High-Tg Polynorbornene-Based Block and Random Copolymers for Butanol Pervaporation Membranes

NASA Astrophysics Data System (ADS)

Register, Richard A.; Kim, Dong-Gyun; Takigawa, Tamami; Kashino, Tomomasa; Burtovyy, Oleksandr; Bell, Andrew

Vinyl addition polymers of substituted norbornene (NB) monomers possess desirably high glass transition temperatures (Tg); however, until very recently, the lack of an applicable living polymerization chemistry has precluded the synthesis of such polymers with controlled architecture, or copolymers with controlled sequence distribution. We have recently synthesized block and random copolymers of NB monomers bearing hydroxyhexafluoroisopropyl and n-butyl substituents (HFANB and BuNB) via living vinyl addition polymerization with Pd-based catalysts. Both series of polymers were cast into the selective skin layers of thin film composite (TFC) membranes, and these organophilic membranes investigated for the isolation of n-butanol from dilute aqueous solution (model fermentation broth) via pervaporation. The block copolymers show well-defined microphase-separated morphologies, both in bulk and as the selective skin layers on TFC membranes, while the random copolymers are homogeneous. Both block and random vinyl addition copolymers are effective as n-butanol pervaporation membranes, with the block copolymers showing a better flux-selectivity balance. While polyHFANB has much higher permeability and n-butanol selectivity than polyBuNB, incorporating BuNB units into the polymer (in either a block or random sequence) limits the swelling of the polyHFANB and thereby improves the n-butanol pervaporation selectivity.

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.

Cyclic Multiblock Copolymers via Combination of Iterative Cu(0)-Mediated Radical Polymerization and Cu(I)-Catalyzed Azide-Alkyne Cycloaddition Reaction.

PubMed

Xiao, Lifen; Zhu, Wen; Chen, Jiqiang; Zhang, Ke

2017-02-01

Cyclic multiblock polymers with high-order blocks are synthesized via the combination of single-electron transfer living radical polymerization (SET-LRP) and copper-catalyzed azide-alkyne cycloaddition (CuAAC). The linear α,ω-telechelic multiblock copolymer is prepared via SET-LRP by sequential addition of different monomers. The SET-LRP approach allows well control of the block length and sequence as A-B-C-D-E, etc. The CuAAC is then performed to intramolecularly couple the azide and alkyne end groups of the linear copolymer and produce the corresponding cyclic copolymer. The block sequence and the cyclic topology of the resultant cyclic copolymer are confirmed by the characterization of 1 H nuclear magnetic resonance spectroscopy, gel permeation chromatography, Fourier transform infrared spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of Bottlebrush Block Copolymers as Photonic Crystals.

PubMed

Liberman-Martin, Allegra L; Chu, Crystal K; Grubbs, Robert H

2017-07-01

Brush block copolymers are a class of comb polymers that feature polymeric side chains densely grafted to a linear backbone. These polymers display interesting properties due to their dense functionality, low entanglement, and ability to rapidly self-assemble to highly ordered nanostructures. The ability to prepare brush polymers with precise structures has been enabled by advancements in controlled polymerization techniques. This Feature Article highlights the development of brush block copolymers as photonic crystals that can reflect visible to near-infrared wavelengths of light. Fabrication of these materials relies on polymer self-assembly processes to achieve nanoscale ordering, which allows for the rapid preparation of photonic crystals from common organic chemical feedstocks. The characteristic physical properties of brush block copolymers are discussed, along with methods for their preparation. Strategies to induce self-assembly at ambient temperatures and the use of blending techniques to tune photonic properties are emphasized. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anionic polymerization of p-(2,2'-diphenylethyl)styrene and applications to graft copolymers.

PubMed

Huang, Minglu; Han, Bingyong; Lu, Jianmin; Yang, Wantai; Fu, Zhifeng

2017-01-01

Well-controlled anionic polymerization of an initiator-functionalized monomer, p -(2,2'-diphenylethyl)styrene (DPES), was achieved for the first time. The polymerization was performed in a mixed solvent of cyclohexane and tetrahydrofuran (THF) at 40 °C with n -BuLi as initiator. When the volume ratio of cyclohexane to THF was 20, the anionic polymerization of DPES showed living polymerization characteristics, and well-defined block copolymer PDPES- b -PS was successfully synthesized. Furthermore, radical polymerization of methyl methacrylate in the presence of PDPES effectively afforded a graft copolymer composed of a polystyrene backbone and poly(methyl methacrylate) branches. The designation of analogous monomers and polymers was of great significance to synthesize a variety of sophisticated copolymer and functionalize polymer materials.

Cathepsin S-cleavable, multi-block HPMA copolymers for improved SPECT/CT imaging of pancreatic cancer.

PubMed

Fan, Wei; Shi, Wen; Zhang, Wenting; Jia, Yinnong; Zhou, Zhengyuan; Brusnahan, Susan K; Garrison, Jered C

2016-10-01

This work continues our efforts to improve the diagnostic and radiotherapeutic effectiveness of nanomedicine platforms by developing approaches to reduce the non-target accumulation of these agents. Herein, we developed multi-block HPMA copolymers with backbones that are susceptible to cleavage by cathepsin S, a protease that is abundantly expressed in tissues of the mononuclear phagocyte system (MPS). Specifically, a bis-thiol terminated HPMA telechelic copolymer containing 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Three maleimide modified linkers with different sequences, including cathepsin S degradable oligopeptide, scramble oligopeptide and oligo ethylene glycol, were subsequently synthesized and used for the extension of the HPMA copolymers by thiol-maleimide click chemistry. All multi-block HPMA copolymers could be labeled by (177)Lu with high labeling efficiency and exhibited high serum stability. In vitro cleavage studies demonstrated highly selective and efficient cathepsin S mediated cleavage of the cathepsin S-susceptible multi-block HPMA copolymer. A modified multi-block HPMA copolymer series capable of Förster Resonance Energy Transfer (FRET) was utilized to investigate the rate of cleavage of the multi-block HPMA copolymers in monocyte-derived macrophages. Confocal imaging and flow cytometry studies revealed substantially higher rates of cleavage for the multi-block HPMA copolymers containing the cathepsin S-susceptible linker. The efficacy of the cathepsin S-cleavable multi-block HPMA copolymer was further examined using an in vivo model of pancreatic ductal adenocarcinoma. Based on the biodistribution and SPECT/CT studies, the copolymer extended with the cathepsin S susceptible linker exhibited significantly faster clearance and lower non-target retention without compromising tumor targeting. Overall, these results indicate that exploitation of the cathepsin S activity in MPS tissues can be utilized to substantially lower non-target accumulation, suggesting this is a promising approach for the development of diagnostic and radiotherapeutic nanomedicine platforms. Copyright © 2016 Elsevier Ltd. All rights reserved.

Side-chain amino-acid-based pH-responsive self-assembled block copolymers for drug delivery and gene transfer.

PubMed

Kumar, Sonu; Acharya, Rituparna; Chatterji, Urmi; De, Priyadarsi

2013-12-10

Developing safe and effective nanocarriers for multitype of delivery system is advantageous for several kinds of successful biomedicinal therapy with the same carrier. In the present study, we have designed amino acid biomolecules derived hybrid block copolymers which can act as a promising vehicle for both drug delivery and gene transfer. Two representative natural chiral amino acid-containing (l-phenylalanine and l-alanine) vinyl monomers were polymerized via reversible addition-fragmentation chain transfer (RAFT) process in the presence of monomethoxy poly(ethylene glycol) based macro-chain transfer agents (mPEGn-CTA) for the synthesis of well-defined side-chain amino-acid-based amphiphilic block copolymers, monomethoxy poly(ethylene glycol)-b-poly(Boc-amino acid methacryloyloxyethyl ester) (mPEGn-b-P(Boc-AA-EMA)). The self-assembled micellar aggregation of these amphiphilic block copolymers were studied by fluorescence spectroscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Potential applications of these hybrid polymers as drug carrier have been demonstrated in vitro by encapsulation of nile red dye or doxorubicin drug into the core of the micellar nanoaggregates. Deprotection of side-chain Boc- groups in the amphiphilic block copolymers subsequently transformed them into double hydrophilic pH-responsive cationic block copolymers having primary amino groups in the side-chain terminal. The DNA binding ability of these cationic block copolymers were further investigated by using agarose gel retardation assay and AFM. The in vitro cytotoxicity assay demonstrated their biocompatible nature and these polymers can serve as "smart" materials for promising bioapplications.

Preparation and Structural Studies on Hybrid Core-Shell Nanoparticles Consisting of Silica Core and Conjugated Block Copolymer Shell Prepared by Surface-Initiated Polymerization

NASA Astrophysics Data System (ADS)

Chatterjee, Sourav; Karam, Tony; Rosu, Cornelia; Li, Xin; Do, Changwoo; Youm, Sang Gil; Haber, Louis; Russo, Paul; Nesterov, Evgueni

Controlled Kumada catalyst-transfer polymerization occurring by chain-growth mechanism was developed for the synthesis of conjugated polymers and block copolymers from the surface of inorganic substrates such as silica nanoparticles. Although synthesis of conjugated polymers via Kumada polymerization became an established method for solution polymerization, carrying out the same reaction in heterogeneous conditions to form monodisperse polymer chains still remains a challenge. We developed and described a simple and efficient approach to the preparation of surface-immobilized layer of catalytic Ni(II) initiator, and demonstrated using it to prepare polymers and block copolymers on silica nanoparticle. The structure of the resulting hybrid nanostructures was thoroughly studied using small-angle neutron and X-ray scattering, thermal analysis, and optical spectroscopy. The photoexcitation energy transfer processes in the conjugated polymer shell were studied via steady-state and time resolved transient absorption spectroscopy. This study uncovered important details of the energy transfer, which will be discussed in this presentation.

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

NASA Astrophysics Data System (ADS)

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

2014-06-01

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

Complex and hierarchical micelle architectures from diblock copolymers using living, crystallization-driven polymerizations.

PubMed

Gädt, Torben; Ieong, Nga Sze; Cambridge, Graeme; Winnik, Mitchell A; Manners, Ian

2009-02-01

Block copolymers consist of two or more chemically distinct polymer segments, or blocks, connected by a covalent link. In a selective solvent for one of the blocks, core-corona micelle structures are formed. We demonstrate that living polymerizations driven by the epitaxial crystallization of a core-forming metalloblock represent a synthetic tool that can be used to generate complex and hierarchical micelle architectures from diblock copolymers. The use of platelet micelles as initiators enables the formation of scarf-like architectures in which cylindrical micelle tassels of controlled length are grown from specific crystal faces. A similar process enables the fabrication of brushes of cylindrical micelles on a crystalline homopolymer substrate. Living polymerizations driven by heteroepitaxial growth can also be accomplished and are illustrated by the formation of tri- and pentablock and scarf architectures with cylinder-cylinder and platelet-cylinder connections, respectively, that involve different core-forming metalloblocks.

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

Polymeric micellar pH-sensitive drug delivery system for doxorubicin.

PubMed

Hrubý, Martin; Konák, Cestmír; Ulbrich, Karel

2005-03-02

A novel polymeric micellar pH-sensitive system for delivery of doxorubicin (DOX) is described. Polymeric micelles were prepared by self-assembly of amphiphilic diblock copolymers in aqueous solutions. The copolymers consist of a biocompatible hydrophilic poly(ethylene oxide) (PEO) block and a hydrophobic block containing covalently bound anthracycline antibiotic DOX. The starting block copolymers poly(ethylene oxide)-block-poly(allyl glycidyl ether) (PEO-PAGE) with a very narrow molecular weight distribution (Mw/Mn ca. 1.05) were prepared by anionic ring opening polymerization using sodium salt of poly(ethylene oxide) monomethyl ether as macroinitiator and allyl glycidyl ether as functional monomer. The copolymers were covalently modified via reactive double bonds by the addition of methyl sulfanylacetate. The resulting ester subsequently reacted with hydrazine hydrate yielding polymer hydrazide. The hydrazide was coupled with DOX yielding pH-sensitive hydrazone bonds between the drug and carrier. The resulting conjugate containing ca. 3 wt.% DOX forms micelles with Rh(a)=104 nm in phosphate-buffered saline. After incubation in buffers at 37 degrees C DOX was released faster at pH 5.0 (close to pH in endosomes; 43% DOX released within 24 h) than at pH 7.4 (pH of blood plasma; 16% DOX released within 24 h). Cleavage of hydrazone bonds between DOX and carrier continues even after plateau in the DOX release from micelles incubated in aqueous solutions is reached.

Amphiphilic Ferrocene-Containing PEG Block Copolymers as Micellar Nanocarriers and Smart Surfactants.

PubMed

Alkan, Arda; Wald, Sarah; Louage, Benoit; De Geest, Bruno G; Landfester, Katharina; Wurm, Frederik R

2017-01-10

An important and usually the only function of most surfactants in heterophase systems is stabilizing one phase in another, for example, droplets or particles in water. Surfactants with additional chemical or physical handles are promising in controlling the colloidal properties by external stimuli. The redox stimulus is an attractive feature; however, to date only a few ionic redox-responsive surfactants have been reported. Herein, the first nonionic and noncytotoxic ferrocene-containing block copolymers are prepared, carrying a hydrophilic poly(ethylene glycol) (PEG) chain and multiple ferrocenes in the hydrophobic segment. These amphiphiles were studied as redox-sensitive surfactants that destabilize particles as obtained in miniemulsion polymerization. Because of the nonionic nature of such PEG-based copolymers, they can stabilize nanoparticles even after the addition of ions, whereas particles stabilized with ionic surfactants would be destabilized by the addition of salt. The redox-active surfactants were prepared by the anionic ring-opening polymerization of ferrocenyl glycidyl ether, with PEG monomethyl ether as the macroinitiator. The resultant block copolymers with molecular weights (M n ) between 3600 and 8600 g mol -1 and narrow molecular weight distributions (M w /M n = 1.04-1.10) were investigated via 1 H nuclear magnetic resonance and diffusion ordered spectroscopy, size exclusion chromatography, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Furthermore, the block copolymers were used as building blocks for redox-responsive micelles and as redox-responsive surfactants in radical polymerization in miniemulsion to stabilize model polystyrene nanoparticles. Oxidation of iron to the ferrocenium species converted the amphiphilic block copolymers into double hydrophilic macromolecules, which led to the destabilization of the nanoparticles. This destabilization of nanoparticle dispersions may be useful for the formation of coatings and the recovery of surfactants.

Electrically conductive doped block copolymer of polyacetylene and polyisoprene

DOEpatents

Aldissi, Mahmoud

1985-01-01

An electrically conductive block copolymer of polyisoprene and polyacetyl and a method of making the same are disclosed. The polymer is prepared by first polymerizing isoprene with n-butyllithium in a toluene solution to form an active isoprenyllithium polymer. The active polymer is reacted with an equimolar amount of titanium butoxide and subsequently exposed to gaseous acetylene. A block copolymer of polyisoprene and polyacetylene is formed. The copolymer is soluble in common solvents and may be doped with I.sub.2 to give it an electrical conductivity in the metallic regime.

Ultra-Fast RAFT-HDA Click Conjugation: An Efficient Route to High Molecular Weight Block Copolymers.

PubMed

Inglis, Andrew J; Stenzel, Martina H; Barner-Kowollik, Christopher

2009-11-02

The use of the reversible addition fragmentation chain transfer-hetero Diels-Alder (RAFT-HDA) click reaction for the modular construction of block copolymers is extended to the generation of high molecular weight materials. Cyclopentadienyl end-functionalized polystyrene (PS-Cp) prepared via both atom transfer radical polymerization (ATRP) and the RAFT process are conjugated to poly(isobornyl acrylate) (PiBoA) (also prepared via RAFT polymerization) to achieve well-defined block copolymers with molecular weights ranging from 34 000 to over 100 000 g · mol(-1) and with small polydispersities (PDI < 1.2). The conjugation reactions proceeded in a very rapid fashion (less than 10 min in the majority of cases) under ambient conditions of temperature and atmosphere. The present study demonstrates-for the first time-that RAFT-HDA click chemistry can provide access to high molecular weight block copolymers in a simple and straight-forward fashion. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels.

PubMed

Hemp, Sean T; Smith, Adam E; Bunyard, W Clayton; Rubinstein, Michael H; Long, Timothy E

2014-05-13

Reversible-addition fragmentation chain transfer (RAFT) polymerization enabled the synthesis of novel, stimuli-responsive, AB and ABA block copolymers. The B block contained oligo(ethylene glycol) methyl ether methacrylate (OEG) and was permanently hydrophilic in the conditions examined. The A block consisted of diethylene glycol methyl ether methacrylate (DEG) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMA). The A block displayed both salt- and temperature-response with lower critical solution temperatures (LCSTs) dependent on the molar content of TMA and the presence of salt. Higher TMA content in the AB diblock copolymers increased the critical micelle temperatures (CMT) in HPLC-grade water due to an increased hydrophilicity of the A block. Upon addition of 0.9 wt% NaCl, the CMTs of poly(OEG- b -DEG 95 TMA 5 ) decreased from 50 °C to 36 °C due to screening of electrostatic repulsion between the TMA units. ABA triblock copolymers displayed excellent hydrogel properties with salt- and temperature-dependent gel points. TMA incorporation in the A block increased the gel points for all triblock copolymers, and salt-response increased with higher TMA composition in the A block. For example, poly(DEG 98 TMA 2 - b -OEG- b -DEG 98 TMA 2 ) formed a hydrogel at 40 °C in HPLC-grade water and 26 °C in 0.9 wt% NaCl aqueous solution. These salt- and temperature-responsive AB diblock and ABA triblock copolymers find applications as drug delivery vehicles, adhesives, and hydrogels.

Development of materials from copolyacrylates via atom transfer radical polymerization

NASA Astrophysics Data System (ADS)

Jones, Melody Mersadez

Homopolymerization of 2-(trimethylsilyl)ethyl acrylate, 3,3-dimethylbutyl acrylate, methyl acrylate, and methyl methacrylate using atom transfer radical polymerization (ATRP) is reported. In addition, polymethyl acrylate and polymethyl methacrylate were used as macroinitiators for diblock copolymerizations (via ATRP) with various monomers to yield pMA-b-TMSEA, pMMA-b-TMSEA, and pMMA-b-GMA copolymers; these results are also reported. Controlled polymerizations were performed using the CuBr/hexamethyltriethylenetetramine catalyst system in combination with methyl bromopropionate as the initiator. The protected acid block copolymers pMA-b-TMSEA and pMMA-b-TMSEA were deprotected to afford acrylic and meth acrylic acid block copolymers pMA-b-AA and pMMA-b-AA. Methylene chloride was used to micellize the amphiphilic copolymers in order to obtain the critical micelle concentration of the polymers (CMCpMA-b-AA = 10 mg/mL, CMCpMMA-b-AA = 0.4 mg/mL). The majority of polymerization were done in bulk; however, since poly(trimethylsilyl)ethyl acrylate displayed polydispersity (Mn = 11459, PDI = 1.437) on the high end of the acceptable range, various solvents were utilized to decrease the polymerization rate and afford low polydispersity materials. This differs from the ATRP of polymethyl acrylate or polymethyl methacrylate using this catalytic system, which do not require the addition of a solvent to obtain well-defined polymers. Also, for this polymerization system three different temperatures (60°C, 90°C, and 120°C) were used, in order to reduce the concentration of radicals and the contribution of termination. The homopolymers and protected acid block copolymers were characterized by gel permeation chromatography to determine the relative molecular weights. Differential scanning calorimetry was used to obtain the glass transition temperature of all polymers. Characterization using NMR (1H and 13C) and FTIR confirmed homopolymerization of 3,3-dimethylbutyl acrylate, 2-(trimethylsilyl)ethyl acrylate and complete cleavage of the (trimethylsilyl)ethyl group from the protected acid copolymers.

Metallocene-Containing Homopolymers and Heterobimetallic Block Copolymers via Photoinduced RAFT Polymerization

PubMed Central

Yang, Peng; Pageni, Parasmani; Kabir, Mohammad Pabel; Zhu, Tianyu; Tang, Chuanbing

2017-01-01

We report the synthesis of cationic cobaltocenium and neutral ferrocene containing homopolymers mediated by photoinduced reversible addition-fragmentation chain transfer (RAFT) polymerization with a photocatalyst fac-[Ir(ppy)3]. The homopolymers were further used as macromolecular chain transfer agents to synthesize diblock copolymers via chain extension. Controlled/“living” feature of photoinduced RAFT polymerization was confirmed by kinetic studies even without prior deoxygenation. A light switch between ON and OFF provided a spatiotemporal control of polymerization. PMID:29276651

Block Copolymer Membranes for Biofuel Purification

NASA Astrophysics Data System (ADS)

Evren Ozcam, Ali; Balsara, Nitash

2012-02-01

Purification of biofuels such as ethanol is a matter of considerable concern as they are produced in complex multicomponent fermentation broths. Our objective is to design pervaporation membranes for concentrating ethanol from dilute aqueous mixtures. Polystyrene-b-polydimethylsiloxane-b-polystyrene block copolymers were synthesized by anionic polymerization. The polydimethylsiloxane domains provide ethanol-transporting pathways, while the polystyrene domains provide structural integrity for the membrane. The morphology of the membranes is governed by the composition of the block copolymer while the size of the domains is governed by the molecular weight of the block copolymer. Pervaporation data as a function of these two parameters will be presented.

Formation of nanophases in epoxy thermosets containing amphiphilic block copolymers with linear and star-like topologies.

PubMed

Wang, Lei; Zhang, Chongyin; Cong, Houluo; Li, Lei; Zheng, Sixun; Li, Xiuhong; Wang, Jie

2013-07-11

In this work, we investigated the effect of topological structures of block copolymers on the formation of the nanophase in epoxy thermosets containing amphiphilic block copolymers. Two block copolymers composed of poly(ε-caprolactone) (PCL) and poly(2,2,2-trifluoroethyl acrylate) (PTFEA) blocks were synthesized to possess linear and star-shaped topologies. The star-shaped block copolymer composed a polyhedral oligomeric silsesquioxane (POSS) core and eight poly(ε-caprolactone)-block-poly(2,2,2-trifluoroethyl acrylate) (PCL-b-PTFEA) diblock copolymer arms. Both block copolymers were synthesized via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) process; they were controlled to have identical compositions of copolymerization and lengths of blocks. Upon incorporating both block copolymers into epoxy thermosets, the spherical PTFEA nanophases were formed in all the cases. However, the sizes of PTFEA nanophases from the star-like block copolymer were significantly lower than those from the linear diblock copolymer. The difference in the nanostructures gave rise to the different glass transition behavior of the nanostructured thermosets. The dependence of PTFEA nanophases on the topologies of block copolymers is interpreted in terms of the conformation of the miscible subchain (viz. PCL) at the surface of PTFEA microdomains and the restriction of POSS cages on the demixing of the thermoset-philic block (viz. PCL).

Mechanistic insights for block copolymer morphologies: how do worms form vesicles?

PubMed

Blanazs, Adam; Madsen, Jeppe; Battaglia, Giuseppe; Ryan, Anthony J; Armes, Steven P

2011-10-19

Amphiphilic diblock copolymers composed of two covalently linked, chemically distinct chains can be considered to be biological mimics of cell membrane-forming lipid molecules, but with typically more than an order of magnitude increase in molecular weight. These macromolecular amphiphiles are known to form a wide range of nanostructures (spheres, worms, vesicles, etc.) in solvents that are selective for one of the blocks. However, such self-assembly is usually limited to dilute copolymer solutions (<1%), which is a significant disadvantage for potential commercial applications such as drug delivery and coatings. In principle, this problem can be circumvented by polymerization-induced block copolymer self-assembly. Here we detail the synthesis and subsequent in situ self-assembly of amphiphilic AB diblock copolymers in a one pot concentrated aqueous dispersion polymerization formulation. We show that spherical micelles, wormlike micelles, and vesicles can be predictably and efficiently obtained (within 2 h of polymerization, >99% monomer conversion) at relatively high solids in purely aqueous solution. Furthermore, careful monitoring of the in situ polymerization by transmission electron microscopy reveals various novel intermediate structures (including branched worms, partially coalesced worms, nascent bilayers, "octopi", "jellyfish", and finally pure vesicles) that provide important mechanistic insights regarding the evolution of the particle morphology during the sphere-to-worm and worm-to-vesicle transitions. This environmentally benign approach (which involves no toxic solvents, is conducted at relatively high solids, and requires no additional processing) is readily amenable to industrial scale-up, since it is based on commercially available starting materials.

Tailor-made polyfluoroacrylate and its block copolymer by RAFT polymerization in miniemulsion; improved hydrophobicity in the core-shell block copolymer.

PubMed

Chakrabarty, Arindam; Singha, Nikhil K

2013-10-15

Controlled/living radical polymerization (CRP) of a fluoroacrylate was successfully carried out in miniemulsion by Reversible Addition Fragmentation chain Transfer (RAFT) process. In this case, 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA) was polymerized using 2-cyanopropyl dodecyl trithiocarbonate (CPDTC) as RAFT agent, Triton X-405 and sodium dodecyl sulfonate (SDS) as surfactant, and potassium persulphate (KPS) or 2,2'-azobis isobutyronitrile (AIBN) as initiator. Being compatible with hydrophobic fluoroacrylate, this RAFT agent offered very high conversion and good control over the molecular weight of the polymer. The miniemulsion was stable without any costabilizer. The long chain dodecyl group (-C12H25) (Z-group in the RAFT agent) had beneficial effect in stabilizing the miniemulsion. When 2-cyano 2-propyl benzodithioate (CPBD) (Z=-C6H5) was used as RAFT agent, the conversion was less and particle size distribution was very broad. Block copolymerization with butyl acrylate (BA) using PHFBA as macro-RAFT agent showed core-shell morphology with the aggregation of PHFBA segment in the shell. GPC as well as DSC analysis confirmed the formation of block copolymer. The core-shell morphology was confirmed by TEM analysis. The block copolymers (PHFBA-b-PBA) showed significantly higher water contact angle (WCA) showing much better hydrophobicity compared to PHFBA alone. Copyright © 2013 Elsevier Inc. All rights reserved.

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

Interaction chromatography for characterization and large-scale fractionation of chemically heterogeneous copolymers

NASA Astrophysics Data System (ADS)

Han, Junwon

The remarkable development of polymer synthesis techniques to make complex polymers with controlled chain architectures has inevitably demanded the advancement of polymer characterization tools to analyze the molecular dispersity in polymeric materials beyond size exclusion chromatography (SEC). In particular, man-made synthetic copolymers that consist of more than one monomer type are disperse mixtures of polymer chains that have distributions in terms of both chemical heterogeneity and chain length (molar mass). While the molecular weight distribution has been quite reliably estimated by the SEC, it is still challenging to properly characterize the chemical composition distribution in the copolymers. Here, I have developed and applied adsorption-based interaction chromatography (IC) techniques as a promising tool to characterize and fractionate polystyrene-based block, random and branched copolymers in terms of their chemical heterogeneity. The first part of this thesis is focused on the adsorption-desorption based purification of PS-b-PMMA diblock copolymers using nanoporous silica. The liquid chromatography analysis and large scale purification are discussed for the PS-b-PMMA block copolymers that have been synthesized by sequential anionic polymerization. SEC and IC are compared to critically analyze the contents of PS homopolymers in the as-synthesized block copolymers. In addition, I have developed an IC technique to provide faster and more reliable information on the chemical heterogeneity in the as-synthesized block copolymers. Finally, a large scale (multi-gram) separation technique is developed to obtain "homopolymer-free" block copolymers via a simple chromatographic filtration technique. By taking advantage of the large specific surface area of nanoporous silica (≈300m 2/g), large scale purification of neat PS-b-PMMA has successfully been achieved by controlling adsorption and desorption of the block copolymers on the silica gel surface using a gravity column. The second part of this thesis is focused on the liquid chromatography analysis and fractionation of RAFT-polymerized PS-b -PMMA diblock copolymers and AFM studies. In this study, PS- b-PMMA block copolymers were synthesized by a RAFT free radical polymerization process---the PMMA block with a phenyldithiobenzoate end group was synthesized first. The contents of unreacted PS and PMMA homopolymers in as-synthesized PS-b-PMMA block copolymers were quantitatively analyzed by solvent gradient interaction chromatography (SGIC) technique employing bare silica and C18-bonded silica columns, respectively. In addition, by 2-dimensional large-scale IC fractionation method, atomic force microscopy (AFM) study of these fractionated samples revealed various morphologies with respect to the chemical composition of each fraction. The third part of this thesis is to analyze random copolymers with tunable monomer sequence distributions using interaction chromatography. Here, IC was used for characterizing the composition and monomer sequence distribution in statistical copolymers of poly(styrene-co-4-bromostyrene) (PBrxS). The PBrS copolymers were synthesized by the bromination of monodisperse polystyrenes; the degree of bromination (x) and the sequence distribution were adjusted by varying the bromination time and the solvent quality, respectively. Both normal-phase (bare silica) and reversed-phase (C18-bonded silica) columns were used at different combinations of solvents and non-solvents to monitor the content of the 4-bromostyrene units in the copolymer and their average monomer sequence distribution. The fourth part of this thesis is to analyze and fractionate highly branched polymers such as dendronized polymers and star-shaped homo and copolymers. I have developed an interaction chromatography technique to separate polymers with nonlinear chain architecture. Specifically, the IC technique has been used to separate dendronized polymers and PS-based highly branched copolymers and to ultimately obtain well-defined dendronized or branched copolymers with a low polydispersity. The effects of excess arm-polymers on (1) the micellar self-assembly of dendronized polymers and (2) the regularity of the pore morphology in the low-k applications by the sol-gel process have been studied.

Star-shaped PHB-PLA block copolymers: immortal polymerization with dinuclear indium catalysts.

PubMed

Yu, I; Ebrahimi, T; Hatzikiriakos, S G; Mehrkhodavandi, P

2015-08-28

The first example of a one-component precursor to star-shaped polyesters, and its utilization in the synthesis of previously unknown star-shaped poly(hydroxybutyrate)-poly(lactic acid) block copolymers, is reported. A series of such mono- and bis-benzyl alkoxy-bridged complexes were synthesized, fully characterized, and their solvent dependent solution structures and reactivity were examined. These complexes were highly active catalysts for the controlled polymerization of β-butyrolactone to form poly(hydroxybutyrate) at room temperature. Solution studies indicate that a mononuclear propagating species formed in THF and that the dimer-monomer equilibrium affects the rates of BBL polymerization. In the presence of linear and branched alcohols, these complexes catalyze well-controlled immortal polymerization and copolymerization of β-butyrolactone and lactide.

Electrically conductive doped block copolymer of polyacetylene and polyisoprene. [Soluble in organic solvents

DOEpatents

Aldissi, M.

1984-06-27

An electrically conductive block copolymer of polyisoprene and polyacetylene and a method of making the same are disclosed. The polymer is prepared by first polymerizing isoprene with n-butyllithium in a toluene solution to form an active isoprenyllithium polymer. The active polymer is reacted with an equimolar amount of titanium butoxide and subsequently exposed to gaseous acetylene. A block copolymer of polyisoprene and polyacetylene is formed. The copolymer is soluble in common solvents and may be doped with I/sub 2/ to give it an electrical conductivity in the metallic regime.

Injectible bodily prosthetics employing methacrylic copolymer gels

DOEpatents

Mallapragada, Surya K.; Anderson, Brian C.

2007-02-27

The present invention provides novel block copolymers as structural supplements for injectible bodily prosthetics employed in medical or cosmetic procedures. The invention also includes the use of such block copolymers as nucleus pulposus replacement materials for the treatment of degenerative disc disorders and spinal injuries. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol) methyl ether polymer.

Synthesis of carboxylic block copolymers via reversible addition fragmentation transfer polymerization for tooth erosion prevention.

