB immobilized silica gel particles showed higher enzymatic activity and higher mechanical stability compared to that of Novozym-435.

Inhibition of FUSCA3 degradation at high temperature is dependent on ABA signaling and is regulated by the ABA/GA ratio.

PubMed

Chiu, Rex Shun; Saleh, Yazan; Gazzarrini, Sonia

2016-11-01

During seed imbibition at supra-optimal temperature, an increase in the abscisic acid (ABA)/gibberellin (GA) ratio imposes secondary dormancy to prevent germination (thermoinhibition). FUSCA3 (FUS3), a positive regulator of seed dormancy, accumulates in seeds imbibed at high temperature and increases ABA levels to inhibit germination. Recently, we showed that ABA inhibits FUS3 degradation at high temperature, and that ABA and high temperature also inhibit the ubiquitin-proteasome system, by dampening both proteasome activity and protein polyubiquitination. Here, we investigated the role of ABA signaling components and the ABA antagonizing hormone, GA, in the regulation of FUS3 levels. We show that the ABA receptor mutant, pyl1-1, is less sensitive to ABA and thermoinhibition. In this mutant background, FUS3 degradation in vitro is faster. Similarly, GA alleviates thermoinhibition and also increases FUS3 degradation. These results indicate that inhibition of FUS3 degradation at high temperature is dependent on a high ABA/GA ratio and a functional ABA signaling pathway. Thus, FUS3 constitutes an important node in ABA-GA crosstalk during germination at supra-optimal temperature.

Stretchable, adhesive and ultra-conformable elastomer thin films.

PubMed

Sato, Nobutaka; Murata, Atsushi; Fujie, Toshinori; Takeoka, Shinji

2016-11-16

Thermoplastic elastomers are attractive materials because of the drastic changes in their physical properties above and below the glass transition temperature (T g ). In this paper, we report that free-standing polystyrene (PS, T g : 100 °C) and polystyrene-polybutadiene-polystyrene triblock copolymer (SBS, T g : -70 °C) thin films with a thickness of hundreds of nanometers were prepared by a gravure coating method. Among the mechanical properties of these thin films determined by bulge testing and tensile testing, the SBS thin films exhibited a much lower elastic modulus (ca. 0.045 GPa, 212 nm thickness) in comparison with the PS thin films (ca. 1.19 GPa, 217 nm thickness). The lower elastic modulus and lower thickness of the SBS thin films resulted in higher conformability and thus higher strength of adhesion to an uneven surface such as an artificial skin model with roughness (R a = 10.6 μm), even though they both have similar surface energies. By analyzing the mechanical properties of the SBS thin films, the elastic modulus and thickness of the thin films were strongly correlated with their conformability to a rough surface, which thus led to a high adhesive strength. Therefore, the SBS thin films will be useful as coating layers for a variety of materials.

Synthetic Design of Polysulfone Membranes: Morphological Effect on Property and Performance in Flow Batteries

NASA Astrophysics Data System (ADS)

Gindt, Brandon

This dissertation outlines a novel path towards improved understanding and function of proton exchange membranes (PEMs) for redox flow batteries, a large-scale battery storage device. This research uses synthetic methods and nanotechnology through two different approaches to prepare tailored polymer membranes: 1) Ion exchange membranes with enhanced chemical structures to promote membrane morphology on the nano-scale were prepared. Specifically, functional polysulfones (PSUs) were synthesized from different pre-sulfonated monomers. These PSUs have controlled placement and content of unique sulfonic acid moieties. PEMs were fabricated and characterized. The new PEMs showed desirable physical properties and performance in a vanadium redox flow battery (VRFB) cell. 2) Nanoporous PSU membranes were fabricated via post-hydrolysis of polylactide (PLA) from PLA-PSU-PLA triblock copolymer membranes. The controlled morphology and pore size of the resulting nanoporous membranes were evaluated by different microscopy and scattering techniques to understand structure-property relationships. Further, the resulting nanopore surface was chemically modified with sulfonic acid moieties. Membranes were analyzed and evaluated as separators for a VRFB. The chemically modified nanoporous PEMs exhibited unique behavior with respect to their ion conductivity when exposed to solutions of increasing acid concentration. In addition, the hierarchical micro-nanoporous membranes developed further showed promising structure and properties.

Application of controlled radical polymerization (CRP) in the design of functional biomedical architectures

NASA Astrophysics Data System (ADS)

Siegwart, Daniel John

In this thesis, atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization were utilized in the design of synthetic polymers to create tissue engineering scaffolds and drug delivery systems with improved control over structure and functionality. Thermo-sensitive injectable hydrogels based on poly(NIPAAm) with degradable ester units within the polymer backbone and at the cross-linking sites were prepared using ATRP and RAFT. Solvent induced morphologies of poly(methyl methacrylate-b-ethylene oxide-b-methyl methacrylate) triblock copolymers synthesized by ATRP were described. A micellar structure, composed of a hydrophobic PMMA core and a PEO shell was constructed for delivery of hydrophobic drugs. ATRP was carried out in inverse miniemulsion to prepare well defined functional nanogels that were capable of entrapping and releasing various molecules (Doxorubicin, carbohydrate-based drugs, fluorophores, and gold nanoparticles). The results demonstrated that nanogels prepared by ATRP in inverse miniemulsion could be internalized into cells via clathrin-mediated endocytosis. Nanogels functionalized with integrin-binding peptides increased cellular uptake. A process called Atom Transfer Radical Coupling (ATRC) was also described, which illustrated the power of functionality in ATRP. Finally, linear polymers and cross-linked nanogels were synthesized by ATRP and functionalized with biotin, pyrene, and peptide sequences, tying together the overall themes of structural control and functionality.

Organic-inorganic hybrid mesoporous silicas: functionalization, pore size, and morphology control.

PubMed

Park, Sung Soo; Ha, Chang-Sik

2006-01-01

Topological design of mesoporous silica materials, pore architecture, pore size, and morphology are currently major issues in areas such as catalytic conversion of bulky molecules, adsorption, host-guest chemistry, etc. In this sense, we discuss the pore size-controlled mesostructure, framework functionalization, and morphology control of organic-inorganic hybrid mesoporous silicas by which we can improve the applicability of mesoporous materials. First, we explain that the sizes of hexagonal- and cubic-type pores in organic-inorganic hybrid mesoporous silicas are well controlled from 24.3 to 98.0 A by the direct micelle-control method using an organosilica precursor and surfactants with different alkyl chain lengths or triblock copolymers as templates and swelling agents incorporated in the formed micelles. Second, we describe that organic-inorganic hybrid mesoporous materials with various functional groups form various external morphologies such as rod, cauliflower, film, rope, spheroid, monolith, and fiber shapes. Third, we discuss that transition metals (Ti and Ru) and rare-earth ions (Eu(3+) and Tb(3+)) are used to modify organic-inorganic hybrid mesoporous silica materials. Such hybrid mesoporous silica materials are expected to be applied as excellent catalysts for organic reactions, photocatalysis, optical devices, etc. c) 2006 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

Surface charge-specific interactions between polymer nanoparticles and ABC transporters in Caco-2 cells

NASA Astrophysics Data System (ADS)

Bhattacharjee, Sourav; van Opstal, Edward J.; Alink, Gerrit M.; Marcelis, Antonius T. M.; Zuilhof, Han; Rietjens, Ivonne M. C. M.

2013-06-01

The surface charge-dependent transport of polymeric nanoparticles (PNPs) across Caco-2 monolayers grown on transwell culture systems as an in vitro model for intestinal transport was tested. The transport of well-characterized, monodisperse, and fluorescent tri-block copolymer nanoparticles (TCNPs/size 45 nm) and polystyrene nanoparticles (PSNPs/size 50 nm), with different surface charges (positive and negative), was quantified. The positive PNPs showed a higher intracellular uptake and flux across the Caco-2 monolayers than the negative PNPs. Multidrug resistance/P-glycoprotein (MDR1/P-gp), a specific ATP-binding cassette (ABC) transporter, was found to play a major role in the cellular efflux of positive PNPs, whereas the multidrug resistance protein 1 took part in the efflux of negative PNPs from Caco-2 cells. The positive PNPs also caused an increased cellular uptake and apical to basolateral transport of the carcinogen PhIP across the Caco-2 monolayer. The flavonoid quercetin, which is known to interact with ABC transporters, promoted the intracellular uptake of different PNPs and interfered with the normal distribution patterns of PNPs in the transwell system. These results indicate that PNPs display surface charge-specific interactions with ABC transporters and can even affect the bioavailability of toxic food-borne compounds (like pro-carcinogens).

Folic acid modified Pluronic F127 coating Ag2S quantum dot for photoacoustic imaging of tumor cell-targeting

NASA Astrophysics Data System (ADS)

Zhang, Ruo-Yun; Wang, Zhao-Yang; Yang, Xiao-Quan; Xuan, Yang; Cheng, Kai; Li, Cheng; Song, Xian-Lin; An, Jie; Hou, Xiao-Lin; Zhao, Yuan-Di

2018-02-01

In this study, an oil-soluble Ag2S quantum dot (QD) was synthesized through thermal decomposition using the single-source precursor method, and Pluronic F127 (PF127), a triblock copolymer functionalized with folic acid (FA), was deposited on the surface of the QD, then a water-soluble PF127-FA@Ag2S nanoprobe with targeting ability was fabricated. The as-prepared PF127-FA@Ag2S exhibited spheroidal morphology and high dispersibility, with average diameters of 115 ± 20.7 nm (as observed by transmission electron microscopy). No obvious toxicity of the PF127-FA@Ag2S nanoprobe was found in standard 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide assay and colony-formation assay, indicating good biocompatibility and safety. The resulting PF127-FA@Ag2S exhibited excellent stability between 4 °C-40 °C. Additionally, the capacity of the tumor cell-targeting high contrast enhanced photoacoustic imaging of PF127-FA@Ag2S was verified in comparison with A547 and HeLa cells. In other words, the excellent properties of PF127-FA@Ag2S show great potential in further research for targeting and photoacoustic imaging.

Hematite Thin Films with Various Nanoscopic Morphologies Through Control of Self-Assembly Structures

NASA Astrophysics Data System (ADS)

Liu, Jingling; Kim, Yong-Tae; Kwon, Young-Uk

2015-05-01

Hematite (α-Fe2O3) thin films with various nanostructures were synthesized through self-assembly between iron oxide hydroxide particles, generated by hydrolysis and condensation of Fe(NO3)3 · 6H2O, and a Pluronic triblock copolymer (F127, (EO)106(PO)70(EO)106, EO = ethylene oxide, PO = propylene oxide), followed by calcination. The self-assembly structure can be tuned by introducing water in a controlled manner through the control of the humidity level in the surrounding of the as-cast films during aging stage. For the given Fe(NO3)3 · 6H2O:F127 ratio, there appear to be three different thermodynamically stable self-assembly structures depending on the water content in the film material, which correspond to mesoporous, spherical micellar, and rod-like micellar structures after removal of F127. Coupled with the thermodynamic driving forces, the kinetics of the irreversible reactions of coalescence of iron oxide hydroxide particles into larger ones induce diverse nanostructures of the resultant films. The length scale of so-obtained nanostructures ranges from 6 nm to a few hundred nanometers. In addition to water content, the effects of other experimental parameters such as aging temperature, spin rate during spin coating, type of substrate, and type of iron reagent were investigated.

Low-voltage electron microscopy of polymer and organic molecular thin films.

PubMed

Drummy, Lawrence F; Yang, Junyan; Martin, David C

2004-06-01

We have demonstrated the capabilities of a novel low-voltage electron microscope (LVEM) for imaging polymer and organic molecular thin films. The LVEM can operate in transmission electron microscopy, scanning transmission electron microscopy, scanning electron microscopy, and electron diffraction modes. The microscope operates at a nominal accelerating voltage of 5 kV and fits on a tabletop. A detailed discussion of the electron-sample interaction processes is presented, and the mean free path for total electron scattering was calculated to be 15 nm for organic samples at 5 kV. The total end point dose for the destruction of crystallinity at 5 kV was estimated at 5 x 10(-4) and 3.5 x 10(-2) C/cm2 for polyethylene and pentacene, respectively. These values are significantly lower than those measured at voltages greater than 100 kV. A defocus series of colloidal gold particles allowed us to estimate the experimental contrast transfer function of the microscope. Images taken of several organic materials have shown high contrast for low atomic number elements and a resolution of 2.5 nm. The materials studied here include thin films of the organic semiconductor pentacene, triblock copolymer films, single-molecule dendrimers, electrospun polymer fibers and gold nanoparticles. Copyright 2004 Elsevier B.V.

In situ diselenide-crosslinked polymeric micelles for ROS-mediated anticancer drug delivery.

PubMed

Deepagan, V G; Kwon, Seunglee; You, Dong Gil; Nguyen, Van Quy; Um, Wooram; Ko, Hyewon; Lee, Hansang; Jo, Dong-Gyu; Kang, Young Mo; Park, Jae Hyung

2016-10-01

Stimuli-responsive micelles have emerged as the drug carrier for cancer therapy since they can exclusively release the drug via their structural changes in response to the specific stimuli of the target site. Herein, we developed the in situ diselenide-crosslinked micelles (DCMs), which are responsive to the abnormal ROS levels of tumoral region, as anticancer drug carriers. The DCMs were spontaneously derived from selenol-bearing triblock copolymers consisting of polyethylene glycol (PEG) and polypeptide derivatives. During micelle formation, doxorubicine (DOX) was effectively encapsulated in the hydrophobic core, and diselenide crosslinks were formed in the shell. The DCMs maintained their structural integrity, at least for 6 days in physiological conditions, even in the presence of destabilizing agents. However, ROS-rich conditions triggered rapid release of DOX from the DOX-encapsulating DCMs (DOX-DCMs) because the hydrophobic diselenide bond was cleaved into hydrophilic selenic acid derivatives. Interestingly, after their systemic administration into the tumor-bearing mice, DOX-DCMs delivered significantly more drug to tumors (1.69-fold and 3.73-fold higher amount compared with their non-crosslinked counterparts and free drug, respectively) and effectively suppressed tumor growth. Overall, our data indicate that DCMs have great potential as drug carriers for anticancer therapy. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dose-dependent sustained local release of dexamethasone from biodegradable thermosensitive hydrogel of PEG-PLGA-PEG triblock copolymers in the possible prevention of TMJ re-ankylosis (Arakeri's TMJ release technique).