PubMed

Lei, Y; Wang, T; Mitchell, J W; Qiu, J; Kilpatrick-Liverman, L

2014-12-01

Dental professionals are seeing a growing population of patients with visible signs of dental erosion. The approach currently being used to address the problem typically leverages the enamel protection benefits of fluoride. In this report, an alternative new block copolymer with a hydrophilic polyacrylic acid (PAA) block and a hydrophobic poly(methyl methacrylate) (PMMA) block was developed to similarly reduce the mineral loss from enamel under acidic conditions. This series of PMMA-b-PAA block copolymers was synthesized by reversible addition fragmentation transfer (RAFT) polymerization. Their structures were characterized by gel permeation chromatography (GPC) and (1)H nuclear magnetic resonance (NMR) spectra. The molar fractions of acrylic acid (AA) in the final block copolymer were finely controlled from 0.25 to 0.94, and the molecular weight (Mn) of PMMA-b-PAA was controlled from 10 kDa to 90 kDa. The binding capability of the block copolymer with hydroxyapatite (HAP) was investigated by ultraviolet-visible spectroscopy (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. FTIR spectra confirmed that the PMMA-b-PAA block copolymer could bind to HAP via bridging bidentate bonds. Both UV-Vis and FTIR spectra additionally indicated that a high polymer concentration and low solution pH favored the polymer binding to HAP. The erosion-preventing efficacy of the PMMA-b-PAA block copolymer in inhibiting HAP mineral loss was quantitatively evaluated by atomic absorption spectroscopy (AAS). Based on the results, polymer treatment reduced the amount of calcium released by 27% to 30% in comparison with the unprotected samples. Scanning electron microscope (SEM) observations indicated that PMMA-b-PAA polymer treatment protected enamel from acid erosion. This new amphiphilic block copolymer has significant potential to be integrated into dentifrices or mouthrinses as an alternative non-fluoride ingredient to reduce tooth erosion. © International & American Associations for Dental Research.

Synthesis of Carboxylic Block Copolymers via Reversible Addition Fragmentation Transfer Polymerization for Tooth Erosion Prevention

PubMed Central

Lei, Y.; Wang, T.; Mitchell, J.W.; Qiu, J.; Kilpatrick-Liverman, L.

2014-01-01

Dental professionals are seeing a growing population of patients with visible signs of dental erosion. The approach currently being used to address the problem typically leverages the enamel protection benefits of fluoride. In this report, an alternative new block copolymer with a hydrophilic polyacrylic acid (PAA) block and a hydrophobic poly(methyl methacrylate) (PMMA) block was developed to similarly reduce the mineral loss from enamel under acidic conditions. This series of PMMA-b-PAA block copolymers was synthesized by reversible addition fragmentation transfer (RAFT) polymerization. Their structures were characterized by gel permeation chromatography (GPC) and 1H nuclear magnetic resonance (NMR) spectra. The molar fractions of acrylic acid (AA) in the final block copolymer were finely controlled from 0.25 to 0.94, and the molecular weight (Mn) of PMMA-b-PAA was controlled from 10 kDa to 90 kDa. The binding capability of the block copolymer with hydroxyapatite (HAP) was investigated by ultraviolet–visible spectroscopy (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy. FTIR spectra confirmed that the PMMA-b-PAA block copolymer could bind to HAP via bridging bidentate bonds. Both UV-Vis and FTIR spectra additionally indicated that a high polymer concentration and low solution pH favored the polymer binding to HAP. The erosion-preventing efficacy of the PMMA-b-PAA block copolymer in inhibiting HAP mineral loss was quantitatively evaluated by atomic absorption spectroscopy (AAS). Based on the results, polymer treatment reduced the amount of calcium released by 27% to 30% in comparison with the unprotected samples. Scanning electron microscope (SEM) observations indicated that PMMA-b-PAA polymer treatment protected enamel from acid erosion. This new amphiphilic block copolymer has significant potential to be integrated into dentifrices or mouthrinses as an alternative non-fluoride ingredient to reduce tooth erosion. PMID:25248611

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

Proposed uses of laser light scattering instruments for polymerization studies

NASA Technical Reports Server (NTRS)

Mathias, Lon J.; Hoyle, Charles E.; Mclaughlin, Kevin; Mcmanus, Samuel P.; Caruthers, James M.; Runge, Michael L.

1989-01-01

Microgravity offers a unique environment for studying polymer diffusion and polymer polymerization reactions. The absence of convection currents, which are the major mode of mixing at the molecular level on Earth, are eliminated or reduced in the microgravity environment. More importantly, the prediction of unique copolymer composition development in microgravity allows controlled formation of new compositions of matter. The absence of mixing at the molecular level should produce unique short block copolymers available for the first time for comonomer compositions which normally lead to random or long block copolymer under good mixing. The investigation of fundamental polymer diffusion and polymer polymerization processes in microgravity is proposed. This effort will involve fundamental studies of monomer and polymer diffusion; their effects on initiation, propagation, and especially termination kinetics rate constant; and the accurate evaluation of copolymerization reactivity ratios in microgravity. The experimental design is presented for these studies along with an evaluation technique for in situ monitoring of polymer diffusion and polymerization kinetics.

Biodegradable polydepsipeptides.

PubMed

Feng, Yakai; Guo, Jintang

2009-02-01

This paper reviews the synthesis, characterization, biodegradation and usage of bioresorbable polymers based on polydepsipeptides. The ring-opening polymerization of morpholine-2,5-dione derivatives using organic Sn and enzyme lipase is discussed. The dependence of the macroscopic properties of the block copolymers on their structure is also presented. Bioresorbable polymers based on polydepsipeptides could be used as biomaterials in drug controlled release, tissue engineering scaffolding and shape-memory materials.

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

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

PubMed

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

2017-08-01

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

Structure-directing star-shaped block copolymers: supramolecular vesicles for the delivery of anticancer drugs.

PubMed

Yang, Chuan; Liu, Shao Qiong; Venkataraman, Shrinivas; Gao, Shu Jun; Ke, Xiyu; Chia, Xin Tian; Hedrick, James L; Yang, Yi Yan

2015-06-28

Amphiphilic polycarbonate/PEG copolymer with a star-like architecture was designed to facilitate a unique supramolecular transformation of micelles to vesicles in aqueous solution for the efficient delivery of anticancer drugs. The star-shaped amphipilic block copolymer was synthesized by initiating the ring-opening polymerization of trimethylene carbonate (TMC) from methyl cholate through a combination of metal-free organo-catalytic living ring-opening polymerization and post-polymerization chain-end derivatization strategies. Subsequently, the self-assembly of the star-like polymer in aqueous solution into nanosized vesicles for anti-cancer drug delivery was studied. DOX was physically encapsulated into vesicles by dialysis and drug loading level was significant (22.5% in weight) for DOX. Importantly, DOX-loaded nanoparticles self-assembled from the star-like copolymer exhibited greater kinetic stability and higher DOX loading capacity than micelles prepared from cholesterol-initiated diblock analogue. The advantageous disparity is believed to be due to the transformation of micelles (diblock copolymer) to vesicles (star-like block copolymer) that possess greater core space for drug loading as well as the ability of such supramolecular structures to encapsulate DOX. DOX-loaded vesicles effectively inhibited the proliferation of 4T1, MDA-MB-231 and BT-474 cells, with IC50 values of 10, 1.5 and 1.0mg/L, respectively. DOX-loaded vesicles injected into 4T1 tumor-bearing mice exhibited enhanced accumulation in tumor tissue due to the enhanced permeation and retention (EPR) effect. Importantly, DOX-loaded vesicles demonstrated greater tumor growth inhibition than free DOX without causing significant body weight loss or cardiotoxicity. The unique ability of the star-like copolymer emanating from the methyl cholate core provided the requisite modification in the block copolymer interfacial curvature to generate vesicles of high loading capacity for DOX with significant kinetic stability that have potential for use as an anti-cancer drug delivery carrier for cancer therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

Nanoporous polymeric nanofibers based on selectively etched PS-b-PDMS block copolymers.

PubMed

Demirel, Gokcen B; Buyukserin, Fatih; Morris, Michael A; Demirel, Gokhan

2012-01-01

One-dimensional nanoporous polymeric nanofibers have been fabricated within an anodic aluminum oxide (AAO) membrane by a facile approach based on selective etching of poly(dimethylsiloxane) (PDMS) domains in polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS) block copolymers that had been formed within the AAO template. It was observed that prior to etching, the well-ordered PS-b-PDMS nanofibers are solid and do not have any porosity. The postetched PS nanofibers, on the other hand, had a highly porous structure having about 20-50 nm pore size. The nanoporous polymeric fibers were also employed as a drug carrier for the native, continuous, and pulsatile drug release using Rhodamine B (RB) as a model drug. These studies showed that enhanced drug release and tunable drug dosage can be achieved by using ultrasound irradiation. © 2011 American Chemical Society

WATER-BORNE BLOCK COPOLYMER SYNTHESIS AND A SIMPLE AND EFFECTIVE ONE-POT SYNTHESIS OF ACRYLATE-METHACRYLATE BLOCK COPOLYMERS BY ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Synthesis of Photocrosslinkable and Amine Containing Multifunctional Nanoparticles via Polymerization-Induced Self-Assembly.

PubMed

Huang, Jianbing; Li, Decai; Liang, Hui; Lu, Jiang

2017-08-01

Photo-crosslinkable and amine-containing block copolymer nanoparticles are synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly of a multifunctional core-forming monomer, 2-((3-(4-(diethylamino)phenyl)acryloyl)oxy)ethyl methacrylate (DEMA), using poly(2-hydroxypropyl methacrylate) macromolecular chain transfer agent as a steric stabilizer in methanol at 65 °C. By tuning the chain length of PDEMA, a range of nanoparticle morphologies (sphere, worm, and vesicle) can be obtained. Since cinnamate groups can easily undergo a [2 + 2] cycloaddition of the carbon-carbon double bonds upon UV irradiation, the as-prepared block copolymer nanoparticles are readily stabilized by photo-crosslinking to produce anisotropic nanoparticles. The crosslinked block copolymer nanoparticles can be used as templates for in situ formation polymer/gold hybrid nanoparticles. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A One-Step Route to CO2 -Based Block Copolymers by Simultaneous ROCOP of CO2 /Epoxides and RAFT Polymerization of Vinyl Monomers.

PubMed

Wang, Yong; Zhao, Yajun; Ye, Yunsheng; Peng, Haiyan; Zhou, Xingping; Xie, Xiaolin; Wang, Xianhong; Wang, Fosong

2018-03-26

The one-step synthesis of well-defined CO 2 -based diblock copolymers was achieved by simultaneous ring-opening copolymerization (ROCOP) of CO 2 /epoxides and RAFT polymerization of vinyl monomers using a trithiocarbonate compound bearing a carboxylic group (TTC-COOH) as the bifunctional chain transfer agent (CTA). The double chain-transfer effect allows for independent and precise control over the molecular weight of the two blocks and ensures narrow polydispersities of the resultant block copolymers (1.09-1.14). Notably, an unusual axial group exchange reaction between the aluminum porphyrin catalyst and TTC-COOH impedes the formation of homopolycarbonates. By taking advantage of the RAFT technique, it is able to meet the stringent demand for functionality control to well expand the application scopes of CO 2 -based polycarbonates. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

Campbell, Ian Patrick

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

Rheology of Hyperbranched Poly(triglyceride)-Based Thermoplastic Elastomers via RAFT polymerization

NASA Astrophysics Data System (ADS)

Yan, Mengguo; Cochran, Eric

2014-03-01

In this contribution we discuss how melt- and solid-state properties are influenced by the degree of branching and molecular weight in a family of hyperbranched thermoplastics derived from soybean oil. Acrylated epoxidized triglycerides from soybean oils have been polymerized to hyperbranched thermoplastic elastomers using reversible addition-fragmentation chain transfer (RAFT) polymerization. With the proper choice of chain transfer agent, both homopolymer and block copolymer can be synthesized. By changing the number of acrylic groups per triglycerides, the chain architectures can range from nearly linear to highly branched. We show how the fundamental viscoelastic properties (e.g. entanglement molecular weight, plateau modulus, etc.) are influenced by chain architecture and molecular weight.

Facile fabrication of core cross-linked micelles by RAFT polymerization and enzyme-mediated reaction.

PubMed

Wu, Yukun; Lai, Quanyong; Lai, Shuqi; Wu, Jing; Wang, Wei; Yuan, Zhi

2014-06-01

Polymeric micelles formed in aqueous solution by assembly of amphiphilic block copolymers have been extensively investigated due to their great potential as drug carriers. However, the stability of polymeric assembly is still one of the major challenges in delivering drugs to tissues and cells. Here, we report a facile route to fabricate core cross-linked (CCL) micelles using an enzymatic polymerization as the cross-linking method. We present synthesis of poly(ethylene glycol)-block-poly(N-isopropyl acrylamide-co-N-(4-hydroxyphenethyl) acrylamide) diblock copolymer PEG-b-P(NIPAAm-co-NHPAAm) via reversible addition-fragmentation chain transfer (RAFT) polymerization. The diblock copolymer was then self-assembled into non-cross-linked (NCL) micelles upon heating above the lower critical solution temperature (LCST), and subsequently cross-linked using horseradish peroxidase (HRP) and hydrogen peroxide (H2O2) as enzyme and oxidant. The characterization of the diblock copolymer and micelles were studied by NMR, DLS, UV-vis, and fluorescence spectroscopy. The fluorescence study reveals that the cross-linking process endows the micelles with much lower critical micelle concentration (CMC). In addition, the drug release study shows that the CCL micelles have lower release amount of doxorubicin (DOX) than the NCL micelles due to the enhanced stability of the CCL micelles by core cross-linking process. Copyright © 2014 Elsevier B.V. All rights reserved.

Dual-Functional Polyethylene Glycol-b-polyhexanide Surface Coating with in Vitro and in Vivo Antimicrobial and Antifouling Activities.

PubMed

Zhi, Zelun; Su, Yajuan; Xi, Yuewei; Tian, Liang; Xu, Miao; Wang, Qianqian; Padidan, Sara; Li, Peng; Huang, Wei

2017-03-29

In recent years, microbial colonization on the surface of biomedical implants/devices has become a severe threat to human health. Herein, surface-immobilized guanidine derivative block copolymers create an antimicrobial and antifouling dual-functional coating. We report the preparation of an antimicrobial and antifouling block copolymer by the conjugation of polyhexanide (PHMB) with either allyl glycidyl ether or allyloxy polyethylene glycol (APEG; MW 1200 and 2400). The allyl glycidyl ether modified PHMB (A-PHMB) and allyloxy polyethylene glycol 1200/2400 modified PHMB (APEG 1200/2400 -PHMB) copolymers were grafted onto a silicone rubber surface as a bottlebrush-like coating, respectively, using a plasma-UV-assisted surface-initiated polymerization. Both A-PHMB and APEG 1200/2400 -PHMB coatings exhibited excellent broad-spectrum antimicrobial properties against Gram-negative/positive bacteria and fungi. The APEG 2400 -PHMB coating displayed an improved antibiofilm as well as antifouling properties and a long reusable cycle, compared with two other coatings, due to its abundant PEG blocks among those copolymers. Also, the APEG 2400 -PHMB-coated silicone coupons were biocompatible toward mammalian cells, as revealed by in vitro hemocompatibile and cytotoxic assays. An in vivo study showed a significant decline of Escherichia coli colonies with a 5-log reduction, indicating the APEG 2400 -PHMB coating surface worked effectively in the rodent subcutaneous infection model. This PHMB-based block copolymer coating is believed to be an effective strategy to prevent biomaterial-associated infections.

Synthesis and characterization of poly(L-alanine)-block-poly(ethylene glycol) monomethyl ether as amphiphilic biodegradable co-polymers.

PubMed

Zhang, Guolin; Ma, Jianbiao; Li, Yanhong; Wang, Yinong

2003-01-01

Di-block co-polymers of poly(L-alanine) with poly(ethylene glycol) monomethyl ether (MPEG) were synthesized as amphiphilic biodegradable co-polymers. The ring-opening polymerization of N-carboxy-L-alanine anhydride (NCA) in dichloromethane was initiated by amino-terminated poly(ethylene glycol) monomethyl ether (MPEG-NH2, M(n) = 2000) to afford poly(L-alanine)-block-MPEG. The weight ratio of two blocks in the co-polymers could be altered by adjusting the feeding ratio of NCA to MPEG-NH2. Their chemical structures were characterized on the basis of infrared spectrometry and nuclear magnetic resonance. According to circular dichroism measurement, the poly(L-alanine) chain on the co-polymers in an aqueous medium had a alpha-helix conformation. Two melting points from MPEG block and poly(L-alanine), respectively, could be observed in differential scanning calorimetry curves of the co-polymers, suggesting that a micro-domain phase separation appeared in their bulky states. The co-polymers could take up some water and the capacity was dependent on the ratio of poly(L-alanine) block to MPEG. Such co-polymers might be useful in drug-delivery systems and other biomedical applications.

Preparation and properties of immobilized pectinase onto the amphiphilic PS-b-PAA diblock copolymers.

PubMed

Lei, Zhongli; Bi, Shuxian

2007-01-30

Well-defined amphiphilic block copolymers poly(styrene-b-acrylic acid) (PS-b-PAA) with controlled block length were synthesized using atom transfer radical polymerization (ATRP). Pectinase enzyme was immobilized on the well-defined amphiphilic block copolymers PS-b-PAA. The carboxyl groups on the amphiphilic PS-b-PAA diblock copolymers present a very simple, mild, and time-saving process for enzyme immobilization. Various characteristics of immobilized pectinase such as the pH and temperature stability, thermal stability, and storage stability were valuated. Among them the pH optimum and temperature optimum of free and immobilized pectinase were found to be pH 6.0 and 65 degrees C.

Evaluation of Isoprene Chain Extension from PEO Macromolecular Chain Transfer Agents for the Preparation of Dual, Invertible Block Copolymer Nanoassemblies.

PubMed

Bartels, Jeremy W; Cauët, Solène I; Billings, Peter L; Lin, Lily Yun; Zhu, Jiahua; Fidge, Christopher; Pochan, Darrin J; Wooley, Karen L

2010-09-14

Two RAFT-capable PEO macro-CTAs, 2 and 5 kDa, were prepared and used for the polymerization of isoprene which yielded well-defined block copolymers of varied lengths and compositions. GPC analysis of the PEO macro-CTAs and block copolymers showed remaining unreacted PEO macro-CTA. Mathematical deconvolution of the GPC chromatograms allowed for the estimation of the blocking efficiency, about 50% for the 5 kDa PEO macro-CTA and 64% for the 2 kDa CTA. Self assembly of the block copolymers in both water and decane was investigated and the resulting regular and inverse assemblies, respectively, were analyzed with DLS, AFM, and TEM to ascertain their dimensions and properties. Assembly of PEO-b-PIp block copolymers in aqueous solution resulted in well-defined micelles of varying sizes while the assembly in hydrophobic, organic solvent resulted in the formation of different morphologies including large aggregates and well-defined cylindrical and spherical structures.

Synthesis of Well-defined Amphiphilic Block Copolymers by Organotellurium-Mediated Living Radical Polymerization (TERP).

PubMed

Kumar, Santosh; Changez, Mohammad; Murthy, C N; Yamago, Shigeru; Lee, Jae-Suk

2011-10-04

Low-molecular weight amphiphilic diblock copolymers, polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), and (P2VP-b-PS) with different block ratios were synthesized for the first time via organotellurium-mediated living radical polymerization (TERP). For both the homo- and block copolymerizations, good agreement between the theoretical, and experimental molecular weights was found with nearly 100% yield in every case. The molecular weight distribution for all the samples ranged between 1.10 and 1.24, which is well below the theoretical lower limit of 1.50 for a conventional free radical polymerization. Furthermore, a very simple approach to producing highly dense arrays of titania nanoparticles (TiO2 ) is presented using a site-selective reaction of titanium tetraisopropoxide within the P2VP domains of micellar film of P2VP-b-PS in toluene through the sol-gel method. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polybenzimidazole block copolymers for fuel cell: synthesis and studies of block length effects on nanophase separation, mechanical properties, and proton conductivity of PEM.

PubMed

Maity, Sudhangshu; Jana, Tushar

2014-05-14

A series of meta-polybenzimidazole-block-para-polybenzimidazole (m-PBI-b-p-PBI), segmented block copolymers of PBI, were synthesized with various structural motifs and block lengths by condensing the diamine terminated meta-PBI (m-PBI-Am) and acid terminated para-PBI (p-PBI-Ac) oligomers. NMR studies and existence of two distinct glass transition temperatures (Tg), obtained from dynamical mechanical analysis (DMA) results, unequivocally confirmed the formation of block copolymer structure through the current polymerization methodology. Appropriate and careful selection of oligomers chain length enabled us to tailor the block length of block copolymers and also to make varieties of structural motifs. Increasingly distinct Tg peaks with higher block length of segmented block structure attributed the decrease in phase mixing between the meta-PBI and para-PBI blocks, which in turn resulted into nanophase segregated domains. The proton conductivities of proton exchange membrane (PEM) developed from phosphoric acid (PA) doped block copolymer membranes were found to be increasing substantially with increasing block length of copolymers even though PA loading of these membranes did not alter appreciably with varying block length. For example when molecular weight (Mn) of blocks were increased from 1000 to 5500 then the proton conductivities at 160 °C of resulting copolymers increased from 0.05 to 0.11 S/cm. Higher block length induced nanophase separation between the blocks by creating less morphological barrier within the block which facilitated the movement of the proton in the block and hence resulting higher proton conductivity of the PEM. The structural varieties also influenced the phase separation and proton conductivity. In comparison to meta-para random copolymers reported earlier, the current meta-para segmented block copolymers were found to be more suitable for PBI-based PEM.

Living olefin polymerization processes

DOEpatents

Schrock, Richard R.; Baumann, Robert

1999-01-01

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

Living olefin polymerization processes

DOEpatents

Schrock, R.R.; Baumann, R.

1999-03-30

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

Living olefin polymerization processes

DOEpatents

Schrock, Richard R.; Baumann, Robert

2003-08-26

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

Living olefin polymerization processes

DOEpatents

Schrock, Richard R.; Bauman, Robert

2006-11-14

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

Thermally Stable Gold Nanoparticles with a Crosslinked Diblock Copolymer Shell

NASA Astrophysics Data System (ADS)

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

2010-03-01

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

Cluster-mediated assembly enables step-growth copolymerization from binary nanoparticle mixtures with rationally designed architectures† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c8sc00220g

PubMed Central

Zhang, Xianfeng; Lv, Longfei; Wu, Guanhong; Yang, Dong

2018-01-01

Directed co-assembly of binary nanoparticles (NPs) into one-dimensional copolymer-like chains is fascinating but challenging in the realm of material science. While many strategies have been developed to induce the polymerization of NPs, it remains a grand challenge to produce colloidal copolymers with widely tailored compositions and precisely controlled architectures. Herein we report a robust colloidal polymerization strategy, which enables the growth of sophisticated NP chains with elaborately designed structures. By quantifying NP assembly statistics and kinetics, we establish that the linear assembly of colloidal NPs, with the assistance of PbSO4 clusters, follows a step-growth polymerization mechanism, and on the basis of this, we design and fabricate NP chains structurally analogous to random, block, and alternating copolymers, respectively. Our studies offer mechanistic insights into cluster-mediated colloidal polymerization, paving the way toward the rational synthesis of colloidal copolymers with quantitatively predicted architectures and functionalities. PMID:29862003

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

Morphological and physical characterization of poly(styrene-isobutylene-styrene) block copolymers and ionomers thereof

NASA Astrophysics Data System (ADS)

Baugh, Daniel Webster, III

Poly(styrene-isobutylene-styrene) block copolymers made by living cationic polymerization using a difunctional initiator and the sequential monomer addition technique were analyzed using curve-resolution software in conjunction with high-resolution GPC. Fractional precipitation and selective solvent extraction were applied to a representative sample in order to confirm the identity of contaminating species. The latter were found to be low molecular weight polystyrene homopolymer, diblock copolymer, and higher molecular weight segmented block copolymers formed by intermolecular electrophilic aromatic substitution linking reactions occurring late in the polymerization of the styrene outer blocks. Solvent-cast films of poly(styrene-isobutylene-styrene) (PS-PIB-PS) block copolymers and block ionomers were analyzed using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Four block copolymer samples with center block molecular weights of 52,000 g/mol and PS volume fractions (o sbPS) ranging from 0.17 to 0.31 were studied. All samples exhibited hexagonally packed cylinders of PS within the PIB matrix. Cylinder spacing was in the range 32 to 36 nm for most samples, while cylinder diameters varied from 14 to 21 nm. Porod analysis of the scattering data indicated the presence of isolated phase mixing and sharp phase boundaries. PS-PIB-PS block copolymers and ionomers therefrom were analyzed using dynamic mechanical analysis (DMA) and tensile testing. The study encompassed five block copolymer samples with similar PIB center blocks with molecular weights of approx52,000 g/mol and PS weight fractions ranging from 0.127 to 0.337. Ionomers were prepared from two of these materials by lightly sulfonating the PS outer blocks. Sulfonation levels varied from 1.7 to 4.7 mol % and the sodium and potassium neutralized forms were compared to the parent block copolymers. Dynamic mechanical analysis (DMA) of the block copolymer films indicated the existence of a third phase attributed to PIB chains near the PS domain interface which experience reduced mobility due to their firm attachment to the hard PS domain. The relative amount of this phase decreased in samples with larger PS blocks, while the temperature of the associated transition increased. Tensile testing showed increased tensile strength but decreased elongation at break with larger PS blocks. DMA of the ionomers indicated improved dynamic modulus at temperatures above 100spcirc$C. Tensile testing of the ionomers indicated slight improvements in tensile strength with little loss in elongation at break. PS-PIB-PS block copolymer ionomer (BCP01, center block molecular weight = 53,000 g/mole; 25.5 wt % polystyrene, 4.7% sulfonation of phenyl units, 100% neutralized with KOH) was compounded with various organic and inorganic acid salts of 2-ethylhexyl-p-dimethyl aminobenzoate (ODAB) to explore the efficacy of these compounds as ionic plasticizers. (Abstract shortened by UMI.)

Polymeric micelles as a new drug carrier system and their required considerations for clinical trials.

PubMed

Yokoyama, Masayuki

2010-02-01

A polymeric micelle is a macromolecular assembly composed of an inner core and an outer shell, and most typically is formed from block copolymers. In the last two decades, polymeric micelles have been actively studied as a new type of drug carrier system, in particular for drug targeting of anticancer drugs to solid tumors. In this review, polymeric micelle drug carrier systems are discussed with a focus on toxicities of the polymeric micelle carrier systems and on pharmacological activities of the block copolymers. In the first section, the importance of the above-mentioned evaluation of these properties is explained, as this importance does not seem to be well recognized compared with the importance of targeting and enhanced pharmacological activity of drugs, particularly in the basic studies. Then, designs, types and classifications of the polymeric micelle system are briefly summarized and explained, followed by a detailed discussion regarding several examples of polymeric micelle carrier systems. Readers will gain a strategy of drug delivery with polymeric carriers as well as recent progress of the polymeric micelle carrier systems in their basic studies and clinical trials. The purpose of this review is to achieve tight connections between the basic studies and clinical trials.

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.

Recyclable magnetic nanocluster crosslinked with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) copolymer for adsorption with antibody.

PubMed

Prai-In, Yingrak; Boonthip, Chatchai; Rutnakornpituk, Boonjira; Wichai, Uthai; Montembault, Véronique; Pascual, Sagrario; Fontaine, Laurent; Rutnakornpituk, Metha

2016-10-01

Surface modification of magnetic nanoparticle (MNP) with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) (PEO-b-PVDM) diblock copolymers and its application as recyclable magnetic nano-support for adsorption with antibody were reported herein. PEO-b-PVDM copolymers were first synthesized via a reversible addition-fragmentation chain-transfer (RAFT) polymerization using poly(ethylene oxide) chain-transfer agent as a macromolecular chain transfer agent to mediate the RAFT polymerization of VDM. They were then grafted on amino-functionalized MNP by coupling with some azlactone rings of the PVDM block to form magnetic nanoclusters with tunable cluster size. The nanocluster size could be tuned by adjusting the chain length of the PVDM block. The nanoclusters were successfully used as efficient and recyclable nano-supports for adsorption with anti-rabbit IgG antibody. They retained higher than 95% adsorption of the antibody during eight adsorption-separation-desorption cycles, indicating the potential feasibility in using this novel hybrid nanocluster as recyclable support in cell separation applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Fabrication of supramolecular star-shaped amphiphilic copolymers for ROS-triggered drug release.

PubMed

Zuo, Cai; Peng, Jinlei; Cong, Yong; Dai, Xianyin; Zhang, Xiaolong; Zhao, Sijie; Zhang, Xianshuo; Ma, Liwei; Wang, Baoyan; Wei, Hua

2018-03-15

Star-shaped copolymers with branched structures can form unimolecular micelles with better stability than the micelles self-assembled from conventional linear copolymers. However, the synthesis of star-shaped copolymers with precisely controlled degree of branching (DB) suffers from complicated sequential polymerizations and multi-step purification procedures, as well as repeated optimizations of polymer compositions. The use of a supramolecular host-guest pair as the block junction would significantly simplify the preparation. Moreover, the star-shaped copolymer-based unimolecular micelle provides an elegant solution to the tradeoff between extracellular stability and intracellular high therapeutic efficacy if the association/dissociation of the supramolecular host-guest joint can be triggered by the biologically relevant stimuli. For this purpose, in this study, a panel of supramolecular star-shaped amphiphilic block copolymers with 9, 12, and 18 arms were designed and fabricated by host-guest complexations between the ring-opening polymerization (ROP)-synthesized star-shaped poly(ε-caprolactone) (PCL) with 3, 4, and 6 arms end-capped with ferrocene (Fc) (PCL-Fc) and the atom transfer radical polymerization (ATRP)-produced 3-arm poly(oligo ethylene glycol) methacrylates (POEGMA) with different degrees of polymerization (DPs) of 24, 30, 47 initiated by β-cyclodextrin (β-CD) (3Br-β-CD-POEGMA). The effect of DB and polymer composition on the self-assembled properties of the five star-shaped copolymers was investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), and fluorescence spectrometery. Interestingly, the micelles self-assembled from 12-arm star-shaped copolymers exhibited greater stability than the 9- and 18-arm formulations. The potential of the resulting supramolecular star-shaped amphiphilic copolymers as drug carriers was evaluated by an in vitro drug release study, which confirmed the ROS-triggered accelerated drug release from the doxorubicin (DOX)-loaded supramolecular star-shaped micelles due to the oxidation-induced dissociation of β-CD/Fc pair and the consequent loss of the colloidal stability of the star-shaped micelles. Studies of the delivery efficacy by an in vitro cytotoxicity study further indicated that higher DBs and longer hydrophilic arm compromised the therapeutic efficacy of the DOX-loaded supramolecular star-shaped micelles, resulting in significantly reduced cytotoxicity, as measured by increased IC 50 value. Overall, our results revealed that the screening of hydrophilic block by DB and MW for an optimized star-shaped copolymer should balance the stability versus therapeutic efficacy tradeoff for a comprehensive consideration. Therefore, the 12-arm star-shaped copolymer with POEGMA 30 is the best formulation tested. Copyright © 2017 Elsevier Inc. All rights reserved.

Doxorubicin-loaded micelles of reverse poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) block copolymers as efficient "active" chemotherapeutic agents.

PubMed

Cambón, A; Rey-Rico, A; Mistry, D; Brea, J; Loza, M I; Attwood, D; Barbosa, S; Alvarez-Lorenzo, C; Concheiro, A; Taboada, P; Mosquera, V

2013-03-10

Five reverse poly(butylene oxide)-poly(ethylene oxide)-poly(butylene oxide) block copolymers, BOnEOmBOn, with BO ranging from 8 to 21 units and EO from 90 to 411 were synthesized and evaluated as efficient chemotherapeutic drug delivery nanocarriers and inhibitors of the P-glycoprotein (P-gp) efflux pump in a multidrug resistant (MDR) cell line. The copolymers were obtained by reverse polymerization of poly(butylene oxide), which avoids transfer reaction and widening of the EO block distribution, commonly found in commercial poly(ethylene oxide)-poly(propylene oxide) block copolymers (poloxamers). BOnEOmBOn copolymers formed spherical micelles of 10-40 nm diameter at lower concentrations (one order of magnitude) than those of equivalent poloxamers. The influence of copolymer block lengths and BO/EO ratios on the solubilization capacity and protective environment for doxorubicin (DOXO) was investigated. Micelles showed drug loading capacity ranging from ca. 0.04% to 1.5%, more than 150 times the aqueous solubility of DOXO, and protected the cargo from hydrolysis for more than a month due to their greater colloidal stability in solution. Drug release profiles at various pHs, and the cytocompatibility and cytotoxicity of the DOXO-loaded micelles were assessed in vitro. DOXO loaded in the polymeric micelles accumulated more slowly inside the cells than free DOXO due to its sustained release. All copolymers were found to be cytocompatible, with viability extents larger than 95%. In addition, the cytotoxicity of DOXO-loaded micelles was higher than that observed for free drug solutions in a MDR ovarian NCI-ADR-RES cell line which overexpressed P-gp. The inhibition of the P-gp efflux pump by some BOnEOmBOn copolymers, similar to that measured for the common P-gp inhibitor verapamil, favored the retention of DOXO inside the cell increasing its cytotoxic activity. Therefore, poly(butylene oxide)-poly(ethylene oxide) block copolymers offer interesting features as cell response modifiers to complement their role as efficient nanocarriers for cancer chemotherapy. Copyright © 2013 Elsevier B.V. All rights reserved.

Highly conductive side chain block copolymer anion exchange membranes.

PubMed

Wang, Lizhu; Hickner, Michael A

2016-06-28

Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days.

Highly efficient one-pot/one-step synthesis of multiblock copolymers from three-component polymerization of carbon dioxide, epoxide and lactone.

PubMed

Li, Yang; Hong, Jiali; Wei, Renjian; Zhang, Yingying; Tong, Zaizai; Zhang, Xinghong; Du, Binyang; Xu, Junting; Fan, Zhiqiang

2015-02-01

It is a long-standing challenge to combine mixed monomers into multiblock copolymer (MBC) in a one-pot/one-step polymerization manner. We report the first example of MBC with biodegradable polycarbonate and polyester blocks that were synthesized from highly efficient one-pot/one-step polymerization of cyclohexene oxide (CHO), CO 2 and ε-caprolactone (ε-CL) in the presence of zinc-cobalt double metal cyanide complex and stannous octoate. In this protocol, two cross-chain exchange reactions (CCER) occurred at dual catalysts respectively and connected two independent chain propagation procedures ( i.e. , polycarbonate formation and polyester formation) simultaneously in a block-by-block manner, affording MBC without tapering structure. The multiblock structure of MBC was determined by the rate ratio of CCER to the two chain propagations and could be simply tuned by various kinetic factors. This protocol is also of significance due to partial utilization of renewable CO 2 and improved mechanical properties of the resultant MBC.

Synthesis and Self-Assembly of Block Copolymers Containing Temperature Sensitive and Degradable Chain Segments.

PubMed

Gong, Hong-Liang; Lei, Lei; Shi, Shu-Xian; Xia, Yu-Zheng; Chen, Xiao-Nong

2018-05-01

In this work, polylactide-b-poly(N-isopropylacrylamide) were synthesized by the combination of controlled ring-opening polymerization and reversible addition fragmentation chain transfer polymerization. These block copolymers with molecular weight range from 7,900 to 12,000 g/mol and narrow polydispersity (≤1.19) can self-assemble into micelles (polylactide core, poly(N-isopropylacrylamide) shell) in water at certain temperature range, which have been evidenced by laser particle size analyzer proton nuclear magnetic resonance and transmission electron microscopy. Such micelles exhibit obvious thermo-responsive properties: (1) Poly(N-isopropylacrylamide) blocks collapse on the polylactide core as system temperature increase, leading to reduce of micelle size. (2) Micelles with short poly(N-isopropylacrylamide) blocks tend to aggregate together when temperature increased, which is resulted from the reduction of the system hydrophilicity and the decreased repulsive force between micelles.

Degradable ketal-based block copolymer nanoparticles for anticancer drug delivery: a systematic evaluation.

PubMed

Louage, Benoit; Zhang, Qilu; Vanparijs, Nane; Voorhaar, Lenny; Vande Casteele, Sofie; Shi, Yang; Hennink, Wim E; Van Bocxlaer, Jan; Hoogenboom, Richard; De Geest, Bruno G

2015-01-12

Low solubility of potent (anticancer) drugs is a major driving force for the development of noncytotoxic, stimuli-responsive nanocarriers, including systems based on amphiphilic block copolymers. In this regard, we investigated the potential of block copolymers based on 2-hydroxyethyl acrylate (HEA) and the acid-sensitive ketal-containing monomer (2,2-dimethyl-1,3-dioxolane-4-yl)methyl acrylate (DMDMA) to form responsive drug nanocarriers. Block copolymers were successfully synthesized by sequential reversible addition-fragmentation chain transfer (RAFT) polymerization, in which we combined a hydrophilic poly(HEA)x block with a (responsive) hydrophobic poly(HEAm-co-DMDMAn)y copolymer block. The DMDMA content of the hydrophobic block was systematically varied to investigate the influence of polymer design on physicochemical properties and in vitro biological performance. We found that a DMDMA content higher than 11 mol % is required for self-assembly behavior in aqueous medium. All particles showed colloidal stability in PBS at 37 °C for at least 4 days, with sizes ranging from 23 to 338 nm, proportional to the block copolymer DMDMA content. Under acidic conditions, the nanoparticles decomposed into soluble unimers, of which the decomposition rate was inversely proportional to the block copolymer DMDMA content. Flow cytometry and confocal microscopy showed dose-dependent, active in vitro cellular uptake of the particles loaded with hydrophobic octadecyl rhodamine B chloride (R18). The block copolymers showed no intrinsic in vitro cytotoxicity, while loaded with paclitaxel (PTX), a significant decrease in cell viability was observed comparable or better than the two commercial PTX nanoformulations Abraxane and Genexol-PM at equal PTX dose. This systematic approach evaluated and showed the potential of these block copolymers as nanocarriers for hydrophobic drugs.

DISPERSION POLYMERIZATION OF 2-HYDROXYETHYL METHACRYLATE IN SUPERCRITICAL CARBON DIOXIDE. (R826115)

EPA Science Inventory

Herein we report a successful dispersion polymerization of 2-hydroxyethyl methacrylate (HEMA) in a carbon dioxide continuous phase with a block copolymer consisting of polystyrene and poly(1,1-dihydroperfluorooctyl acrylate) as a stabilizer. Poly(2-hydroxyethyl methacrylate) was ...

Influence of Chirality in Ordered Block Copolymer Phases

NASA Astrophysics Data System (ADS)

Prasad, Ishan; Grason, Gregory

2015-03-01

Block copolymers are known to assemble into rich spectrum of ordered phases, with many complex phases driven by asymmetry in copolymer architecture. Despite decades of study, the influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has played a major role in prediction of physical properties of polymeric systems. Only recently, a polar orientational self-consistent field (oSCF) approach was adopted to model chiral BCP having a thermodynamic preference for cholesteric ordering in chiral segments. We implement oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar chiral interactions, and focus our study on the thermodynamic stability of bi-continuous network morphologies, and the transfer of molecular chirality to mesoscale chirality of networks. Unique photonic properties observed in butterfly wings have been attributed to presence of chiral single-gyroid networks, this has made it an attractive target for chiral metamaterial design.

Magnetic hydrogels from alkyne/cobalt carbonyl-functionalized ABA triblock copolymers

DOE PAGES

Jiang, Bingyin; Hom, Wendy L.; Chen, Xianyin; ...

2016-03-09

A series of alkyne-functionalized poly(4-(phenylethynyl)styrene)- block-poly(ethylene oxide)- block-poly(4-(phenylethynyl)styrene) (PPES-b-PEO-b-PPES) ABA triblock copolymers was synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. PES n[Co 2(CO) 6] x-EO 800-PES n[Co 2(CO) 6] x ABA triblock copolymer/cobalt adducts (10–67 wt % PEO) were subsequently prepared by reaction of the alkyne-functionalized PPES block with Co 2(CO) 8 and their phase behavior was studied by TEM. Heating triblock copolymer/cobalt carbonyl adducts at 120 °C led to cross-linking of the PPES/Co domains and the formation of magnetic cobalt nanoparticles within the PPES/Co domains. Magnetic hydrogels could be prepared by swelling the PEO domains of the cross-linkedmore » materials with water. Furthermore, swelling tests, rheological studies and actuation tests demonstrated that the water capacity and modulus of the hydrogels were dependent upon the composition of the block copolymer precursors.« less

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

EPA Science Inventory

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

Synthesis and Characterization of High Molecular Weight Peptide Polymers and Copolymers Containing L-Dopa Residues

DTIC Science & Technology

1988-07-01

decapeptide (GLUE-12) with blocked lysines with DPPA for 24 hours. A parallel reaction was carried out to polymerize E- aminocaproic acid with DPPA for...shear adhesive strength tests. OPPA has also been used to prepare block copolymers between GLUE polypeptides and poly(e-amino caproic acid ). Concurrent...amino acid residues towards intramolecular or intermolecular bond formation. Polypeptides with repeating amino acid sequences have also been produced

Structure and Dynamics Ionic Block co-Polymer Melts: Computational Study

NASA Astrophysics Data System (ADS)

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

Tethering ionomer blocks into co-polymers enables engineering of polymeric systems designed to encompass transport while controlling structure. Here the structure and dynamics of symmetric pentablock copolymers melts are probed by fully atomistic molecular dynamics simulations. The center block consists of randomly sulfonated polystyrene with sulfonation fractions f = 0 to 0.55 tethered to a hydrogenated polyisoprene (PI), end caped with poly(t-butyl styrene). We find that melts with f = 0.15 and 0.30 consist of isolated ionic clusters whereas melts with f = 0.55 exhibit a long-range percolating ionic network. Similar to polystyrene sulfonate, a small number of ionic clusters slow the mobility of the center of mass of the co-polymer, however, formation of the ionic clusters is slower and they are often intertwined with PI segments. Surprisingly, the segmental dynamics of the other blocks are also affected. NSF DMR-1611136; NERSC; Palmetto Cluster Clemson University; Kraton Polymers US, LLC.

Synthesis and Properties of Poly(l-lactide)-b-poly (l-phenylalanine) Hybrid Copolymers

PubMed Central

Planellas, Marc; Puiggalí, Jordi

2014-01-01

Hybrid materials constituted by peptides and synthetic polymers have nowadays a great interest since they can combine the properties and functions of each constitutive block, being also possible to modify the final characteristics by using different topologies. Poly(l-lactide-b-l-phenylalanine) copolymers with various block lengths were synthesized by sequential ring-opening polymerization of l-lactide and the N-carboxyanhydride of l-phenylalanine. The resulting block copolymers were characterized by NMR spectrometry, IR spectroscopy, gel permeation chromatography, MALDI-TOF and UV-vis, revealing the successful incorporation of the polyphenylalanine (PPhe) peptide into the previously formed poly(l-lactide) (PLLA) polymer chain. X-ray diffraction and DSC data also suggested that the copolymers were phase-separated in domains containing either crystalline PLLA or PPhe phases. A peculiar thermal behavior was also found by thermogravimetric analysis when polyphenylalanine blocks were incorporated into polylactide. PMID:25075980

Synthesis and properties of poly(L-lactide)-b-poly (L-phenylalanine) hybrid copolymers.

PubMed

Planellas, Marc; Puiggalí, Jordi

2014-07-29

Hybrid materials constituted by peptides and synthetic polymers have nowadays a great interest since they can combine the properties and functions of each constitutive block, being also possible to modify the final characteristics by using different topologies. Poly(l-lactide-b-l-phenylalanine) copolymers with various block lengths were synthesized by sequential ring-opening polymerization of l-lactide and the N-carboxyanhydride of l-phenylalanine. The resulting block copolymers were characterized by NMR spectrometry, IR spectroscopy, gel permeation chromatography, MALDI-TOF and UV-vis, revealing the successful incorporation of the polyphenylalanine (PPhe) peptide into the previously formed poly(l-lactide) (PLLA) polymer chain. X-ray diffraction and DSC data also suggested that the copolymers were phase-separated in domains containing either crystalline PLLA or PPhe phases. A peculiar thermal behavior was also found by thermogravimetric analysis when polyphenylalanine blocks were incorporated into polylactide.

Morphological studies on block copolymer modified PA 6 blends

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

Poindl, M., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de; Bonten, C., E-mail: marcus.poindl@ikt.uni-stuttgart.de, E-mail: christian.bonten@ikt.uni-stuttgart.de

Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymermore » was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.« less

Microwave-assisted synthesis and micellization behavior of soy-based copoly(2-oxazoline)s.

PubMed

Hoogenboom, Richard; Leenen, Mark A M; Huang, Haiying; Fustin, Charles-André; Gohy, Jean-François; Schubert, Ulrich S

2006-01-01

Polymers based on renewable resources are promising candidates for replacing common organic polymers, and thus, for reducing oil consumption. In this contribution we report the microwave-assisted synthesis of block and statistical copolymers from 2-ethyl-2-oxazoline and 2-"soy alkyl"-2-oxazoline via a cationic ring-opening polymerization mechanism. The synthesized copolymers were characterized by gel permeation chromatography and 1 H-NMR spectroscopy. The micellization of these amphiphilic copolymers was investigated by dynamic light scattering and atomic force microscopy to examine the effect of hydrophobic block length and monomer distribution on the resulting micellar characteristics.

Effect of Monomer Solubility on the Evolution of Copolymer Morphology during Polymerization-Induced Self-Assembly in Aqueous Solution

PubMed Central

2017-01-01

Polymerization-induced self-assembly (PISA) has become a widely used technique for the rational design of diblock copolymer nano-objects in concentrated aqueous solution. Depending on the specific PISA formulation, reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization typically provides straightforward access to either spheres, worms, or vesicles. In contrast, RAFT aqueous emulsion polymerization formulations often lead to just kinetically-trapped spheres. This limitation is currently not understood, and only a few empirical exceptions have been reported in the literature. In the present work, the effect of monomer solubility on copolymer morphology is explored for an aqueous PISA formulation. Using 2-hydroxybutyl methacrylate (aqueous solubility = 20 g dm–3 at 70 °C) instead of benzyl methacrylate (0.40 g dm–3 at 70 °C) for the core-forming block allows access to an unusual “monkey nut” copolymer morphology over a relatively narrow range of target degrees of polymerization when using a poly(methacrylic acid) RAFT agent at pH 5. These new anisotropic nanoparticles have been characterized by transmission electron microscopy, dynamic light scattering, aqueous electrophoresis, shear-induced polarized light imaging (SIPLI), and small-angle X-ray scattering. PMID:28216792

Thermal characterization of poly(ethylene glycol)-poly(D,L-lactide) block copolymer micelles based on pyrene excimer formation.

PubMed

Jule, Eduardo; Yamamoto, Yuji; Thouvenin, Muriel; Nagasaki, Yukio; Kataoka, Kazunori

2004-07-07

Poly(ethylene glycol)--poly(D,L-lactide) (PEG-PDLLA) block copolymers were prepared by anionic ring-opening polymerization, resulting in block sizes effectively controlled by initial monomer/initiator ratios and low molecular weight distributions (<1.12). A pyrene derivative (1-pyrenyl carbonyl cyanide--Py) was conjugated to the end of the hydrophobic block (PDLLA) in a quantitative manner, with coupling efficiencies >95%. The so-obtained PEG-PDLLA-Py copolymers displayed fluorescent properties that were associated with the pyrene monomers, when placed in good solvents for both the hydrophilic and hydrophobic blocks. When placed in selective solvents, these copolymers self-assembled into micelles in the 30-nm range, also with low particle size distributions (<0.09), within which Py could be readily entrapped in the hydrophobic PDLLA core. Py entrapment resulted in the formation of excimers, as evident from fluorescence measurements. Observation of excimer formation/dissociation further conveyed information on the physicochemical properties of the core. Thermal characterization of these systems showed that an increase in the temperature resulted in changes in the properties of excimer fluorescence, an occurrence attributed to a higher mobility of the otherwise glassy PDLLA. This, in turn, greatly affected the inter-molecular distance between pyrene molecules, a crucial factor for excimer formation. The glass transition of the PDLLA block, approximately 38 degrees C, defined the onset for increasing chain mobility and whence excimer dissociation. Excimer fluorescence appeared to be time-dependent. Based on these observations, chain exchange processes were clearly evidenced through the time-dependent dissociation of excimers into unimers, a process that was influenced by changes in temperature.

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.

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

Aquaporin-Based Biomimetic Polymeric Membranes: Approaches and Challenges

PubMed Central

Habel, Joachim; Hansen, Michael; Kynde, Søren; Larsen, Nanna; Midtgaard, Søren Roi; Jensen, Grethe Vestergaard; Bomholt, Julie; Ogbonna, Anayo; Almdal, Kristoffer; Schulz, Alexander; Hélix-Nielsen, Claus

2015-01-01

In recent years, aquaporin biomimetic membranes (ABMs) for water separation have gained considerable interest. Although the first ABMs are commercially available, there are still many challenges associated with further ABM development. Here, we discuss the interplay of the main components of ABMs: aquaporin proteins (AQPs), block copolymers for AQP reconstitution, and polymer-based supporting structures. First, we briefly cover challenges and review recent developments in understanding the interplay between AQP and block copolymers. Second, we review some experimental characterization methods for investigating AQP incorporation including freeze-fracture transmission electron microscopy, fluorescence correlation spectroscopy, stopped-flow light scattering, and small-angle X-ray scattering. Third, we focus on recent efforts in embedding reconstituted AQPs in membrane designs that are based on conventional thin film interfacial polymerization techniques. Finally, we describe some new developments in interfacial polymerization using polyhedral oligomeric silsesquioxane cages for increasing the physical and chemical durability of thin film composite membranes. PMID:26264033

Ring-Opening Metathesis Polymerization in Aqueous Media using a Macroinitiator Approach.

PubMed

Foster, Jeffery; Varlas, Spyridon; Blackman, Lewis; Arkinstall, Lucy; O'Reilly, Rachel Kerry

2018-06-26

Water-soluble and amphiphilic polymers are of great interest to industry and academia, as they can be used in applications such as biomaterials and drug delivery. Whilst ring-opening metathesis polymerization (ROMP) is a fast and functional group tolerant methodology for the synthesis of a wide range of polymers, its full potential for the synthesis of water-soluble polymers has yet to be realized. To address this we report a general strategy for the synthesis of block copolymers in aqueous milieu using a commercially available ROMP catalyst and a macroinitiator approach. This allows for excellent control in the preparation of block copolymers in water. If the second monomer is chosen such that it forms a water-insoluble polymer, polymerization-induced self-assembly (PISA) occurs and a variety of self-assembled nano-object morphologies can be accessed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Elucidation of the Structure Formation of Polymer-Conjugated Proteins in Solution and Block Copolymer Templates

NASA Astrophysics Data System (ADS)

Ferebee, Rachel L.

The broader technical objective of this work is to contribute to the development of enzyme-functionalized nanoporous membranes that can function as autonomous and target selective dynamic separators. The scientific objective of the research performed within this thesis is to elucidate the parameters that control the mixing of proteins in organic host materials and in block copolymers templates in particular. A "biomimetic" membrane system that uses enzymes to selectively neutralize targets and trigger a change in permeability of nanopores lined with a pH-responsive polymer has been fabricated and characterized. Mechanical and functional stability, as well as scalability, have been demonstrated for this system. Additional research has focused on the role of polymeric ligands on the solubility characteristics of the model protein, Bovine Serum Albumin (BSA). For this purpose BSA was conjugated with poly(ethylene glycol) (PEG) ligands of varied degree of polymerization and grafting density. Combined static and dynamic light scattering was used (in conjunction with MALDI-TOF) to determine the second virial coefficient in PBS solutions. At a given mass fraction PEG or average number of grafts, the solubility of BSA-PEG conjugates is found to increase with the degree of polymerization of conjugated PEG. This result informs the synthesis of protein-conjugate systems that are optimized for the fabrication of block copolymer blend materials with maximum protein loading. Blends of BSA-PEG conjugates and block copolymer (BCP) matrices were fabricated to evaluate the dispersion morphology and solubility limits in a model system. Electron microscopy was used to evaluate the changes in lamellar spacing with increased filling fraction of BSA-PEG conjugates.

Block versus Random Amphiphilic Glycopolymer Nanopaticles as Glucose-Responsive Vehicles.

PubMed

Guo, Qianqian; Zhang, Tianqi; An, Jinxia; Wu, Zhongming; Zhao, Yu; Dai, Xiaomei; Zhang, Xinge; Li, Chaoxing

2015-10-12

To explore the effect of polymer structure on their self-assembled aggregates and their unique characteristics, this study was devoted to developing a series of amphiphilic block and random phenylboronic acid-based glycopolymers by RAFT polymerization. The amphiphilic glycopolymers were successfully self-assembled into spherically shaped nanoparticles with narrow size distribution in aqueous solution. For block and random copolymers with similar monomer compositions, block copolymer nanoparticles exhibited a more regular transmittance change with the increasing glucose level, while a more evident variation of size and quicker decreasing tendency in I/I0 behavior in different glucose media were observed for random copolymer nanoparticles. Cell viability of all the polymer nanoparticles investigated by MTT assay was higher than 80%, indicating that both block and random copolymers had good cytocompatibility. Insulin could be encapsulated into both nanoparticles, and insulin release rate for random glycopolymer was slightly quicker than that for the block ones. We speculate that different chain conformations between block and random glycopolymers play an important role in self-assembled nanoaggregates and underlying glucose-sensitive behavior.

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

NASA Astrophysics Data System (ADS)

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

2013-01-01

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

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.

Photoconductivity enhancement and charge transport properties in ruthenium-containing block copolymer/carbon nanotube hybrids.

PubMed

Lo, Kin Cheung; Hau, King In; Chan, Wai Kin

2018-04-05

Functional polymer/carbon nanotube (CNT) hybrid materials can serve as a good model for light harvesting systems based on CNTs. This paper presents the synthesis of block copolymer/CNT hybrids and the characterization of their photocurrent responses by both experimental and computational approaches. A series of functional diblock copolymers was synthesized by reversible addition-fragmentation chain transfer polymerizations for the dispersion and functionalization of CNTs. The block copolymers contain photosensitizing ruthenium complexes and modified pyrene-based anchoring units. The photocurrent responses of the polymer/CNT hybrids were measured by photoconductive atomic force microscopy (PCAFM), from which the experimental data were analyzed by vigorous statistical models. The difference in photocurrent response among different hybrids was correlated to the conformations of the hybrids, which were elucidated by molecular dynamics simulations, and the electronic properties of polymers. The photoresponse of the block copolymer/CNT hybrids can be enhanced by introducing an electron-accepting block between the photosensitizing block and the CNT. We have demonstrated that the application of a rigorous statistical methodology can unravel the charge transport properties of these hybrid materials and provide general guidelines for the design of molecular light harvesting systems.

Prediction of the solubility of cucurbitacin drugs in self-associating poly(ethylene oxide)-b-poly(alpha-benzyl carboxylate epsilon-caprolactone) block copolymer with different tacticities using molecular dynamics simulation.

PubMed

Patel, Sarthak K; Lavasanifar, Afsaneh; Choi, Phillip

2010-01-01

Molecular dynamics (MD) simulation was used to investigate the solubility of two hydrophobic drugs Cucurbitacin B (CuB) and Cucurbitacin I (CuI) in poly(ethylene oxide)-b-poly(alpha-benzyl carboxylate epsilon-caprolactone) (PEO-b-PBCL) block copolymers with different tacticities. In particular, di-block copolymer with three different tacticities viz. PEO-b-iPBCL, PEO-b-sPBCL, and PEO-b-aPBCL were used. The solubility was quantified by calculating the corresponding Flory-Huggins interaction parameters (chi) using random binary mixture models with 10wt% of drug. The tacticity of the di-block copolymer was found to influence significantly the solubility of two drugs in it. In particular, based on MD simulation results, only PEO-b-sPBCL exhibited solubility while the other two did not. Given the fact that the drugs were shown to be soluble in PEO-b-PBCL experimentally, it is predicted that the tacticity of the di-block copolymer synthesized in experiment is syndiotactic. This predication matches well with the dominant ring opening polymerization of cyclic lactones to syndiotactic polymers by stannous octoate as catalyst used to prepare PEO-b-PBCL block copolymers in our previous experiments. The simulation results showed that the solubility of the drugs in PEO-b-sPBCL is attributed to the favorable intra-molecular interaction of the di-block copolymer and favorable intermolecular interaction between the di-block copolymer and the drugs. Radial distribution function analysis provides useful insights into the nature and type of the intermolecular interactions.

Degradable Polymers and Block Copolymers from Electron-deficient Carbonyl Compounds (STIR) (7.3 Polymer Chemistry - Synthesis: Architecture and Composition)

DTIC Science & Technology

2015-04-23

polymerization results Illustrations: Scheme 1. Polymerization of aldehydes and depolymerization of polyacetals. Scheme 2. Optimized methods for...oligomers) to the pure aldehyde monomer requires several distillations and transfer of the monomer at reflux directly to the polymerization vessel. Low...the controlled organocatalytic chain polymerization of ethyl glyoxylate and other reactive aldehydes , which will enable the preparation of

Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies

DOE PAGES

Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe; ...

2016-07-19

Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporatingmore » them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellarto- lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. In conclusion, this study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials.« less

Thermoreversible Morphology and Conductivity of a Conjugated Polymer Network Embedded in Block Copolymer Self-Assemblies

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

Han, Youngkyu; Carrillo, Jan-Michael Y.; Zhang, Zhe

Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporatingmore » them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellarto- lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. In conclusion, this study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials.« less

Effect of PEG-PDMAEMA Block Copolymer Architecture on Polyelectrolyte Complex Formation with Heparin.

PubMed

Välimäki, Salla; Khakalo, Alexey; Ora, Ari; Johansson, Leena-Sisko; Rojas, Orlando J; Kostiainen, Mauri A

2016-09-12

Heparin is a naturally occurring polyelectrolyte consisting of a sulfated polysaccharide backbone. It is widely used as an anticoagulant during major surgical operations. However, the associated bleeding risks require rapid neutralization after the operation. The only clinically approved antidote for heparin is protamine sulfate, which is, however, ineffective against low molecular weight heparin and can cause severe adverse reactions in patients. In this study, the facile synthesis of cationic-neutral diblock copolymers and their effective heparin binding is presented. Poly(ethylene glycol)-poly(2-(dimethylamino)ethyl methacrylate) (PEG-PDMAEMA) block copolymers were synthesized in two steps via atom-transfer radical polymerization (ATRP) using PEG as a macroinitiator. Solution state binding between heparin and a range of PEG-PDMAEMA block copolymers and one homopolymer was studied with dynamic light scattering and methylene blue displacement assay. Also in vitro binding in plasma was studied by utilizing a chromogenic heparin anti-Xa assay. Additionally, quartz crystal microbalance and multiparametric surface plasmon resonance were used to study the surface adsorption kinetics of the polymers on a heparin layer. It was shown that the block copolymers and heparin form electrostatically bound complexes with varying colloidal properties, where the block lengths play a key role in controlling the heparin binding affinity, polyelectrolyte complex size and surface charge. With the optimized polymers (PEG114PDMAEMA52 and PEG114PDMAEMA100), heparin could be neutralized in a dose-dependent manner, and bound efficiently into small neutral complexes, with a hydrodynamic radius less than 100 nm. These complexes had only a limited effect on cell viability. Based on these studies, our approach paves the way for the development of new polymeric heparin binding agents.

Toxicity evaluation of methoxy poly(ethylene oxide)-block-poly(ε-caprolactone) polymeric micelles following multiple oral and intraperitoneal administration to rats.

PubMed

Binkhathlan, Ziyad; Qamar, Wajhul; Ali, Raisuddin; Kfoury, Hala; Alghonaim, Mohammed

2017-09-01

Methoxy poly(ethylene oxide)- block -poly(ɛ-caprolactone) (PEO- b -PCL) copolymers are amphiphilic and biodegradable copolymers designed to deliver a variety of drugs and diagnostic agents. The aim of this study was to synthesize PEO- b -PCL block copolymers and assess the toxic effects of drug-free PEO- b -PCL micelles after multiple-dose administrations via oral or intraperitoneal (ip) administration in rats. Assembly of block copolymers was achieved by co-solvent evaporation method. To investigate the toxicity profile of PEO- b -PCL micelles, sixty animals were divided into two major groups: The first group received PEO- b -PCL micelles (100 mg/kg) by oral gavage daily for seven days, while the other group received the same dose of micelles by ip injections daily for seven days. Twenty-four hours following the last dose, half of the animals from each group were sacrificed and blood and organs (lung, liver, kidneys, heart and spleen) were collected. Remaining animals were observed for further 14 days and was sacrificed at the end of the third week, and blood and organs were collected. None of the polymeric micelles administered caused any significant effects on relative organ weight, animal body weight, leucocytes count, % lymphocytes, liver and kidney toxicity markers and organs histology. Although the dose of copolymers used in this study is much higher than those used for drug delivery, it did not cause any significant toxic effects in rats. Histological examination of all the organs confirmed the nontoxic nature of the micelles.

Nitroxide-mediated radical ring-opening copolymerization: chain-end investigation and block copolymer synthesis.

PubMed

Delplace, Vianney; Harrisson, Simon; Tardy, Antoine; Gigmes, Didier; Guillaneuf, Yohann; Nicolas, Julien

2014-02-01

Well-defined, degradable copolymers are successfully prepared by nitroxide-mediated radical ring opening polymerization (NMrROP) of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or methyl methacrylate (MMA), a small amount of acrylonitrile (AN) and cyclic ketene acetals (CKAs) of different structures. Phosphorous nuclear magnetic resonance allows in-depth chain-end characterization and gives crucial insights into the nature of the copoly-mer terminal sequences and the living chain fractions. By using a small library of P(OEGMA-co-AN-co-CKA) and P(MMA-co-AN-co-CKA) as macroinitiators, chain extensions with styrene are performed to furnish (amphiphilic) block copolymers comprising a degradable segment. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

pH-Dependent, Thermosensitive Polymeric Nanocarriers for Drug Delivery to Solid Tumors

PubMed Central

Chen, Ching-Yi; Kim, Tae Hee; Wu, Wen-Chung; Huang, Chi-Ming; Wei, Hua; Mount, Christopher W.; Tian, Yanqing; Jang, Sei-Hum; Pun, Suzie H.; Jen, Alex K-Y

2013-01-01

Polymeric micelles are promising carriers for anticancer agents due to their small size, ease of assembly, and versatility for functionalization. A current challenge in the use of polymeric micelles is the sensitive balance that must be achieved between stability during prolonged blood circulation and release of active drug at the tumor site. Stimuli-responsive materials provide a mechanism for triggered drug release in the acidic tumor and intracellular microenvironments. In this work, we synthesized a series of dual pH- and temperature-responsive block copolymers containing a poly(ε-caprolactone) (PCL) hydrophobic block with a poly(triethylene glycol) block that were copolymerized with an amino acid-functionalized monomer. The block copolymers formed micellar structures in aqueous solutions. An optimized polymer that was functionalized with 6-aminocaproic acid (ACA) possessed pH-sensitive phase transitions at mildly acidic pH and body temperature. Doxorubicin-loaded micelles formed from these polymers were stable at blood pH (~7.4) and showed increased drug release at acidic pH. In addition, these micelles displayed more potent anti-cancer activity than free doxorubicin when tested in a tumor xenograft model in mice. PMID:23498892

Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

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

Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon

Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which aremore » anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.« less

Simulations of the gyroid phase in diblock copolymers with the Gaussian disphere model

NASA Astrophysics Data System (ADS)

Karatchentsev, A.; Sommer, J.-U.

2010-12-01

Pure melts of asymmetric diblock copolymers are studied by means of the off-lattice Gaussian disphere model with Monte-Carlo kinetics. In this model, a diblock copolymer chain is mapped onto two soft repulsive spheres with fluctuating radii of gyration and distance between centers of mass of the spheres. Microscopic input quantities of the model such as the combined probability distribution for the radii of gyration and the distance between the spheres as well as conditional monomer number densities assigned to each block were derived in the previous work of F. Eurich and P. Maass [J. Chem. Phys. 114, 7655 (2001)] within an underlying Gaussian chain model. The polymerization degree of the whole chain as well as those of the individual blocks are freely tunable parameters thus enabling a precise determination of the regions of stability of various phases. The model neglects entanglement effects which are irrelevant for the formation of ordered structures in diblock copolymers and which would otherwise unnecessarily increase the equilibration time of the system. The gyroid phase was reproduced in between the cylindrical and lamellar phases in systems with box sizes being commensurate with the size of the unit cell of the gyroid morphology. The region of stability of the gyroid phase was studied in detail and found to be consistent with the prediction of the mean-field theory. Packing frustration was observed in the form of increased radii of gyration of both blocks of the chains located close to the gyroid nodes.