PubMed

Arakeri, Gururaj; Brennan, Peter A

2012-05-01

Temporomandibular joint (TMJ) ankylosis is a devastating anatomico-pathological condition which severely affects the quality of human health. Over the last 70 years various treatments have been described to treat this distressing condition. But no single method has uniformly produced successful results. Although various surgical techniques have been improved periodically, the treatment results remain inefficient due to its recurrence as TMJ re-adhesion. Since recurrence remains as a problem in many cases, the TMJ ankylosis presents a major therapeutic challenge in head and neck surgery. The re-ankylosis is a unique phenomenon that so far has defied a full and logical explanation, based upon biological and mechanical factors that are linked together in a coherent fashion. Many factors have been implicated in the development of re-adhesion following TMJ surgery. But still the mechanism by which the TMJ re-adhesion develops is unclear. Hence, TMJ ankylosis demands an alternative effective treatment modality to prevent its recurrence as re-ankylosis. This paper postulates some critical biological factors responsible for re-ankylosis based on which a novel treatment modality is also proposed. Copyright © 2012 Elsevier Ltd. All rights reserved.

One-Pot synthesis of phosphorylated mesoporous carbon heterogeneous catalysts with tailored surface acidity

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

Fulvio, Pasquale F; Mahurin, Shannon Mark; Mayes, Richard T

2012-01-01

Soft-templated phosphorylated mesoporous carbons with homogeneous distributions of phosphate groups were prepared by a 'one-pot' synthesis method using mixtures of phosphoric acid with hydrochloric, or nitric acids in the presence of Pluronic F127 triblock copolymer. Adjusting the various ratios of phosphoric acid used in these mixtures resulted in carbons with distinct adsorption, structural and surface acidity properties. The pore size distributions (PSDs) from nitrogen adsorption at -196 C showed that mesoporous carbons exhibit specific surface areas as high as 551 m{sup 2}/g and mesopores as large as 13 nm. Both structural ordering of the mesopores and the final phosphate contentsmore » were strongly dependent on the ratios of H{sub 3}PO{sub 4} in the synthesis gels, as shown by transmission electron microscopy (TEM), X-ray photoelectron (XPS) and energy dispersive X-ray spectroscopy (EDS). The number of surface acid sites determined from temperature programmed desorption of ammonia (NH{sub 3}-TPD) were in the range of 0.3-1.5 mmol/g while the active surface areas are estimated to comprise 5-54% of the total surface areas. Finally, the conversion temperatures for the isopropanol dehydration were lowered by as much as 100 C by transitioning from the least acidic to the most acidic catalysts surface.« less

The nanoscale phase distinguishing of PCL-PB-PCL blended in epoxy resin by tapping mode atomic force microscopy

NASA Astrophysics Data System (ADS)

Li, Huiqin; Sun, Limin; Shen, Guangxia; Liang, Qi

2012-02-01

In this work, we investigated the bulk phase distinguishing of the poly(ɛ-caprolactone)-polybutadiene-poly(ɛ-caprolactone) (PCL-PB-PCL) triblock copolymer blended in epoxy resin by tapping mode atomic force microscopy (TM-AFM). We found that at a set-point amplitude ratio ( r sp) less than or equal to 0.85, a clear phase contrast could be obtained using a probe with a force constant of 40 N/m. When r sp was decreased to 0.1 or less, the measured size of the PB-rich domain relatively shrank; however, the height images of the PB-rich domain would take reverse (translating from the original light to dark) at r sp = 0.85. Force-probe measurements were carried out on the phase-separated regions by TM-AFM. According to the phase shift angle vs. r sp curve, it could be concluded that the different force exerting on the epoxy matrix or on the PB-rich domain might result in the height and phase image reversion. Furthermore, the indentation depth vs. r sp plot showed that with large tapping force (lower r sp), the indentation depth for the PB-rich domain was nearly identical for the epoxy resin matrix.

Synergistic effect of selectively distributed AlN/MWCNT hybrid fillers on the morphological, mechanical and thermal properties of polycarbonate/maleated poly[styrene-b-(ethylene-co-butylene)- b-styrene] triblock copolymer (SEBS-g-MA) composites

NASA Astrophysics Data System (ADS)

Xiao, Chao; Leng, Xinyu; Wang, Hui; Su, Zheng; Zhang, Xian; Chen, Lin; Zheng, Kang; Tian, Xingyou

2017-02-01

A quaternary nanocomposite polycarbonate (PC)- multi-walled carbon nanotubes (MWCNT)/SEBS-g-MA (SM)-AlN is prepared by controlling the selective distribution of nano-fillers via melt-blending. Through a two-step mixing method, surface modified AlN is selectively dispersed in the island-like SM phase; meanwhile, MWCNT acting as bridges are mainly located in the continuous phase of PC. This ‘island-bridge’ morphology is confirmed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The selective localization results agree well with the theoretical predictions. Dynamic mechanical analysis (DMA) indicates that the addition of hybrid fillers improved the storage modulus selectively. Thermogravimetric analysis (TGA) shows that the thermal stability of the PC/SM blends increased significantly; the degradation kinetic has also been changed due to the synergistic effects of the fillers. This novel ‘island-bridge’ network contributes a higher thermal conductivity at low filler content as the effective thermal conductivity reached 0.72 W m-1 K-1, which is three times higher than that of 70PC/30SM. The experimental observations coincide well with the optimizing model results.

Porous MnO2 prepared by sol-gel method for electrochemical supercapacitor

NASA Astrophysics Data System (ADS)

Bazzi, K.; Kumar, A.; Jayakumar, O. D.; Nazri, G. A.; Naik, V. M.; Naik, R.

2015-03-01

MnO2 has attracted great attention as material for electrochemical pseudocapacitor due to its high theoretical specific faradic capacitance (~ 1370 F .g-1) , environmental friendliness and wide potential window in both aqueous and nonaqueous electrolytes. However, the MnO2 has a low surface area which depresses its electrochemical performance. The amorphous α-MnO2 composite was synthesized by sol gel method in the presence of the tri-block copolymer P123. Our aim is to investigate the role of P123 on the electrochemical performance of MnO2. The samples with and without P123 were prepared and characterized by x-ray diffraction (XRD), SEM, TEM and Brunauer-Emmett-Teller (BET) method. The electrochemical performances of the amorphous MnO2 composites as the electrode materials for supercapacitors were evaluated by cyclic voltammetry and AC impedance measurements in a 1M Na2SO4 solution. The results show that the sample prepared without P123 exhibited a relatively low specific capacitance of 28F .g-1, whereas the porous MnO2 prepared with P123 exhibited 117 F .g-1at 5 mV/s. The results of crystalline MnO2 composites will also be presented. The authors acknowledge the support from the Richard J. Barber Foundation for Interdisciplinary Research.

Evaluation of intratympanic formulations for inner ear delivery: methodology and sustained release formulation testing

PubMed Central

Liu, Hongzhuo; Feng, Liang; Tolia, Gaurav; Liddell, Mark R.; Hao, Jinsong; Li, S. Kevin

2013-01-01

A convenient and efficient in vitro diffusion cell method to evaluate formulations for inner ear delivery via the intratympanic route is currently not available. The existing in vitro diffusion cell systems commonly used to evaluate drug formulations do not resemble the physical dimensions of the middle ear and round window membrane. The objectives of this study were to examine a modified in vitro diffusion cell system of a small diffusion area for studying sustained release formulations in inner ear drug delivery and to identify a formulation for sustained drug delivery to the inner ear. Four formulations and a control were examined in this study using cidofovir as the model drug. Drug release from the formulations in the modified diffusion cell system was slower than that in the conventional diffusion cell system due to the decrease in the diffusion surface area of the modified diffusion cell system. The modified diffusion cell system was able to show different drug release behaviors among the formulations and allowed formulation evaluation better than the conventional diffusion cell system. Among the formulations investigated, poly(lactic-co-glycolic acid)–poly(ethylene glycol)–poly(lactic-co-glycolic acid) triblock copolymer systems provided the longest sustained drug delivery, probably due to their rigid gel structures and/or polymer-to-cidofovir interactions. PMID:23631539

Carbon dioxide capture by activated methyl diethanol amine impregnated mesoporous carbon

NASA Astrophysics Data System (ADS)

Ardhyarini, N.; Krisnandi, Y. K.

2017-07-01

Activated Methyl Diethanol Amine (aMDEA) were impregnated onto the surface of the mesoporous carbon to increase carbon dioxide (CO2) adsorption capacity. The mesoporous carbon was synthesized through soft template method with phloroglucinol as carbon precursor and triblock copolymer (Pluronic F127) as structure directing agent. These activated MDEA impregnated mesoporous carbon (aMDEA-MC) were characterized using various solid characterization techniques. CO2 adsorption was investigated using autoclaved-reactor in the batch system. The FTIR spectrum of aMDEA-MC had absorption peaks at 3395 cm-1 and 1031 cm-1 which are characteristic for O-H stretch and amine C-N stretch in MDEA. The elemental analyzer showed that nitrogen content on the mesoporous carbon increased after impregnation by 23 wt.%. The BET surface area and total pore volume of mesoporous carbon decreased after impregnation, 43 wt.% and 50 wt.%, respectively. The maximum CO2 adsorption capacity of aMDEA43-MC was 2.63 mmol/g (298 K, 5 psi and pure CO2). This is 64 % and 35 % higher compared to the CO2 adsorption capacity of the starting MC and also commercially available activated carbon with higher surface area. All the results suggest that MDEA-MC is a promising adsorbent for CO2 capture.

Morphological Consequences of Frustration in ABC Triblock Polymers

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

Radlauer, Madalyn R.; Sinturel, Christophe; Asai, Yusuke

2016-12-19

Three poly(styrene)-block-poly(isoprene)-block-poly(lactide) (PS-b-PI-b-PLA, SIL) triblock terpolymers were synthesized and characterized in the bulk and as thin films. The pronounced incompatibility of the covalently connected PI and PLA led to significant frustration and the tendency to minimize their intermaterial dividing surface area. This resulted in the formation of a core–shell cylinder morphology with exaggerated nonconstant mean curvature from triblock polymers with equal block volume fractions rather than the more typical lamellar morphology. The effect of frustration was magnified in thin films by both confinement and interfacial interactions such that the PI domains became discontinuous. Self-consistent field theory (SCFT) calculations emphasize thatmore » the marked difference in the PS/PI and PI/PLA interaction parameters promotes the formation of nonlamellar morphologies. However, SCFT predicts that lamellar morphology is more stable than the observed cylindrical morphology, demonstrating a limitation that arises from the underlying assumptions.« less

FRET-based reporters for the direct visualization of abscisic acid concentration changes and distribution in Arabidopsis

PubMed Central

Waadt, Rainer; Hitomi, Kenichi; Nishimura, Noriyuki; Hitomi, Chiharu; Adams, Stephen R; Getzoff, Elizabeth D; Schroeder, Julian I

2014-01-01

Abscisic acid (ABA) is a plant hormone that regulates plant growth and development and mediates abiotic stress responses. Direct cellular monitoring of dynamic ABA concentration changes in response to environmental cues is essential for understanding ABA action. We have developed ABAleons: ABA-specific optogenetic reporters that instantaneously convert the phytohormone-triggered interaction of ABA receptors with PP2C-type phosphatases to send a fluorescence resonance energy transfer (FRET) signal in response to ABA. We report the design, engineering and use of ABAleons with ABA affinities in the range of 100–600 nM to map ABA concentration changes in plant tissues with spatial and temporal resolution. High ABAleon expression can partially repress Arabidopsis ABA responses. ABAleons report ABA concentration differences in distinct cell types, ABA concentration increases in response to low humidity and NaCl in guard cells and to NaCl and osmotic stress in roots and ABA transport from the hypocotyl to the shoot and root. DOI: http://dx.doi.org/10.7554/eLife.01739.001 PMID:24737861

Abscisic acid negatively regulates post-penetration resistance of Arabidopsis to the biotrophic powdery mildew fungus.

PubMed

Xiao, Xiang; Cheng, Xi; Yin, Kangquan; Li, Huali; Qiu, Jin-Long

2017-08-01

Pytohormone abscisic acid (ABA) plays important roles in defense responses. Nonetheless, how ABA regulates plant resistance to biotrophic fungi remains largely unknown. Arabidopsis ABA-deficient mutants, aba2-1 and aba3-1, displayed enhanced resistance to the biotrophic powdery mildew fungus Golovinomyces cichoracearum. Moreover, exogenously administered ABA increased the susceptibility of Arabidopsis to G. cichoracearum. Arabidopsis ABA perception components mutants, abi1-1 and abi2-1, also displayed similar phenotypes to ABA-deficient mutants in resistance to G. cichoracearum. However, the resistance to G. cichoracearum is not changed in downstream ABA signaling transduction mutants, abi3-1, abi4-1, and abi5-1. Microscopic examination revealed that hyphal growth and conidiophore production of G. cichoracearum were compromised in the ABA deficient mutants, even though pre-penetration and penetration growth of the fungus were not affected. In addition, salicylic acid (SA) and MPK3 are found to be involved in ABA-regulated resistance to G. cichoracearum. Our work demonstrates that ABA negatively regulates post-penetration resistance of Arabidopsis to powdery mildew fungus G. cichoracearum, probably through antagonizing the function of SA.

An ABA-mimicking ligand that reduces water loss and promotes drought resistance in plants

PubMed Central

Cao, Minjie; Liu, Xue; Zhang, Yan; Xue, Xiaoqian; Zhou, X Edward; Melcher, Karsten; Gao, Pan; Wang, Fuxing; Zeng, Liang; Zhao, Yang; Zhao, Yang; Deng, Pan; Zhong, Dafang; Zhu, Jian-Kang; Xu, H Eric; Xu, Yong

2013-01-01

Abscisic acid (ABA) is the most important hormone for plants to resist drought and other abiotic stresses. ABA binds directly to the PYR/PYL family of ABA receptors, resulting in inhibition of type 2C phosphatases (PP2C) and activation of downstream ABA signaling. It is envisioned that intervention of ABA signaling by small molecules could help plants to overcome abiotic stresses such as drought, cold and soil salinity. However, chemical instability and rapid catabolism by plant enzymes limit the practical application of ABA itself. Here we report the identification of a small molecule ABA mimic (AM1) that acts as a potent activator of multiple members of the family of ABA receptors. In Arabidopsis, AM1 activates a gene network that is highly similar to that induced by ABA. Treatments with AM1 inhibit seed germination, prevent leaf water loss, and promote drought resistance. We solved the crystal structure of AM1 in complex with the PYL2 ABA receptor and the HAB1 PP2C, which revealed that AM1 mediates a gate-latch-lock interacting network, a structural feature that is conserved in the ABA-bound receptor/PP2C complex. Together, these results demonstrate that a single small molecule ABA mimic can activate multiple ABA receptors and protect plants from water loss and drought stress. Moreover, the AM1 complex crystal structure provides a structural basis for designing the next generation of ABA-mimicking small molecules. PMID:23835477

A mutational analysis of the ABA1 gene of Arabidopsis thaliana highlights the involvement of ABA in vegetative development.

PubMed

Barrero, José María; Piqueras, Pedro; González-Guzmán, Miguel; Serrano, Ramón; Rodríguez, Pedro L; Ponce, María Rosa; Micol, José Luis

2005-08-01

Much of the literature on the phytohormone abscisic acid (ABA) describes it as a mediator in triggering plant responses to environmental stimuli, as well as a growth inhibitor. ABA-deficient mutants, however, display a stunted phenotype even under well-watered conditions and high relative humidity, which suggests that growth promotion may also be one of the roles of endogenous ABA. Zeaxanthin epoxidase, the product of the ABA1 gene of Arabidopsis thaliana, catalyses the epoxidation of zeaxanthin to antheraxanthin and violaxanthin, generating the epoxycarotenoid precursor of the ABA biosynthetic pathway. This paper gives a description of the molecular and phenotypic characterization of a large series of mutant alleles of the ABA1 gene, which cause different degrees of ABA deficiency, four of them previously isolated (aba1-1, aba1-3, aba1-4, and aba1-6) and the remaining five novel (sañ1-1, sañ1-2, sañ1-3, sañ1-4, and sre3). Molecular analysis of these alleles provides insights into the domains in which they compromise zeaxanthin epoxidase function. The size of the leaves, inflorescences, and flowers of these mutants is reduced, and their rosettes have lower fresh and dry weights than their wild types, as a result of a diminished cell size. Low concentrations of exogenous ABA increase the fresh weight of mutant and wild-type plants, as well as the dry weight of the mutants. The leaves of aba1 mutants are abnormally shaped and fail to develop clearly distinct spongy and palisade mesophyll layers. Taken together, these phenotypic traits indicate, as suggested by previous authors, that ABA acts as a growth promoter during vegetative development. The abnormal shape and internal structure of the leaves of aba1 mutants suggests, in addition, a role for ABA in organogenesis.

Dormancy termination of western white pine (Pinus monticola Dougl. Ex D. Don) seeds is associated with changes in abscisic acid metabolism.

PubMed

Feurtado, J Allan; Ambrose, Stephen J; Cutler, Adrian J; Ross, Andrew R S; Abrams, Suzanne R; Kermode, Allison R

2004-02-01

Western white pine (Pinus monticola) seeds exhibit deep dormancy at maturity and seed populations require several months of moist chilling to reach their uppermost germination capacities. Abscisic acid (ABA) and its metabolites, phaseic acid (PA), dihydrophaseic acid (DPA), 7'-hydroxy ABA (7'OH ABA) and ABA-glucose ester (ABA-GE), were quantified in western white pine seeds during dormancy breakage (moist chilling) and germination using an HPLC-tandem mass spectrometry method with multiple reaction monitoring and internal standards incorporating deuterium-labeled analogs. In the seed coat, ABA and metabolite levels were high in dry seeds, but declined precipitously during the pre-moist-chilling water soak to relatively low levels thereafter. In the embryo and megagametophyte, ABA levels decreased significantly during moist chilling, coincident with an increase in the germination capacity of seeds. ABA catabolism occurred via several routes, depending on the stage and the seed tissue. Moist chilling of seeds led to increases in PA and DPA levels in both the embryo and megagametophyte. Within the embryo, 7'OH ABA and ABA-GE also accumulated during moist chilling; however, 7'OH ABA peaked early in germination. Changes in ABA flux, i.e. shifts in the ratio between biosynthesis and catabolism, occurred at three distinct stages during the transition from dormant seed to seedling. During moist chilling, the relative rate of ABA catabolism exceeded ABA biosynthesis. This trend became even more pronounced during germination, and germination was also accompanied by a decrease in the ABA catabolites DPA and PA, presumably as a result of their further metabolism and/or leaching/transport. The transition from germination to post-germinative growth was accompanied by a shift toward ABA biosynthesis. Dormant imbibed seeds, kept in warm moist conditions for 30 days (after an initial 13 days of soaking), maintained high ABA levels, while the amounts of PA, 7'OH ABA, and DPA decreased or remained at steady-state levels. Thus, in the absence of conditions required to break dormancy there were no net changes in ABA biosynthesis and catabolism.

Comparative Study on Reagents Involved in Grape Bud Break and Their Effects on Different Metabolites and Related Gene Expression during Winter

PubMed Central

Khalil-Ur-Rehman, Muhammad; Wang, Wu; Xu, Yan-Shuai; Haider, Muhammad S.; Li, Chun-Xia; Tao, Jian-Min

2017-01-01

To elucidate promoting and inhibiting effects of hydrogen cynamide (HC) and abscisic acid (ABA) on quiescence release of grape buds, physiological and molecular approaches were used to explore the mechanisms of quiescence based on metabolic and gene expression analysis. Physiological and molecular mechanisms involved in bud quiescence of grape were studied before and after application of HC, ABA, and ABA-HC. The data showed that ABA inhibited proclamation of quiescence in grape buds and attenuated the influence of HC. Bud quiescence was promoted and regulated by HC and ABA pre-treatment on buds of grape cultivar “Shine Muscat” with 5% HC, 100 μM ABA and combination of ABA-HC (5% HC+100 μM ABA) during quiescence under forcing condition. Exogenous application of ABA elevated superoxide dismutase (SOD), peroxidase (POD) and ascorbate peroxidase (APX) related specific activities, while catalase (CAT) activity was increased during initial period of forcing and then decreased. The concentration of plant growth hormones including gibberellins (GA) and indole acetic acid increased by HC application but decreased the ABA contents under forcing condition. ABA increased the fructose content during quiescence under forcing condition while sucrose and total soluble sugars peaked in HC treated buds as compared to control. Genes related to ABA pathway, protein phosphatase 2C (PP2C family) were down regulated in the buds treated with HC, ABA and ABA-HC as compared to control while two genes related to GA pathway (GID1 family), out of which one gene showed down regulation during initial period of forcing while other gene was up regulated in response to HC and ABA-HC treatments as compared to control. Exogenous ABA application up regulated genes related to antioxidant enzymes as compared to control. The gene probable fructose-bisphosphate aldolase 1, chloroplastic-like, was up regulated in response to ABA treatment as compared to control. Analysis of metabolites and related gene expression pattern would provide a comprehensive view of quiescence after HC, ABA, and ABA-HC treatments in grape buds which may helpful for ultimate improvement in table grape production. PMID:28824676

Local root abscisic acid (ABA) accumulation depends on the spatial distribution of soil moisture in potato: implications for ABA signalling under heterogeneous soil drying

PubMed Central

Puértolas, Jaime; Conesa, María R.; Ballester, Carlos; Dodd, Ian C.

2015-01-01

Patterns of root abscisic acid (ABA) accumulation ([ABA]root), root water potential (Ψroot), and root water uptake (RWU), and their impact on xylem sap ABA concentration ([X-ABA]) were measured under vertical partial root-zone drying (VPRD, upper compartment dry, lower compartment wet) and horizontal partial root-zone drying (HPRD, two lateral compartments: one dry, the other wet) of potato (Solanum tuberosum L.). When water was withheld from the dry compartment for 0–10 d, RWU and Ψroot were similarly lower in the dry compartment when soil volumetric water content dropped below 0.22cm3 cm–3 for both spatial distributions of soil moisture. However, [ABA]root increased in response to decreasing Ψroot in the dry compartment only for HPRD, resulting in much higher ABA accumulation than in VPRD. The position of the sampled roots (~4cm closer to the surface in the dry compartment of VPRD than in HPRD) might account for this difference, since older (upper) roots may accumulate less ABA in response to decreased Ψroot than younger (deeper) roots. This would explain differences in root ABA accumulation patterns under vertical and horizontal soil moisture gradients reported in the literature. In our experiment, these differences in root ABA accumulation did not influence [X-ABA], since the RWU fraction (and thus ABA export to shoots) from the dry compartment dramatically decreased simultaneously with any increase in [ABA]root. Thus, HPRD might better trigger a long-distance ABA signal than VPRD under conditions allowing simultaneous high [ABA]root and relatively high RWU fraction. PMID:25547916

Local root abscisic acid (ABA) accumulation depends on the spatial distribution of soil moisture in potato: implications for ABA signalling under heterogeneous soil drying.

PubMed

Puértolas, Jaime; Conesa, María R; Ballester, Carlos; Dodd, Ian C

2015-04-01

Patterns of root abscisic acid (ABA) accumulation ([ABA]root), root water potential (Ψroot), and root water uptake (RWU), and their impact on xylem sap ABA concentration ([X-ABA]) were measured under vertical partial root-zone drying (VPRD, upper compartment dry, lower compartment wet) and horizontal partial root-zone drying (HPRD, two lateral compartments: one dry, the other wet) of potato (Solanum tuberosum L.). When water was withheld from the dry compartment for 0-10 d, RWU and Ψroot were similarly lower in the dry compartment when soil volumetric water content dropped below 0.22cm(3) cm(-3) for both spatial distributions of soil moisture. However, [ABA]root increased in response to decreasing Ψroot in the dry compartment only for HPRD, resulting in much higher ABA accumulation than in VPRD. The position of the sampled roots (~4cm closer to the surface in the dry compartment of VPRD than in HPRD) might account for this difference, since older (upper) roots may accumulate less ABA in response to decreased Ψroot than younger (deeper) roots. This would explain differences in root ABA accumulation patterns under vertical and horizontal soil moisture gradients reported in the literature. In our experiment, these differences in root ABA accumulation did not influence [X-ABA], since the RWU fraction (and thus ABA export to shoots) from the dry compartment dramatically decreased simultaneously with any increase in [ABA]root. Thus, HPRD might better trigger a long-distance ABA signal than VPRD under conditions allowing simultaneous high [ABA]root and relatively high RWU fraction. © The Author 2014. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Stomatal VPD Response: There Is More to the Story Than ABA.

PubMed

Merilo, Ebe; Yarmolinsky, Dmitry; Jalakas, Pirko; Parik, Helen; Tulva, Ingmar; Rasulov, Bakhtier; Kilk, Kalle; Kollist, Hannes

2018-01-01

Guard cells shrink and close stomatal pores when air humidity decreases (i.e. when the difference between the vapor pressures of leaf and atmosphere [VPD] increases). The role of abscisic acid (ABA) in VPD-induced stomatal closure has been studied using ABA-related mutants that respond to VPD in some studies and not in others. The importance of ABA biosynthesis in guard cells versus vasculature for whole-plant stomatal regulation is unclear as well. Here, we show that Arabidopsis ( Arabidopsis thaliana ) lines carrying mutations in different steps of ABA biosynthesis as well as pea ( Pisum sativum ) wilty and tomato ( Solanum lycopersicum ) flacca ABA-deficient mutants had higher stomatal conductance compared with wild-type plants. To characterize the role of ABA production in different cells, we generated transgenic plants where ABA biosynthesis was rescued in guard cells or phloem companion cells of an ABA-deficient mutant. In both cases, the whole-plant stomatal conductance, stunted growth phenotype, and leaf ABA level were restored to wild-type values, pointing to the redundancy of ABA sources and to the effectiveness of leaf ABA transport. All ABA-deficient lines closed their stomata rapidly and extensively in response to high VPD, whereas plants with mutated protein kinase OST1 showed stunted VPD-induced responses. Another strongly ABA-insensitive mutant, defective in the six ABA PYR/RCAR receptors, responded to changes in VPD in both directions strongly and symmetrically, indicating that its VPD-induced closure could be passive hydraulic. We discuss that both the VPD-induced passive hydraulic stomatal closure and the stomatal VPD regulation of ABA-deficient mutants may be conditional on the initial pretreatment stomatal conductance. © 2018 American Society of Plant Biologists. All Rights Reserved.

Shoot-derived abscisic acid promotes root growth.

PubMed

McAdam, Scott A M; Brodribb, Timothy J; Ross, John J

2016-03-01

The phytohormone abscisic acid (ABA) plays a major role in regulating root growth. Most work to date has investigated the influence of root-sourced ABA on root growth during water stress. Here, we tested whether foliage-derived ABA could be transported to the roots, and whether this foliage-derived ABA had an influence on root growth under well-watered conditions. Using both application studies of deuterium-labelled ABA and reciprocal grafting between wild-type and ABA-biosynthetic mutant plants, we show that both ABA levels in the roots and root growth in representative angiosperms are controlled by ABA synthesized in the leaves rather than sourced from the roots. Foliage-derived ABA was found to promote root growth relative to shoot growth but to inhibit the development of lateral roots. Increased root auxin (IAA) levels in plants with ABA-deficient scions suggest that foliage-derived ABA inhibits root growth through the root growth-inhibitor IAA. These results highlight the physiological and morphological importance, beyond the control of stomata, of foliage-derived ABA. The use of foliar ABA as a signal for root growth has important implications for regulating root to shoot growth under normal conditions and suggests that leaf rather than root hydration is the main signal for regulating plant responses to moisture. © 2015 John Wiley & Sons Ltd.

Movement of Abscisic Acid into the Apoplast in Response to Water Stress in Xanthium strumarium L.

PubMed

Cornish, K; Zeevaart, J A

1985-07-01

The effect of water stress on the redistribution of abcisic acid (ABA) in mature leaves of Xanthium strumarium L. was investigated using a pressure dehydration technique. In both turgid and stressed leaves, the ABA in the xylem exudate, the ;apoplastic' ABA, increased before ;bulk leaf' stress-induced ABA accumulation began. In the initially turgid leaves, the ABA level remained constant in both the apoplast and the leaf as a whole until wilting symptoms appeared. Following turgor loss, sufficient quantities of ABA moved into the apoplast to stimulate stomatal closure. Thus, the initial increase of apoplastic ABA may be relevant to the rapid stomatal closure seen in stressed leaves before their bulk leaf ABA levels rise.Following recovery from water stress, elevated levels of ABA remained in the apoplast after the bulk leaf contents had returned to their prestress values. This apoplastic ABA may retard stomatal reopening during the initial recovery period.

Exogenous strigolactone interacts with abscisic acid-mediated accumulation of anthocyanins in grapevine berries.