Nanostructures and surface hydrophobicity of self-assembled thermosets involving epoxy resin and poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) amphiphilic diblock copolymer.

PubMed

Yi, Fangping; Zheng, Sixun; Liu, Tianxi

2009-02-19

Poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) (PTFEA-b-PEO) amphiphilic diblock copolymer was synthesized via the reversible addition-fragmentation transfer polymerization of 2,2,2-triffluroethyl acrylate with dithiobenzoyl-terminated poly(ethylene oxide) as a chain-transfer agent. The amphiphilic diblock copolymer was incorporated into epoxy resin to prepare the nanostructured epoxy thermosets. The nanostructures were investigated by means of atomic force microscopy, small-angle X-ray scattering, and dynamic mechanical analysis. In terms of the miscibility of the subchains of the block copolymer with epoxy after and before curing reaction, it is judged that the formation of the nanostructures follows the mechanism of self-assembly. The static contact angle measurements indicate that the nanostructured thermosets containing PTFEA-b-PEO diblock copolymer displayed a significant enhancement in surface hydrophobicity as well as a reduction in surface free energy. The improvement in surface properties was ascribed to the enrichment of the fluorine-containing subchain (i.e., PTFEA block) of the amphiphilic diblock copolymer on the surface of the nanostructured thermosets, which was evidenced by surface atomic force microscopy and energy-dispersive X-ray spectroscopy.

Imidazolium-based Block Copolymers as Solid-State Separators for Alkaline Fuel Cells and Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

Nykaza, Jacob Richard

In this study, polymerized ionic liquid (PIL) diblock copolymers were explored as solid-state polymer separators as an anion exchange membrane (AEM) for alkaline fuel cells AFCs and as a solid polymer electrolyte (SPE) for lithium-ion batteries. Polymerized ionic liquid (PIL) block copolymers are a distinct set of block copolymers that combine the properties of both ionic liquids (e.g., high conductivity, high electrochemical stability) and block copolymers (e.g., self-assembly into various nanostructures), which provides the opportunity to design highly conductive robust solid-state electrolytes that can be tuned for various applications including AFCs and lithium-ion batteries via simple anion exchange. A series of bromide conducting PIL diblock copolymers with an undecyl alkyl side chain between the polymer backbone and the imidazolium moiety were first synthesized at various compositions comprising of a PIL component and a non-ionic component. Synthesis was achieved by post-functionalization from its non-ionic precursor PIL diblock copolymer, which was synthesized via the reverse addition fragmentation chain transfer (RAFT) technique. This PIL diblock copolymer with long alkyl side chains resulted in flexible, transparent films with high mechanical strength and high bromide ion conductivity. The conductivity of the PIL diblock copolymer was three times higher than its analogous PIL homopolymer and an order of magnitude higher than a similar PIL diblock copolymer with shorter alkyl side chain length, which was due to the microphase separated morphology, more specifically, water/ion clusters within the PIL microdomains in the hydrated state. Due to the high conductivity and mechanical robustness of this novel PIL block copolymer, its application as both the ionomer and AEM in an AFC was investigated via anion exchange to hydroxide (OH-), where a maximum power density of 29.3 mW cm-1 (60 °C with H2/O2 at 25 psig (172 kPa) backpressure) was achieved. Rotating disk electrode (RDE) experiments determined the interfacial resistance imposed during cell assembly between the AEM, catalyst, and ionomer was a factor in fuel cell performance. Further RDE studies investigated the electrochemical stability of the PIL block copolymer ionomer under applied potentials, where it was determined that potential cycling increased the degradation compared to constant voltage or open circuit voltage studies. The PIL diblock copolymer was then anion exchanged to the bis(trifluoromethane)sulfonamide (TFSI-) anion form and imbibed with a lithium salt and ionic liquid solution for use as a SPE in lithium-ion batteries resulting in a maximum discharge capacity of 112 mAh g-1 at 0.1 C with a Coulombic efficiency greater than 94% over 100 cycles. PIL block copolymers have promising mechanical properties and transport properties (i.e., ion conductivity) in both the hydrated (hydrophilic anions; Br-, OH-) and dry (hydrophobic anions; TFSI-) states resulting in highly conductive, chemically/thermally stable, and mechanically robust solid-state polymer separators for use as AEMs in AFCs and as SPEs in lithium-ion batteries.

Compartmentalization Technologies via Self-Assembly and Cross-Linking of Amphiphilic Random Block Copolymers in Water.

PubMed

Matsumoto, Mayuko; Terashima, Takaya; Matsumoto, Kazuma; Takenaka, Mikihito; Sawamoto, Mitsuo

2017-05-31

Orthogonal self-assembly and intramolecular cross-linking of amphiphilic random block copolymers in water afforded an approach to tailor-make well-defined compartments and domains in single polymer chains and nanoaggregates. For a double compartment single-chain polymer, an amphiphilic random block copolymer bearing hydrophilic poly(ethylene glycol) (PEG) and hydrophobic dodecyl, benzyl, and olefin pendants was synthesized by living radical polymerization (LRP) and postfunctionalization; the dodecyl and benzyl units were incorporated into the different block segments, whereas PEG pendants were statistically attached along a chain. The copolymer self-folded via the orthogonal self-assembly of hydrophobic dodecyl and benzyl pendants in water, followed by intramolecular cross-linking, to form a single-chain polymer carrying double yet distinct hydrophobic nanocompartments. A single-chain cross-linked polymer with a chlorine terminal served as a globular macroinitiator for LRP to provide an amphiphilic tadpole macromolecule comprising a hydrophilic nanoparticle and a hydrophobic polymer tail; the tadpole thus self-assembled into multicompartment aggregates in water.

Nanotransforming Assemblies

NASA Astrophysics Data System (ADS)

Discher, Dennis

2005-03-01

Degradable polymeric materials with hydrolysable backbones have attracted much attention because they break down to non-toxic metabolites. They are the key solutions to many environmental problems, and are particularly useful for various biomedical applications. Much work has been focused on degradable polymers and their co-polymers as bulk, or films and monolayers.^2 Only limited work has explored the degradable amphiphilic copolymer self-assemblies (spherical micelles, worm micelles and vesicles) in solutions, which are quite important for soft-material engineering. Mostly spherical micelles, and in rare cases, vesicles, have been reported made from copolymers with degradable polyester, typically polylactide or polycaprolactone, as the hydrophobic block, connected to biocompatible, stealthy poly (ethylene oxide) as hydrophilic block. Morphological change of such spherical micelles induced by degradation is subtle, and the degradation kinetics and mechanism in assemblies, which can be quite different from that in bulk or film, are not well understood. Here we will describe the phase transformations of worm micelles and vesicles as they degrade and also highlight how these polymeric self-assemblies interact with lipid membranes.

Folate-conjugated pH-responsive nanocarrier designed for active tumor targeting and controlled release of doxorubicin

NASA Astrophysics Data System (ADS)

Wei, Lulu; Lu, Beibei; Cui, Lin; Peng, Xueying; Wu, Jianning; Li, Deqiang; Liu, Zhiyong; Guo, Xuhong

2017-12-01

A novel type of amphiphilic pH-responsive folate-poly(ɛ-caprolactone)- block-poly(2-hydroxyethylmethacrylate)- co-poly(2-(dimethylamino)-ethylmethacrylate) (FA-PCL- b-P(HEMA- co-DMAEMA)) (MFP) block copolymers were designed and synthesized via atom transfer radical polymerization (ATRP) and ring opening polymerization (ROP) techniques. The molecular structures of the copolymers were confirmed with 1H NMR, FTIR and GPC measurements. The critical micelle concentration (CMC) of MFP in aqueous solution was extremely low (about 6.54 mg/L). The in vitro release behavior of DOX-loaded micelles was significantly accelerated when the pH value of solution decreased from 7.4 to 5.0. In vitro antitumor efficiency was evaluated by incubating DOX-loaded micelles with Hela cells. The results demonstrated that this copolymer possessed excellent biocompatibility, and FA-decorated micelles MFP showed higher cellular uptake than those micelles without the FA moiety, indicating their unique targetability. These folate-conjugated biodegradable micelles are highly promising for targeted cancer chemothe-rapy.

Single- and Multilayered Nanostructures via Laser-Induced Block Copolymer Self-Assembly

NASA Astrophysics Data System (ADS)

Majewski, Pawel; Yager, Kevin; Rahman, Atikur; Black, Charles

We present a novel method of accelerated self-assembly of block copolymer thin films utilizing laser light, called Laser Zone Annealing (LZA). In our approach, steep temperature transients are induced in block copolymer films by rastering narrowly focused laser line over the light-absorbing substrate. Extremely steep temperature gradients accelerate the process of self-assembly by several orders-of-magnitude compared to conventional oven annealing, and, when coupled to photo-thermal shearing, lead to global alignment of block copolymer domains assessed by GISXAS diffraction studies and real-space SEM imaging. We demonstrate monolithic alignment of various block-copolymer thin films including PS-b-PMMA, PS-b-PEO, PS-b-P2VP, PS-b-PI and observe different responsiveness to the shearing rate depending on the characteristic relaxation timescale of the particular material. Subsequently, we use the aligned polymeric films as templates for synthesis of single- and multi-layered arrays of inorganic, metallic or semiconducting nanowires and nanomeshes and investigate their anisotropic electro-optical properties. Research carried out in part at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

A pH- and temperature-responsive bioresorbable injectable hydrogel based on polypeptide block copolymers for the sustained delivery of proteins in vivo.

PubMed

Turabee, Md Hasan; Thambi, Thavasyappan; Duong, Huu Thuy Trang; Jeong, Ji Hoon; Lee, Doo Sung

2018-02-27

Sustained delivery of protein therapeutics is limited owing to the fragile nature of proteins. Despite its great potential, delivery of proteins without any loss of bioactivity remains a challenge in the use of protein therapeutics in the clinic. To surmount this shortcoming, we report a pH- and temperature-responsive in situ-forming injectable hydrogel based on comb-type polypeptide block copolymers for the controlled delivery of proteins. Polypeptide block copolymers, composed of hydrophilic polyethylene glycol (PEG), temperature-responsive poly(γ-benzyl-l-glutamate) (PBLG), and pH-responsive oligo(sulfamethazine) (OSM), exhibit pH- and temperature-induced sol-to-gel transition behavior in aqueous solutions. Polypeptide block copolymers were synthesized by combining N-carboxyanhydride-based ring-opening polymerization and post-functionalization of the chain-end using N-hydroxy succinimide ester activated OSM. The physical properties of polypeptide-based hydrogels were tuned by varying the composition of temperature- and pH-responsive PBLG and OSM in block copolymers. Polypeptide block copolymers were non-toxic to human embryonic kidney cells at high concentrations (2000 μg mL -1 ). Subcutaneous administration of polypeptide block copolymer sols formed viscoelastic gel instantly at the back of Sprague-Dawley (SD) rats. The in vivo gels exhibited sustained degradation and were found to be bioresorbable in 6 weeks without any noticeable inflammation at the injection site. Anionic characteristics of hydrogels allow efficient loading of a cationic model protein, lysozyme, through electrostatic interaction. Lysozyme-loaded polypeptide block copolymer sols readily formed a viscoelastic gel in vivo and sustained lysozyme release for at least a week. Overall, the results demonstrate an elegant approach to control the release of certain charged proteins and open a myriad of therapeutic possibilities in protein therapeutics.

EUV lithographic radiation grafting of thermo-responsive hydrogel nanostructures

NASA Astrophysics Data System (ADS)

Farquet, Patrick; Padeste, Celestino; Solak, Harun H.; Gürsel, Selmiye Alkan; Scherer, Günther G.; Wokaun, Alexander

2007-12-01

Nanostructures of the thermoresponsive poly( N-isopropyl acrylamide) (PNIPAAm) and of PNIPAAm-block-poly(acrylic acid) copolymers were produced on poly(tetrafluoroethylene-co-ethyelene) (ETFE) films using extreme ultraviolet (EUV) lithographic exposure with subsequent graft-polymerization. The phase transition of PNIPAAm nanostructures at the low critical solution temperature (LCST) at 32 °C was imaged by atomic force microscopy (AFM) phase contrast measurements in pure water. Results show a higher phase contrast for samples measured below the LCST temperature than for samples above the LCST, proving that the soft PNIPAAm hydrogel transforms into a much more compact conformation above the LCST. EUV lithographic exposures were combined with the reversible addition-fragment chain transfer (RAFT)-mediated polymerization using cyanoisopropyl dithiobenzoate (CPDB) as chain transfer agent to synthesize PNIPAAm block-copolymer nanostructures.

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

Y Hu; D Samanta; S Parelkar

Controlled free radical polymerization chemistry is used to graft polymer chains to the corona of horse spleen ferritin (HSF) nanocages. Specifically, poly(methacryloyloxyethyl phosphorylcholine) (polyMPC) and poly(PEG methacrylate) (polyPEGMA) chains are grafted onto the nanocages by atom transfer radical polymerization (ATRP), in which the molecular weight of the polymer grafts is controlled by the monomer-to-initiator feed ratio. PolyMPC and polyPEGMA-grafted ferritin show a generally suppressed inclusion into diblock copolymer films relative to native ferritin, and the polymer coating is seen to mask the ferritin nanocages from antibody recognition. The solubility of polyPEGMA-coated ferritin in organic solvents enables its processing with polystyrene-block-poly(ethylenemore » oxide) copolymers, and selective integration into the PEO domains of microphase-separated copolymer structures.« less

Three-dimensional organization of block copolymers on "DNA-minimal" scaffolds.

PubMed

McLaughlin, Christopher K; Hamblin, Graham D; Hänni, Kevin D; Conway, Justin W; Nayak, Manoj K; Carneiro, Karina M M; Bazzi, Hassan S; Sleiman, Hanadi F

2012-03-07

Here, we introduce a 3D-DNA construction method that assembles a minimum number of DNA strands in quantitative yield, to give a scaffold with a large number of single-stranded arms. This DNA frame is used as a core structure to organize other functional materials in 3D as the shell. We use the ring-opening metathesis polymerization (ROMP) to generate block copolymers that are covalently attached to DNA strands. Site-specific hybridization of these DNA-polymer chains on the single-stranded arms of the 3D-DNA scaffold gives efficient access to DNA-block copolymer cages. These biohybrid cages possess polymer chains that are programmably positioned in three dimensions on a DNA core and display increased nuclease resistance as compared to unfunctionalized DNA cages. © 2012 American Chemical Society

Natural and Synthetic Polymers as Inhibitors of Drug Efflux Pumps

PubMed Central

2007-01-01

Inhibition of efflux pumps is an emerging approach in cancer therapy and drug delivery. Since it has been discovered that polymeric pharmaceutical excipients such as Tweens® or Pluronics® can inhibit efflux pumps, various other polymers have been investigated regarding their potential efflux pump inhibitory activity. Among them are polysaccharides, polyethylene glycols and derivatives, amphiphilic block copolymers, dendrimers and thiolated polymers. In the current review article, natural and synthetic polymers that are capable of inhibiting efflux pumps as well as their application in cancer therapy and drug delivery are discussed. PMID:17896100

Bactericidal Specificity and Resistance Profile of Poly(Quaternary Ammonium) Polymers and Protein-Poly(Quaternary Ammonium) Conjugates.

PubMed

Ji, Weihang; Koepsel, Richard R; Murata, Hironobu; Zadan, Sawyer; Campbell, Alan S; Russell, Alan J

2017-08-14

Antibacterial polymers are potentially powerful biocides that can destroy bacteria on contact. Debate in the literature has surrounded the mechanism of action of polymeric biocides and the propensity for bacteria to develop resistance to them. There has been particular interest in whether surfaces with covalently coupled polymeric biocides have the same mechanism of action and resistance profile as similar soluble polymeric biocides. We designed and synthesized a series of poly(quaternary ammonium) polymers, with tailorable molecular structures and architectures, to engineer their antibacterial specificity and their ability to delay the development of bacterial resistance. These linear poly(quaternary ammonium) homopolymers and block copolymers, generated using atom transfer radical polymerization, had structure-dependent antibacterial specificity toward Gram positive and negative bacterial species. When single block copolymers contained two polymer segments of differing antibacterial specificity, the polymer combined the specificities of its two components. Nanoparticulate human serum albumin-poly(quaternary ammonium) conjugates of these same polymers, synthesized via "grafting from" atom transfer radical polymerization, were strongly biocidal and also exhibited a marked decrease in the rate of bacterial resistance development relative to linear polymers. These protein-biocide conjugates mimicked the behavior of surface-presented polycationic biocides rather than their nonproteinaceous counterparts.

Design and synthesis study of the thermo-sensitive poly (N-vinylpyrrolidone-b- N, N-diethylacrylamide).

PubMed

Zhang, Xiayun; Yang, Zhongduo; Xie, Dengmin; Liu, Donglei; Chen, Zhenbin; Li, Ke; Li, Zhizhong; Tichnell, Brandon; Liu, Zhen

2018-01-01

The reversible addition fragmentation chain transfer (RAFT) polymerization method was adopted here to prepare a series of thermo-sensitive copolymers, poly (N,N-diethyl- acrylamide-b-N-vinylpyrrolidone). Their structures, molecular weight distribution and temperature sensitivity performances were characterized by the nuclear magnetic resonance ( 1 HNMR), the gel permeation chromatography (GPC) and the fluorescence spectrophotometer, respectively. It has been identified that the synthesis reaction of the block copolymer was living polymerization. The thermo-sensitivity study suggested that N-vinylpyrrolidone (NVP), played a key role on the lower critical solution temperature (LCST) performance.

Patchy micelles based on coassembly of block copolymer chains and block copolymer brushes on silica particles.

PubMed

Zhu, Shuzhe; Li, Zhan-Wei; Zhao, Hanying

2015-04-14

Patchy particles are a type of colloidal particles with one or more well-defined patches on the surfaces. The patchy particles with multiple compositions and functionalities have found wide applications from the fundamental studies to practical uses. In this research patchy micelles with thiol groups in the patches were prepared based on coassembly of free block copolymer chains and block copolymer brushes on silica particles. Thiol-terminated and cyanoisopropyl-capped polystyrene-block-poly(N-isopropylacrylamide) block copolymers (PS-b-PNIPAM-SH and PS-b-PNIPAM-CIP) were synthesized by reversible addition-fragmentation chain transfer polymerization and chemical modifications. Pyridyl disulfide-functionalized silica particles (SiO2-SS-Py) were prepared by four-step surface chemical reactions. PS-b-PNIPAM brushes on silica particles were prepared by thiol-disulfide exchange reaction between PS-b-PNIPAM-SH and SiO2-SS-Py. Surface micelles on silica particles were prepared by coassembly of PS-b-PNIPAM-CIP and block copolymer brushes. Upon cleavage of the surface micelles from silica particles, patchy micelles with thiol groups in the patches were obtained. Dynamic light scattering, transmission electron microscopy, and zeta-potential measurements demonstrate the preparation of patchy micelles. Gold nanoparticles can be anchored onto the patchy micelles through S-Au bonds, and asymmetric hybrid structures are formed. The thiol groups can be oxidized to disulfides, which results in directional assembly of the patchy micelles. The self-assembly behavior of the patchy micelles was studied experimentally and by computer simulation.

Mechanism-Based Enhanced Delivery of Drug-Loaded Targeted Nanoparticles for Breast Cancer Therapy

DTIC Science & Technology

2012-02-01

the chemotherapeutics on the normal tissue. Anti-ErbB2 antibody- conjugated polymeric nanoparticles with a capacity to load multiple drugs at high...copolymers containing anionic and nonionic hydrophilic polymeric segments (block ionomers) were used for the synthesis of nanogels. Polymethacrylic...where x and y represent the degree of polymerization of the PEO segment and PMA or PGA segment, respectively. Nanogels were synthesized using the

pH-sensitive methacrylic copolymer gels and the production thereof

DOEpatents

Mallapragada, Surya K [Ames, IA; Anderson, Brian C [Lake Bluff, IA

2007-05-15

The present invention provides novel gel forming methacrylic blocking copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol)methyl ether polymer. The polymers may be used for drug and gene delivery, protein separation, as structural supplements, and more.

Amphiphilic graft copolymers from end-functionalized starches: synthesis, characterization, thin film preparation, and small molecule loading.

PubMed

Ryno, Lisa M; Reese, Cassandra; Tolan, McKenzie; O'Brien, Jeffrey; Short, Gabriel; Sorriano, Gerardo; Nettleton, Jason; Fulton, Kayleen; Iovine, Peter M

2014-08-11

End-functionalized macromolecular starch reagents, prepared by reductive amination, were grafted onto a urethane-linked polyester-based backbone using copper-catalyzed azide-alkyne cycloaddition (CuAAC) chemistry to produce novel amphiphilic hybrid graft copolymers. These copolymers represent the first examples of materials where the pendant chains derived from starch biopolymers have been incorporated into a host polymer by a grafting-to approach. The graft copolymers were prepared in good yields (63-90%) with high grafting efficiencies (66-98%). Rigorous quantitative spectroscopic analyses of both the macromolecular building blocks and the final graft copolymers provide a comprehensive analytical toolbox for deciphering the reaction chemistry. Due to the modular nature of both the urethane-linked polyester synthesis and the postpolymerization modification, the starch content of these novel hybrid graft copolymers was easily tuned from 28-53% (w/w). The uptake of two low molecular weight guest molecules into the hybrid polymer thin films was also studied. It was found that binding of 1-naphthol and pterostilbene correlated linearly with amount of starch present in the hybrid polymer. The newly synthesized graft copolymers were highly processable and thermally stable, therefore, opening up significant opportunities in film and coating applications. These results represent a proof-of-concept system for not only the construction of starch-containing copolymers, but also the loading of these novel polymeric materials with active agents.

Ordering kinetics in two-dimensional hexagonal pattern of cylinder-forming PS-b -PMMA block copolymer thin films: Dependence on the segregation strength

NASA Astrophysics Data System (ADS)

Seguini, Gabriele; Zanenga, Fabio; Laus, Michele; Perego, Michele

2018-05-01

This paper reports the experimental determination of the growth exponents and activation enthalpies for the ordering process of standing cylinder-forming all-organic polystyrene-block-poly (methyl methacrylate) block copolymer (BCP) thin films as a function of the BCP degree of polymerization (N). The maximum growth exponent of 1/3 is observed for the BCP with the lowest N at the border of the order-disorder transition. Both the growth exponents and the activation enthalpies exponentially decrease with the BCP segregation strength (χN) following the same path of the diffusivity.

Mesoporous Polymer Frameworks from End-Reactive Bottlebrush Copolymers

DOE PAGES

Altay, Esra; Nykypanchuk, Dmytro; Rzayev, Javid

2017-08-07

Reticulated nanoporous materials generated by versatile molecular framework approaches are limited to pore dimensions on the scale of the utilized rigid molecular building blocks (<5 nm). The inherent flexibility of linear polymers precludes their utilization as long framework connectors for the extension of this strategy to larger length scales. We report a method for the fabrication of mesoporous frameworks by using bottlebrush copolymers with reactive end blocks serving as rigid macromolecular interconnectors with directional reactivity. End-reactive bottlebrush copolymers with pendant alkene functionalities were synthesized by a combination of controlled radical polymerization and polymer modification protocols. Ru-catalyzed cross-metathesis cross-linking of bottlebrushmore » copolymers with two reactive end blocks resulted in the formation of polymer frameworks where isolated cross-linked domains were interconnected with bottlebrush copolymer bridges. The resulting materials were characterized by a continuous network pore structure with average pore sizes of 9–50 nm, conveniently tunable by the length of the utilized bottlebrush copolymer building blocks. As a result, the materials fabrication strategy described in this work expands the length scale of molecular framework materials and provides access to mesoporous polymers with a molecularly tunable reticulated pore structure without the need for templating, sacrificial component etching, or supercritical fluid drying.« less

Biodegradable thermoresponsive polymeric magnetic nanoparticles: a new drug delivery platform for doxorubicin

NASA Astrophysics Data System (ADS)

Andhariya, Nidhi; Chudasama, Bhupendra; Mehta, R. V.; Upadhyay, R. V.

2011-04-01

The use of nanoparticles as drug delivery systems for anticancer therapeutics has great potential to revolutionize the future of cancer therapy. The aim of this study is to construct a novel drug delivery platform comprising a magnetic core and biodegradable thermoresponsive shell of tri-block-copolymer. Oleic acid-coated Fe3O4 nanoparticles and hydrophilic anticancer drug "doxorubicin" are encapsulated with PEO-PLGA-PEO (polyethylene oxide-poly d, l lactide-co-glycolide-polyethylene oxide) tri-block-copolymer. Structural, magnetic, and physical properties of Fe3O4 core are determined by X-ray diffraction, vibrating sample magnetometer, and transmission electron microscopy techniques, respectively. The hydrodynamic size of composite nanoparticles is determined by dynamic light scattering and is found to be 36.4 nm at 25 °C. The functionalization of magnetic core with various polymeric chain molecules and their weight proportions are determined by Fourier transform infrared spectroscopy and thermogravimetric analysis, respectively. Encapsulation of doxorubicin into the polymeric magnetic nanoparticles, its loading efficiency, and kinetics of drug release are investigated by UV-vis spectroscopy. The loading efficiency of drug is 89% with a rapid release for the initial 7 h followed by the sustained release over a period of 36 h. The release of drug is envisaged to occur in response to the physiological temperature by deswelling of thermoresponsive PEO-PLGA-PEO block-copolymer. This study demonstrates that temperature can be exploited successfully as an external parameter to control the release of drug.

HPMA-based polymeric micelles for curcumin solubilization and inhibition of cancer cell growth.

PubMed

Naksuriya, Ornchuma; Shi, Yang; van Nostrum, Cornelus F; Anuchapreeda, Songyot; Hennink, Wim E; Okonogi, Siriporn

2015-08-01

Curcumin (CM) has been reported as a potential anticancer agent. However, its pharmaceutical applications as therapeutic agent are hampered because of its poor aqueous solubility. The present study explores the advantages of polymeric micelles composed of block copolymers of methoxypoly(ethylene glycol) (mPEG) and N-(2-hydroxypropyl) methacrylamide (HPMA) modified with monolactate, dilactate and benzoyl side groups to enhance CM solubility and inhibitory activity against cancer cells. Amphiphilic block copolymers, ω-methoxypoly(ethylene glycol)-b-(N-(2-benzoyloxypropyl) methacrylamide) (PEG-HPMA-Bz) were synthesized and characterized by (1)H NMR and GPC. One polymer with a molecular weight of 28,000Da was used to formulate CM and compared with other aromatic substituted polymers. CM was loaded by a fast heating method (PEG-HPMA-DL and PEG-HPMA-Bz-L) and a nanoprecipitation method (PEG-HPMA-Bz). Physicochemical characteristics and cytotoxicity/cytocompatibility of the CM loaded polymeric micelles were evaluated. It was found that HPMA-based polymeric micelles significantly enhanced the solubility of CM. The PEG-HPMA-Bz micelles showed the best solubilization properties. CM loaded polymeric micelles showed sustained release of the loading CM for more than 20days. All of CM loaded polymeric micelles formulations showed a significantly potent cytotoxic effect against three cancer cell lines. HPMA-based polymeric micelles are therefore promising nanodelivery systems of CM for cancer therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

RAFT Aqueous Dispersion Polymerization Yields Poly(ethylene glycol)-Based Diblock Copolymer Nano-Objects with Predictable Single Phase Morphologies

PubMed Central

2013-01-01

A poly(ethylene glycol) (PEG) macromolecular chain transfer agent (macro-CTA) is prepared in high yield (>95%) with 97% dithiobenzoate chain-end functionality in a three-step synthesis starting from a monohydroxy PEG113 precursor. This PEG113-dithiobenzoate is then used for the reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). Polymerizations conducted under optimized conditions at 50 °C led to high conversions as judged by 1H NMR spectroscopy and relatively low diblock copolymer polydispersities (Mw/Mn < 1.25) as judged by GPC. The latter technique also indicated good blocking efficiencies, since there was minimal PEG113 macro-CTA contamination. Systematic variation of the mean degree of polymerization of the core-forming PHPMA block allowed PEG113-PHPMAx diblock copolymer spheres, worms, or vesicles to be prepared at up to 17.5% w/w solids, as judged by dynamic light scattering and transmission electron microscopy studies. Small-angle X-ray scattering (SAXS) analysis revealed that more exotic oligolamellar vesicles were observed at 20% w/w solids when targeting highly asymmetric diblock compositions. Detailed analysis of SAXS curves indicated that the mean number of membranes per oligolamellar vesicle is approximately three. A PEG113-PHPMAx phase diagram was constructed to enable the reproducible targeting of pure phases, as opposed to mixed morphologies (e.g., spheres plus worms or worms plus vesicles). This new RAFT PISA formulation is expected to be important for the rational and efficient synthesis of a wide range of biocompatible, thermo-responsive PEGylated diblock copolymer nano-objects for various biomedical applications. PMID:24400622

Hybrid Silicon-Based Organic/Inorganic Block Copolymers with Sol-Gel Active Moieties: Synthetic Advances, Self-Assembly and Applications in Biomedicine and Materials Science.

PubMed

Czarnecki, Sebastian; Bertin, Annabelle

2018-03-07

Hybrid silicon-based organic/inorganic (multi)block copolymers are promising polymeric precursors to create robust nano-objects and nanomaterials due to their sol-gel active moieties via self-assembly in solution or in bulk. Such nano-objects and nanomaterials have great potential in biomedicine as nanocarriers or scaffolds for bone regeneration as well as in materials science as Pickering emulsifiers, photonic crystals or coatings/films with antibiofouling, antibacterial or water- and oil-repellent properties. Thus, this Review outlines recent synthetic efforts in the preparation of these hybrid inorganic/organic block copolymers, gives an overview of their self-assembled structures and finally presents recent examples of their use in the biomedical field and material science. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

One-Pot Synthesis of Multifunctional Polymers by Light-Controlled Radical Polymerization and Enzymatic Catalysis with Candida antarctica Lipase B.

PubMed

Hrsic, Emin; Keul, Helmut; Möller, Martin

2015-12-01

The preparation of multifunctional polymers and block copolymers by a straightforward one-pot reaction process that combines enzymatic transacylation with light-controlled polymerization is described. Functional methacrylate monomers are synthesized by enzymatic transacylation and used in situ for light-controlled polymerization, leading to multifunctional methacrylate-based polymers with well-defined microstructure. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Targeted polymeric micelles for delivery of poorly soluble drugs.

PubMed

Torchilin, V P

2004-10-01

Polymeric micelles (micelles formed by amphiphilic block copolymers) demonstrate a series of attractive properties as drug carriers, such as high stability both in vitro and in vivo and good biocompatibility, and can be successfully used for the solubilization of various poorly soluble pharmaceuticals. These micelles can also be used as targeted drug delivery systems. The targeting can be achieved via the enhanced permeability and retention effect (into the areas with the compromised vasculature), by making micelles of stimuli-responsive amphiphilic block copolymers, or by attaching specific targeting ligand molecules to the micelle surface. Immunomicelles prepared by coupling monoclonal antibody molecules to p-nitrophenylcarbonyl groups on the water-exposed termini of the micelle corona-forming blocks demonstrate high binding specificity and targetability. Immunomicelles prepared with cancer-specific monoclonal antibody 2C5 specifically bind to different cancer cells in vitro and demonstrate increased therapeutic activity in vivo. This new family of pharmaceutical carriers can be used for the solubilization and targeted delivery of poorly soluble drugs to various pathological sites in the body.

Synthesis of biocompatible poly(ɛ-caprolactone)- block-poly(propylene adipate) copolymers appropriate for drug nanoencapsulation in the form of core-shell nanoparticles

PubMed Central

Nanaki, Stavroula G; Pantopoulos, Kostas; Bikiaris, Dimitrios N

2011-01-01

Poly(propylene adipate)-block-poly(ɛ-caprolactone) copolymers were synthesized using a combination of polycondensation and ring-opening polymerization of ɛ-caprolactone in the presence of poly(propylene adipate). Gel permeation chromatography was used for molecular weight determination, whereas hydrogen-1 nuclear magnetic resonance and carbon-13 nuclear magnetic resonance spectroscopy were employed for copolymer characterization and composition evaluation. The copolymers were found to be block while their composition was similar to the feeding ratio. They formed semicrystalline structures, while only poly(ɛ-caprolactone) formed crystals, as shown by wide angle X-ray diffraction. Differential scanning calorimetry data suggest that the melting point and heat of fusion of copolymers decreased by increasing the poly(propylene adipate) amount. The synthesized polymers exhibited low cytotoxicity and were used to encapsulate desferrioxamine, an iron-chelating drug. The desferrioxamine nanoparticles were self-assembled into core shell structures, had mean particle size <250 nm, and the drug remained in crystalline form. Further studies revealed that the dissolution rate was mainly related to the melting temperature, as well as to the degree of crystallinity of copolymers. PMID:22162656

Synthesis of biocompatible poly(ɛ-caprolactone)- block-poly(propylene adipate) copolymers appropriate for drug nanoencapsulation in the form of core-shell nanoparticles.