PubMed

Ferrero, Manuela; Pagliarani, Chiara; Novák, Ondrej; Ferrandino, Alessandra; Cardinale, Francesca; Visentin, Ivan; Schubert, Andrea

2018-04-23

Besides signalling to soil organisms, strigolactones (SLs) control above- and below-ground morphology, in particular shoot branching. Furthermore, SLs interact with stress responses, possibly thanks to a crosstalk with the abscisic acid (ABA) signal. In grapevine (Vitis vinifera L.), ABA drives the accumulation of anthocyanins over the ripening season. In this study, we investigated the effects of treatment with a synthetic strigolactone analogue, GR24, on anthocyanin accumulation in grape berries, in the presence or absence of exogenous ABA treatment. Experiments were performed both on severed, incubated berries, and on berries attached to the vine. Furthermore, we analysed the corresponding transcript concentrations of genes involved in anthocyanin biosynthesis, and in ABA biosynthesis, metabolism, and membrane transport. During the experiment time courses, berries showed the expected increase in soluble sugars and anthocyanins. GR24 treatment had no or little effect on anthocyanin accumulation, or on gene expression levels. Exogenous ABA treatment activated soluble sugar and anthocyanin accumulation, and enhanced expression of anthocyanin and ABA biosynthetic genes, and that of genes involved in ABA hydroxylation and membrane transport. Co-treatment of GR24 with ABA delayed anthocyanin accumulation, decreased expression of anthocyanin biosynthetic genes, and negatively affected ABA concentration. GR24 also enhanced the ABA-induced activation of ABA hydroxylase genes, while it down-regulated the ABA-induced activation of ABA transport genes. Our results show that GR24 affects the ABA-induced activation of anthocyanin biosynthesis in this non-climacteric fruit. We discuss possible mechanisms underlying this effect, and the potential role of SLs in ripening of non-ABA-treated berries.

Metabolism of the Folate Precursor p-Aminobenzoate in Plants

PubMed Central

Eudes, Aymerick; Bozzo, Gale G.; Waller, Jeffrey C.; Naponelli, Valeria; Lim, Eng-Kiat; Bowles, Dianna J.; Gregory, Jesse F.; Hanson, Andrew D.

2008-01-01

Plants produce p-aminobenzoate (pABA) in chloroplasts and use it for folate synthesis in mitochondria. In plant tissues, however, pABA is known to occur predominantly as its glucose ester (pABA-Glc), and the role of this metabolite in folate synthesis has not been defined. In this study, the UDP-glucose:pABA acyl-glucosyltransferase (pAGT) activity in Arabidopsis extracts was found to reside principally (95%) in one isoform with an apparent Km for pABA of 0.12 mm. Screening of recombinant Arabidopsis UDP-glycosyltransferases identified only three that recognized pABA. One of these (UGT75B1) exhibited a far higher kcat/Km value than the others and a far lower apparent Km for pABA (0.12 mm), suggesting its identity with the principal enzyme in vivo. Supporting this possibility, ablation of UGT75B1 reduced extractable pAGT activity by 95%, in vivo [14C]pABA glucosylation by 77%, and the endogenous pABA-Glc/pABA ratio by 9-fold. The Keq for the pABA esterification reaction was found to be 3 × 10-3. Taken with literature data on the cytosolic location of pAGT activity and on cytosolic UDP-glucose/UDP ratios, this Keq value allowed estimation that only 4% of cytosolic pABA is esterified. That pABA-Glc predominates in planta therefore implies that it is sequestered away from the cytosol and, consistent with this possibility, vacuoles isolated from [14C]pABA-fed pea leaves were estimated to contain≥88% of the [14C]pABA-Glc formed. In total, these data and the fact that isolated mitochondria did not take up [3H]pABA-Glc, suggest that the glucose ester represents a storage form of pABA that does not contribute directly to folate synthesis. PMID:18385129

The ABA receptors -- we report you decide.

PubMed

McCourt, Peter; Creelman, Robert

2008-10-01

The plant hormone abscisic acid (ABA) has been implicated in a variety of physiological responses ranging from seed dormancy to stomatal conductance. Recently, three groups have reported the molecular identification of three disparate ABA receptors. Unlike the identification of other hormone receptors, in these three cases high affinity binding to ABA rather than the isolation of ABA insensitive mutants led to these receptor genes. Interestingly, two of the receptors encode genes involved in floral timing and chlorophyll biosynthesis, which are not considered traditional ABA responses. And the third receptor has been clouded in issues of its molecular identity. To clearly determine the roles of these genes in ABA perception it will require placing of these ABA-binding proteins into the rich ABA physiological context that has built up over the years.

Trapping of vesicles on patterned surfaces by physisorption for potential biosensing applications.

PubMed

Bera, L K; Ong, Kian Soo; Wong, Zheng Zheng; Fu, Zhikang; Nallani, Madhavan; Shea, Sean O'

2012-01-01

The pre-defined selective positioning of a controlled number of vesicles on a rigid substrate is crucial in many potential applications such as diagnostics, biosensors, lab-on-a chip, microanalyses and reaction chambers. In this paper, the vesicles made up of block copolymer using Poly [-(2-methyloxazoline) -poly- (dimethylsiloxane)-poly- (2-methyloxazoline)] (ABA) with dimensions of 100-200 nm are trapped by physisorption on hydrophilic surfaces. We discuss the protocols established for vesicle trapping. The optimum conditions obtained for physisorption is 15 minutes incubation followed by one cycle of DI water rinse. Trapping of 1-10 vesicles in lobe shape micro-wells fabricated by photo lithography using photoresist on UltraStick(™) slides was demonstrated. To overcome the issue of amalgamation of emitted light from optically sensitive photoresist and fluorescently tagged vesicles, an alternative approach of Si/SiO(2) microwell array coupled with APTES (3-AminoPropylTriEthoxySilane) treated bottom surfaces was developed.

Abscisic Acid as Pathogen Effector and Immune Regulator

PubMed Central

Lievens, Laurens; Pollier, Jacob; Goossens, Alain; Beyaert, Rudi; Staal, Jens

2017-01-01

Abscisic acid (ABA) is a sesquiterpene signaling molecule produced in all kingdoms of life. To date, the best known functions of ABA are derived from its role as a major phytohormone in plant abiotic stress resistance. Different organisms have developed different biosynthesis and signal transduction pathways related to ABA. Despite this, there are also intriguing common themes where ABA often suppresses host immune responses and is utilized by pathogens as an effector molecule. ABA also seems to play an important role in compatible mutualistic interactions such as mycorrhiza and rhizosphere bacteria with plants, and possibly also the animal gut microbiome. The frequent use of ABA in inter-species communication could be a possible reason for the wide distribution and re-invention of ABA as a signaling molecule in different organisms. In humans and animal models, it has been shown that ABA treatment or nutrient-derived ABA is beneficial in inflammatory diseases like colitis and type 2 diabetes, which confer potential to ABA as an interesting nutraceutical or pharmacognostic drug. The anti-inflammatory activity, cellular metabolic reprogramming, and other beneficial physiological and psychological effects of ABA treatment in humans and animal models has sparked an interest in this molecule and its signaling pathway as a novel pharmacological target. In contrast to plants, however, very little is known about the ABA biosynthesis and signaling in other organisms. Genes, tools and knowledge about ABA from plant sciences and studies of phytopathogenic fungi might benefit biomedical studies on the physiological role of endogenously generated ABA in humans. PMID:28469630

Synthesis and characterizations of novel polymer electrolytes

NASA Astrophysics Data System (ADS)

Chanthad, Chalathorn

Polymer electrolytes are an important component of many electrochemical devices. The ability to control the structures, properties, and functions of polymer electrolytes remains a key subject for the development of next generation functional polymers. Taking advantage of synthetic strategies is a promising approach to achieve the desired chemical structures, morphologies, thermal, mechanical, and electrochemical properties. Therefore, the major goal of this thesis is to develop synthetic methods for of novel proton exchange membranes and ion conductive membranes. In Chapter 2, new classes of fluorinated polymer- polysilsesquioxane nanocomposites have been designed and synthesized. The synthetic method employed includes radical polymerization using the functional benzoyl peroxide initiator for the telechelic fluorinated polymers with perfluorosulfonic acids in the side chains and a subsequent in-situ sol-gel condensation of the prepared triethoxylsilane-terminated fluorinated polymers with alkoxide precursors. The properties of the composite membranes have been studied as a function of the content and structure of the fillers. The proton conductivity of the prepared membranes increases steadily with the addition of small amounts of the polysilsesquioxane fillers. In particular, the sulfopropylated polysilsesquioxane based nanocomposites display proton conductivities greater than Nafion. This is attributed to the presence of pendant sulfonic acids in the fillers, which increases ion-exchange capacity and offers continuous proton transport channels between the fillers and the polymer matrix. The methanol permeability of the prepared membranes has also been examined. Lower methanol permeability and higher electrochemical selectivity than those of Nafion have been demonstrated in the polysilsesquioxane based nanocomposites. In Chapter 3, the synthesis of a new class of ionic liquid-containing triblock copolymers with fluoropolymer mid-block and imidazolium methacrylate end-blocks is described for the first time. The synthetic strategy involves the preparation of the telechelic fluoropolymers using a functional benzoyl peroxide initiator as the macro-chain transfer agent for subsequent RAFT polymerization of the imidazolium methacrylate monomer. As revealed in DSC, SAXS and dielectric relaxation spectroscopy (DRS) measurements, there was no microphase separation in the triblock copolymers, likely due to solubility of ionic liquid moieties in the fluoropolymer matrix. The anionic counterion has direct impact on the thermal properties, ionic conductivity and segmental dynamics of the polymers. The temperature dependence of the ionic conductivity is well described by the Vogel-Tamman-Fulcher model, suggesting that ion motion is closely coupled to segmental motion. In Chapter 4 and 5, new solid electrolytes for lithium cations have been synthesized by catalyzed hydrosilylation reaction involving hydrogen atoms of polysiloxane and polyhedral oligomeric silsesquioxane (POSS) and double bonds of vinyl tris17-bromo-3,6,9,12,15- pentaoxaheptadecan-1-ol silane. The obtained structures are based on branched or dendritic with ionic liquid-ethylene oxide oligomer. High room temperature ionic conductivities have been obtained in the range of 10-4-10-5 can be regarded as solid electrolytes. This is attributed to the high concentration of ions from ionic liquid moieties in the tripodand molecule, high segmental mobility, and high ion dissociation from ethylene oxide spacers. The influence of anion structures and lithium salts and concentration has been investigated.

Synthesis and biological activity of amino acid conjugates of abscisic acid.

PubMed

Todoroki, Yasushi; Narita, Kenta; Muramatsu, Taku; Shimomura, Hajime; Ohnishi, Toshiyuki; Mizutani, Masaharu; Ueno, Kotomi; Hirai, Nobuhiro

2011-03-01

We prepared 19 amino acid conjugates of the plant hormone abscisic acid (ABA) and investigated their biological activity, enzymatic hydrolysis by a recombinant Arabidopsis amidohydrolases GST-ILR1 and GST-IAR3, and metabolic fate in rice seedlings. Different sets of ABA-amino acids induced ABA-like responses in different plants. Some ABA-amino acids, including some that were active in bioassays, were hydrolyzed by recombinant Arabidopsis GST-IAR3, although GST-ILR1 did not show hydrolysis activity for any of the ABA-amino acids. ABA-L-Ala, which was active in all the bioassays, an Arabidopsis seed germination, spinach seed germination, and rice seedling elongation assays, except in a lettuce seed germination assay and was hydrolyzed by GST-IAR3, was hydrolyzed to free ABA in rice seedlings. These findings suggest that some plant amidohydrolases hydrolyze some ABA-amino acid conjugates. Because our study indicates the possibility that different plants have hydrolyzing activity toward different ABA-amino acids, an ABA-amino acid may function as a species-selective pro-hormone of ABA. Copyright © 2011 Elsevier Ltd. All rights reserved.

Importance of ABA homeostasis under terminal drought stress in regulating grain filling events

PubMed Central

Govind, Geetha; Seiler, Christiane; Wobus, Ulrich

2011-01-01

Recent studies suggest that abscisic acid (ABA) at its basal level plays an important role during seed set and grain filling events. Under drought stress ABA levels were found to be significantly enhanced in the developing seed. Until now we lacked an understanding of (1) ABA homeostasis in developing seeds under terminal drought and (2) the interactive role of ABA in regulating the starch biosynthesis pathway in developing grains under terminal drought. We have recently reported the possible regulation of ABA homeostasis in source (flag leaf) and sink (developing grains) tissues under post-anthesis drought stress in barley and concluded that significantly enhanced ABA levels in developing grains are due to strong activation of the ABA deconjugation pathway and fine regulation of the ABA biosynthesis-degradation pathway.1 Additionally, we provided evidence for the role of ABA in differential regulation of starch biosynthesis genes and a significant upregulation of starch degradation beta amylase genes under drought, i.e., ABA not only influences the rate of starch accumulation but also starch quality. PMID:21778825

Abscisic acid content and the expression of genes related to its metabolism during maturation of triticale grains of cultivars differing in pre-harvest sprouting susceptibility.

PubMed

Fidler, Justyna; Zdunek-Zastocka, Edyta; Prabucka, Beata; Bielawski, Wiesław

2016-12-01

Abscisic acid (ABA) is a plant hormone that plays a predominant role in the onset and maintenance of primary dormancy. Peak ABA accumulation in embryos of triticale grains was observed before any significant loss of water and was higher in Fredro, a cultivar less susceptible to pre-harvest sprouting (PHS), than in Leontino, a cultivar more sensitive to PHS. At full maturity, embryonic ABA content in Fredro was twice as high as in Leontino. Two full-length cDNAs of 9-cis-epoxycarotenoid dioxygenase (TsNCED1, TsNCED2), an enzyme involved in ABA biosynthesis, and two full-length cDNAs of ABA 8'-hydroxylase (TsABA8'OH1 and TsABA8'OH2), an enzyme involved in ABA catabolism, were identified in triticale grains and characterized. The maximum transcript level of both TsNCED1 and TsNCED2 preceded the peak of ABA accumulation, suggesting that both TsNCEDs contribute to reach this peak, although the expression of TsNCED1 was significantly higher in Fredro than in Leontino. High expression of TsABA8'OH2 and TsABA8'OH1 was observed long before and at the end of the ABA accumulation peak, respectively, but no differences were observed between cultivars. The obtained results suggest that mainly TsNCED1 might be related to the higher ABA content and higher resistance of Fredro to PHS. However, Fredro embryos not only have higher ABA content, but also exhibit greater sensitivity to ABA, which may also have a significant effect on grain dormancy and lower susceptibility to PHS for grains of this cultivar. Copyright © 2016 Elsevier GmbH. All rights reserved.