PubMed

Nanaki, Stavroula G; Pantopoulos, Kostas; Bikiaris, Dimitrios N

2011-01-01

Poly(propylene adipate)-block-poly(ɛ-caprolactone) copolymers were synthesized using a combination of polycondensation and ring-opening polymerization of ɛ-caprolactone in the presence of poly(propylene adipate). Gel permeation chromatography was used for molecular weight determination, whereas hydrogen-1 nuclear magnetic resonance and carbon-13 nuclear magnetic resonance spectroscopy were employed for copolymer characterization and composition evaluation. The copolymers were found to be block while their composition was similar to the feeding ratio. They formed semicrystalline structures, while only poly(ɛ-caprolactone) formed crystals, as shown by wide angle X-ray diffraction. Differential scanning calorimetry data suggest that the melting point and heat of fusion of copolymers decreased by increasing the poly(propylene adipate) amount. The synthesized polymers exhibited low cytotoxicity and were used to encapsulate desferrioxamine, an iron-chelating drug. The desferrioxamine nanoparticles were self-assembled into core shell structures, had mean particle size <250 nm, and the drug remained in crystalline form. Further studies revealed that the dissolution rate was mainly related to the melting temperature, as well as to the degree of crystallinity of copolymers.

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

Poly(Acrylic Acid-b-Styrene) Amphiphilic Multiblock Copolymers as Building Blocks for the Assembly of Discrete Nanoparticles

PubMed Central

Greene, Anna C.; Zhu, Jiahua; Pochan, Darrin J.; Jia, Xinqiao; Kiick, Kristi L.

2011-01-01

In order to expand the utility of current polymeric micellar systems, we have developed amphiphilic multiblock copolymers containing alternating blocks of poly(acrylic acid) and poly(styrene). Heterotelechelic poly(tert-butyl acrylate-b-styrene) diblock copolymers containing an α-alkyne and an ω-azide were synthesized by atom transfer radical polymerization (ATRP), allowing control over the molecular weight while maintaining narrow polydispersity indices. The multiblock copolymers were constructed by copper-catalyzed azide-alkyne cycloaddition of azide-alkyne end functional diblock copolymers which were then characterized by 1H NMR, FT-IR and SEC. The tert-butyl moieties of the poly(tert-butyl acrylate-b-styrene) multiblock copolymers were easily removed to form the poly(acrylic acid-b-styrene) multiblock copolymer ((PAA-PS)9), which contained up to 9 diblock repeats. The amphiphilic multiblock (PAA-PS)9 (Mn = 73.3 kg/mol) was self-assembled by dissolution into tetrahydrofuran and extensive dialysis against deionized water for 4 days. The critical micelle concentration (CMC) for (PAA-PS)9 was determined by fluorescence spectroscopy using pyrene as a fluorescent probe and was found to be very low at 2 × 10-4 mg/mL. The (PAA-PS)9 multiblock was also analyzed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The hydrodynamic diameter of the particles was found to be 11 nm. Discrete spherical particles were observed by TEM with an average particle diameter of 14 nm. The poly(acrylic acid) periphery of the spherical particles should allow for future conjugation of biomolecules. PMID:21552373

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

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

Functional Interfaces Constructed by Controlled/Living Radical Polymerization for Analytical Chemistry.

PubMed

Wang, Huai-Song; Song, Min; Hang, Tai-Jun

2016-02-10

The high-value applications of functional polymers in analytical science generally require well-defined interfaces, including precisely synthesized molecular architectures and compositions. Controlled/living radical polymerization (CRP) has been developed as a versatile and powerful tool for the preparation of polymers with narrow molecular weight distributions and predetermined molecular weights. Among the CRP system, atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) are well-used to develop new materials for analytical science, such as surface-modified core-shell particles, monoliths, MIP micro- or nanospheres, fluorescent nanoparticles, and multifunctional materials. In this review, we summarize the emerging functional interfaces constructed by RAFT and ATRP for applications in analytical science. Various polymers with precisely controlled architectures including homopolymers, block copolymers, molecular imprinted copolymers, and grafted copolymers were synthesized by CRP methods for molecular separation, retention, or sensing. We expect that the CRP methods will become the most popular technique for preparing functional polymers that can be broadly applied in analytical chemistry.

Polystyrene-block-Poly(ionic liquid) Copolymers as Work Function Modifiers in Inverted Organic Photovoltaic Cells.

PubMed

Park, Jong Baek; Isik, Mehmet; Park, Hea Jung; Jung, In Hwan; Mecerreyes, David; Hwang, Do-Hoon

2018-02-07

Interfacial layers play a critical role in building up the Ohmic contact between electrodes and functional layers in organic photovoltaic (OPV) solar cells. These layers are based on either inorganic oxides (ZnO and TiO 2 ) or water-soluble organic polymers such as poly[(9,9-dioctyl-2,7-fluorene)-alt-(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)] and polyethylenimine ethoxylated (PEIE). In this work, we have developed a series of novel poly(ionic liquid) nonconjugated block copolymers for improving the performance of inverted OPV cells by using them as work function modifiers of the indium tin oxide (ITO) cathode. Four nonconjugated polyelectrolytes (n-CPEs) based on polystyrene and imidazolium poly(ionic liquid) (PSImCl) were synthesized by reversible addition-fragmentation chain transfer polymerization. The ratio of hydrophobic/hydrophilic block copolymers was varied depending on the ratio of polystyrene to the PSImCl block. The ionic density, which controls the work function of the electrode by forming an interfacial dipole between the electrode and the block copolymers, was easily tuned by simply changing the PSImCl molar ratio. The inverted OPV device with the ITO/PS 29 -b-PSImCl 60 cathode achieved the best power conversion efficiency (PCE) of 7.55% among the synthesized block copolymers, exhibiting an even higher PCE than that of the reference OPV device with PEIE (7.30%). Furthermore, the surface properties of the block copolymers films were investigated by contact angle measurements to explore the influence of the controlled hydrophobic/hydrophilic characters on the device performances.

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).

Supramolecular Assembly of Gold Nanoparticles in PS-b-P2VP Diblock Copolymers via Hydrogen Bonding

NASA Astrophysics Data System (ADS)

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

2011-03-01

We report a simple route to control the spatial distribution of Au nanoparticles (Au-NPs) in PS- b -P2VP diblock copolymers using hydrogen bonding between P2VP and the hydroxyl-containing (PI-OH) units in PS- b -PIOH thiol-terminated ligands on Au-NP. End-functional thiol ligands of poly(styrene- b -1,2&3,4-isoprene-SH) are synthesized by anionic polymerization. After synthesis of Au-NPs, the inner PI block is hydroxylated by hydroboration and the resulting micelle-like Au-NPs consist of a hydrophobic PS outer brush and a hydrophilic inner PI-OH block. The influence of the hydroxyl groups is significant with strong segregation being observed to the PS/P2VP interface and then to the P2VP domain of lamellar-forming PS-b-P2VP diblock copolymers as the length of the PI-OH block is increased. The strong hydrogen bonding between nanoparticle block copolymer ligands and the P2VP block allows the Au-NPs to be incorporated within the P2VP domain to high Au--NP volume fractions ϕp without macrophase separation, driving transitions from lamellar to bicontinuous morphologies as ϕp increases.

Synthesis and Structure of Fully Conjugated Block Copolymers Utilized in Organic Photovoltaics

NASA Astrophysics Data System (ADS)

Lee, Youngmin; Aplan, Melissa; Wang, Qing; Gomez, Enrique D.

2015-03-01

Fully conjugated block copolymers have the potential to overcome many of the limitations of mixtures and blends as photoactive layers in solar cells; furthermore, they may serve as model systems to study fundamental questions regarding optoelectric properties and charge transfer. However, the synthesis of fully conjugated block copolymers remains a challenging issue in the fieldchallenge. We have optimized the two-step synthesis of P3HT-b-PFTBT, which is composed comprised of Grignard metathesis for polymerization of P3HT followed by chain extension through a Suzuki-Miyaura polycondenstation. We find that the concentration of the Grignard reagent is critical for end-group control such that P3HT is terminated by H at one end and Br at the other. Furthermore, we can utilize an asymmetric feed ratio of monomers for the Suzuki-Miyaura reaction to minimize the amount of uncoupled homopolymers and to control the molecular weight of the second block. We investigated the chemical composition, structure and electrical characteristics of the polymers prepared by the different synthetic methods, and demonstrate that we can utilize these strategies for the synthesis of block copolymers beyond P3HT-b-PFTBT.

Porous and non-porous water soluble polymer nanospheres

NASA Astrophysics Data System (ADS)

Henselwood, Fred William

Water soluble polymer nanospheres have been prepared from the photo-cross-linking of diblock copolymer micelles formed either in water or in N,N-dimethylformamide/water mixtures. The diblock copolymers utilized in this study were poly(2-cinnamoyl-ethyl methacrylate)-block-poly(acrylic acid), poly ((2-cinnamoylethyl methacrylate)-random-(2-octanoylethyl methacrylate)) -block-poly(acrylic acid), and poly ((2-cinnamoyl-ethyl methacrylate)-random-(2-oleoylethyl methacrylate)) -block-poly(acrylic acid). These polymers were synthesized by the functionalization of diblock copolymers prepared by anionic polymerization. The photo-cross-linking was achieved through the dimerization of cinnamoyl groups by ultraviolet irradiation. Transmission electron microscopy confirmed that the polymer nanospheres had an inner core region formed by the cinnamoyl containing polymer blocks, and an outer shell layer formed by the acrylic acid polymer blocks. The hydrodynamic radius of the polymer nanospheres in water was approximately 50 to 75 nm as determined by dynamic light scattering. It has been found that the polymer nanospheres, when in water, could be readily impregnated with organic molecules. Fluorescence measurements showed that the polymer nanospheres could uptake polyaromatic hydrocarbons by the direct mixing of polyaromatic hydrocarbons with the polymer nanospheres in water. Perylene was found to be between 2.0 × 10sp5 and 4.0 × 10sp5 times more soluble in the core region of the polymer nanospheres than in water. The addition of divalent cations was shown to induce aggregation of the polymer nanospheres and resulted in the precipitation of the polymer nanospheres along with any captured perylene. This suggests that the polymer nanospheres may be useful in water remediation. Porous polymer nanospheres were prepared by the incorporation of low molecular weight polymeric porogens within the core region of the polymer nanospheres. Following photo-cross-linking the polymeric porogens were extracted out of the polymer nanospheres resulting in pore formation. Perylene loading experiments revealed that the loading of the porous polymer nanospheres was 41% higher than that achieved for non-porous polymer nanospheres prepared from the same initial diblock copolymer. This indicates that the porous polymer nanospheres may be preferred over the non-porous polymer nanospheres in applications such as drug delivery.

End Groups of Functionalized Siloxane Oligomers Direct Block-Copolymeric or Liquid-Crystalline Self-Assembly Behavior

PubMed Central

2016-01-01

Monodisperse oligodimethylsiloxanes end-functionalized with the hydrogen-bonding ureidopyrimidinone (UPy) motif undergo phase separation between their aromatic end groups and dimethylsiloxane midblocks to form ordered nanostructures with domain spacings of <5 nm. The self-assembly behavior of these well-defined oligomers resembles that of high degree of polymerization (N)–high block interaction parameter (χ) linear diblock copolymers despite their small size. Specifically, the phase morphology varies from lamellar to hexagonal to body-centered cubic with increasing asymmetry in molecular volume fraction. Mixing molecules with different molecular weights to give dispersity >1.13 results in disorder, showing importance of molecular monodispersity for ultrasmall ordered phase separation. In contrast, oligodimethylsiloxanes end-functionalized with an O-benzylated UPy derivative self-assemble into lamellar nanostructures regardless of volume fraction because of the strong preference of the end groups to aggregate in a planar geometry. Thus, these molecules display more classically liquid-crystalline self-assembly behavior where the lamellar bilayer thickness is determined by the siloxane midblock. Here the lamellar nanostructure is tolerant to molecular polydispersity. We show the importance of end groups in high χ–low N block molecules, where block-copolymer-like self-assembly in our UPy-functionalized oligodimethylsiloxanes relies upon the dominance of phase separation effects over directional end group aggregation. PMID:27054381

Clays as possible catalysts for peptide formation in the prebiotic era

NASA Technical Reports Server (NTRS)

Paecht-Horowitz, M.

1976-01-01

From the point of view of prebiotic synthesis, clays might have performed functions of concentration, catalysis, and protection of molecules. The degrees of polymerization obtained, when amino acid adenylates are added to montmorillonite suspensions in water, are much higher than those obtained by polymerization in the absence of such a clay. In addition, they are of a discrete spectrum, usually multiples of 6 or 7, and reach values of up to 40 mers. In the absence of clay a continuous spectrum of degrees of polymerization is obtained, and usually up to 4-6 mers only. Copolymerization in the absence of clays yields mostly random copolymers, in their presence mostly block copolymers are obtained. Optical density measurements show that after adsorption has taken place on the clay, stacking of its layers occurs. Polymerization starts only after these stacked layers have been formed

(1-Adamantyl)methyl glycidyl ether: a versatile building block for living polymerization.

PubMed

Moers, Christian; Wrazidlo, Robert; Natalello, Adrian; Netz, Isabelle; Mondeshki, Mihail; Frey, Holger

2014-06-01

(1-Adamantyl)methyl glycidyl ether (AdaGE) is introduced as a versatile monomer for oxyanionic polymerization, enabling controlled incorporation of adamantyl moieties in aliphatic polyethers. Via copolymerization with ethoxyethyl glycidyl ether (EEGE) and subsequent cleavage of the acetal protection groups of EEGE, hydrophilic linear polyglycerols with an adjustable amount of pendant adamantyl moieties are obtained. The adamantyl unit permits control over thermal properties and solubility profile of these polymers (LCST). Additionally, AdaGE is utilized as a termination agent in carbanionic polymerization, affording adamantyl-terminated polymers. Using these structures as macroinitiators for the polymerization of ethylene oxide affords amphiphilic, in-chain adamantyl-functionalized block copolymers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new class of dual responsive self-healable hydrogels based on a core crosslinked ionic block copolymer micelle prepared via RAFT polymerization and Diels-Alder "click" chemistry.

PubMed

Banerjee, Sovan Lal; Singha, Nikhil K

2017-12-06

Amphiphilic diblock copolymers of poly(furfuryl methacrylate) (PFMA) with cationic poly(2-(methacryloyloxy)ethyltrimethyl ammonium chloride) (PFMA-b-PMTAC) and anionic poly(sodium 4-vinylbenzenesulfonate) (PFMA-b-PSS) were prepared via reversible addition fragmentation chain-transfer (RAFT) polymerization by using PFMA as a macro-RAFT agent. The formation of the block copolymer was confirmed by FTIR and 1 H NMR analyses. In water, the amphiphilic diblock copolymers, (PFMA-b-PMTAC) and (PFMA-b-PSS), formed micelles with PFMA in the core and the rest of the hydrophilic polymers like PMTAC and PSS in the corona. The PFMA core was crosslinked by using Diels-Alder (DA) "Click" chemistry in water at 60 °C where bismaleimide acted as a crosslinker. Afterwards, both the core crosslinked micelles were mixed at an almost equal charge ratio which was determined by zeta potential analysis to prepare the self-assembled hydrogel. The de-crosslinking of the hydrophobic PFMA core in the self-assembled hydrogel via rDA reaction took place at 165 °C as determined from DSC analysis. This hydrogel showed self-healing behavior using ionic interaction (in the presence of water) and DA chemistry (in the presence of heat).

Extrudable polymer-polymer composites based on ultra-high molecular weight polyethylene

NASA Astrophysics Data System (ADS)

Panin, S. V.; Kornienko, L. A.; Alexenko, V. O.; Buslovich, D. G.; Dontsov, Yu. V.

2017-12-01

Mechanical and tribotechnical characteristics of polymer-polymeric composites of UHMWPE are studied with the aim of developing extrudable, wear-resistant, self-lubricant polymer mixtures for Additive Manufacturing (AM). The motivation of the study is their further application as feedstocks for 3D printing. Blends of UHMWPE with graft- and block copolymers of low-density polyethylene (HDPE-g-VTMS, HDPE-g-SMA, HDPE-b-EVA), polypropylene (PP), block copolymers of polypropylene and polyamide with linear low density polyethylene (PP-b-LLDPE, PA-b-LLDPE), as well as cross-linked polyethylene (PEX-b), are examined. The choice of compatible polymer components for an ultra- high molecular weight matrix for increasing processability (extrudability) is motivated by the search for commercially available and efficient additives aimed at developing wear-resistant extrudable polymer composites for additive manufacturing. The extrudability, mechanical properties and wear resistance of UHMWPE-based polymer-polymeric composites under sliding friction with different velocities and loads are studied.

Factors affecting the stability of drug-loaded polymeric micelles and strategies for improvement

NASA Astrophysics Data System (ADS)

Zhou, Weisai; Li, Caibin; Wang, Zhiyu; Zhang, Wenli; Liu, Jianping

2016-09-01

Polymeric micelles (PMs) self-assembled by amphiphilic block copolymers have been used as promising nanocarriers for tumor-targeted delivery due to their favorable properties, such as excellent biocompatibility, prolonged circulation time, favorable particle sizes (10-100 nm) to utilize enhanced permeability and retention effect and the possibility for functionalization. However, PMs can be easily destroyed due to dilution of body fluid and the absorption of proteins in system circulation, which may induce drug leakage from these micelles before reaching the target sites and compromise the therapeutic effect. This paper reviewed the factors that influence stability of micelles in terms of thermodynamics and kinetics consist of the critical micelle concentration of block copolymers, glass transition temperature of hydrophobic segments and polymer-polymer and polymer-cargo interaction. In addition, some effective strategies to improve the stability of micelles were also summarized.

Silicon crystallization in nanodot arrays organized by block copolymer lithography

NASA Astrophysics Data System (ADS)

Perego, Michele; Andreozzi, Andrea; Seguini, Gabriele; Schamm-Chardon, Sylvie; Castro, Celia; BenAssayag, Gerard

2014-12-01

Asymmetric polystyrene- b-polymethylmethacrylate (PS- b-PMMA) block copolymers are used to fabricate nanoporous PS templates with different pore diameter depending on the specific substrate neutralization protocol. The resulting polymeric templates are used as masks for the subsequent deposition of a thin ( h = 5 nm) amorphous Si layer by electron beam evaporation. After removal of the polymeric film and of the silicon excess, well-defined hexagonally packed amorphous Si nanodots are formed on the substrate. Their average diameter ( d < 20 nm), density (1.2 × 1011 cm-2), and lateral distribution closely mimic the original nanoporous template. Upon capping with SiO2 and high temperature annealing (1050 °C, N2), each amorphous Si nanodot rearranges in agglomerates of Si nanocrystals ( d < 4 nm). The average diameter and shape of these Si nanocrystals strongly depend on the size of the initial Si nanodot.

Synthesis of block copolymers consists on vinylidene chloride and α- Methylstyrene by cationic polymerization using an acid exchanged motmorillonite clay as heterogeneous catalyst (Algerian MMT)

NASA Astrophysics Data System (ADS)

Ayat, Moulkheir; Belbachir, Mohamed; Rahmouni, Abdelkader

2017-07-01

The aim of this study was to develop the efficient and versatile method for the synthesis of block copolymers consists by cationic polymerization vinylidene chloride (VDC) and alpha-methylstyrene (alpha-MS) in the presence of a natural Algerian montmorillonite clay modified by 0.05-0.35 M H2SO4 (Algerian MMT-H+). It was found that H2SO4 concentration allows controlling the chemical composition, the porous structure of the acid-activated clays and their catalytic performance. The maximal yield of polymer is observed in the presence of Algerian MMT modified by 0.25 M H2SO4. Effects of VDC/MS molar ration, catalyst concentration, reaction time, reaction temperature and polarity medium on yield and molecular weight of polymer were revealed in the presence of the most active sample.

Block copolymer with simultaneous electric and ionic conduction for use in lithium ion batteries

DOEpatents

Javier, Anna Esmeralda K; Balsara, Nitash Pervez; Patel, Shrayesh Naran; Hallinan, Jr., Daniel T

2013-10-08

Redox reactions that occur at the electrodes of batteries require transport of both ions and electrons to the active centers. Reported is the synthesis of a block copolymer that exhibits simultaneous electronic and ionic conduction. A combination of Grignard metathesis polymerization and click reaction was used successively to synthesize the block copolymer containing regioregular poly(3-hexylthiophene) (P3HT) and poly(ethylene oxide) (PEO) segments. The P3HT-PEO/LiTFSI mixture was then used to make a lithium battery cathode with LiFePO.sub.4 as the only other component. All-solid lithium batteries of the cathode described above, a solid electrolyte and a lithium foil as the anode showed capacities within experimental error of the theoretical capacity of the battery. The ability of P3HT-PEO to serve all of the transport and binding functions required in a lithium battery electrode is thus demonstrated.

Self-Assembly of Narrowly Dispersed Brush Diblock Copolymers with Domain Spacing more than 100 nm

NASA Astrophysics Data System (ADS)

Gu, Weiyin; Sveinbjornsson, Benjamin; Hong, Sung Woo; Grubbs, Robert; Russell, Thomas

2012-02-01

Self-assembled structures of high molecular weight (MW), narrow molecular weight distribution brush block copolymers containing polylactic acid (PLA) and polystyrene (PS) side chains with similar MWs were studied in both the melt and thin films. The polynorbornene-backbone-based brush diblock copolymers containing approximately equal volume fractions of each block self-assembled into highly ordered lamellae with domain spacing over 100 nm, as revealed by SAXS, GISAXS and AFM. The domain size increased approximately linearly with backbone length, which indicated an extended conformation of the backbone in the ordered state. The length of side chains also played a significant role in terms of controlling the domain size. As the degree of polymerization (DP) increased, the symmetric brush diblock copolymers with longer side chains tended to form larger lamellar microdomains in comparison to those that have the same DP but shorter side chains.

High-concentration graphene dispersion stabilized by block copolymers in ethanol.

PubMed

Perumal, Suguna; Lee, Hyang Moo; Cheong, In Woo

2017-07-01

This article describes a comprehensive study for the preparation of graphene dispersions by liquid-phase exfoliation using amphiphilic diblock copolymers; poly(ethylene oxide)-block-poly(styrene) (PEO-b-PS), poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO-b-PVP), and poly(ethylene oxide)-block-poly(pyrenemethyl methacrylate) (PEO-b-PPy) with similar block lengths. Block copolymers were prepared from PEO using the Steglich coupling reaction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. Graphite platelets (G) and reduced graphene oxide (rGO) were used as graphene sources. The dispersion stability of graphene in ethanol was comparatively investigated by on-line turbidity, and the graphene concentration in the dispersions was determined gravimetrically. Our results revealed that the graphene dispersions with PEO-b-PVP were much more stable and included graphene with fewer defects than that with PEO-b-PS or PEO-b-PPy, as confirmed by turbidity and Raman analyses. Gravimetry confirmed that graphene concentrations up to 1.7 and 1.8mg/mL could be obtained from G and rGO dispersions, respectively, using PEO-b-PVP after one week. Distinctions in adhesion forces of PS, VP, PPy block units with graphene surface and the variation in solubility of the block copolymers in ethanol medium significantly affected the stability of the graphene dispersion. Copyright © 2017 Elsevier Inc. All rights reserved.

Thermosensitive mPEG-b-PA-g-PNIPAM comb block copolymer micelles: effect of hydrophilic chain length and camptothecin release behavior.

PubMed

Yang, Xiao-Li; Luo, Yan-Ling; Xu, Feng; Chen, Ya-Shao

2014-02-01

Block copolymer micelles are extensively used as drug controlled release carriers, showing promising application prospects. The comb or brush copolymers are especially of great interest, whose densely-grafted side chains may be important for tuning the physicochemical properties and conformation in selective solvents, even in vitro drug release. The purpose of this work was to synthesize novel block copolymer combs via atom transfer radical polymerization, to evaluate its physicochemical features in solution, to improve drug release behavior and to enhance the bioavailablity, and to decrease cytotoxicity. The physicochemical properties of the copolymer micelles were examined by modulating the composition and the molecular weights of the building blocks. A dialysis method was used to load hydrophobic camptothecin (CPT), and the CPT release and stability were detected by UV-vis spectroscopy and high-performance liquid chromatography, and the cytotoxicity was evaluated by MTT assays. The copolymers could self-assemble into well-defined spherical core-shell micelle aggregates in aqueous solution, and showed thermo-induced micellization behavior, and the critical micelle concentration was 2.96-27.64 mg L(-1). The micelles were narrow-size-distribution, with hydrodynamic diameters about 128-193 nm, depending on the chain length of methoxy polyethylene glycol (mPEG) blocks and poly(N-isopropylacrylamide) (PNIPAM) graft chains or/and compositional ratios of mPEG to PNIPAM. The copolymer micelles could stably and effectively load CPT but avoid toxicity and side-effects, and exhibited thermo-dependent controlled and targeted drug release behavior. The copolymer micelles were safe, stable and effective, and could potentially be employed as CPT controlled release carriers.

Characterization of a Poly(styrene-block-methylacrylate-random-octadecylacrylate-block-styrene) Shape Memory ABA Triblock Copolymer

NASA Astrophysics Data System (ADS)

Fei, Pengzhan; Cavicchi, Kevin

2011-03-01

A new ABA triblock copolymer of poly(styrene-block- methylacrylate-random-octadecylacrylate-block-styrene) (PS-b- PMA-r-PODA-b-PS) was synthesized by reversible addition fragmentation chain transfer polymerization. The triblock copolymer can generate a three-dimensional, physically crosslinked network by self-assembly, where the glassy PS domains physically crosslink the midblock chains. The side chain crystallization of the polyoctadecylacrylare (PODA) side chain generates a second reversible network enabling shape memory properties. Shape memory tests by uniaxial deformation and recovery of molded dog-bone shape samples demonstrate that shape fixities above 96% and shape recoveries above 98% were obtained for extensional strains up to 300%. An outstanding advantage of this shape memory material is that it can be very easily shaped and remolded by elevating the temperature to 140circ; C, and after remolding the initial shape memory properties are totally recovered by eliminating the defects introduced by the previous deformation cycling.

Responsive linear-dendritic block copolymers.

PubMed

Blasco, Eva; Piñol, Milagros; Oriol, Luis

2014-06-01

The combination of dendritic and linear polymeric structures in the same macromolecule opens up new possibilities for the design of block copolymers and for applications of functional polymers that have self-assembly properties. There are three main strategies for the synthesis of linear-dendritic block copolymers (LDBCs) and, in particular, the emergence of click chemistry has made the coupling of preformed blocks one of the most efficient ways of obtaining libraries of LDBCs. In these materials, the periphery of the dendron can be precisely functionalised to obtain functional LDBCs with self-assembly properties of interest in different technological areas. The incorporation of stimuli-responsive moieties gives rise to smart materials that are generally processed as self-assemblies of amphiphilic LDBCs with a morphology that can be controlled by an external stimulus. Particular emphasis is placed on light-responsive LDBCs. Furthermore, a brief review of the biomedical or materials science applications of LDBCs is presented. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Poly(Lactic Acid) Hemodialysis Membranes with Poly(Lactic Acid)-block-Poly(2-Hydroxyethyl Methacrylate) Copolymer As Additive: Preparation, Characterization, and Performance.

PubMed

Zhu, Lijing; Liu, Fu; Yu, Xuemin; Xue, Lixin

2015-08-19

Poly(lactic acid) (PLA) hemodialysis membranes with enhanced antifouling capability and hemocompatibility were developed using poly(lactic acid)-block-poly(2-hydroxyethyl methacrylate) (PLA-PHEMA) copolymers as the blending additive. PLA-PHEMA block copolymers were synthesized via reversible addition-fragmentation (RAFT) polymerization from aminolyzed PLA. Gel permeation chromatography (GPC) and (1)H-nuclear magnetic resonance ((1)H NMR) were applied to characterize the synthesized products. By blending PLA with the amphiphilic block copolymer, PLA/PLA-PHEMA membranes were prepared by nonsolvent induced phase separation (NIPS) method. Their chemistry and structure were characterized with X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and atomic force microscopy (AFM). The results revealed that PLA/PLA-PHEMA membranes with high PLA-PHEMA contents exhibited enhanced hydrophilicity, water permeability, antifouling and hemocompatibility. Especially, when the PLA-PHEMA concentration was 15 wt %, the water flux of the modified membrane was about 236 L m(-2) h(-1). Its urea and creatinine clearance was more than 0.70 mL/min, lysozyme clearance was about 0.50 mL/min, BSA clearance was as less as 0.31 mL/min. All the results suggest that PLA-PHEMA copolymers had served as effective agents for optimizing the property of PLA-based membrane for hemodialysis applications.

Synthesis of cyclopentadienyl capped polyethylene and subsequent block copolymer formation via hetero Diels-Alder (HDA) chemistry.

PubMed

Espinosa, Edgar; Glassner, Mathias; Boisson, Christophe; Barner-Kowollik, Christopher; D'Agosto, Franck

2011-09-15

In the current contribution it is demonstrated - for the first time - that poly(ethylene) (M(n) = 1,400 as well as 2,800 g  ·  mol(-1) , PDI = 1.2) can be readily equipped with highly reactive cyclopentadienyl (Cp) end groups. The Cp terminal poly(ethylene) can subsequently be reacted in an efficient hetero Diels-Alder (HDA) reaction with macromolecules (poly(isobornyl acrylate) (M(n) = 4,600 g  ·  mol(-1) , PDI = 1.10) and poly(styrene) (M(n) = 6,300 g  ·  mol(-1) , PDI = 1.13) featuring strongly electron withdrawing thiocarbonyl thio end groups, prepared via reversible addition fragmentation chain transfer (RAFT) polymerization employing benzylpyridin-2-yldithioformate (BPDF) as transfer agent. The resulting block copolymers have been analyzed via high-temperature size exclusion chromatography (SEC) as well as nuclear magnetic resonance (NMR) spectroscopy. The current system allows for the removal of the excess of the non-poly(ethylene) containing segment via filtration of the poly(ethylene)-containing block copolymer. However, the reaction temperatures need to be judiciously selected. Characterization of the generated block copolymers at elevated temperatures can lead - depending on the block copolymer type - to the occurrence of retro Diels-Alder processes. The present study thus demonstrates that RAFT-HDA ligation can be effectively employed for the generation of block copolymers containing poly(ethylene) segments. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Towards Well-Defined Polysilylenes and Polyphosphazenes

DTIC Science & Technology

1992-05-25

distribution), non - controlled degrees of polymerization and unknown end cyclopentasilanes 2 8 . The anionic intermediates have been observed groups. Some... control in polysilanes will be presented: ring-opening polymerization, and polymer modications.. Block and graft copolymers based on polysilanes will be...34sticks" to the surface of alkali metal and continues to grow to high possible to prepare polymers with controlled molecular weight, with low m"m

Well-defined block copolymers for gene delivery to dendritic cells: probing the effect of polycation chain-length.