Abscisic acid synergizes with rosiglitazone to improve glucose tolerance, down-modulate macrophage accumulation in adipose tissue: possible action of the cAMP/PKA/PPAR γ axis

PubMed Central

Guri, Amir J; Hontecillas, Raquel; Bassaganya-Riera, Josep

2010-01-01

Background & Aims Abscisic acid (ABA) is effective in preventing insulin resistance and obesity-related inflammation through a PPAR γ-dependent mechanism. The objective of this study was to assess the efficacy ABA in improving glucose homeostasis and suppress inflammation when administered in combination with rosiglitazone (Ros) and to determine whether PPAR γ activation by ABA is initiated via cAMP/protein kinase A (PKA) signaling. Methods Obese db/db mice were fed high-fat diets containing 0, 10, or 70 mg/kg Ros with and without racemic ABA (100 mg/kg) for 60 days. Glucose tolerance and fasting insulin levels were assessed at 6 and 8 weeks, respectively, and adipose tissue macrophage (ATM) infiltration was examined by flow cytometry. Gene expression was examined on white adipose tissue (WAT) and stromal vascular cells (SVCs) cultured with ABA, Ros, or an ABA/Ros combination. Results Both Ros and ABA improved glucose tolerance, and ABA decreased plasma insulin levels while having no effect on Ros-induced weight gain. ABA in combination with low-dose Ros (10 mg/kg; Roslo) synergistically inhibited ATM infiltration. Treatment of SVCs with Ros, ABA or ABA/Ros suppressed expression of the M1 marker CCL17. ABA and Ros synergistically increased PPAR γ activity and pretreatment with a cAMP-inhibitor or a PKA-inhibitor abrogated ABA-induced PPAR γ activation. Conclusions ABA and Ros act synergistically to modulate PPAR γ activity and macrophage accumulation in WAT and ABA enhances PPAR γ activity through a membrane-initiated mechanism dependent on cAMP/PKA signaling. PMID:20207056

Abscisic acid synergizes with rosiglitazone to improve glucose tolerance and down-modulate macrophage accumulation in adipose tissue: possible action of the cAMP/PKA/PPAR γ axis.

PubMed

Guri, Amir J; Hontecillas, Raquel; Bassaganya-Riera, Josep

2010-10-01

Abscisic acid (ABA) is effective in preventing insulin resistance and obesity-related inflammation through a PPAR γ-dependent mechanism. The objective of this study was to assess the efficacy ABA in improving glucose homeostasis and suppress inflammation when administered in combination with rosiglitazone (Ros) and to determine whether PPAR γ activation by ABA is initiated via cAMP/protein kinase A (PKA) signaling. Obese db/db mice were fed high-fat diets containing 0, 10, or 70 mg/kg Ros with and without racemic ABA (100 mg/kg) for 60 days. Glucose tolerance and fasting insulin levels were assessed at 6 and 8 weeks, respectively, and adipose tissue macrophage (ATM) infiltration was examined by flow cytometry. Gene expression was examined on white adipose tissue (WAT) and stromal vascular cells (SVCs) cultured with ABA, Ros, or an ABA/Ros combination. Both Ros and ABA improved glucose tolerance, and ABA decreased plasma insulin levels while having no effect on Ros-induced weight gain. ABA in combination with low-dose Ros (10 mg/kg; Roslo) synergistically inhibited ATM infiltration. Treatment of SVCs with Ros, ABA or ABA/Ros suppressed expression of the M1 marker CCL17. ABA and Ros synergistically increased PPAR γ activity and pretreatment with a cAMP-inhibitor or a PKA-inhibitor abrogated ABA-induced PPAR γ activation. ABA and Ros act synergistically to modulate PPAR γ activity and macrophage accumulation in WAT and ABA enhances PPAR γ activity through a membrane-initiated mechanism dependent on cAMP/PKA signaling. Copyright © 2010 Elsevier Ltd and European Society for Clinical Nutrition and Metabolism. All rights reserved.

Common and unique elements of the ABA-regulated transcriptome of Arabidopsis guard cells

PubMed Central

2011-01-01

Background In the presence of drought and other desiccating stresses, plants synthesize and redistribute the phytohormone abscisic acid (ABA). ABA promotes plant water conservation by acting on specialized cells in the leaf epidermis, guard cells, which border and regulate the apertures of stomatal pores through which transpirational water loss occurs. Following ABA exposure, solute uptake into guard cells is rapidly inhibited and solute loss is promoted, resulting in inhibition of stomatal opening and promotion of stomatal closure, with consequent plant water conservation. There is a wealth of information on the guard cell signaling mechanisms underlying these rapid ABA responses. To investigate ABA regulation of gene expression in guard cells in a systematic genome-wide manner, we analyzed data from global transcriptomes of guard cells generated with Affymetrix ATH1 microarrays, and compared these results to ABA regulation of gene expression in leaves and other tissues. Results The 1173 ABA-regulated genes of guard cells identified by our study share significant overlap with ABA-regulated genes of other tissues, and are associated with well-defined ABA-related promoter motifs such as ABREs and DREs. However, we also computationally identified a unique cis-acting motif, GTCGG, associated with ABA-induction of gene expression specifically in guard cells. In addition, approximately 300 genes showing ABA-regulation unique to this cell type were newly uncovered by our study. Within the ABA-regulated gene set of guard cells, we found that many of the genes known to encode ion transporters associated with stomatal opening are down-regulated by ABA, providing one mechanism for long-term maintenance of stomatal closure during drought. We also found examples of both negative and positive feedback in the transcriptional regulation by ABA of known ABA-signaling genes, particularly with regard to the PYR/PYL/RCAR class of soluble ABA receptors and their downstream targets, the type 2C protein phosphatases. Our data also provide evidence for cross-talk at the transcriptional level between ABA and another hormonal inhibitor of stomatal opening, methyl jasmonate. Conclusions Our results engender new insights into the basic cell biology of guard cells, reveal common and unique elements of ABA-regulation of gene expression in guard cells, and set the stage for targeted biotechnological manipulations to improve plant water use efficiency. PMID:21554708

Movement of Abscisic Acid into the Apoplast in Response to Water Stress in Xanthium strumarium L. 1

PubMed Central

Cornish, Katrina; Zeevaart, Jan A. D.

1985-01-01

The effect of water stress on the redistribution of abcisic acid (ABA) in mature leaves of Xanthium strumarium L. was investigated using a pressure dehydration technique. In both turgid and stressed leaves, the ABA in the xylem exudate, the `apoplastic' ABA, increased before `bulk leaf' stress-induced ABA accumulation began. In the initially turgid leaves, the ABA level remained constant in both the apoplast and the leaf as a whole until wilting symptoms appeared. Following turgor loss, sufficient quantities of ABA moved into the apoplast to stimulate stomatal closure. Thus, the initial increase of apoplastic ABA may be relevant to the rapid stomatal closure seen in stressed leaves before their bulk leaf ABA levels rise. Following recovery from water stress, elevated levels of ABA remained in the apoplast after the bulk leaf contents had returned to their prestress values. This apoplastic ABA may retard stomatal reopening during the initial recovery period. PMID:16664294

Function of ABA in Stomatal Defense against Biotic and Drought Stresses

PubMed Central

Lim, Chae Woo; Baek, Woonhee; Jung, Jangho; Kim, Jung-Hyun; Lee, Sung Chul

2015-01-01

The plant hormone abscisic acid (ABA) regulates many key processes involved in plant development and adaptation to biotic and abiotic stresses. Under stress conditions, plants synthesize ABA in various organs and initiate defense mechanisms, such as the regulation of stomatal aperture and expression of defense-related genes conferring resistance to environmental stresses. The regulation of stomatal opening and closure is important to pathogen defense and control of transpirational water loss. Recent studies using a combination of approaches, including genetics, physiology, and molecular biology, have contributed considerably to our understanding of ABA signal transduction. A number of proteins associated with ABA signaling and responses—especially ABA receptors—have been identified. ABA signal transduction initiates signal perception by ABA receptors and transfer via downstream proteins, including protein kinases and phosphatases. In the present review, we focus on the function of ABA in stomatal defense against biotic and abiotic stresses, through analysis of each ABA signal component and the relationships of these components in the complex network of interactions. In particular, two ABA signal pathway models in response to biotic and abiotic stress were proposed, from stress signaling to stomatal closure, involving the pyrabactin resistance (PYR)/PYR-like (PYL) or regulatory component of ABA receptor (RCAR) family proteins, 2C-type protein phosphatases, and SnRK2-type protein kinases. PMID:26154766

On the role of abscisic acid in seed dormancy of red rice.

PubMed

Gianinetti, Alberto; Vernieri, Paolo

2007-01-01

Abscisic acid (ABA) is commonly assumed to be the primary effector of seed dormancy, but conclusive evidence for this role is lacking. This paper reports on the relationships occurring in red rice between ABA and seed dormancy. Content of free ABA in dry and imbibed caryopses, both dormant and after-ripened, the effects of inhibitors, and the ability of applied ABA to revert dormancy breakage were considered. The results indicate: (i) no direct correlation of ABA content with the dormancy status of the seed, either dry or imbibed; (ii) different sensitivity to ABA of non-dormant seed and seed that was forced to germinate by fluridone; and (iii) an inability of exogenous ABA to reinstate dormancy in fluridone-treated seed, even though applied at a pH which favoured high ABA accumulation. These considerations suggest that ABA is involved in regulating the first steps of germination, but unidentified developmental effectors that are specific to dormancy appear to stimulate ABA synthesis and to enforce the responsiveness to this phytohormone. These primary effectors appear physiologically to modulate dormancy and via ABA they effect the growth of the embryo. Therefore, it is suggested that ABA plays a key role in integrating the dormancy-specific developmental signals with the control of growth.

Abscisic Acid Regulates Auxin Homeostasis in Rice Root Tips to Promote Root Hair Elongation

PubMed Central

Wang, Tao; Li, Chengxiang; Wu, Zhihua; Jia, Yancui; Wang, Hong; Sun, Shiyong; Mao, Chuanzao; Wang, Xuelu

2017-01-01

Abscisic acid (ABA) plays an essential role in root hair elongation in plants, but the regulatory mechanism remains to be elucidated. In this study, we found that exogenous ABA can promote rice root hair elongation. Transgenic rice overexpressing SAPK10 (Stress/ABA-activated protein kinase 10) had longer root hairs; rice plants overexpressing OsABIL2 (OsABI-Like 2) had attenuated ABA signaling and shorter root hairs, suggesting that the effect of ABA on root hair elongation depends on the conserved PYR/PP2C/SnRK2 ABA signaling module. Treatment of the DR5-GUS and OsPIN-GUS lines with ABA and an auxin efflux inhibitor showed that ABA-induced root hair elongation depends on polar auxin transport. To examine the transcriptional response to ABA, we divided rice root tips into three regions: short root hair, long root hair and root tip zones; and conducted RNA-seq analysis with or without ABA treatment. Examination of genes involved in auxin transport, biosynthesis and metabolism indicated that ABA promotes auxin biosynthesis and polar auxin transport in the root tip, which may lead to auxin accumulation in the long root hair zone. Our findings shed light on how ABA regulates root hair elongation through crosstalk with auxin biosynthesis and transport to orchestrate plant development. PMID:28702040

Expression studies of the zeaxanthin epoxidase gene in nicotiana plumbaginifolia

PubMed

Audran; Borel; Frey; Sotta; Meyer; Simonneau; Marion-Poll

1998-11-01

Abscisic acid (ABA) is a plant hormone involved in the control of a wide range of physiological processes, including adaptation to environmental stress and seed development. In higher plants ABA is a breakdown product of xanthophyll carotenoids (C40) via the C15 intermediate xanthoxin. The ABA2 gene of Nicotiana plumbaginifolia encodes zeaxanthin epoxidase, which catalyzes the conversion of zeaxanthin to violaxanthin. In this study we analyzed steady-state levels of ABA2 mRNA in N. plumbaginifolia. The ABA2 mRNA accumulated in all plant organs, but transcript levels were found to be higher in aerial parts (stems and leaves) than in roots and seeds. In leaves ABA2 mRNA accumulation displayed a day/night cycle; however, the ABA2 protein level remained constant. In roots no diurnal fluctuation in mRNA levels was observed. In seeds the ABA2 mRNA level peaked around the middle of development, when ABA content has been shown to increase in many species. In conditions of drought stress, ABA levels increased in both leaves and roots. A concomitant accumulation of ABA2 mRNA was observed in roots but not in leaves. These results are discussed in relation to the role of zeaxanthin epoxidase both in the xanthophyll cycle and in the synthesis of ABA precursors.

Expression Studies of the Zeaxanthin Epoxidase Gene in Nicotiana plumbaginifolia1

PubMed Central

Audran, Corinne; Borel, Charlotte; Frey, Anne; Sotta, Bruno; Meyer, Christian; Simonneau, Thierry; Marion-Poll, Annie

1998-01-01

Abscisic acid (ABA) is a plant hormone involved in the control of a wide range of physiological processes, including adaptation to environmental stress and seed development. In higher plants ABA is a breakdown product of xanthophyll carotenoids (C40) via the C15 intermediate xanthoxin. The ABA2 gene of Nicotiana plumbaginifolia encodes zeaxanthin epoxidase, which catalyzes the conversion of zeaxanthin to violaxanthin. In this study we analyzed steady-state levels of ABA2 mRNA in N. plumbaginifolia. The ABA2 mRNA accumulated in all plant organs, but transcript levels were found to be higher in aerial parts (stems and leaves) than in roots and seeds. In leaves ABA2 mRNA accumulation displayed a day/night cycle; however, the ABA2 protein level remained constant. In roots no diurnal fluctuation in mRNA levels was observed. In seeds the ABA2 mRNA level peaked around the middle of development, when ABA content has been shown to increase in many species. In conditions of drought stress, ABA levels increased in both leaves and roots. A concomitant accumulation of ABA2 mRNA was observed in roots but not in leaves. These results are discussed in relation to the role of zeaxanthin epoxidase both in the xanthophyll cycle and in the synthesis of ABA precursors. PMID:9808747

Release of GTP Exchange Factor Mediated Down-Regulation of Abscisic Acid Signal Transduction through ABA-Induced Rapid Degradation of RopGEFs

PubMed Central

Waadt, Rainer; Schroeder, Julian I.