PubMed

Tang, Rupei; Palumbo, R Noelle; Nagarajan, Lakshmi; Krogstad, Emily; Wang, Chun

2010-03-03

The development of safe and efficient polymer carriers for DNA vaccine delivery requires mechanistic understanding of structure-function relationship of the polymer carriers and their interaction with antigen-presenting cells. Here we have synthesized a series of diblock copolymers with well-defined chain-length using atom transfer radical polymerization and characterized the influence of polycation chain-length on the physico-chemical properties of the polymer/DNA complexes as well as the interaction with dendritic cells. The copolymers consist of a hydrophilic poly(ethylene glycol) block and a cationic poly(aminoethyl methacrylate) (PAEM) block. The average degree of polymerization (DP) of the PAEM block was varied among 19, 39, and 75, with nearly uniform distribution. With increasing PAEM chain-length, polyplexes formed by the diblock copolymers and plasmid DNA had smaller average particle size and showed higher stability against electrostatic destabilization by salt and heparin. The polymers were not toxic to mouse dendritic cells (DCs) and only displayed chain-length-dependent toxicity at a high concentration (1mg/mL). In vitro gene transfection efficiency and polyplex uptake in DCs were also found to correlate with chain-length of the PAEM block with the longer polymer chain favoring transfection and cellular uptake. The polyplexes induced a modest up-regulation of surface markers for DC maturation that was not significantly dependent on PAEM chain-length. Finally, the polyplex prepared from the longest PAEM block (DP of 75) achieved an average of 20% enhancement over non-condensed anionic dextran in terms of uptake by DCs in the draining lymph nodes 24h after subcutaneous injection into mice. Insights gained from studying such structurally well-defined polymer carriers and their interaction with dendritic cells may contribute to improved design of practically useful DNA vaccine delivery systems. Copyright 2009 Elsevier B.V. All rights reserved.

Block copolymers for alkaline fuel cell membrane materials

NASA Astrophysics Data System (ADS)

Li, Yifan

Alkaline fuel cells (AFCs) using anion exchange membranes (AEMs) as electrolyte have recently received considerable attention. AFCs offer some advantages over proton exchange membrane fuel cells, including the potential of non-noble metal (e.g. nickel, silver) catalyst on the cathode, which can dramatically lower the fuel cell cost. The main drawback of traditional AFCs is the use of liquid electrolyte (e.g. aqueous potassium hydroxide), which can result in the formation of carbonate precipitates by reaction with carbon dioxide. AEMs with tethered cations can overcome the precipitates formed in traditional AFCs. Our current research focuses on developing different polymer systems (blend, block, grafted, and crosslinked polymers) in order to understand alkaline fuel cell membrane in many aspects and design optimized anion exchange membranes with better alkaline stability, mechanical integrity and ionic conductivity. A number of distinct materials have been produced and characterized. A polymer blend system comprised of poly(vinylbenzyl chloride)-b-polystyrene (PVBC-b-PS) diblock copolymer, prepared by nitroxide mediated polymerization (NMP), with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) or brominated PPO was studied for conversion into a blend membrane for AEM. The formation of a miscible blend matrix improved mechanical properties while maintaining high ionic conductivity through formation of phase separated ionic domains. Using anionic polymerization, a polyethylene based block copolymer was designed where the polyethylene-based block copolymer formed bicontinuous morphological structures to enhance the hydroxide conductivity (up to 94 mS/cm at 80 °C) while excellent mechanical properties (strain up to 205%) of the polyethylene block copolymer membrane was observed. A polymer system was designed and characterized with monomethoxy polyethylene glycol (mPEG) as a hydrophilic polymer grafted through substitution of pendent benzyl chloride groups of a PVBC-b-PS. The incorporation of the hydrophilic polymer allows for an investigation of the effect of hydration on ionic conductivity, resulting in the increase in membrane water affinity, enhancement of conductivity and reduced dependence of conductivity on relative humidity. A study of crosslinking of block copolymers was done wherein the crosslinking occurs in the non-matrix phase in order to maintain mechanical properties. The formation of a cationic crosslinked structure improves the mechanical integrity of the membrane in water while showing little deleterious effect on ionic conductivity and mechanical properties.

Membrane surface engineering for protein separations: experiments and simulations.

PubMed

Liu, Zizhao; Du, Hongbo; Wickramasinghe, S Ranil; Qian, Xianghong

2014-09-09

A bisphosphonate derived ligand was successfully synthesized and grafted from the surface of regenerated cellulose membrane using atom transfer radical polymerization (ATRP) for protein separations. This ligand has a remarkable affinity for arginine (Arg) residues on protein surface. Hydrophilic residues N-(2-hydroxypropyl) methacrylamide (HPMA) was copolymerized to enhance the flexibility of the copolymer ligand and further improve specific protein adsorption. The polymerization of bisphosphonate derivatives was successful for the first time using ATRP. Static and dynamic binding capacities were determined for binding and elution of Arg rich lysozyme. The interaction mechanism between the copolymer ligand and lysozyme was elucidated using classical molecular dynamics (MD) simulations.

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).

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.

Polymeric micelles based on poly(methacrylic acid) block-containing copolymers with different membrane destabilizing properties for cellular drug delivery.

PubMed

Mebarek, Naila; Aubert-Pouëssel, Anne; Gérardin, Corine; Vicente, Rita; Devoisselle, Jean-Marie; Bégu, Sylvie

2013-10-01

Poly(methacrylic acid)-b-poly(ethylene oxide) are double hydrophilic block copolymers, which are able to form micelles by complexation with a counter-polycation, such as poly-l-lysine. A study was carried out on the ability of the copolymers to interact with model membranes as a function of their molecular weights and as a function of pH. Different behaviors were observed: high molecular weight copolymers respect the membrane integrity, whereas low molecular weight copolymers with a well-chosen asymmetry degree can induce a membrane alteration. Hence by choosing the appropriate molecular weight, micelles with distinct membrane interaction behaviors can be obtained leading to different intracellular traffics with or without endosomal escape, making them interesting tools for cell engineering. Especially micelles constituted of low molecular weight copolymers could exhibit the endosomal escape property, which opens vast therapeutic applications. Moreover micelles possess a homogeneous nanometric size and show variable properties of disassembly at acidic pH, of stability in physiological conditions, and finally of cyto-tolerance. Copyright © 2013 Elsevier B.V. All rights reserved.

Spontaneously self-assembled micelles from poly(ethylene glycol)-b-poly(epsilon-caprolactone-co-trimethylene carbonate) for drug solubilization.

PubMed

Latere, Dwan'Isa J P; Rouxhet, L; Brewster, M E; Préat, V; Ariën, A

2008-03-01

Di-block copolymers composed of polyethylene glycol (PEG) and a second block of (co)polyesters of epsilon-caprolactone (CL) and/or trimethylene carbonate (TMC) were synthesized and characterized. Tin octoate was used as catalyst and polymerization were completed over a period of 24 h with high conversion (> 95%). Self-assembling properties in water were evaluated. All di-block copolymers behave similarly except when PCL served as the second block. Stable crew-cut micelles of about 20 nm were obtained by direct dissolution of the liquid di-block copolymers in water at room temperature. When PCL was present as the second block, no solubilization occurred. Drug encapsulation of poorly water-soluble drugs belonging to biopharmaceutics classification system (BCS) class II (ketoprofen and furosemide) was evaluated. Experimental solubility for these two drugs shows a significant enhancement such that a maximum value of 23.4 mg/ml was obtained for ketoprofen in a 10% w/v micellar solution as compared to 0.14 mg in water. In the case of furosemide, the solubility increased from 0.04 mg/ml in water to about 3.2 mg/ml in a 10% w/v micellar solution. Enzymatic degradation of diblock copolymers was also studied in the presence of Pseudomonas lipase in a phosphate buffer solution (pH 7.4). Results indicated rapid degradation of copolymers containing relatively higher amounts of CL compared to TMC suggesting the potential in vivo degradation.

Hyperbranched PEGmethacrylate linear pDMAEMA block copolymer as an efficient non-viral gene delivery vector.

PubMed

Mathew, Asha; Cao, Hongliang; Collin, Estelle; Wang, Wenxin; Pandit, Abhay

2012-09-15

A unique hyperbranched polymeric system with a linear poly-2-dimethylaminoethyl methacrylate (pDMAEMA) block and a hyperbranched polyethylene glycol methyl ether methacrylate (PEGMEMA) and ethylene dimethacrylate (EGDMA) block was designed and synthesized via deactivation enhanced atom transfer radical polymerisation (DE-ATRP) for efficient gene delivery. Using this unique structure, with a linear pDMAEMA block, which efficiently binds to plasmid DNA (pDNA) and hyperbranched polyethylene glycol (PEG) based block as a protective shell, we were able to maintain high transfection levels without sacrificing cellular viability even at high doses. The transfection capability and cytotoxicity of the polymers over a range of pDNA concentration were analysed and the results were compared to commercially available transfection vectors such as polyethylene imine (branched PEI, 25 kDa), partially degraded poly(amido amine)dendrimer (dPAMAM; commercial name: SuperFect(®)) in fibroblasts and adipose tissue derived stem cells (ADSCs). Copyright © 2012 Elsevier B.V. All rights reserved.

Ion solvation in polymer blends and block copolymer melts: effects of chain length and connectivity on the reorganization of dipoles.

PubMed

Nakamura, Issei

2014-05-29

We studied the thermodynamic properties of ion solvation in polymer blends and block copolymer melts and developed a dipolar self-consistent field theory for polymer mixtures. Our theory accounts for the chain connectivity of polymerized monomers, the compressibility of the liquid mixtures under electrostriction, the permanent and induced dipole moments of monomers, and the resultant dielectric contrast among species. In our coarse-grained model, dipoles are attached to the monomers and allowed to rotate freely in response to electrostatic fields. We demonstrate that a strong electrostatic field near an ion reorganizes dipolar monomers, resulting in nonmonotonic changes in the volume fraction profile and the dielectric function of the polymers with respect to those of simple liquid mixtures. For the parameter sets used, the spatial variations near an ion can be in the range of 1 nm or larger, producing significant differences in the solvation energy among simple liquid mixtures, polymer blends, and block copolymers. The solvation energy of an ion depends substantially on the chain length in block copolymers; thus, our theory predicts the preferential solvation of ions arising from differences in chain length.

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

PubMed

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

2018-04-14

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

Controlling the Pore Size of Mesoporous Carbon Thin Films through Thermal and Solvent Annealing.

PubMed

Zhou, Zhengping; Liu, Guoliang

2017-04-01

Herein an approach to controlling the pore size of mesoporous carbon thin films from metal-free polyacrylonitrile-containing block copolymers is described. A high-molecular-weight poly(acrylonitrile-block-methyl methacrylate) (PAN-b-PMMA) is synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The authors systematically investigate the self-assembly behavior of PAN-b-PMMA thin films during thermal and solvent annealing, as well as the pore size of mesoporous carbon thin films after pyrolysis. The as-spin-coated PAN-b-PMMA is microphase-separated into uniformly spaced globular nanostructures, and these globular nanostructures evolve into various morphologies after thermal or solvent annealing. Surprisingly, through thermal annealing and subsequent pyrolysis of PAN-b-PMMA into mesoporous carbon thin films, the pore size and center-to-center spacing increase significantly with thermal annealing temperature, different from most block copolymers. In addition, the choice of solvent in solvent annealing strongly influences the block copolymer nanostructure and the pore size of mesoporous carbon thin films. The discoveries herein provide a simple strategy to control the pore size of mesoporous carbon thin films by tuning thermal or solvent annealing conditions, instead of synthesizing a series of block copolymers of various molecular weights and compositions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent-Vapor-Mitigation of Electrostatics in 3D Cyclopropenium Diblock Copolyelectrolyte Network

NASA Astrophysics Data System (ADS)

Russell, Sebastian; Kumar, Sanat; Campos, Luis

Photolithography is progressively becoming an obsolete manufacturing technique in the microelectronic industry as block copolymer (BCP) nanoassembles approach sub 10-nm features sizes. Thermodynamically, the morphology and limiting feature size, for BCP, are determined by the relative volume fraction and magnitude of the incompatibility (χN) between each block. Therefore, to achieve smaller dimensions, it is imperative to devise copolymer systems that are strongly segregating (χN >>10) by utilizing high monomer incompatibility, large χ. For synthetic cylinder forming BCPs, achieving sub-10 nm features with a high degree of lateral ordering still remains a challenge. Covalently bound ions could potentially be a route towards enhancing the segmental incompatibility and this presentation will focus on the self-assembly of post-polymerization functionalized cyclopropenium-ion diblock copolyelectrolytes (DBCPE) through solvent vapor annealing. By varying the BCPE's total degree of polymerization and charge fraction we have mapped the kinetic phase-space. This control over morphology has opened the door to sub-10nm features with tunable densities by varying the length of the neutral and polyelectrolyte block, respectively. Chemical Engineering Department.

Poly(DL-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate): synthesis, characterization, micellization behavior in aqueous solutions, and encapsulation of the hydrophobic drug dipyridamole.

PubMed

Karanikolopoulos, Nikos; Zamurovic, Miljana; Pitsikalis, Marinos; Hadjichristidis, Nikos

2010-02-08

We synthesized a series of well-defined poly(dl-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) (PDLLA-b-PDMAEMA) amphiphilic diblock copolymers by employing a three-step procedure: (a) ring-opening polymerization (ROP) of dl-lactide using n-decanol and stannous octoate, Sn(Oct)(2), as the initiating system, (b) reaction of the PDLLA hydroxyl end groups with bromoisobutyryl bromide, and (c) atom transfer radical polymerization, ATRP, of DMAEMA with the newly created bromoisobutyryl initiating site. The aggregation behavior of the prepared block copolymers was investigated by dynamic light scattering and zeta potential measurements at 25 degrees C in aqueous solutions of different pH values. The hydrophobic drug dipyridamole was efficiently incorporated into the copolymer aggregates in aqueous solutions of pH 7.40. High partition coefficient values were determined by fluorescence spectroscopy.

Mechanically Resilient Polymeric Films Doped with a Lithium Compound

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B. (Inventor); Kinder, James D. (Inventor)

2005-01-01

This invention is a series of mechanically resilient polymeric films, comprising rod-coil block polyimide copolymers, which are doped with a lithium compound providing lithium ion conductivity, that are easy to fabricate into mechanically resilient films with acceptable ionic or protonic conductivity at a variety of temperatures. The copolymers consists of short-rigid polyimide rod segments alternating with polyether coil segments. The rods and coil segments can be linear, branched or mixtures of linear and branched segments. The highly incompatible rods and coil segments phase separate, providing nanoscale channels for ion conduction. The polyimide segments provide dimensional and mechanical stability and can be functionalized in a number of ways to provide specialized functions for a given application. These rod-coil black polyimide copolymers are particularly useful in the preparation of ion conductive membranes for use in the manufacture of fuel cells and lithium based polymer batteries.

Simultaneous Size Control of Microcapsule and Its Nanopores Using Polymer Concentration

NASA Astrophysics Data System (ADS)

Cha, Jemyung; Jeong, Eun Ho; Takahiro, Arakawa; Kim, Kyung Chun; Shoji, Shuich; Go, Jeung Sang

2010-03-01

Polymeric microcapsules with nanopores are produced using the droplet-based self-assembly of a block copolymer in the microfluidic channel. Differently from the conventional wise, the sizes of the microcapsule and its nanopores are controlled by changing the concentration of the block copolymer dissolved in an organic solvent. The increase in the polymer concentration shows the increase in the size of the microcapsule and the decrease of the size and number of the nanopores. Also, to obtain the optimal morphology of the nanopores in the microcapsule, the removal process of a surfactant is newly developed by using a microporous metal mesh.

Block copolymer modified surfaces for conjugation of biomacromolecules with control of quantity and activity.

PubMed

Li, Xin; Wang, Mengmeng; Wang, Lei; Shi, Xiujuan; Xu, Yajun; Song, Bo; Chen, Hong

2013-01-29

Polymer brush layers based on block copolymers of poly(oligo(ethylene glycol) methacrylate) (POEGMA) and poly(glycidyl methacrylate) (PGMA) were formed on silicon wafers by activators generated by electron transfer atom transfer radical polymerization (AGET ATRP). Different types of biomolecule can be conjugated to these brush layers by reaction of PGMA epoxide groups with amino groups in the biomolecule, while POEGMA, which resists nonspecific protein adsorption, provides an antifouling environment. Surfaces were characterized by water contact angle, ellipsometry, and Fourier transform infrared spectroscopy (FTIR) to confirm the modification reactions. Phase segregation of the copolymer blocks in the layers was observed by AFM. The effect of surface properties on protein conjugation was investigated using radiolabeling methods. It was shown that surfaces with POEGMA layers were protein resistant, while the quantity of protein conjugated to the diblock copolymer modified surfaces increased with increasing PGMA layer thickness. The activity of lysozyme conjugated on the surface could also be controlled by varying the thickness of the copolymer layer. When biotin was conjugated to the block copolymer grafts, the surface remained resistant to nonspecific protein adsorption but showed specific binding of avidin. These properties, that is, well-controlled quantity and activity of conjugated biomolecules and specificity of interaction with target biomolecules may be exploited for the improvement of signal-to-noise ratio in sensor applications. More generally, such surfaces may be useful as biological recognition elements of high specificity for functional biomaterials.

Investigation of a new thermosensitive block copolymer micelle: hydrolysis, disruption, and release.

PubMed

Pelletier, Maxime; Babin, Jérôme; Tremblay, Luc; Zhao, Yue

2008-11-04

Thermosensitive polymer micelles are generally obtained with block copolymers in which one block exhibits a lower critical solution temperature in aqueous solution. We investigate a different design that is based on the use of one block bearing a thermally labile side group, whose hydrolysis upon heating shifts the hydrophilic-hydrophobic balance toward the destabilization of block copolymer micelles. Atom transfer radical polymerization was utilized to synthesize a series of diblock copolymers composed of hydrophilic poly(ethylene oxide) (PEO) and hydrophobic poly(2-tetrahydropyranyl methacrylate) (PTHPMA). We show that micelles of PEO-b-PTHPMA in aqueous solution can be destabilized as a result of the thermosensitive hydrolytic cleavage of tetrahydropyranyl (THP) groups that transforms PTHPMA into hydrophilic poly(methacrylic acid). The three related processes occurring in aqueous solution, namely, hydrolytic cleavage of THP, destabilization of micelles, and release of loaded Nile Red (NR), were investigated simultaneously using 1H NMR, dynamic light scattering, and fluorescence spectroscopy, respectively. At 80 degrees C, the results suggest that the three events proceed with a similar kinetics. Although slower than at elevated temperatures, the disruption of PEO-b-PTHPMA micelles can take place at the body temperature (approximately 37 degrees C), and the release kinetics of NR can be adjusted by changing the relative lengths of the two blocks or the pH of the solution.

Novel Redox-Responsive Amphiphilic Copolymer Micelles for Drug Delivery: Synthesis and Characterization.

PubMed

Bae, Jungeun; Maurya, Abhijeet; Shariat-Madar, Zia; Murthy, S Narasimha; Jo, Seongbong

2015-11-01

A novel redox-responsive amphiphilic polymer was synthesized with bioreductive trimethyl-locked quinone propionic acid for a potential triggered drug delivery application. The aim of this study was to synthesize and characterize the redox-responsive amphiphilic block copolymer micelles containing pendant bioreductive quinone propionic acid (QPA) switches. The redox-responsive hydrophobic block (polyQPA), synthesized from QPA-serinol and adipoyl chloride, was end-capped with methoxy poly(ethylene glycol) of molecular weight 750 (mPEG750) to achieve a redox-responsive amphiphilic block copolymer, polyQPA-mPEG750. PolyQPA-mPEG750 was able to self-assemble as micelles to show a critical micelle concentration (CMC) of 0.039% w/v (0.39 mg/ml, 0.107 mM) determined by a dye solubilization method using 1,6-diphenyl-1,3,5-hexatriene (DPH) in phosphate-buffered saline (PBS). The mean diameter of polymeric micelles was found to be 27.50 nm (PI = 0.064) by dynamic light scattering. Furthermore, redox-triggered destabilization of the polymeric micelles was confirmed by (1)H-NMR spectroscopy and particle size measurements in a simulated redox state. PolyQPA-mPEG750 underwent triggered reduction to shed pendant redox-responsive QPA groups and its polymeric micelles were swollen to be dissembled in the presence of a reducing agent, thereby enabling the release of loaded model drug, paclitaxel. The redox-responsive polyQPA-mPEG750 polymer micelles would be useful as a drug delivery system allowing triggered drug release in an altered redox state such as tumor microenvironments with an altered redox potential and/or redox enzyme upregulation.

Syntheses, structures and properties of polycarbosilanes formed directly by polymerization of Alkenylsilanes

NASA Technical Reports Server (NTRS)

Masnovi, John; Bu, Xin Y.; Beyene, Kassahun; Heimann, Paula; Kacik, Terrence; Andrist, A. Harry; Hurwitz, Frances I.

1993-01-01

Vinylsilane polymerizes to form predominantly a carbosilane polymer using dimethyltitanocene catalyst. This is in contrast to alkylsilanes, which afford polysilanes under the same conditions. The mechanism of polymerization of alkenylsilanes has been shown to be fundamentally different from that for the polymerization of alkylsilanes. The silyl substitute apparently activates a double bond to participate in a number of polymerization processes in this system, particularly hydrosilation. Isotopic labeling indicates the involvement of silametallocyclic intermediates, accompanied by extensive nuclear rearrangement. Polymers and copolymers derived from alkenylsilanes have relatively high char yields even for conditions which afford low molecular weight distributions. Formation of crystalline beta-SiC is optimum for a copolymer of an alkylsilane and an alkenylsilane having a silane/carbosilane backbone ratio of 85/15 and a C/Si ratio of 1.3/1.

PAA-PAMPS copolymers as an efficient tool to control CaCO3 scale formation.

PubMed

Dietzsch, Michael; Barz, Matthias; Schüler, Timo; Klassen, Stefanie; Schreiber, Martin; Susewind, Moritz; Loges, Niklas; Lang, Michael; Hellmann, Nadja; Fritz, Monika; Fischer, Karl; Theato, Patrick; Kühnle, Angelika; Schmidt, Manfred; Zentel, Rudolf; Tremel, Wolfgang

2013-03-05

Scale formation, the deposition of certain minerals such as CaCO3, MgCO3, and CaSO4·2H2O in industrial facilities and household devices, leads to reduced efficiency or severe damage. Therefore, incrustation is a major problem in everyday life. In recent years, double hydrophilic block copolymers (DHBCs) have been the focus of interest in academia with regard to their antiscaling potential. In this work, we synthesized well-defined blocklike PAA-PAMPS copolymers consisting of acrylic acid (AA) and 2-acrylamido-2-methyl-propane sulfonate (AMPS) units in a one-step reaction by RAFT polymerization. The derived copolymers had dispersities of 1.3 and below. The copolymers have then been investigated in detail regarding their impact on the different stages of the crystallization process of CaCO3. Ca(2+) complexation, the first step of a precipitation process, and polyelectrolyte stability in aqueous solution have been investigated by potentiometric measurements, isothermal titration calorimetry (ITC), and dynamic light scattering (DLS). A weak Ca(2+) induced copolymer aggregation without concomitant precipitation was observed. Nucleation, early particle growth, and colloidal stability have been monitored in situ with DLS. The copolymers retard or even completely suppress nucleation, most probably by complexation of solution aggregates. In addition, they stabilize existing CaCO3 particles in the nanometer regime. In situ AFM was used as a tool to verify the coordination of the copolymer to the calcite (104) crystal surface and to estimate its potential as a growth inhibitor in a supersaturated CaCO3 environment. All investigated copolymers instantly stopped further crystal growth. The carboxylate richest copolymer as the most promising antiscaling candidate proved its enormous potential in scale inhibition as well in an industrial-filming test (Fresenius standard method).

Soft nanoparticles: nano ionic networks of associated ionic polymers

DOE PAGES

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

2017-01-01

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

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

General Syntheses of Nanotubes Induced by Block Copolymer Self-Assembly.

PubMed

Zhao, Jianming; Huang, Wei; Si, Pengchao; Ulstrup, Jens; Diao, Fangyuan; Zhang, Jingdong

2018-06-01

Amphiphilic block copolymer templating strategies are extensively used for syntheses of mesoporous materials. However, monodisperse tubular nanostructures are limited. Here, a general method is developed to synthesize monodisperse nanotubes with narrow diameter distribution induced by self-assembly of block copolymer. 3-Aminophenol (AP) and formaldehyde (F) polymerize and self-assemble with cylindrical PS-b-PEO micelles into worm-like PS-b-PEO@APF composites with uniform diameter (49 ± 3 nm). After template extraction, worm-like APF polymer nanotubes are formed. The structure and morphology of the polymer nanotubes can be tuned by regulating the synthesis conditions. Furthermore, PS-b-PEO@APF composites are uniformly converted to isomorphic carbon nanotubes with large surface area of 662 m 2 g -1 , abundant hierarchical porous frameworks and nitrogen doping. The synthesis can be extended to silica nanotubes. These findings open an avenue to the design of porous materials with controlled structural framework, composition, and properties for a wide range of applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A simple approach to characterizing block copolymer assemblies: graphene oxide supports for high contrast multi-technique imaging†

PubMed Central

Patterson, Joseph P.; Sanchez, Ana M.; Petzetakis, Nikos; Smart, Thomas P.; Epps, Thomas H.; Portman, Ian

2013-01-01

Block copolymers are well-known to self-assemble into a range of 3-dimensional morphologies. However, due to their nanoscale dimensions, resolving their exact structure can be a challenge. Transmission electron microscopy (TEM) is a powerful technique for achieving this, but for polymeric assemblies chemical fixing/staining techniques are usually required to increase image contrast and protect specimens from electron beam damage. Graphene oxide (GO) is a robust, water-dispersable, and nearly electron transparent membrane: an ideal support for TEM. We show that when using GO supports no stains are required to acquire high contrast TEM images and that the specimens remain stable under the electron beam for long periods, allowing sample analysis by a range of electron microscopy techniques. GO supports are also used for further characterization of assemblies by atomic force microscopy. The simplicity of sample preparation and analysis, as well as the potential for significantly increased contrast background, make GO supports an attractive alternative for the analysis of block copolymer assemblies. PMID:24049544

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).

WATER-BORNE BLOCK AND STATISTICAL COPOLYMERS SYNTHESIZED USING ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Morphology Control of Multicomponent Polymeric Surfactants Using Pressure

NASA Astrophysics Data System (ADS)

Cho, Junhan

The development of nanoscale morphologies for a molten polymeric surfactant under pressure is investigated by using a recently formulated self-consistent field theory. A linear ABC block copolymer is taken as our model system that allows a disparity in the propensities for curved interfaces and pressure responses of ij-pairs. The interplay of those features lead the copolymer to new morphologies at a moderate segregation level and at ambient condition such as networks and pillars of 2-dimensional array. It is shown that pressure is an effective means of morphology control and identification for those new structures. The role of volume fluctuations in the development of those structures is discussed. J.C. acknowledges the support from Center for Photofunctional Energy Materials through Gyeonggi Regional Research Program.

Contact Active Antimicrobial Coatings Prepared by Polymer Blending.

PubMed

Cuervo-Rodríguez, Rocío; López-Fabal, Fátima; Gómez-Garcés, José L; Muñoz-Bonilla, Alexandra; Fernández-García, Marta

2017-11-01

Herein, contact active antimicrobial films are prepared by simply blending cationic amphiphilic block copolymers with commercial polystyrene (PS). The copolymers are prepared by combining atom transfer radical polymerization and "click chemistry." A variety of copolymers are synthesized, and composed of a PS segment and an antimicrobial block bearing flexible side chain with thiazole and triazole groups, 4-(1-(2-(4-methylthiazol-5-yl)ethyl)-1H-1,2,3-triazol-4-yl) butyl methacrylate (TTBM). The length of the TTBM block is varied as well as the alkylating agent. Different films are prepared from N,N-dimethylformamide solution, containing variable PS-b-PTTBM/PS ratio: from 0 to 100 wt%. Remarkably, the blend films, especially those with 30 and 50 wt% of copolymers, exhibit excellent antimicrobial activities against Gram-positive, Gram-negative bacteria and fungi, even higher than films prepared exclusively from the cationic copolymers. Blends composed of 50 wt% of the copolymers present a more than 99.999% killing efficiency against the studied microorganisms. The better activity found in blends can be due to the higher roughness, which increases the surface area and consequently the contact with the microorganisms. These results demonstrate that the use of blends implies a reduction of the content of antimicrobial agent and also enhances the antimicrobial activity, providing new insights for the better designing of antimicrobial coatings. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties

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

Lu, Wei; Huang, Caili; Hong, Kunlun

Living anionic polymerization of acrylates is challenging due to intrinsic side reactions including backbiting reactions of propagating enolate anions and aggregation of active chain ends. In this study, the controlled synthesis of poly(1-adamatyl acrylate) (PAdA) was performed successfully for the first time via living anionic polymerization through investigation of the initiation systems of sec-butyllithium/diphenylethylene/lithium chloride (sec-BuLi/DPE/LiCl), diphenylmethylpotassium/diethylzinc (DPMK/Et 2Zn), and sodium naphthalenide/dipenylethylene/diethylzinc (Na-Naph/DPE/Et2Zn) in tetrahydrofuran at -78 °C using custom glass-blowing and high-vacuum techniques. PAdA synthesized via anionic polymerization using DPMK with a large excess (more than 40-fold to DPMK) of Et 2Zn as the ligand exhibited predicted molecular weightsmore » from 4.3 to 71.8 kg/mol and polydispersity indices of around 1.10. In addition, the produced PAdAs exhibit a low level of isotactic content (mm triads of 2.1%). The block copolymers of AdA and methyl methacrylate (MMA) were obtained by sequential anionic polymerization, and the distinct living property of PAdA over other acrylates was demonstrated based on the observation that the resulting PAdA-b-PMMA block copolymers were formed with no residual PAdA homopolymer. The PAdA homopolymers exhibit a very high glass transition temperature (133 °C) and outstanding thermal stability (T d: 376 °C) as compared to other acrylic polymers such as poly(tert-butyl acrylate) and poly(methyl acrylate). These merits make PAdA a promising candidate for acrylic-based thermoplastic elastomers with high upper service temperature and enhanced mechanical strength.« less

Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties

DOE PAGES

Lu, Wei; Huang, Caili; Hong, Kunlun; ...

2016-12-06

Living anionic polymerization of acrylates is challenging due to intrinsic side reactions including backbiting reactions of propagating enolate anions and aggregation of active chain ends. In this study, the controlled synthesis of poly(1-adamatyl acrylate) (PAdA) was performed successfully for the first time via living anionic polymerization through investigation of the initiation systems of sec-butyllithium/diphenylethylene/lithium chloride (sec-BuLi/DPE/LiCl), diphenylmethylpotassium/diethylzinc (DPMK/Et 2Zn), and sodium naphthalenide/dipenylethylene/diethylzinc (Na-Naph/DPE/Et2Zn) in tetrahydrofuran at -78 °C using custom glass-blowing and high-vacuum techniques. PAdA synthesized via anionic polymerization using DPMK with a large excess (more than 40-fold to DPMK) of Et 2Zn as the ligand exhibited predicted molecular weightsmore » from 4.3 to 71.8 kg/mol and polydispersity indices of around 1.10. In addition, the produced PAdAs exhibit a low level of isotactic content (mm triads of 2.1%). The block copolymers of AdA and methyl methacrylate (MMA) were obtained by sequential anionic polymerization, and the distinct living property of PAdA over other acrylates was demonstrated based on the observation that the resulting PAdA-b-PMMA block copolymers were formed with no residual PAdA homopolymer. The PAdA homopolymers exhibit a very high glass transition temperature (133 °C) and outstanding thermal stability (T d: 376 °C) as compared to other acrylic polymers such as poly(tert-butyl acrylate) and poly(methyl acrylate). These merits make PAdA a promising candidate for acrylic-based thermoplastic elastomers with high upper service temperature and enhanced mechanical strength.« less

The effect of the processing and formulation parameters on the size of nanoparticles based on block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) with and without hydrolytically sensitive groups.

PubMed

Neradovic, D; Soga, O; Van Nostrum, C F; Hennink, W E

2004-05-01

Block copolymers of poly(ethylene glycol) (PEG) as a hydrophilic block and N-isopropylacrylamide (PNIPAAm) or poly (NIPAAm-co-N-(2-hydroxypropyl) methacrylamide-dilactate) (poly(NIPAAm-co-HPMAm-dilactate)) as a thermosensitive block, are able to self-assemble in water into nanoparticles above the cloud point (CP) of the thermosensitive block. The influence of processing and the formulation parameters on the size of the nanoparticles was studied using dynamic light scattering. PNIPAAm-b-PEG 2000 polymers were not suitable for the formation of small and stable particles. Block copolymers with PEG 5000 and 10000 formed relatively small and stable particles in aqueous solutions at temperatures above the CP of the thermosensitive block. Their size decreased with increasing molecular weight of the thermosensitive block, decreasing polymer concentration and using water instead of phosphate buffered saline as solvent. Extrusion and ultrasonication were inefficient methods to size down the polymeric nanoparticles. The heating rate of the polymer solutions was a dominant factor for the size of the nanoparticles. When an aqueous polymer solution was slowly heated through the CP, rather large particles (> or = 200 nm) were formed. Regardless the polymer composition, small nanoparticles (50-70 nm) with a narrow size distribution were formed, when a small volume of an aqueous polymer solution below the CP was added to a large volume of heated water. In this way the thermosensitive block copolymers rapidly pass their CP ('heat shock' procedure), resulting in small and stable nanoparticles.