2016-01-01

The phytohormone abscisic acid (ABA) is critical to plant development and stress responses. Abiotic stress triggers an ABA signal transduction cascade, which is comprised of the core components PYL/RCAR ABA receptors, PP2C-type protein phosphatases, and protein kinases. Small GTPases of the ROP/RAC family act as negative regulators of ABA signal transduction. However, the mechanisms by which ABA controls the behavior of ROP/RACs have remained unclear. Here, we show that an Arabidopsis guanine nucleotide exchange factor protein RopGEF1 is rapidly sequestered to intracellular particles in response to ABA. GFP-RopGEF1 is sequestered via the endosome-prevacuolar compartment pathway and is degraded. RopGEF1 directly interacts with several clade A PP2C protein phosphatases, including ABI1. Interestingly, RopGEF1 undergoes constitutive degradation in pp2c quadruple abi1/abi2/hab1/pp2ca mutant plants, revealing that active PP2C protein phosphatases protect and stabilize RopGEF1 from ABA-mediated degradation. Interestingly, ABA-mediated degradation of RopGEF1 also plays an important role in ABA-mediated inhibition of lateral root growth. The presented findings point to a PP2C-RopGEF-ROP/RAC control loop model that is proposed to aid in shutting off ABA signal transduction, to counteract leaky ABA signal transduction caused by “monomeric” PYL/RCAR ABA receptors in the absence of stress, and facilitate signaling in response to ABA. PMID:27192441

ABA crosstalk with ethylene and nitric oxide in seed dormancy and germination

PubMed Central

Arc, Erwann; Sechet, Julien; Corbineau, Françoise; Rajjou, Loïc; Marion-Poll, Annie

2013-01-01

Dormancy is an adaptive trait that enables seed germination to coincide with favorable environmental conditions. It has been clearly demonstrated that dormancy is induced by abscisic acid (ABA) during seed development on the mother plant. After seed dispersal, germination is preceded by a decline in ABA in imbibed seeds, which results from ABA catabolism through 8′-hydroxylation. The hormonal balance between ABA and gibberellins (GAs) has been shown to act as an integrator of environmental cues to maintain dormancy or activate germination. The interplay of ABA with other endogenous signals is however less documented. In numerous species, ethylene counteracts ABA signaling pathways and induces germination. In Brassicaceae seeds, ethylene prevents the inhibitory effects of ABA on endosperm cap weakening, thereby facilitating endosperm rupture and radicle emergence. Moreover, enhanced seed dormancy in Arabidopsis ethylene-insensitive mutants results from greater ABA sensitivity. Conversely, ABA limits ethylene action by down-regulating its biosynthesis. Nitric oxide (NO) has been proposed as a common actor in the ABA and ethylene crosstalk in seed. Indeed, convergent evidence indicates that NO is produced rapidly after seed imbibition and promotes germination by inducing the expression of the ABA 8′-hydroxylase gene, CYP707A2, and stimulating ethylene production. The role of NO and other nitrogen-containing compounds, such as nitrate, in seed dormancy breakage and germination stimulation has been reported in several species. This review will describe our current knowledge of ABA crosstalk with ethylene and NO, both volatile compounds that have been shown to counteract ABA action in seeds and to improve dormancy release and germination. PMID:23531630

Interaction Between ABA Signaling and Copper Homeostasis in Arabidopsis thaliana.

PubMed

Carrió-Seguí, Àngela; Romero, Paco; Sanz, Amparo; Peñarrubia, Lola

2016-07-01

ABA is involved in plant responses to non-optimal environmental conditions, including nutrient availability. Since copper (Cu) is a very important micronutrient, unraveling how ABA affects Cu uptake and distribution is relevant to ensure adequate Cu nutrition in plants subjected to stress conditions. Inversely, knowledge about how the plant nutritional status can interfere with ABA biosynthesis and signaling mechanisms is necessary to optimize stress tolerance in horticultural crops. Here the reciprocal influence between ABA and Cu content was addressed by using knockout mutants and overexpressing transgenic plants of high affinity plasma membrane Cu transporters (pmCOPT) with altered Cu uptake. Exogenous ABA inhibited pmCOPT expression and drastically modified COPT2-driven localization in roots. ABA regulated SPL7, the main transcription factor responsive for Cu deficiency responses, and subsequently affected expression of its targets. ABA biosynthesis (aba2) and signaling (hab1-1 abi1-2) mutants differentially responded to ABA according to Cu levels. Alteration of Cu homeostasis in the pmCOPT mutants affected ABA biosynthesis, transport and signaling as genes such as NCED3, WRKY40, HY5 and ABI5 were differentially modulated by Cu status, and also in the pmCOPT and ABA mutants. Altered Cu uptake resulted in modified plant sensitivity to salt-mediated increases in endogenous ABA. The overall results provide evidence for reciprocal cross-talk between Cu status and ABA metabolism and signaling. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

A Novel Chemical Inhibitor of ABA Signaling Targets All ABA Receptors.

PubMed

Ye, Yajin; Zhou, Lijuan; Liu, Xue; Liu, Hao; Li, Deqiang; Cao, Minjie; Chen, Haifeng; Xu, Lin; Zhu, Jian-Kang; Zhao, Yang

2017-04-01

Abscisic acid (ABA), the most important stress-induced phytohormone, regulates seed dormancy, germination, plant senescence, and the abiotic stress response. ABA signaling is repressed by group A type 2C protein phosphatases (PP2Cs), and then ABA binds to its receptor of the ACTIN RESISTANCE1 (PYR1), PYR1-LIKE (PYL), and REGULATORY COMPONENTS OF ABA RECEPTORS (RCAR) family, which, in turn, inhibits PP2Cs and activates downstream ABA signaling. The agonist/antagonist of ABA receptors have the potential to reveal the ABA signaling machinery and to become lead compounds for agrochemicals; however, until now, no broad-spectrum antagonists of ABA receptors blocking all PYR/PYL-PP2C interactions have been identified. Here, using chemical genetics screenings, we identified ABA ANTAGONIST1 (AA1), the first broad-spectrum antagonist of ABA receptors in Arabidopsis ( Arabidopsis thaliana ). Physiological analyses revealed that AA1 is sufficiently active to block ABA signaling. AA1 interfered with all the PYR/PYL-HAB1 interactions, and the diminished PYR/PYL-HAB1 interactions, in turn, restored the activity of HAB1. AA1 binds to all 13 members. Molecular dockings, the non-AA1-bound PYL2 variant, and competitive binding assays demonstrated that AA1 enters into the ligand-binding pocket of PYL2. Using AA1, we tested the genetic relationships of ABA receptors with other core components of ABA signaling, demonstrating that AA1 is a powerful tool with which to sidestep this genetic redundancy of PYR/PYLs. In addition, the application of AA1 delays leaf senescence. Thus, our study developed an efficient broad-spectrum antagonist of ABA receptors and demonstrated that plant senescence can be chemically controlled through AA1, with a simple and easy-to-synthesize structure, allowing its availability and utility as a chemical probe synthesized in large quantities, indicating its potential application in agriculture. © 2017 American Society of Plant Biologists. All Rights Reserved.

A Novel Chemical Inhibitor of ABA Signaling Targets All ABA Receptors1

PubMed Central

Ye, Yajin; Liu, Xue; Liu, Hao; Li, Deqiang; Cao, Minjie; Chen, Haifeng; Zhu, Jian-kang

2017-01-01

Abscisic acid (ABA), the most important stress-induced phytohormone, regulates seed dormancy, germination, plant senescence, and the abiotic stress response. ABA signaling is repressed by group A type 2C protein phosphatases (PP2Cs), and then ABA binds to its receptor of the ACTIN RESISTANCE1 (PYR1), PYR1-LIKE (PYL), and REGULATORY COMPONENTS OF ABA RECEPTORS (RCAR) family, which, in turn, inhibits PP2Cs and activates downstream ABA signaling. The agonist/antagonist of ABA receptors have the potential to reveal the ABA signaling machinery and to become lead compounds for agrochemicals; however, until now, no broad-spectrum antagonists of ABA receptors blocking all PYR/PYL-PP2C interactions have been identified. Here, using chemical genetics screenings, we identified ABA ANTAGONIST1 (AA1), the first broad-spectrum antagonist of ABA receptors in Arabidopsis (Arabidopsis thaliana). Physiological analyses revealed that AA1 is sufficiently active to block ABA signaling. AA1 interfered with all the PYR/PYL-HAB1 interactions, and the diminished PYR/PYL-HAB1 interactions, in turn, restored the activity of HAB1. AA1 binds to all 13 members. Molecular dockings, the non-AA1-bound PYL2 variant, and competitive binding assays demonstrated that AA1 enters into the ligand-binding pocket of PYL2. Using AA1, we tested the genetic relationships of ABA receptors with other core components of ABA signaling, demonstrating that AA1 is a powerful tool with which to sidestep this genetic redundancy of PYR/PYLs. In addition, the application of AA1 delays leaf senescence. Thus, our study developed an efficient broad-spectrum antagonist of ABA receptors and demonstrated that plant senescence can be chemically controlled through AA1, with a simple and easy-to-synthesize structure, allowing its availability and utility as a chemical probe synthesized in large quantities, indicating its potential application in agriculture. PMID:28193765

Abscisic acid-activated SNRK2 protein kinases function in the gene-regulation pathway of ABA signal transduction by phosphorylating ABA response element-binding factors.

PubMed

Kobayashi, Yuhko; Murata, Michiharu; Minami, Hideyuki; Yamamoto, Shuhei; Kagaya, Yasuaki; Hobo, Tokunori; Yamamoto, Akiko; Hattori, Tsukaho

2005-12-01

The plant hormone abscisic acid (ABA) induces gene expression via the ABA-response element (ABRE) present in the promoters of ABA-regulated genes. A group of bZIP proteins have been identified as ABRE-binding factors (ABFs) that activate transcription through this cis element. A rice ABF, TRAB1, has been shown to be activated via ABA-dependent phosphorylation. While a large number of signalling factors have been identified that are involved in stomatal regulation by ABA, relatively less is known about the ABA-signalling pathway that leads to gene expression. We have shown recently that three members of the rice SnRK2 protein kinase family, SAPK8, SAPK9 and SAPK10, are activated by ABA signal as well as by hyperosmotic stress. Here we show that transient overexpression in cultured cell protoplasts of these ABA-activated SnRK2 protein kinases leads to the activation of an ABRE-regulated promoter, suggesting that these kinases are involved in the gene-regulation pathway of ABA signalling. We further show several lines of evidence that these ABA-activated SnRK2 protein kinases directly phosphorylate TRAB1 in response to ABA. Kinetic analysis of SAPK10 activation and TRAB1 phosphorylation indicated that the latter immediately followed the former. TRAB1 was found to be phosphorylated not only in response to ABA, but also in response to hyperosmotic stress, which was interpreted as the consequence of phosphorylation of TRAB1 by hyperosmotically activated SAPKs. Physical interaction between TRAB1 and SAPK10 in vivo was demonstrated by a co-immunoprecipitation experiment. Finally, TRAB1 was phosphorylated in vitro by the ABA-activated SnRK2 protein kinases at Ser102, which is phosphorylated in vivo in response to ABA and is critical for the activation function.

Comparable Efficacy of Abatacept Used as First-line or Second-line Biological Agent for Severe Juvenile Idiopathic Arthritis-related Uveitis.

PubMed

Birolo, Carolina; Zannin, Maria Elisabetta; Arsenyeva, Svetlana; Cimaz, Rolando; Miserocchi, Elisabetta; Dubko, Margarita; Deslandre, Chantal Job; Falcini, Fernanda; Alessio, Maria; La Torre, Francesco; Denisova, Ekaterina; Martini, Giorgia; Nikishina, Irina; Zulian, Francesco

2016-11-01

Abatacept (ABA) has recently been proposed as second-line treatment in patients with juvenile idiopathic arthritis (JIA)-associated uveitis refractory to anti-tumor necrosis factor-α (anti-TNF) agents, but little is known about its efficacy as a first-line approach. The aim of the present study was to compare the safety and efficacy of ABA as a first-line biological agent (ABA-1) with that of ABA as a second-line treatment after 1 or more anti-TNF agents (ABA-2), in patients with severe JIA-related uveitis. In this multicenter study, we collected data on patients with severe JIA-related uveitis treated with ABA as a first-line or second-line biological agent. Changes in frequency of uveitis flares/year and ocular complications before and after ABA treatment, clinical remission, and side effects were recorded. Thirty-five patients with a mean age of 10.8 years were treated with ABA for a mean period of 19.6 months. In 4 patients, ABA administration was discontinued, owing to inefficacy on arthritis in 3 cases and allergic reaction in 1. Thirty-one patients, 14 in the ABA-1 group and 17 in the ABA-2 group, completed the 12-month followup period; of these, 17 (54.8%) had clinical remission. The mean frequency of uveitis flares decreased from 4.1 to 1.2 in the ABA-1 group (p = 0.002) and from 3.7 to 1.2 in the ABA-2 group (p = 0.004). Preexisting ocular complications improved or remained stable in all but 5 patients, all in the ABA-2 group. No significant difference was found between the efficacy of the 2 treatment modalities. ABA confirmed its good safety profile. ABA, used as first-line biological treatment or after 1 or more anti-TNF agents, induces a comparable improvement in severe refractory JIA-related uveitis.

Rapid Phosphoproteomic Effects of Abscisic Acid (ABA) on Wild-Type and ABA Receptor-Deficient A. thaliana Mutants*

PubMed Central

Minkoff, Benjamin B.; Stecker, Kelly E.; Sussman, Michael R.

2015-01-01

Abscisic acid (ABA)1 is a plant hormone that controls many aspects of plant growth, including seed germination, stomatal aperture size, and cellular drought response. ABA interacts with a unique family of 14 receptor proteins. This interaction leads to the activation of a family of protein kinases, SnRK2s, which in turn phosphorylate substrates involved in many cellular processes. The family of receptors appears functionally redundant. To observe a measurable phenotype, four of the fourteen receptors have to be mutated to create a multilocus loss-of-function quadruple receptor (QR) mutant, which is much less sensitive to ABA than wild-type (WT) plants. Given these phenotypes, we asked whether or not a difference in ABA response between the WT and QR backgrounds would manifest on a phosphorylation level as well. We tested WT and QR mutant ABA response using isotope-assisted quantitative phosphoproteomics to determine what ABA-induced phosphorylation changes occur in WT plants within 5 min of ABA treatment and how that phosphorylation pattern is altered in the QR mutant. We found multiple ABA-induced phosphorylation changes that occur within 5 min of treatment, including three SnRK2 autophosphorylation events and phosphorylation on SnRK2 substrates. The majority of robust ABA-dependent phosphorylation changes observed were partially diminished in the QR mutant, whereas many smaller ABA-dependent phosphorylation changes observed in the WT were not responsive to ABA in the mutant. A single phosphorylation event was increased in response to ABA treatment in both the WT and QR mutant. A portion of the discovery data was validated using selected reaction monitoring-based targeted measurements on a triple quadrupole mass spectrometer. These data suggest that different subsets of phosphorylation events depend upon different subsets of the ABA receptor family to occur. Altogether, these data expand our understanding of the model by which the family of ABA receptors directs rapid phosphoproteomic changes. PMID:25693798

Synthesis, photostability and bioactivity of 2,3-cyclopropanated abscisic acid.

PubMed

Wenjian, Liu; Xiaoqiang, Han; Yumei, Xiao; Jinlong, Fan; Yuanzhi, Zhang; Huizhe, Lu; Mingan, Wang; Zhaohai, Qin

2013-12-01

The plant hormone abscisic acid (ABA) plays a central role in the regulation of plant development and adaptation to environmental stress. The isomerization of ABA to the biologically inactive 2E-isomer by light considerably limits its applications in agricultural fields. To overcome this shortcoming, an ABA analogue, cis-2,3-cyclopropanated ABA, was synthesized, and its photostability and biological activities were investigated. This compound showed high photostability under UV light exposure, which was 4-fold higher than that of (±)-ABA. cis-2,3-cyclopropanated ABA exhibited high ABA-like activity, including the ability to effectively inhibit seed germination, seedling growth and stomatal movements of Arabidopsis. In some cases, its bioactivity approaches that of (±)-ABA. trans-2,3-cyclopropanated abscisic acid was also prepared, an isomer that was more photostable but which showed weak ABA-like activity. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

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

Rock, C.D.; Zeevaart, J.A.D.

We have isolated ABA-aldehyde and ABA-t-diol from postharvest apple fruits, cv. Granny Smith and confirmed their structure by GC-MS. These putative ABA biosynthetic precursors incorporate {sup 18}O to a similar degree as ABA during 48 hours under {sup 18}O{sub 2} atmospheres. The presence of significant amounts of ABA-aldehyde can explain the unique {sup 18}O labeling pattern of ABA in this tissue, where a majority of ABA molecules containing {sup 18}O is labeled in the 1{prime}-hydroxyl group and not in the side chain carboxyl group, the primary site of incorporation for stressed leaves. Exchange of the carbonyl oxygen of ABA-aldehyde withmore » water would decrease {sup 18}O enrichment in the side chain. Results of {sup 18}O{sub 2} experiments and feeding studies using hexadeutero-ABA-aldehyde will be presented and the biosynthetic relationship of these compounds discussed.« less

A novel zinc-finger protein with a proline-rich domain mediates ABA-regulated seed dormancy in Arabidopsis.

PubMed

He, Yuehui; Gan, Susheng

2004-01-01

Seed dormancy is an important developmental process that prevents pre-harvest sprouting in many grains and other seeds. Abscisic acid (ABA), a plant hormone, plays a crucial role in regulating dormancy but the underlying molecular regulatory mechanisms are not fully understood. An Arabidopsis zinc-finger gene, MEDIATOR OF ABA-REGULATED DORMANCY 1 ( MARD1 ) was identified and functionally analyzed. MARD1 expression is up-regulated by ABA. A T-DNA insertion in the promoter region downstream of two ABA-responsive elements (ABREs) renders MARD1 unable to respond to ABA. The mard1 seeds are less dormant and germinate in total darkness; their germination is resistant to external ABA at the stage of radicle protrusion. These results suggest that this novel zinc-finger protein with a proline-rich N-terminus is an important downstream component of the ABA signaling pathway that mediates ABA-regulated seed dormancy in Arabidopsis.

A distal ABA responsive element in AtNCED3 promoter is required for positive feedback regulation of ABA biosynthesis in Arabidopsis.

PubMed

Yang, Yan-Zhuo; Tan, Bao-Cai

2014-01-01

The plant hormone abscisic acid (ABA) plays a crucial role in plant development and responses to abiotic stresses. Recent studies indicate that a positive feedback regulation by ABA exists in ABA biosynthesis in plants under dehydration stress. To understand the molecular basis of this regulation, we analyzed the cis-elements of the AtNCED3 promoter in Arabidopsis. AtNCED3 encodes the first committed and highly regulated dioxygenase in the ABA biosynthetic pathway. Through delineated and mutagenesis analyses in stable-transformed Arabidopsis, we revealed that a distal ABA responsive element (ABRE: GGCACGTG, -2372 to -2364 bp) is required for ABA-induced AtNCED3 expression. By analyzing the AtNCED3 expression in ABRE binding protein ABF3 over-expression transgenic plants and knock-out mutants, we provide evidence that the ABA feedback regulation of AtNCED3 expression is not mediated by ABF3.

Abscisic acid dynamics in roots detected with genetically encoded FRET sensors

PubMed Central

Jones, Alexander M; Danielson, Jonas ÅH; ManojKumar, Shruti N; Lanquar, Viviane; Grossmann, Guido; Frommer, Wolf B

2014-01-01

Cytosolic hormone levels must be tightly controlled at the level of influx, efflux, synthesis, degradation and compartmentation. To determine ABA dynamics at the single cell level, FRET sensors (ABACUS) covering a range ∼0.2–800 µM were engineered using structure-guided design and a high-throughput screening platform. When expressed in yeast, ABACUS1 detected concentrative ABA uptake mediated by the AIT1/NRT1.2 transporter. Arabidopsis roots expressing ABACUS1-2µ (Kd∼2 µM) and ABACUS1-80µ (Kd∼80 µM) respond to perfusion with ABA in a concentration-dependent manner. The properties of the observed ABA accumulation in roots appear incompatible with the activity of known ABA transporters (AIT1, ABCG40). ABACUS reveals effects of external ABA on homeostasis, that is, ABA-triggered induction of ABA degradation, modification, or compartmentation. ABACUS can be used to study ABA responses in mutants and quantitatively monitor ABA translocation and regulation, and identify missing components. The sensor screening platform promises to enable rapid fine-tuning of the ABA sensors and engineering of plant and animal hormone sensors to advance our understanding of hormone signaling. DOI: http://dx.doi.org/10.7554/eLife.01741.001 PMID:24737862

Arabidopsis plants deficient in plastidial glyceraldehyde-3-phosphate dehydrogenase show alterations in abscisic acid (ABA) signal transduction: interaction between ABA and primary metabolism

PubMed Central

Muñoz-Bertomeu, Jesús; Bermúdez, María Angeles; Segura, Juan; Ros, Roc

2011-01-01

Abscisic acid (ABA) controls plant development and regulates plant responses to environmental stresses. A role for ABA in sugar regulation of plant development has also been well documented although the molecular mechanisms connecting the hormone with sugar signal transduction pathways are not well understood. In this work it is shown that Arabidopsis thaliana mutants deficient in plastidial glycolytic glyceraldehyde-3-phosphate dehydrogenase (gapcp1gapcp2) are ABA insensitive in growth, stomatal closure, and germination assays. The ABA levels of gapcp1gapcp2 were normal, suggesting that the ABA signal transduction pathway is impaired in the mutants. ABA modified gapcp1gapcp2 gene expression, but the mutant response to the hormone differed from that observed in wild-type plants. The gene expression of the transcription factor ABI4, involved in both sugar and ABA signalling, was altered in gapcp1gapcp2, suggesting that their ABA insensitivity is mediated, at least partially, through this transcriptional regulator. Serine supplementation was able partly to restore the ABA sensitivity of gapcp1gapcp2, indicating that amino acid homeostasis and/or serine metabolism may also be important determinants in the connections of ABA with primary metabolism. Overall, these studies provide new insights into the links between plant primary metabolism and ABA signalling, and demonstrate the importance of plastidial glycolytic glyceraldehyde-3-phosphate dehydrogenase in these interactions. PMID:21068209

Simultaneous requirement of carbon dioxide and abscisic acid for stomatal closing in Xanthium strumarium L.

PubMed

Raschke, K

1975-01-01

Open stomata of detached leaves of Xanthium strumarium L. closed only when carbon dioxide and abscisic acid (ABA) were presented simultaneously. Three parameters of stomatal closing were determined after additions of ABA to the irrigation water of detached leaves, while the leaves were exposed to various CO2 concentrations ([CO2]s) in the air; a) the delay between addition of ABA and a reduction of stomatal conductance by 5%, b) the velocity of stomatal closing, and c) the new conductance. Changes in all three parameters showed that stomatal responses to ABA were enhanced by CO2; this effect followed saturation kinetics. Half saturation occurred at an estimated [CO2] in the stomatal pore of 200 μl l(-1). With respect to ABA, stomata responded in normal air with half their maximal amplitude at [ABA]s between 10(-6) and 10(-5) M(+-)-ABA. The amounts of ABA taken up by the leaves during the delay increased with a power <1 (on the average, 0.67) of the [ABA] in the transpiration stream. The minimal amount of ABA found to produce a stomatal response was about 1 pmol of (+-)-ABA per cm(2) leaf area, almost two orders of magnitude smaller than the original content of the leaves in ABA indicating that most of the endogenous ABA was in a compartment isolated from the guard cells.An interaction between stomatal responses to CO2 and ABA was also found in Gossypium hirsutum L. and Commelina communis L.; it was however much weaker than in X. strumarium.Based on earlier findings and on the results of this investigation it is suggested that stomata close if the cytoplasm of the guard cells contains much malate and H(+). The acid content in turn is determined by the relative rates of production of malic acid (from endogenous as well as exogenous CO2) and its removal (by transport of the anion into the vacuole and exchange of the H(+) for K(+) with the environment of the guard cells). The simultaneous requirement of CO2 and ABA for stomatal closure leads to the inference that ABA inhibits the expulsion of H(+) from guard cells.

The role of abscisic acid in regulating cucumber fruit development and ripening and its transcriptional regulation.

PubMed

Wang, Yanping; Wang, Ya; Ji, Kai; Dai, Shengjie; Hu, Ying; Sun, Liang; Li, Qian; Chen, Pei; Sun, Yufei; Duan, Chaorui; Wu, Yan; Luo, Hao; Zhang, Dian; Guo, Yangdong; Leng, Ping

2013-03-01

Cucumber (Cucumis sativus L.), a kind of fruit usually harvested at the immature green stage, belongs to non-climacteric fruit. To investigate the contribution of abscisic acid (ABA) to cucumber fruit development and ripening, variation in ABA level was investigated and a peak in ABA level was found in pulp before fruit get fully ripe. To clarify this point further, exogenous ABA was applied to cucumber fruits at two different development stages. Results showed that ABA application at the turning stage promotes cucumber fruit ripening, while application at the immature green stage had inconspicuous effects. In addition, with the purpose of understanding the transcriptional regulation of ABA, two partial cDNAs of CsNCED1 and CsNCED2 encoding 9-cis-epoxycarotenoid dioxygenase (NCED), a key enzyme in ABA biosynthetic pathway; one partial cDNA of CsCYP707A1 for 8'-hydroxylase, a key enzyme in the oxidative catabolism of ABA and two partial cDNAs of CsBG1 and CsBG2 for β-glucosidase (BG) that hydrolyzes ABA glucose ester (ABA-GE) to release active ABA were cloned from cucumber. The DNA and deduced amino acid sequences of these obtained genes respectively showed high similarities to their homologous genes in other plants. Real-time PCR analysis revealed that ABA content may be regulated by its biosynthesis (CsNCEDs), catabolism (CsCYP707A1) and reactivation genes (CsBGs) at the transcriptional level during cucumber fruit development and ripening, in response to ABA application, dehydration and pollination, among which CsNCED1, CsCYP707A1 and CsBG1 were highly expressed in pulp and may play more important roles in regulating ABA metabolism. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

Abscisic acid ameliorates the systemic sclerosis fibroblast phenotype in vitro

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

Bruzzone, Santina, E-mail: santina.bruzzone@unige.it; Centre of Excellence for Biomedical Research, University of Genova, Viale Benedetto XV 9, 16132 Genova; Advanced Biotechnology Center, Largo Rosanna Benzi 10, 16132 Genova

Highlights: Black-Right-Pointing-Pointer ABA is an endogenous hormone in humans, regulating different cell responses. Black-Right-Pointing-Pointer ABA reverts some of the functions altered in SSc fibroblasts to a normal phenotype. Black-Right-Pointing-Pointer UV-B irradiation increases ABA content in SSc cultures. Black-Right-Pointing-Pointer SSc fibroblasts could benefit from exposure to ABA and/or to UV-B. -- Abstract: The phytohormone abscisic acid (ABA) has been recently identified as an endogenous hormone in humans, regulating different cell functions, including inflammatory processes, insulin release and glucose uptake. Systemic sclerosis (SSc) is a chronic inflammatory disease resulting in fibrosis of skin and internal organs. In this study, we investigated themore » effect of exogenous ABA on fibroblasts obtained from healthy subjects and from SSc patients. Migration of control fibroblasts induced by ABA was comparable to that induced by transforming growth factor-{beta} (TGF-{beta}). Conversely, migration toward ABA, but not toward TGF-{beta}, was impaired in SSc fibroblasts. In addition, ABA increased cell proliferation in fibroblasts from SSc patients, but not from healthy subjects. Most importantly, presence of ABA significantly decreased collagen deposition by SSc fibroblasts, at the same time increasing matrix metalloproteinase-1 activity and decreasing the expression level of tissue inhibitor of metalloproteinase (TIMP-1). Thus, exogenously added ABA appeared to revert some of the functions altered in SSc fibroblasts to a normal phenotype. Interestingly, ABA levels in plasma from SSc patients were found to be significantly lower than in healthy subjects. UV-B irradiation induced an almost 3-fold increase in ABA content in SSc cultures. Altogether, these results suggest that the fibrotic skin lesions in SSc patients could benefit from exposure to high(er) ABA levels.« less

Abscisic Acid Deficiency Antagonizes High-Temperature Inhibition of Disease Resistance through Enhancing Nuclear Accumulation of Resistance Proteins SNC1 and RPS4 in Arabidopsis[C][W

PubMed Central

Mang, Hyung-Gon; Qian, Weiqiang; Zhu, Ying; Qian, Jun; Kang, Hong-Gu; Klessig, Daniel F.; Hua, Jian