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

A study on amphiphilic fluorinated block copolymer in graphite exfoliation using supercritical CO2 for stable graphene dispersion.

PubMed

Kim, Young Hyun; Lee, Hyang Moo; Choi, Sung Wook; Cheong, In Woo

2018-01-15

In this study, poly(2,2,2-trifluoroethyl methacrylate)-block-poly(4-vinylpyridine) (PTFEMA-b-PVP) was synthesized by stepwise reversible addition-fragmentation chain transfer (RAFT) polymerization for the preparation of graphene by the exfoliation of graphite nanoplatelets (GPs) in supercritical CO 2 (SCCO 2 ). Two different block copolymers (low and high molecular weights) were prepared with the same block ratio and used at different concentrations in the SCCO 2 process. The amount of PTFEMA-b-PVP adsorbed on the GPs and the electrical conductivity of the SCCO 2 -treated GP samples were evaluated using thermogravimetric analysis (TGA) and four-point probe method, respectively. All GP samples treated with SCCO 2 were then dispersed in methanol and the dispersion stability was investigated using online turbidity measurements. The concentration and morphology of few-layer graphene stabilized with PTFEMA-b-PVP in the supernatant solution were investigated by gravimetry, scanning electron microscopy, and Raman spectroscopy. Destabilization study of the graphene dispersions revealed that the longer block copolymer exhibited better affinity for graphene, resulting in a higher yield of stable graphene with minimal defects. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

Self-Assembled Polymeric Micelles Based on Hyaluronic Acid-g-Poly(d,l-lactide-co-glycolide) Copolymer for Tumor Targeting

PubMed Central

Son, Gyung Mo; Kim, Hyun Yul; Ryu, Je Ho; Chu, Chong Woo; Kang, Dae Hwan; Park, Su Bum; Jeong, Young-IL

2014-01-01

Graft copolymer composed hyaluronic acid (HA) and poly(d,l-lactide-co-glycolide) (PLGA) (HAgLG) was synthesized for antitumor targeting via CD44 receptor of tumor cells. The carboxylic end of PLGA was conjugated with hexamethylenediamine (HMDA) to have amine end group in the end of chain (PLGA-amine). PLGA-amine was coupled with carboxylic acid of HA. Self-assembled polymeric micelles of HAgLG have spherical morphologies and their sizes were around 50–200 nm. Doxorubicin (DOX)-incorporated polymeric micelles were prepared by dialysis procedure. DOX was released over 4 days and its release rate was accelerated by the tumoric enzyme hyaluronidase. To assess targetability of polymeric micelles, CD44-positive HepG2 cells were employed treated with fluorescein isothiocyanate (FITC)-labeled polymeric micelles. HepG2 cells strongly expressed green fluorescence at the cell membrane and cytosol. However, internalization of polymeric micelles were significantly decreased when free HA was pretreated to block the CD44 receptor. Furthermore, the CD44-specific anticancer activity of HAgLG polymeric micelles was confirmed using CD44-negative CT26 cells and CD44-positive HepG2 cells. These results indicated that polymeric micelles of HaLG polymeric micelles have targetability against CD44 receptor of tumor cells. We suggest HAgLG polymeric micelles as a promising candidate for specific drug targeting. PMID:25216338

Well-Defined Macromolecules Using Horseradish Peroxidase as a RAFT Initiase.

PubMed

Danielson, Alex P; Bailey-Van Kuren, Dylan; Lucius, Melissa E; Makaroff, Katherine; Williams, Cameron; Page, Richard C; Berberich, Jason A; Konkolewicz, Dominik

2016-02-01

Enzymatic catalysis and control over macromolecular architectures from reversible addition-fragmentation chain transfer polymerization (RAFT) are combined to give a new method of making polymers. Horseradish peroxidase (HRP) is used to catalytically generate radicals using hydrogen peroxide and acetylacetone as a mediator. RAFT is used to control the polymer structure. HRP catalyzed RAFT polymerization gives acrylate and acrylamide polymers with relatively narrow molecular weight distributions. The polymerization is rapid, typically exceeding 90% monomer conversion in 30 min. Complex macromolecular architectures including a block copolymer and a protein-polymer conjugate are synthesized using HRP to catalytically initiate RAFT polymerization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of Hyperbranched Block-Statistical Copolymer-Based Prodrug with Dual Sensitivities for Controlled Release.

PubMed

Zheng, Luping; Wang, Yunfei; Zhang, Xianshuo; Ma, Liwei; Wang, Baoyan; Ji, Xiangling; Wei, Hua

2018-01-17

Dendrimer with hyperbranched structure and multivalent surface is regarded as one of the most promising candidates close to the ideal drug delivery systems, but the clinical translation and scale-up production of dendrimer has been hampered significantly by the synthetic difficulties. Therefore, there is considerable scope for the development of novel hyperbranched polymer that can not only address the drawbacks of dendrimer but maintain its advantages. The reversible addition-fragmentation chain transfer self-condensing vinyl polymerization (RAFT-SCVP) technique has enabled facile preparation of segmented hyperbranched polymer (SHP) by using chain transfer monomer (CTM)-based double-head agent during the past decade. Meanwhile, the design and development of block-statistical copolymers has been proven in our recent studies to be a simple yet effective way to address the extracellular stability vs intracellular high delivery efficacy dilemma. To integrate the advantages of both hyperbranched and block-statistical structures, we herein reported the fabrication of hyperbranched block-statistical copolymer-based prodrug with pH and reduction dual sensitivities using RAFT-SCVP and post-polymerization click coupling. The external homo oligo(ethylene glycol methyl ether methacrylate) (OEGMA) block provides sufficient extracellularly colloidal stability for the nanocarriers by steric hindrance, and the interior OEGMA units incorporated by the statistical copolymerization promote intracellular drug release by facilitating the permeation of GSH and H + for the cleavage of the reduction-responsive disulfide bond and pH-liable carbonate link as well as weakening the hydrophobic encapsulation of drug molecules. The delivery efficacy of the target hyperbranched block-statistical copolymer-based prodrug was evaluated in terms of in vitro drug release and cytotoxicity studies, which confirms both acidic pH and reduction-triggered drug release for inhibiting proliferation of HeLa cells. Interestingly, the simultaneous application of both acidic pH and GSH triggers promoted significantly the cleavage and release of CPT compared to the exertion of single trigger. This study thus developed a facile approach toward hyperbranched polymer-based prodrugs with high therapeutic efficacy for anticancer drug delivery.

Development of mass production technology for block copolymer lithographic materials

NASA Astrophysics Data System (ADS)

Himi, Toshiyuki; Matsuki, Ryota; Kosaka, Terumasa; Ogaki, Ryosuke; Kawaguchi, Yukio; Shimizu, Tetsuo

2017-03-01

We have successfully synthesized various and over wide range molecular weight block copolymers (BCPs): these are polystyrene(PS)-polymethylmethacrylate(PMMA) as general components and poly(4-trimethylsilylstyrene)(PTMSS)- poly(4-hydroxystyrene)(PHS) system as very strong segregated components (high chi) and multiblock type of those copolymers which form the microphase-separated structure pattern using living anionic polymerizing method by which the size of polymer can be precisely controlled. In addition, we were able to observe alternating lamellar and cylinder structures which were formed by our various BCPs using small angle X-ray scattering (SAXS). Moreover, we have successfully developed new apparatus for high volume manufacturing including our original technologies such as purification of monomer, improvement of wetted surface, and mechanical technology for high vacuum. And we have successfully synthesized all the BCPs with narrow molecular weight distribution (PDI <1.1) with large-scale apparatus.

Switchable pH-responsive polymeric membranes prepared via block copolymer micelle assembly.

PubMed

Nunes, Suzana P; Behzad, Ali Reza; Hooghan, Bobby; Sougrat, Rachid; Karunakaran, Madhavan; Pradeep, Neelakanda; Vainio, Ulla; Peinemann, Klaus-Viktor

2011-05-24

A process is described to manufacture monodisperse asymmetric pH-responsive nanochannels with very high densities (pore density >2 × 10(14) pores per m(2)), reproducible in m(2) scale. Cylindric pores with diameters in the sub-10 nm range and lengths in the 400 nm range were formed by self-assembly of metal-block copolymer complexes and nonsolvent-induced phase separation. The film morphology was tailored by taking into account the stability constants for a series of metal-polymer complexes and confirmed by AFM. The distribution of metal-copolymer micelles was imaged by transmission electron microscopy tomography. The pH response of the polymer nanochannels is the strongest reported with synthetic pores in the nm range (reversible flux increase of more than 2 orders of magnitude when switching the pH from 2 to 8) and could be demonstrated by cryo-field emission scanning electron microscopy, SAXS, and ultra/nanofiltration experiments.

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

PubMed Central

Theriot, Jordan C.; Ryan, Matthew D.; French, Tracy A.; Pearson, Ryan M.; Miyake, Garret M.

2016-01-01

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The procedure is performed under an inert atmosphere using air- and water-exclusion techniques. The outcome of the polymerization is affected by the ratios of monomer, initiator, and catalyst used as well as the reaction concentration, solvent, and nature of the light source. Temporal control over the polymerization can be exercised by turning the visible light source off and on. Low dispersities of the resultant polymers as well as the ability to chain-extend to form block copolymers suggest control over the polymerization, while chain end-group analysis provides evidence supporting an atom-transfer radical polymerization mechanism. PMID:27166728

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

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

Kang, Beom-Goo; Pramanik, Nabendu B.; Singha, Nikhil K.

The anionic block copolymerization of 4,4' -vinylphenyl-N,N-bis(4-tert-butylphenyl)benzenamine (A) with furfuryl isocyanate (B) was carried out using potassium naphthalenide (K-Naph) in tetrahydrofuran at -78 and -98 °C to prepare well-defined block copolymers containing furan groups for the formation of thermoreversible networks via a Diels Alder (DA) reaction. While no block copolymerization was observed in the absence of sodium tetraphenylborate (NaBPh 4) due to side reactions, well-defined poly-(B-b-A-b-B) (PBAB) copolymers with controlled molecular weights (M n = 18 700 19 500 g mol -1) and narrow molecular weight distributions (M w/M n = 1.08 -1.17) were successfully synthesized in the presence ofmore » excess NaBPh 4. We prevented the occurrence of the undesirable side reactions during polymerization of B of NaBPh 4, which results in the change in the countercation from K + to Na + for further polymerization of B. Moreover, the cross-linking via the DA reaction between the furan groups of PBAB and bismaleimide was proved by FT-IR and differential scanning calorimetry (DSC), and the thermoreversible properties of the cross-linked polymer were subsequently investigated using DSC and solubility testing.« less

Block Copolymer-Based Supramolecular Elastomers with High Extensibility and Large Stress Generation Capability

NASA Astrophysics Data System (ADS)

Noro, Atsushi; Hayashi, Mikihiro

We prepared block copolymer-based supramolecular elastomers with high extensibility and large stress generation capability. Reversible addition fragmentation chain transfer polymerizations were conducted under normal pressure and high pressure to synthesize several large molecular weight polystyrene-b-[poly(butyl acrylate)-co-polyacrylamide]-b-polystyrene (S-Ba-S) block copolymers. Tensile tests revealed that the largest S-Ba-S with middle block molecular weight of 3140k achieved a breaking elongation of over 2000% with a maximum tensile stress of 3.6 MPa and a toughness of 28 MJ/m3 while the reference sample without any middle block hydrogen bonds, polystyrene-b-poly(butyl acrylate)-b-polystyrene with almost the same molecular weight, was merely viscous and not self-standing. Hence, incorporation of hydrogen bonds into a long soft middle block was found to be beneficial to attain high extensibility and large stress generation capability probably due to concerted combination of entropic changes and internal potential energy changes originaing from the dissociation of multiple hydrogen bonds by elongation. This work was supported by JSPS KAKENHI Grant Numbers 13J02357, 24685035, 15K13785, and 23655213 for M.H. and A.N. A.N. also expresses his gratitude for Tanaka Rubber Science & Technology Award by Enokagaku-Shinko Foundation, Japan.

Exploring Tyrosine-Triazolinedione (TAD) Reactions for the Selective Conjugation and Cross-Linking of N-Carboxyanhydride (NCA) Derived Synthetic Copolypeptides.

PubMed

Hanay, Saltuk B; Ritzen, Bas; Brougham, Dermot; Dias, Aylvin A; Heise, Andreas

2017-07-01

Highly efficient functionalization and cross-linking of polypeptides is achieved via tyrosine-triazolinedione (TAD) conjugation chemistry. The feasibility of the reaction is demonstrated by the reaction of 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) with tyrosine containing block copolymer poly(ethylene glycol)-Tyr 4 as well as a statistical copolymer of tyrosine and lysine (poly(Lys 40 -st-Tyr 10 )) prepared form N-carboxyanhydride polymerization. Selective reaction of PTAD with the tyrosine units is obtained and verified by size exclusion chromatography and NMR spectroscopy. Moreover, two monofunctional and two difunctional TAD molecules are synthesized. It is found that their stability in the aqueous reaction media significantly varied. Under optimized reaction conditions selective functionalization and cross-linking, yielding polypeptide hydrogels, can be achieved. TAD-mediated conjugation can offer an interesting addition in the toolbox of selective (click-like) polypeptide conjugation methodologies as it does not require functional non-natural amino acids. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polyimides containing oxyethylene units. Part 4: Polymerization of dianhydrides containing ether linkages

NASA Technical Reports Server (NTRS)

Harris, F. W.; Karnavas, A. J.; Das, S.; Cucuras, C. N.; Hergenrother, P. M.

1986-01-01

The development of new composite resins for various aerospace applications is attempted. Although it is highly desirable that these polymers be soluble in order to facilitate processing, they must display considerable solvent-resistance in use. A recent approach has involved the synthesis of a new series of polyimides containing flexible linkages. The polymers were prepared by the polymerization of aromatic dianhydrides with diamines containing oxyethylene linkages. For example, the polymerization of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) with 1,2-bis(4-aminophenoxy)ethane (1a) and bis2-(4-aminophenoxy)ethylether (lb), afforded highly crystalline polyimides that were completely insoluble. However, a polyimide that was amorphous and soluble was obtained from the polymerization of BTDA and an isomer of lb, i.e., bis2-(3-aminophenoxy)ethyl ether (4b). In an attempt to obtain a soluble, amorphous polyimide that could be annealed into a crysalline state, block copolymers of 1b and 4b and BTDA were prepared. Copolymers containing less than 20 weight % 1b were soluble in organic solvents. However, these polymers did not crystallize when heated above their Tg's. Copolymers containing higher levels of 1b were semicrystalline and insoluble. The polymerization of the diamines containing oxyethylene linkages with 4,4'-oxydiphthalic anhydride (ODPA) and a new dianhydride, i.e., 4,4'-oxyethyleneoxyethyleneoxydiphthalic anhydride (OEDA) was investigated. It was postulated that the use of these more flexible dianhydrides would result in more processable polyimides.

Branched Rod-Coil Polyimide-Poly(Alkylene Oxide) Copolymers and Electrolyte Compositions

NASA Technical Reports Server (NTRS)

Meador, Maryann B. (Inventor); Tigelaar, Dean M. (Inventor)

2014-01-01

Crosslinked polyimide-poly(alkylene oxide) copolymers capable of holding large volumes of liquid while maintaining good dimensional stability. Copolymers are derived at ambient temperatures from amine endcapped amic-acid oligomers subsequently imidized in solution at increased temperatures, followed by reaction with trifunctional compounds in the presence of various additives. Films of these copolymers hold over four times their weight at room temperature of liquids such as ionic liquids (RTIL) and/or carbonate solvents. These rod-coil polyimide copolymers are used to prepare polymeric electrolytes by adding to the copolymers various amounts of compounds such as ionic liquids (RTIL), lithium trifluoromethane-sulfonimide (LiTFSi) or other lithium salts, and alumina.

Functional Materials from Polymeric Ionic Liquids

NASA Astrophysics Data System (ADS)

Segalman, Rachel; Sanoja, Gabriel; Michenfelder-Schauser, Nicole; Mitragotri, Samir; Seshadri, Ram

Ionic liquids (IL's) have been suggested for applications as diverse as solubilizing cellulose, antimicrobial treatments, and electrolytes in batteries due to their molten salt properties. A polymeric cation (such as imidazolium) is an excellent host for any associated anion. As a result, polymerized ionic liquids are not just solid counterparts to IL's, but are shown to be vectors for the inclusion of a wide variety of functionalities ranging from multi-valent ions to magnetic anions. Moreover, PIL block copolymers allow orthogonal control over mechanical and morphological properties, ultimately leading to a conceptual framework for processable, tunable, multifunctional materials.

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.

Enzymatic preparation of novel thermoplastic di-block copolyesters containing poly[(R)-3-hydroxybutyrate] and poly(epsilon-caprolactone) blocks via ring-opening polymerization.

PubMed

Dai, Shiyao; Li, Zhi

2008-07-01

Enzymatic modification of a microbial polyester was achieved by the ring-opening polymerization of epsilon-caprolactone (CL) with low-molecular weight telechelic hydroxylated poly[( R)-3-hydroxybutyrate] (PHB-diol) as initiator and Novozym 435 (immobilized Candida antarctica Lipase B) as catalyst in anhydrous 1,4-dioxane or toluene. The ring-opening polymerization was investigated at different conditions with two different types of PHB-diols: PHB-diol(P), containing a primary OH and a secondary OH end groups, and PHB-diol(M), consisting of 91% PHB-diol(P) and 9% PHB-diol containing two secondary OH end groups. The reactions were followed by GPC analyses of the resulting polymers at different time points, and the optimal conditions were established to be 70 degrees C at a weight ratio of CL/enzyme/solvent of 8:1:24. The ring-opening polymerization of CL with PHB-diol(M) (Mn of 2380, NMR) at the molar ratio of 50:1 under the optimal conditions in 1,4-dioxane gave the corresponding poly[HB(56 wt %)-co-CL(44 wt %)] with Mn (NMR) of 3900 in 66% yield. Polymerization of CL and PHB-diol(P) ( Mn of 2010, NMR) at the same condition in toluene gave the corresponding poly[HB(28 wt %)-co-CL(72 wt %)] with Mn (NMR) of 7100 in 86% yield. Both polymers were characterized by (1)H and (13)C NMR and IR analyses as di-block copolyesters containing a PHB block with a secondary OH end group and a poly(epsilon-caprolactone) (PCL) block with a primary OH end group. NMR analyses and control experiments suggested no formation of random copolymers and no change of the PHB block during the reaction. The enzymatic ring-opening polymerization was selectively initiated by the primary OH group of PHB-diol, whereas the secondary OH group remained as an end group in the final polymers. The thermal properties of the di-block poly(HB-co-CL)s were analyzed by DSC, with excellent T g values for the elastomer domain: poly[HB(56 wt %)- co-CL(44 wt %)] with M n (NMR) of 3900 demonstrated a T g of -57 degrees C, Tm of 145, 123, and 53 degrees C; and poly[HB(28wt%)-co-CL(72wt%)] with Mn (NMR) of 7100 gave a Tg of -60 degrees C, Tm of 147 and 50 degrees C. Thus, the selective enzymatic ring-opening polymerization with PHB-diol as macro-initiator provides a new method for the preparation of PHB-based block copolymers as biomaterials with good thermoplastic properties and novel structures containing functional end groups.

Magnetic Nanocomposites and Their Incorporation into Higher Order Biosynthetic Functional Architectures

DOE PAGES

Watt, John; Collins, Aaron M.; Vreeland, Erika C.; ...

2018-01-17

A magnetically active Fe 3O 4/poly(ethylene oxide)-block-poly(butadiene) (PEO-b-PBD) nanocomposite is formed by the encapsulation of magnetite nanoparticles with a short-chain amphiphilic block copolymer. This material is then incorporated into the self-assembly of higher order polymer architectures, along with an organic pigment, to yield biosynthetic, bifunctional optical and magnetically active Fe 3O 4/bacteriochlorophyll c/PEO-b-PBD polymeric chlorosomes.

Autoclaving-Derived Surface Coating with In Vitro and In Vivo Antimicrobial and Antibiofilm Efficacies.

PubMed

Su, Yajuan; Zhi, Zelun; Gao, Qiang; Xie, Meihua; Yu, Meng; Lei, Bo; Li, Peng; Ma, Peter X

2017-03-01

Biomedical device-associated infections which engender severe threat to public health require feasible solutions. In this study, block copolymers consisting of antimicrobial, antifouling, and surface-tethering segments in one molecule are synthesized and grafted on polymeric substrates by a facile plasma/autoclave-assisted method. Hetero-bifunctional polyethylene glycol (PEG) with allyl and tosyl groups (APEG-OTs) is first prepared. PEGs with different molecular weights (1200 and 2400 Da) are employed. Polyhexamethylene guanidine (PHMG) which has excellent broad-spectrum antimicrobial activity and thermal/chemical stability, is conjugated with APEG-OTs to generate the block copolymer (APEG-PHMG). Allyl terminated PHMG (A-PHMG) without PEG segments is also synthesized by reacting PHMG with allyl glycidyl ether. The synthesized copolymers are thermal initiated by autoclaving and grafted on plasma pretreated silicone surface, forming permanently bonded bottlebrush-like coatings. Both A-PHMG and APEG 1200/2400 -PHMG coatings exhibit potent antimicrobial activity against gram-positive/negative bacteria and fungus, whereas APEG 1200/2400 -PHMG coatings show superior antifouling activity and long-term reusability to A-PHMG coating. APEG 2400 -PHMG coating demonstrates the most effective in vitro antibiofilm and protein/platelet-resistant properties, as well as excellent hemo/biocompatibility. Furthermore, APEG 2400 -PHMG greatly reduces the bacteria number with 5-log reduction in a rodent subcutaneous infection model. This rationally designed dual-functional antimicrobial and antifouling coating has great potential in combating biomedical devices/implant-associated infections. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cobalt-Mediated Radical Polymerization of Vinyl Acetate and Acrylonitrile in Supercritical Carbon Dioxide.

PubMed

Kermagoret, Anthony; Chau, Ngoc Do Quyen; Grignard, Bruno; Cordella, Daniela; Debuigne, Antoine; Jérôme, Christine; Detrembleur, Christophe

2016-03-01

Cobalt-mediated radical polymerization (CMRP) of vinyl acetate (VAc) is successfully achieved in supercritical carbon dioxide (scCO2). CMRP of VAc is conducted using an alkyl-cobalt(III) adduct that is soluble in scCO2. Kinetics studies coupled to visual observations of the polymerization medium highlight that the melt viscosity and PVAc molar mass (Mn) are key parameters that affect the CMRP in scCO2. It is noticed that CMRP is controlled for Mn up to 10 000 g mol(-1), but loss of control is progressively observed for higher molar masses when PVAc precipitates in the polymerization medium. Low molar mass PVAc macroinitiator, prepared by CMRP in scCO2, is then successfully used to initiate the acrylonitrile polymerization. PVAc-b-PAN block copolymer is collected as a free flowing powder at the end of the process although the dispersity of the copolymer increases with the reaction time. Although optimization is required to decrease the dispersity of the polymer formed, this CMRP process opens new perspectives for macromolecular engineering in scCO2 without the utilization of fluorinated comonomers or organic solvents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessment of novel maleic anhydride copolymers prepared via nitroxide-mediated radical polymerization as CaSO4 crystal growth inhibitors.

PubMed

Al-Roomi, Yousef Mohammad; Hussain, Kaneez Fatema

2017-04-01

Calcium sulfate is one of the dominant scales which, unlike carbonate scale, are not easily removable by acid. To inhibit CaSO 4 scale formation in artificial cooling water systems, well-defined low molecular weight maleic anhydride and n-alkylacrylamide copolymers (YMR-S series) were synthesized via nitroxide-mediated radical polymerization initiated by benzoyl peroxide in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy at varying concentrations. These polymerizations exhibit living polymerization characteristics; that is, they show linear growth in chain length as a function of monomer conversion, and have narrow molecular weight distributions. Resultant polymers were characterized by means of 1 H-NMR and 13 C-NMR. The inhibition behavior of these YMR-S series polymers against CaSO 4 was evaluated using the static scale inhibition method and a dynamic tube block test. The inhibition ability on the CaSO 4 scale is 99.5% with 9 ppm dosage level at pH 10.45 and temperature 70°C. Scanning electronic microscope analysis proved the morphological changes of the CaSO 4 scales due to the strong inhibition action of YMR-S polymers. It is also observed that the antiscaling effect of the copolymers greatly depends on the molecular weight, and the optimum range is below 20,000 and approximately in the range 500-2000.

One-Pot Automated Synthesis of Quasi Triblock Copolymers for Self-Healing Physically Crosslinked Hydrogels.

PubMed

Voorhaar, Lenny; De Meyer, Bernhard; Du Prez, Filip; Hoogenboom, Richard

2016-10-01

The preparation of physically crosslinked hydrogels from quasi ABA-triblock copolymers with a water-soluble middle block and hydrophobic end groups is reported. The hydrophilic monomer N-acryloylmorpholine is copolymerized with hydrophobic isobornyl acrylate via a one-pot sequential monomer addition through reversible addition fragmentation chain-transfer (RAFT) polymerization in an automated parallel synthesizer, allowing systematic variation of polymer chain length and hydrophobic-hydrophilic ratio. Hydrophobic interactions between the outer blocks cause them to phase-separate into larger hydrophobic domains in water, forming physical crosslinks between the polymers. The resulting hydrogels are studied using rheology and their self-healing ability after large strain damage is shown. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers.

PubMed

Chintapalli, Mahati; Timachova, Ksenia; Olson, Kevin R; Banaszak, Michał; Thelen, Jacob L; Mecham, Sue J; DeSimone, Joseph M; Balsara, Nitash P

2017-06-07

Incipient microphase separation is observed by wide angle X-ray scattering (WAXS) in short chain multiblock copolymers consisting of perfluoropolyether (PFPE) and poly(ethylene oxide) (PEO) segments. Two PFPE-PEO block copolymers were studied; one with dihydroxyl end groups and one with dimethyl carbonate end groups. Despite having a low degree of polymerization (N ∼ 10), these materials exhibited significant scattering intensity, due to disordered concentration fluctuations between their PFPE-rich and PEO-rich domains. The disordered scattering intensity was fit to a model based on a multicomponent random phase approximation to determine the value of the interaction parameter, χ, and the radius of gyration, R g . Over the temperature range 30-90 °C, the values of χ were determined to be very large (∼2-2.5), indicating a high degree of immiscibility between the PFPE and PEO blocks. In PFPE-PEO, due to the large electron density contrast between the fluorinated and non-fluorinated block and the high value of χ, disordered scattering was detected at intermediate scattering angles, (q ∼ 2 nm -1 ) for relatively small polymer chains. Our ability to detect concentration fluctuations was enabled by both a relatively large value of χ and significant scattering contrast.

Influence of Block Copolymerization on the Antifreeze Protein Mimetic Ice Recrystallization Inhibition Activity of Poly(vinyl alcohol).

PubMed

Congdon, Thomas R; Notman, Rebecca; Gibson, Matthew I

2016-09-12

Antifreeze (glyco) proteins are produced by many cold-acclimatized species to enable them to survive subzero temperatures. These proteins have multiple macroscopic effects on ice crystal growth which makes them appealing for low-temperature applications-from cellular cryopreservation to food storage. Poly(vinyl alcohol) has remarkable ice recrystallization inhibition activity, but its mode of action is uncertain as is the extent at which it can be incorporated into other high-order structures. Here the synthesis and characterization of well-defined block copolymers containing poly(vinyl alcohol) and poly(vinylpyrrolidone) by RAFT/MADIX polymerization is reported, as new antifreeze protein mimetics. The effect of adding a large second hydrophilic block is studied across a range of compositions, and it is found to be a passive component in ice recrystallization inhibition assays, enabling retention of all activity. In the extreme case, a block copolymer with only 10% poly(vinyl alcohol) was found to retain all activity, where statistical copolymers of PVA lose all activity with very minor changes to composition. These findings present a new method to increase the complexity of antifreeze protein mimetic materials, while retaining activity, and also to help understand the underlying mechanisms of action.

Influence of Block Copolymerization on the Antifreeze Protein Mimetic Ice Recrystallization Inhibition Activity of Poly(vinyl alcohol)

PubMed Central

2016-01-01

Antifreeze (glyco) proteins are produced by many cold-acclimatized species to enable them to survive subzero temperatures. These proteins have multiple macroscopic effects on ice crystal growth which makes them appealing for low-temperature applications—from cellular cryopreservation to food storage. Poly(vinyl alcohol) has remarkable ice recrystallization inhibition activity, but its mode of action is uncertain as is the extent at which it can be incorporated into other high-order structures. Here the synthesis and characterization of well-defined block copolymers containing poly(vinyl alcohol) and poly(vinylpyrrolidone) by RAFT/MADIX polymerization is reported, as new antifreeze protein mimetics. The effect of adding a large second hydrophilic block is studied across a range of compositions, and it is found to be a passive component in ice recrystallization inhibition assays, enabling retention of all activity. In the extreme case, a block copolymer with only 10% poly(vinyl alcohol) was found to retain all activity, where statistical copolymers of PVA lose all activity with very minor changes to composition. These findings present a new method to increase the complexity of antifreeze protein mimetic materials, while retaining activity, and also to help understand the underlying mechanisms of action. PMID:27476873

An insight into polymerization-induced self-assembly by dissipative particle dynamics simulation.

PubMed

Huang, Feng; Lv, Yisheng; Wang, Liquan; Xu, Pengxiang; Lin, Jiaping; Lin, Shaoliang

2016-08-14

Polymerization-induced self-assembly is a one-pot route to produce concentrated dispersions of block copolymer nano-objects. Herein, dissipative particle dynamics simulations with a reaction model were employed to investigate the behaviors of polymerization-induced self-assembly. The polymerization kinetics in the polymerization-induced self-assembly were analyzed by comparing with solution polymerization. It was found that the polymerization rate enhances in the initial stage and decreases in the later stage. In addition, the effects of polymerization rate, length of macromolecular initiators, and concentration on the aggregate morphologies and formation pathway were studied. The polymerization rate and the length of the macromolecular initiators are found to have a marked influence on the pathway of the aggregate formations and the final structures. Morphology diagrams were mapped correspondingly. A comparison between simulation results and experimental findings is also made and an agreement is shown. This work can enrich our knowledge about polymerization-induced self-assembly.

A bio-inspired microstructure induced by slow injection moulding of cylindrical block copolymers.

PubMed

Stasiak, Joanna; Brubert, Jacob; Serrani, Marta; Nair, Sukumaran; de Gaetano, Francesco; Costantino, Maria Laura; Moggridge, Geoff D

2014-08-28

It is well known that block copolymers with cylindrical morphology show alignment with shear, resulting in anisotropic mechanical properties. Here we show that well-ordered bi-directional orientation can be achieved in such materials by slow injection moulding. This results in a microstructure, and anisotropic mechanical properties, similar to many natural tissues, making this method attractive for engineering prosthetic fibrous tissues. An application of particular interest to us is prosthetic polymeric heart valve leaflets, mimicking the shape, microstructure and hence performance of the native valve. Anisotropic layers have been observed for cylinder-forming block copolymers centrally injected into thin circular discs. The skin layers exhibit orientation parallel to the flow direction, whilst the core layer shows perpendicularly oriented domains; the balance of skin to core layers can be controlled by processing parameters such as temperature and injection rate. Heart valve leaflets with a similar layered structure have been prepared by injection moulding. Numerical modelling demonstrates that such complex orientation can be explained and predicted by the balance of shear and extensional flow.

Construction of a thermoresponsive magnetic porous polymer membrane enzyme reactor for glutaminase kinetics study.