2012-01-01

Plant defense responses to pathogens are influenced by abiotic factors, including temperature. Elevated temperatures often inhibit the activities of disease resistance proteins and the defense responses they mediate. A mutant screen with an Arabidopsis thaliana temperature-sensitive autoimmune mutant bonzai1 revealed that the abscisic acid (ABA)–deficient mutant aba2 enhances resistance mediated by the resistance (R) gene SUPPRESSOR OF npr1-1 CONSTITUTIVE1 (SNC1) at high temperature. ABA deficiency promoted nuclear accumulation of SNC1, which was essential for it to function at low and high temperatures. Furthermore, the effect of ABA deficiency on SNC1 protein accumulation is independent of salicylic acid, whose effects are often antagonized by ABA. ABA deficiency also promotes the activity and nuclear localization of R protein RESISTANCE TO PSEUDOMONAS SYRINGAE4 at higher temperature, suggesting that the effect of ABA on R protein localization and nuclear activity is rather broad. By contrast, mutations that confer ABA insensitivity did not promote defense responses at high temperature, suggesting either tissue specificity of ABA signaling or a role of ABA in defense regulation independent of the core ABA signaling machinery. Taken together, this study reveals a new intersection between ABA and disease resistance through R protein localization and provides further evidence of antagonism between abiotic and biotic responses. PMID:22454454

Regulation of Embryo Dormancy by Manipulation of Abscisic Acid in Kernels and Associated Cob Tissue of Zea mays L. Cultured in Vitro1

PubMed Central

Hole, David J.; Smith, J. D.; Cobb, B. Greg

1989-01-01

Sectors of Zea mays cobs, with and without kernels were cultured in vitro in the presence and absence of fluridone. Cultured kernels, cob tissue, and embryos developed similarly to those grown in the field. Abscisic acid (ABA) levels in the embryos were evaluated by enzyme-linked immunosorbant assay. ABA levels in intact embryos cultured in the presence of fluridone were extremely low and indicate an inhibition of ABA synthesis. ABA levels in isolated cob tissue indicate that ABA can be produced by cob tissue. Sections containing kernels cultured in the presence of fluridone were transferred to medium containing fluridone and ABA. Dormancy was induced in more than 50% of the kernels transferred from 13 to 15 days after pollination, but all of the kernels transferred at 16 days after pollination or later were viviparous. ABA recovered from kernels that were placed in medium containing fluridone and ABA suggest that ABA can be transported through the cob tissue into developing embryos and that ABA is required for induction of dormancy in intact embryos. PMID:16666978

Depletion of abscisic acid levels in roots of flooded Carrizo citrange (Poncirus trifoliata L. Raf. × Citrus sinensis L. Osb.) plants is a stress-specific response associated to the differential expression of PYR/PYL/RCAR receptors.

PubMed

Arbona, Vicent; Zandalinas, Sara I; Manzi, Matías; González-Guzmán, Miguel; Rodriguez, Pedro L; Gómez-Cadenas, Aurelio

2017-04-01

Soil flooding reduces root abscisic acid (ABA) levels in citrus, conversely to what happens under drought. Despite this reduction, microarray analyses suggested the existence of a residual ABA signaling in roots of flooded Carrizo citrange seedlings. The comparison of ABA metabolism and signaling in roots of flooded and water stressed plants of Carrizo citrange revealed that the hormone depletion was linked to the upregulation of CsAOG, involved in ABA glycosyl ester (ABAGE) synthesis, and to a moderate induction of catabolism (CsCYP707A, an ABA 8'-hydroxylase) and buildup of dehydrophaseic acid (DPA). Drought strongly induced both ABA biosynthesis and catabolism (CsNCED1, 9-cis-neoxanthin epoxycarotenoid dioxygenase 1, and CsCYP707A) rendering a significant hormone accumulation. In roots of flooded plants, restoration of control ABA levels after stress release was associated to the upregulation of CsBGLU18 (an ABA β-glycosidase) that cleaves ABAGE. Transcriptional profile of ABA receptor genes revealed a different induction in response to soil flooding (CsPYL5) or drought (CsPYL8). These two receptor genes along with CsPYL1 were cloned and expressed in a heterologous system. Recombinant CsPYL5 inhibited ΔNHAB1 activity in vitro at lower ABA concentrations than CsPYL8 or CsPYL1, suggesting its better performance under soil flooding conditions. Both stress conditions induced ABA-responsive genes CsABI5 and CsDREB2A similarly, suggesting the occurrence of ABA signaling in roots of flooded citrus seedlings. The impact of reduced ABA levels in flooded roots on CsPYL5 expression along with its higher hormone affinity reinforce the role of this ABA receptor under soil-flooding conditions and explain the expression of certain ABA-responsive genes.

Response of Cultured Maize Cells to (+)-Abscisic Acid, (-)-Abscisic Acid, and Their Metabolites.

PubMed Central

Balsevich, J. J.; Cutler, A. J.; Lamb, N.; Friesen, L. J.; Kurz, E. U.; Perras, M. R.; Abrams, S. R.

1994-01-01

The metabolism and effects of (+)-S- and (-)-R-abscisic acid (ABA) and some metabolites were studied in maize (Zea mays L. cv Black Mexican Sweet) suspension-cultured cells. Time-course studies of metabolite formation were performed in both cells and medium via analytical high-performance liquid chromatography. Metabolites were isolated and identified using physical and chemical methods. At 10 [mu]M concentration and 28[deg] C, (+)-ABA was metabolized within 24 h, yielding natural (-)-phaseic acid [(-)-PA] as the major product. The unnatural enantiomer (-)-ABA was less than 50% metabolized within 24 h and gave primarily (-)-7[prime]-hydroxyABA [(-)-7[prime]-HOABA], together with (+)-PA and ABA glucose ester. The distribution of metabolites in cells and medium was different, reflecting different sites of metabolism and membrane permeabilities of conjugated and nonconjugated metabolites. The results imply that (+)-ABA was oxidized to (-)-PA inside the cell, whereas (-)-ABA was converted to (-)-7[prime]-HOABA at the cell surface. Growth of maize cells was inhibited by both (+)- and (-)-ABA, with only weak contributions from their metabolites. The concentration of (+)-ABA that caused a 50% inhibition of growth of maize cells was approximately 1 [mu]M, whereas that for its metabolite (-)-PA was approximately 50 [mu]M. (-)-ABA was less active than (+)-ABA, with 50% growth inhibition observed at about 10 [mu]M. (-)-7[prime]-HOABA was only weakly active, with 50% inhibition caused by approximately 500 [mu]M. Time-course studies of medium pH indicated that (+)-ABA caused a transient pH increase (+0.3 units) at 6 h after addition that was not observed in controls or in samples treated with (-)-PA. The effect of (-)-ABA on medium Ph was marginal. No racemization at C-1[prime] of (+)-ABA, (-)-ABA, or metabolites was observed during the studies. PMID:12232311

SCFAtPP2-B11 modulates ABA signaling by facilitating SnRK2.3 degradation in Arabidopsis thaliana

PubMed Central

Ren, Ziyin; Zhi, Liya; Yao, Bin; Su, Chao; Liu, Liu; Li, Xia

2017-01-01

The phytohormone abscisic acid (ABA) is an essential part of the plant response to abiotic stressors such as drought. Upon the perception of ABA, pyrabactin resistance (PYR)/PYR1-like (PYL)/regulatory components of ABA receptor (RCAR) proteins interact with co-receptor protein phosphatase type 2Cs to permit activation Snf1-related protein kinase2 (SnRK2) kinases, which switch on ABA signaling by phosphorylating various target proteins. Thus, SnRK2 kinases are central regulators of ABA signaling. However, the mechanisms that regulate SnRK2 degradation remain elusive. Here, we show that SnRK2.3 is degradated by 26S proteasome system and ABA promotes its degradation. We found that SnRK2.3 interacts with AtPP2-B11 directly. AtPP2-B11 is an F-box protein that is part of a SKP1/Cullin/F-box E3 ubiquitin ligase complex that negatively regulates plant responses to ABA by specifically promoting the degradation of SnRK2.3. AtPP2-B11 was induced by ABA, and the knockdown of AtPP2-B11 expression markedly increased the ABA sensitivity of plants during seed germination and postgerminative development. Overexpression of AtPP2-B11 does not affect ABA sensitivity, but inhibits the ABA hypersensitive phenotypes of SnRK2.3 overexpression lines. These results reveal a novel mechanism through which AtPP2-B11 specifically degrades SnRK2.3 to attenuate ABA signaling and the abiotic stress response in Arabidopsis. PMID:28787436

Cuticle Biosynthesis in Tomato Leaves Is Developmentally Regulated by Abscisic Acid1[OPEN

PubMed Central

2017-01-01

The expansion of aerial organs in plants is coupled with the synthesis and deposition of a hydrophobic cuticle, composed of cutin and waxes, which is critically important in limiting water loss. While the abiotic stress-related hormone abscisic acid (ABA) is known to up-regulate wax accumulation in response to drought, the hormonal regulation of cuticle biosynthesis during organ ontogeny is poorly understood. To address the hypothesis that ABA also mediates cuticle formation during organ development, we assessed the effect of ABA deficiency on cuticle formation in three ABA biosynthesis-impaired tomato mutants. The mutant leaf cuticles were thinner, had structural abnormalities, and had a substantial reduction in levels of cutin. ABA deficiency also consistently resulted in differences in the composition of leaf cutin and cuticular waxes. Exogenous application of ABA partially rescued these phenotypes, confirming that they were a consequence of reduced ABA levels. The ABA mutants also showed reduced expression of genes involved in cutin or wax formation. This difference was again countered by exogenous ABA, further indicating regulation of cuticle biosynthesis by ABA. The fruit cuticles were affected differently by the ABA-associated mutations, but in general were thicker. However, no structural abnormalities were observed, and the cutin and wax compositions were less affected than in leaf cuticles, suggesting that ABA action influences cuticle formation in an organ-dependent manner. These results suggest dual roles for ABA in regulating leaf cuticle formation: one that is fundamentally associated with leaf expansion, independent of abiotic stress, and another that is drought induced. PMID:28483881

Cuticle Biosynthesis in Tomato Leaves Is Developmentally Regulated by Abscisic Acid.

PubMed

Martin, Laetitia B B; Romero, Paco; Fich, Eric A; Domozych, David S; Rose, Jocelyn K C

2017-07-01

The expansion of aerial organs in plants is coupled with the synthesis and deposition of a hydrophobic cuticle, composed of cutin and waxes, which is critically important in limiting water loss. While the abiotic stress-related hormone abscisic acid (ABA) is known to up-regulate wax accumulation in response to drought, the hormonal regulation of cuticle biosynthesis during organ ontogeny is poorly understood. To address the hypothesis that ABA also mediates cuticle formation during organ development, we assessed the effect of ABA deficiency on cuticle formation in three ABA biosynthesis-impaired tomato mutants. The mutant leaf cuticles were thinner, had structural abnormalities, and had a substantial reduction in levels of cutin. ABA deficiency also consistently resulted in differences in the composition of leaf cutin and cuticular waxes. Exogenous application of ABA partially rescued these phenotypes, confirming that they were a consequence of reduced ABA levels. The ABA mutants also showed reduced expression of genes involved in cutin or wax formation. This difference was again countered by exogenous ABA, further indicating regulation of cuticle biosynthesis by ABA. The fruit cuticles were affected differently by the ABA-associated mutations, but in general were thicker. However, no structural abnormalities were observed, and the cutin and wax compositions were less affected than in leaf cuticles, suggesting that ABA action influences cuticle formation in an organ-dependent manner. These results suggest dual roles for ABA in regulating leaf cuticle formation: one that is fundamentally associated with leaf expansion, independent of abiotic stress, and another that is drought induced. © 2017 American Society of Plant Biologists. All Rights Reserved.

Synthesis, resolution and biological evaluation of cyclopropyl analogs of abscisic acid.

PubMed

Han, Xiaoqiang; Fan, Jinlong; Lu, Huizhe; Wan, Chuan; Li, Xiuyun; Li, Hong; Yang, Dongyan; Zhang, Yuanzhi; Xiao, Yumei; Qin, Zhaohai

2015-09-15

cis-2,3-Cyclopropanated abscisic acid (cis-CpABA) has high photostability and good ABA-like activity. To further investigate its activity and action mechanism, 2S,3S-2,3-cyclopropanated ABA (3a) and 2R,3R-2,3-cyclopropanated ABA (3b) were synthesized. Bioassay showed that 3a displayed higher inhibitory activity in germination than that of 3b and ABA at the concentration of 3.0 μM, but 3a and 3b had much weaker inhibitory activity in inhibition seedling growth compared to ABA. The study of photostability revealed that 3a and 3b showed high stability under UV light exposure, which were 4 times and 3 times greater than (±)-ABA, respectively. Action mechanism study showed that 3a presented higher inhibition on phosphatase activity of HAB1 than 3b, although they all inferior to ABA. Molecular docking studies of 3a, 3b and ABA receptor PYL10 were agreement with the bioassay data and confirmed the importance of the configuration of the 2,3-cyclopropyl ABA analogs for their bioactivity in somewhat. This study provides a new approach for the design of ABA analogs, and the results validated structure-based design for this target class. Copyright © 2015 Elsevier Ltd. All rights reserved.

Exogenous auxin represses soybean seed germination through decreasing the gibberellin/abscisic acid (GA/ABA) ratio.

PubMed

Shuai, Haiwei; Meng, Yongjie; Luo, Xiaofeng; Chen, Feng; Zhou, Wenguan; Dai, Yujia; Qi, Ying; Du, Junbo; Yang, Feng; Liu, Jiang; Yang, Wenyu; Shu, Kai

2017-10-03

Auxin is an important phytohormone which mediates diverse development processes in plants. Published research has demonstrated that auxin induces seed dormancy. However, the precise mechanisms underlying the effect of auxin on seed germination need further investigation, especially the relationship between auxins and both abscisic acid (ABA) and gibberellins (GAs), the latter two phytohormones being the key regulators of seed germination. Here we report that exogenous auxin treatment represses soybean seed germination by enhancing ABA biosynthesis, while impairing GA biogenesis, and finally decreasing GA 1 /ABA and GA 4 /ABA ratios. Microscope observation showed that auxin treatment delayed rupture of the soybean seed coat and radicle protrusion. qPCR assay revealed that transcription of the genes involved in ABA biosynthetic pathway was up-regulated by application of auxin, while expression of genes involved in GA biosynthetic pathway was down-regulated. Accordingly, further phytohormone quantification shows that auxin significantly increased ABA content, whereas the active GA 1 and GA 4 levels were decreased, resulting insignificant decreases in the ratiosGA 1 /ABA and GA 4 /ABA.Consistent with this, ABA biosynthesis inhibitor fluridone reversed the delayed-germination phenotype associated with auxin treatment, while paclobutrazol, a GA biosynthesis inhibitor, inhibited soybean seed germination. Altogether, exogenous auxin represses soybean seed germination by mediating ABA and GA biosynthesis.