PubMed

Zhao, Liping; Qiao, Juan; Moon, Meyong Hee; Qi, Li

2018-06-16

Fabrication of polymer membranes with nanopores and a confinement effect toward enzyme immobilization has been an enabling endeavor. In the work reported here, an enzyme reactor based on a thermoresponsive magnetic porous block copolymer membrane was designed and constructed. Reversible addition-fragmentation chain transfer polymerization was used to synthesize the block copolymer, poly(maleic anhydride-styrene-N-isopropylacrylamide), with poly(N-isopropylacrylamide) as the thermoresponsive moiety. The self-assembly property of the block copolymer was used for preparation of magnetic porous thin film matrices with iron oxide nanoparticles. By covalent bonding of glutaminase onto the surface of the membrane matrices and changing the temperature to tune the nanopore size, we observed enhanced enzymolysis efficiency due to the confinement effect. The apparent Michaelis-Menten constant and the maximum rate of the enzyme reactor were determined (K m = 32.3 mM, V max = 33.3 mM min -1 ) by a chiral ligand exchange capillary electrochromatography protocol with L-glutamine as the substrate. Compared with free glutaminase in solution, the proposed enzyme reactor exhibits higher enzymolysis efficiency, greater stability, and greater reusability. Furthermore, the enzyme reactor was applied for a glutaminase kinetics study. The tailored pore sizes and the thermoresponsive property of the block copolymer result in the designed porous membrane based enzyme reactor having great potential for high enzymolysis performance. Graphical abstract ᅟ.

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

Segmental Interactions between Polymers and Small Molecules in Batteries and Biofuel Purification

NASA Astrophysics Data System (ADS)

Balsara, Nitash

2015-03-01

Polymers such as poly(ethylene oxide) (PEO) and poly(dimethyl siloxane) (PDMS) have the potential to play an important role in the emerging clean energy landscape. Mixtures of PEO and lithium salts are the most widely studied non-flammable electrolyte for rechargeable lithium batteries. PDMS membranes are ideally suited for purifying bioethanol and biobutanol from fermentation broths. The ability of PEO and PDMS to function in these applications depends on segmental interactions between the polymeric host and small molecule guests. One experimental approach for studying these interactions is X-ray absorption spectroscopy (XAS). Models for interpreting XAS spectra of amorphous mixtures and charged species such as salts must quantify the effect of segmental interactions on the electronic structure of the atoms of interest (e.g. sulfur). This combination of experiment and theory is used to determine the species formed in during charging and discharging lithium-sulfur batteries; the theoretical specific energy of lithium-sulfur batteries is a factor of four larger than that of current lithium-ion batteries. Selective transport of alcohols in PDMS-containing membranes is controlled by the size, shape, and connectivity of sub-nanometer cavities or free volume that form and disappear spontaneously as the chain segments undergo Brownian motion. We demonstrate that self-assembly of PDMS-containing block copolymers can be used to control segmental relaxation, which, in turn, affects free volume. Positron annihilation was used to determine the size distribution of free volume cavities in the PDMS-containing block copolymers. The effect of this artificial free volume on selective permeation of alcohols formed by fermentation of sugars derived from lignocellulosic biomass is studied. Molecular dynamics simulations are needed to understand the relationship between self-assembly, free volume, and transport in block copolymers.

Stimuli-sensitive polymeric micelles as anticancer drug carriers.

PubMed

Na, Kun; Sethuraman, Vijay T; Bae, You Han

2006-11-01

Amphiphilic block copolymers often form core-shell type micelles by self-organization of the blocks in an aqueous medium or under specific experimental conditions. Polymeric micelles constructed from these polymers that contain a segment whose physical or chemical properties respond to small changes in environmental conditions are collectively called 'stimuli-sensitive' micelles. This class of nano-scaled constructs has been investigated as a promising anti-cancer drug carrier because the micelles are able to utilize small environmental changes and modify drug release kinetics, biodistribution and the interactions with tissues and cells. This review summarizes the recent progress in stimuli-sensitive micelles for tumor chemotherapy, particularly for those responding to hyperthermic conditions, tumor pH and endosomal/lysosomal pH.

Functional Degradable Polymers by Radical Ring-Opening Copolymerization of MDO and Vinyl Bromobutanoate: Synthesis, Degradability and Post-Polymerization Modification.

PubMed

Hedir, Guillaume G; Bell, Craig A; O'Reilly, Rachel K; Dove, Andrew P

2015-07-13

The synthesis of vinyl bromobutanoate (VBr), a new vinyl acetate monomer derivative obtained by the palladium-catalyzed vinyl exchange reaction between vinyl acetate (VAc) and 4-bromobutyric acid is reported. The homopolymerization of this new monomer using the RAFT/MADIX polymerization technique leads to the formation of novel well-defined and controlled polymers containing pendent bromine functional groups able to be modified via postpolymerization modification. Furthermore, the copolymerization of vinyl bromobutanoate with 2-methylene-1,3-dioxepane (MDO) was also performed to deliver a range of novel functional degradable copolymers, poly(MDO-co-VBr). The copolymer composition was shown to be able to be tuned to vary the amount of ester repeat units in the polymer backbone, and hence determine the degradability, while maintaining a control of the final copolymers' molar masses. The addition of functionalities via simple postpolymerization modifications such as azidation and the 1,3-dipolar cycloaddition of a PEG alkyne to an azide is also reported and proven by (1)H NMR spectroscopy, FTIR spectroscopy, and SEC analyses. These studies enable the formation of a novel class of hydrophilic functional degradable copolymers using versatile radical polymerization methods.

Equilibrium Field Theoretic and Dynamic Mean Field Simulations of Inhomogeneous Polymeric Materials

NASA Astrophysics Data System (ADS)

Chao, Huikuan

Inhomogeneous polymeric materials is a large family of promising materials including but limited to block copolymers (BCPs), polymer nanocomposites (PNCs) and microscopically confined polymer films. The promising application of the materials originates from the materials' unique microstructures, which offer enhanced mechanical, thermal, optical and electrical properties to the materials. Due to the complex interactions and the large parameter space, behaviors of the microstructures formed by grafted nanoparticles and nanorods in PNCs are difficult to understand. Separately, because of relatively weak interactions, the microstructures are typically achieved through rapid processing that are kinetically controlled and beyond equilibrium. However, efficient simulation framework to study nonequilbrium dynamics of the materials is currently not available. To attack the first difficulty, I extended an efficient simulation framework, polymer nanocomposite field theory (PNC-FT), to incorporate grafted nanoparticles and nanorods. This extended framework is demonstrated against existing experimental studies and implemented to study how the nanoparticle design affects the nanoparticle distribution in binary homopolymer blends. The grafted nanoparticle model is also used as a platform to adopt an advanced optimization method to inversely design nanoparticles which are able to self-assemble into targeted two dimensional lattices. The nanorod model under PNC-FT framework is used to investigate the design of nanorod and block copolymer thin films to control the nanorod distribution. To attack the second difficulty, I established an efficient framework (SCMF-LD) based on a recently proposed dynamic mean field theory and used SCMF-LD to study how to kinetically control the nanoparticle distribution at the end of solvent annealing block copolymer thin films. The framework is then extended to incorporate hydrodynamics (SCMF-DPD) and the extended framework is implemented to study morphology development in phase inversion processing polymer thin films, where hydrodynamic effects play an important role. By exploring both equilibrium and nonequilibrium properties in a spectrum of inhomogeneous polymeric material systems, I successfully extended PNC-FT and established SCMF-LD and SCMF-DPD frameworks, which are expected to be efficient and powerful tools in studies of inhomogeneous polymeric material design and processing.

Scalable and uniform 1D nanoparticles by synchronous polymerization, crystallization and self-assembly

NASA Astrophysics Data System (ADS)

Boott, Charlotte E.; Gwyther, Jessica; Harniman, Robert L.; Hayward, Dominic W.; Manners, Ian

2017-08-01

The preparation of well-defined nanoparticles based on soft matter, using solution-processing techniques on a commercially viable scale, is a major challenge of widespread importance. Self-assembly of block copolymers in solvents that selectively solvate one of the segments provides a promising route to core-corona nanoparticles (micelles) with a wide range of potential uses. Nevertheless, significant limitations to this approach also exist. For example, the solution processing of block copolymers generally follows a separate synthesis step and is normally performed at high dilution. Moreover, non-spherical micelles—which are promising for many applications—are generally difficult to access, samples are polydisperse and precise dimensional control is not possible. Here we demonstrate the formation of platelet and cylindrical micelles at concentrations up to 25% solids via a one-pot approach—starting from monomers—that combines polymerization-induced and crystallization-driven self-assembly. We also show that performing the procedure in the presence of small seed micelles allows the scalable formation of low dispersity samples of cylindrical micelles of controlled length up to three micrometres.

Tumor-targeting peptide conjugated pH-responsive micelles as a potential drug carrier for cancer therapy.

PubMed

Wu, Xiang Lan; Kim, Jong Ho; Koo, Heebeom; Bae, Sang Mun; Shin, Hyeri; Kim, Min Sang; Lee, Byung-Heon; Park, Rang-Woon; Kim, In-San; Choi, Kuiwon; Kwon, Ick Chan; Kim, Kwangmeyung; Lee, Doo Sung

2010-02-17

Herein, we prepared tumor-targeting peptide (AP peptide; CRKRLDRN) conjugated pH-responsive polymeric micelles (pH-PMs) in cancer therapy by active and pH-responsive tumor targeting delivery systems, simultaneously. The active tumor targeting and tumoral pH-responsive polymeric micelles were prepared by mixing AP peptide conjugated PEG-poly(d,l-lactic acid) block copolymer (AP-PEG-PLA) into the pH-responsive micelles of methyl ether poly(ethylene glycol) (MPEG)-poly(beta-amino ester) (PAE) block copolymer (MPEG-PAE). These mixed amphiphilic block copolymers were self-assembled to form stable AP peptide-conjugated and pH-responsive AP-PEG-PLA/MPEG-PAE micelles (AP-pH-PMs) with an average size of 150 nm. The AP-pH-PMs containing 10 wt % of AP-PEG-PLA showed a sharp pH-dependent micellization/demicellization transition at the tumoral acid pH. Also, they presented the pH-dependent drug release profile at the acidic pH of 6.4. The fluorescence dye, TRITC, encapsulated AP-pH-PMs (TRITC-AP-pH-PMs) presented the higher tumor-specific targeting ability in vitro cancer cell culture system and in vivo tumor-bearing mice, compared to control pH-responsive micelles of MPEG-PAE. For the cancer therapy, the anticancer drug, doxorubicin (DOX), was efficiently encapsulated into the AP-pH-PMs (DOX-AP-pH-PMs) with a higher loading efficiency. DOX-AP-pH-PMs efficiently deliver anticancer drugs in MDA-MB231 human breast tumor-bearing mice, resulted in excellent anticancer therapeutic efficacy, compared to free DOX and DOX encapsulated MEG-PAE micelles, indicating the excellent tumor targeting ability of AP-pH-PMs. Therefore, these tumor-targeting peptide-conjugated and pH-responsive polymeric micelles have great potential application in cancer therapy.

Morphology and Surface Energy of a Si Containing Semifluorinated Di-block Copolymer Thin Films.

NASA Astrophysics Data System (ADS)

Shrestha, Umesh; Clarson, Stephen; Perahia, Dvora

2013-03-01

The structure and composition of an interface influence stability, adhesiveness and response to external stimuli of thin polymeric films. Incorporation of fluorine affects interfacial energy as well as thermal and chemical stability of the layers. The incompatibility between the fluorinated and non-fluorinated blocks induces segregation that leads to long range correlations where the tendency of the fluorine to migrate to interfaces impacts the surface tension of the films. Concurrently Si in a polymeric backbone enhances the flexibility of polymeric chains. Our previous studies of poly trifluoro propyl methyl siloxane-polystyrene thin films with SiF fraction 0.03-0.5 as a function of temperature have shown that the SiF block drives layering parallel to the surface of the diblock. Here in we report the structure and interfacial energies of SiF-PS in the plane of the films, as a function of the volume fraction of the SiF block obtained from Atomic Force microscopy and contact angle measurement studies. This work is supported by NSF DMR - 0907390

pH-responsive polymeric micelles of poly(ethylene glycol)-b-poly(alkyl(meth)acrylate-co-methacrylic acid): influence of the copolymer composition on self-assembling properties and release of candesartan cilexetil.

PubMed

Satturwar, Prashant; Eddine, Mohamad Nasser; Ravenelle, François; Leroux, Jean-Christophe

2007-03-01

The objective of the present study was to investigate the influence of chemical structure and molecular weight of pH-sensitive block copolymers on their self-assembling properties, the loading and the release of candesartan cilexetil (CDN). Block copolymers of poly(ethylene glycol) and t-butyl methacrylate, iso-butyl acrylate, n-butyl acrylate or propyl methacrylate were synthesized by atom transfer radical polymerization. pH-sensitivity was obtained by hydrolysis of t-butyl groups. The poorly water-soluble drug CDN was incorporated in the micelles and the in vitro drug release was evaluated as a function of pH. The critical aggregation concentration of hydrolyzed copolymers (pK(a)=6.2-6.6) was higher compared to the unhydrolyzed ones. Dynamic light scattering studies and atomic force microscopy images revealed uniform size micelles with aggregation numbers ranging from 60 to 160. The entrapment efficiency of CDN was generally found to be above 90%, with drug loading levels reaching approximately 20% (w/w). Differential scanning calorimetry studies showed the amorphous nature of entrapped CDN. The release of CDN from pH-sensitive micelles was triggered upon an increase in pH from 1.2 to 7.2. These findings suggest that the PEG-b-poly(alkyl(meth)acrylate-co-methacrylic acid)s can self-assemble to form micelles which exhibit high loading capacities for CDN and release the drug in a pH-dependent fashion.

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

Synthesis and optoelectronic properties of nanocomposites comprising of poly(9,9-dioctylfluorene)-block-poly(3-hexylthiophene) block copolymer and graphene nanosheets.

PubMed

Chiu, Po-Chun; Su, Reagen Ying-Tai; Yeh, Je-Yuan; Yeh, Cheng-Yang; Tsiang, Raymond Chien-Chao

2013-06-01

A novel conjugated block copolymer, poly(9,9-dioctylfluorene)-block-poly(3-hexylthiophene) (PFBPT) and its nanocomposite containing graphene sheets were synthesized for enhancing optoelectronic performance. Graphene sheets were in-situ formed in the polymer matrix via a reduction of octadecylamine-functionalized graphite oxide, where the graphite oxide came from acidification and exfoliation of graphite. The blue-green light-emitting poly(9,9-dioctylfluorene) block and red-orange light-emitting poly(3-hexylthiophene) block exhibit a combined white electroluminescence when the composite materials were fabricated as the emitting layer of a polymeric light-emitting diode (PLED). Graphene does not alter the optical characteristics wavelength of PFBPT but electric conductivity increases with the amount of graphene. The HOMO and LUMO were measured and the band gap is smaller with existence of graphene. The threshold voltage decreases with an increase in the graphene content. The device fabricated with PFBPT/graphene nanocomposite containing 1% graphene has a maximum white-light luminescence at a voltage of 9.0 V.

Polyisobutylene chain end transformations: Block copolymer synthesis and click chemistry functionalizations

NASA Astrophysics Data System (ADS)

Magenau, Andrew Jackson David

The primary objectives of this research were twofold: (1) development of synthetic procedures for combining quasiliving carbocationic polymerization (QLCCP) of isobutylene (IB) and reversible addition fragmentation chain transfer (RAFT) polymerization for block copolymer synthesis; (2) utilization of efficient, robust, and modular chemistries for facile functionalization of polyisobutylene (PIB). In the first study block copolymers consisting of PIB, and either PMMA or PS block segments, were synthesized by a site transformation approach combining living cationic and reversible addition-fragmentation chain transfer (RAFT) polymerizations. The initial PIB block was synthesized via quasiliving cationic polymerization using the TMPCl/TiCl4 initiation system and was subsequently converted into a hydroxylterminated PIB. Site transformation of the hydroxyl-terminated PIB into a macro chain transfer agent (PIB-CTA) was accomplished by N,N'-dicyclohexylcarbodiimide/dimethylaminopyridine-catalyzed esterification with 4-cyano-4-(dodecylsulfanylthiocarbonylsulfanyl)pentanoic acid. In the second study another site transformation approach was developed to synthesize a novel block copolymer, composed of PIB and PNIPAM segments. The PIB block was prepared via quasiliving cationic polymerization and end functionalized by in-situ quenching to yield telechelic halogen-terminated PIB. Azido functionality was obtained by displacement of the terminal halogen through nucleophilic substitution, which was confirmed by both 1H and 13C NMR. Coupling of an alkyne-functional chain transfer agent (CTA) to azido PIB was successfully accomplished through a copper catalyzed click reaction. Structure of the resulting PIB-based macro-CTA was verified with 1H NMR, FTIR, and GPC; whereas coupling reaction kinetics were monitored by real time variable temperature (VT) 1H NMR. In a third study, a click chemistry functionalization procedure was developed based upon the azide-alkyne 1,3-dipolar cycloaddition reaction. 1-(o-Azidoalkyl)pyrrolyl-terminated PIB was successfully synthesized both by substitution of the terminal halide of 1-(o-haloalkyl)pyrrolyl-terminated PIB with sodium azide and by in situ quenching of quasiliving PIB with a 1-(o-azidoalkyl)pyrrole. GPC indicated the absence of coupled PIB under optimized conditions, confirming exclusive mono-substitution on each pyrrole ring. In a fourth study, radical thiol-ene hydrothiolation "Click" chemistry was explored and adapted to easily and rapidly modify exo -olefin PIB with an array of thiol compounds bearing useful functionalities, including primary halogen, primary amine, primary hydroxyl, and carboxylic acid. The thiol-ene "click" procedure was shown to be applicable to both mono and difunctional exo-olefin polyisobutylene. Telechelic mono- and difunctional exo-olefin PIBs were synthesized via quasiliving cationic polymerization followed by quenching with the hindered amine, 1,2,2,6,6-pentamethylpiperidine. Lower reaction temperatures were found to increase exo-olefin conversion to near quantitative amounts. In the fifth study, thiol-terminated polyisobutylene (PIB-SH) was synthesized by reaction of thiourea with alpha,o-bromine-terminated PIB in a three step one-pot procedure. First the alkylisothiouronium salt was produced using a 1:1 (v:v) DMF:heptane cosolvent mixture at 90°C. Hydrolysis of the salt by aqueous base produced thiolate chain ends, which were then acidified to form the desired thiol functional group. An extension of this reaction was performed by a sequential thiol-ene/thiol-yne procedure to produce tetra-hydroxy functionalized PIB. 1H NMR was used to confirm formation of both alkyne and tetrahydroxyl functional species. Further utility of PIB-SH was demonstrated by base catalyzed thiol-isocyanate reactions. A model reaction was conducted with phenyl isocyanate in THF using triethylamine as the catalyst. Last, conversion of PIB-SH directly into a RAFT macro-CTA was accomplished, as shown by 1H NMR, by treatment of PIB-SH with triethylamine in carbon disulfide and subsequent alkylation with 2-bromopropionic acid. (Abstract shortened by UMI.)

Block copolymer libraries: modular versatility of the macromolecular Lego system.

PubMed

Lohmeijer, Bas G G; Wouters, Daan; Yin, Zhihui; Schubert, Ulrich S

2004-12-21

The synthesis and characterization of a new 4 x 4 library of block copolymers based on polystyrene and poly(ethylene oxide) connected by an asymmetrical octahedral bis(terpyridine) ruthenium complex at the block junction are described, while initial studies on the thin film morphology of the components of the library are presented by the use of Atomic Force Microscopy, demonstrating the impact of a library approach to derive structure-property relationships.

Graft copolymers of ethyl methacrylate on waxy maize starch derivatives as novel excipients for matrix tablets: physicochemical and technological characterisation.

PubMed

Marinich, J A; Ferrero, C; Jiménez-Castellanos, M R

2009-05-01

Nowadays, graft copolymers are being used as an interesting option when developing a direct compression excipient for controlled release matrix tablets. New graft copolymers of ethyl methacrylate (EMA) on waxy maize starch (MS) and hydroxypropylstarch (MHS) were synthesised by free radical polymerization and alternatively dried in a vacuum oven (OD) or freeze-dried (FD). This paper evaluates the performance of these new macromolecules and discusses the effect of the carbohydrate nature and drying process on their physicochemical and technological properties. Grafting of EMA on the carbohydrate backbone was confirmed by IR and NMR spectroscopy, and the grafting yields revealed that graft copolymers present mainly a hydrophobic character. The graft copolymerization also leads to more amorphous materials with larger particle size and lower apparent density and water content than carbohydrates (MS, MHS). All the products show a lack of flow, except MHSEMA derivatives. MSEMA copolymers underwent much plastic flow and less elastic recovery than MHSEMA copolymers. Concerning the effect of drying method, FD derivatives were characterised by higher plastic deformation and less elasticity than OD derivatives. Tablets obtained from graft copolymers showed higher crushing strength and disintegration time than tablets obtained from raw starches. This behaviour suggests that these copolymers could be used as excipients in matrix tablets obtained by direct compression and with a potential use in controlled release.

Biodegradable copolymers carrying cell-adhesion peptide sequences.

PubMed

Proks, Vladimír; Machová, Lud'ka; Popelka, Stepán; Rypácek, Frantisek

2003-01-01

Amphiphilic block copolymers are used to create bioactive surfaces on biodegradable polymer scaffolds for tissue engineering. Cell-selective biomaterials can be prepared using copolymers containing peptide sequences derived from extracellular-matrix proteins (ECM). Here we discuss alternative ways for preparation of amphiphilic block copolymers composed of hydrophobic polylactide (PLA) and hydrophilic poly(ethylene oxide) (PEO) blocks with cell-adhesion peptide sequences. Copolymers PLA-b-PEO were prepared by a living polymerisation of lactide in dioxane with tin(II)2-ethylhexanoate as a catalyst. The following approaches for incorporation of peptides into copolymers were elaborated. (a) First, a side-chain protected Gly-Arg-Gly-Asp-Ser-Gly (GRGDSG) peptide was prepared by solid-phase peptide synthesis (SPPS) and then coupled with delta-hydroxy-Z-amino-PEO in solution. In the second step, the PLA block was grafted to it via a controlled polymerisation of lactide initiated by the hydroxy end-groups of PEO in the side-chain-protected GRGDSG-PEO. Deprotection of the peptide yielded a GRGDSG-b-PEO-b-PLA copolymer, with the peptide attached through its C-end. (b) A protected GRGDSG peptide was built up on a polymer resin and coupled with Z-carboxy-PEO using a solid-phase approach. After cleavage of the delta-hydroxy-PEO-GRGDSG copolymer from the resin, polymerisation of lactide followed by deprotection of the peptide yielded a PLA-b-PEO-b-GRGDSG block copolymer, in which the peptide is linked through its N-terminus.

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.

Photonic Resins: Designing Optical Appearance via Block Copolymer Self-Assembly.

PubMed

Song, Dong-Po; Jacucci, Gianni; Dundar, Feyza; Naik, Aditi; Fei, Hua-Feng; Vignolini, Silvia; Watkins, James J

2018-03-27

Despite a huge variety of methodologies having been proposed to produce photonic structures by self-assembly, the lack of an effective fabrication approach has hindered their practical uses. These approaches are typically limited by the poor control in both optical and mechanical properties. Here we report photonic thermosetting polymeric resins obtained through brush block copolymer (BBCP) self-assembly. We demonstrate that the control of the interplay between order and disorder in the obtained photonic structure offers a powerful tool box for designing the optical appearance of the polymer resins in terms of reflected wavelength and scattering properties. The obtained materials exhibit excellent mechanical properties with hardness up to 172 MPa and Young's modulus over 2.9 GPa, indicating great potential for practical uses as photonic coatings on a variety of surfaces.

Synthesis and Characterization of Polymer-Metal Nanostructured Membranes

DTIC Science & Technology

ions creating unique polymer -metal nanostructured membranes. A comprehensive materials characterization study was performed to understand their...fluoropolymers were also investigated. First the polymer -metal nanostructure of Nafion with several counter-ions was studied upon supercritical fluid CO2...processing. Then, novel fluorinated block copolymers were synthesized using atom transfer radical polymerization (ATRP) and their resulting nanostructure was

Physico-chemical characterization of polymeric micelles loaded with platinum derivatives by capillary electrophoresis and related methods.

PubMed

Oukacine, Farid; Bernard, Stephane; Bobe, Iulian; Cottet, Hervé

2014-12-28

(1,2-diamino-cyclohexane)Platinum(II) ((DACH)Pt) loaded polymeric micelles of poly(ethylene glycol-b-sodium glutamate) (PEG-b-PGlu) are currently studied as a potential candidate to replace oxaliplatin in the treatment of cancers with the aim to reduce side effects like cumulative peripheral distal neurotoxicity and acute dysesthesias. As for all synthetic polymeric drug delivery systems, the characterization of the (co)polymer precursors and of the final drug delivery system (polymeric micelles) is crucial to control the repeatability of the different batches and to get correlation between physico-chemical structure and biological activity. In this work, the use of capillary electrophoresis (CE) and related methods for the characterization of (DACH)Pt-loaded polymeric micelles and their precursor (PEG-b-PGlu copolymer) has been investigated in detail. The separation and quantification of residual PGlu homopolymer in the PEG-b-PGlu sample were performed by free solution capillary zone electrophoresis mode. This mode brought also information on the PEG-b-PGlu copolymer composition and polydispersity. It also permitted to monitor the decomposition of polymeric micelles in the presence of NaCl at room temperature. Interactions between PEG-b-PGlu unimers, on one hand, and polymeric micelles or surfactants, on the other hand, were studied by using the Micellar Electrokinetic Chromatography and Frontal Analysis Capillary Electrophoresis modes. Finally, weight-average hydrodynamic radii of the loaded polymeric micelles and of the PEG-b-PGlu unimers were determined by Taylor Dispersion Analysis (an absolute size determination method that can be easily implemented on CE apparatus). Copyright © 2014 Elsevier B.V. All rights reserved.

Controlled release of cortisone drugs from block copolymers synthetized by ATRP

NASA Astrophysics Data System (ADS)

Valenti, G.; La Carta, S.; Mazzotti, G.; Rapisarda, M.; Perna, S.; Di Gesù, R.; Giorgini, L.; Carbone, D.; Recca, G.; Rizzarelli, P.

2016-05-01

Diseases affecting posterior eye segment, like macular edema, infection and neovascularization, may cause visual impairment. Traditional treatments, such as steroidal-drugs intravitreal injections, involve chronic course of therapy usually over a period of years. Moreover, they can require frequent administrations of drug in order to have an adequately disease control. This dramatically reduce patient's compliance. Efforts have been made to develop implantable devices that offer an alternative therapeutic approach to bypass many challenges of conventional type of therapy. Implantable drug delivery systems (DDS) have been developed to optimize therapeutic properties of drugs and ensure their slow release in the specific site. Polymeric materials can play an essential role in modulating drug delivery and their use in such field has become indispensable. During last decades, acrylic polymers have obtained growing interest. Biocompatibility and chemical properties make them extremely versatile, allowing their use in many field such as biomedical. In particular, block methacrylate copolymer with a balance of hydrophilic and hydrophobic properties can be suitable for prolonged DDS in biomedical devices. In this work, we focused on the realization of a system for controlled and long term release of betamethasone 17,21-dipropionate (BDP), a cortisone drug, from methacrylic block copolymers, to be tested in the treatment of the posterior eye's diseases. Different series of methyl methacrylate/hydroxyethyl methacrylate (MMA/HEMA) block and random copolymers, with different monomer compositions (10-60% HEMA), were synthetized by Atom Transfer Radical Polymerization (ATRP) to find the best hydrophilic/hydrophobic ratio, able to ensure optimal kinetic release. Copolymer samples were characterized by NMR spectroscopy (1H-NMR, 13C-NMR, CosY), SEC, TGA and DSC. Monitoring of drug release from films loaded with BDP was carried out by HPLC analysis. Evaluation of different kinetic models allowed to deduce that release of BDP is controlled over time from PMMA-b-PHEMA 53/47. In particular, PMMA-b-PHEMA 53/47 showed the best release profile to achieve the therapeutic reference dose of 3 µg/die, employed in treatment of posterior eye disease, up to four months. Accordingly, PMMA-b-PHEMA 53/47 has been tested to prepare ocular inserts. Ocular inserts with different shape and the same area of polymer films have been obtained using silicon moulds made by a 3D printer.

Controlled release of cortisone drugs from block copolymers synthetized by ATRP

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

Valenti, G.; La Carta, S.; Rapisarda, M.

Diseases affecting posterior eye segment, like macular edema, infection and neovascularization, may cause visual impairment. Traditional treatments, such as steroidal-drugs intravitreal injections, involve chronic course of therapy usually over a period of years. Moreover, they can require frequent administrations of drug in order to have an adequately disease control. This dramatically reduce patient’s compliance. Efforts have been made to develop implantable devices that offer an alternative therapeutic approach to bypass many challenges of conventional type of therapy. Implantable drug delivery systems (DDS) have been developed to optimize therapeutic properties of drugs and ensure their slow release in the specific site.more » Polymeric materials can play an essential role in modulating drug delivery and their use in such field has become indispensable. During last decades, acrylic polymers have obtained growing interest. Biocompatibility and chemical properties make them extremely versatile, allowing their use in many field such as biomedical. In particular, block methacrylate copolymer with a balance of hydrophilic and hydrophobic properties can be suitable for prolonged DDS in biomedical devices. In this work, we focused on the realization of a system for controlled and long term release of betamethasone 17,21-dipropionate (BDP), a cortisone drug, from methacrylic block copolymers, to be tested in the treatment of the posterior eye’s diseases. Different series of methyl methacrylate/hydroxyethyl methacrylate (MMA/HEMA) block and random copolymers, with different monomer compositions (10–60% HEMA), were synthetized by Atom Transfer Radical Polymerization (ATRP) to find the best hydrophilic/hydrophobic ratio, able to ensure optimal kinetic release. Copolymer samples were characterized by NMR spectroscopy ({sup 1}H-NMR, {sup 13}C-NMR, CosY), SEC, TGA and DSC. Monitoring of drug release from films loaded with BDP was carried out by HPLC analysis. Evaluation of different kinetic models allowed to deduce that release of BDP is controlled over time from PMMA-b-PHEMA 53/47. In particular, PMMA-b-PHEMA 53/47 showed the best release profile to achieve the therapeutic reference dose of 3 µg/die, employed in treatment of posterior eye disease, up to four months. Accordingly, PMMA-b-PHEMA 53/47 has been tested to prepare ocular inserts. Ocular inserts with different shape and the same area of polymer films have been obtained using silicon moulds made by a 3D printer.« less

Polymer grafted magnetic nanoparticles for delivery of anticancer drug at lower pH and elevated temperature.

PubMed

Dutta, Sujan; Parida, Sheetal; Maiti, Chiranjit; Banerjee, Rakesh; Mandal, Mahitosh; Dhara, Dibakar

2016-04-01

Efficient and controlled delivery of therapeutics to tumor cells is one of the important issues in cancer therapy. In the present work, a series of pH- and temperature-responsive polymer grafted iron oxide nanoparticles were prepared by simple coupling of aminated iron oxide nanoparticle with poly(N-isopropylacrylamide-ran-poly(ethylene glycol) methyl ether acrylate)-block-poly(acrylic acid) (P(NIPA-r-PEGMEA)-b-PAA). For this, three water soluble block polymers were prepared via reversible addition fragmentation transfer (RAFT) polymerization technique. At first, three different block copolymers were prepared by polymerizing mixture of NIPA and PEGMEA (with varying mole ratio) in presence of poly(tert-butyl acrylate) (PtBA) macro chain transfer agent. Subsequently, P(NIPA-r-PEGMEA)-b-PAA copolymers were synthesized by hydrolyzing tert-butyl acrylate groups of the P(NIPA-r-PEGMEA)-b-PtBA copolymers. The resulting polymers were then grafted to iron oxide nanoparticles, and these functionalized nanoparticles were thoroughly characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), zeta potential measurements, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), vibrating sample magnetometer (VSM) and Fourier transform infrared spectroscopy (FTIR). Doxorubicin (DOX), an anti-cancer drug, was loaded into the polymer coated nanoparticles and its release behavior was subsequently studied at different pH and temperatures. The drug release pattern revealed a sustained release of DOX preferentially at the desired lysosomal pH of cancer cells (pH 5.0) and slightly above the physiological temperature depending upon the composition of the copolymers. The potential anticancer activity of the polymer grafted DOX loaded nanoparticles were established by MTT assay and apoptosis study of cervical cancer ME 180cells in presence of the nanoparticles. Thus, these particles can be utilized for controlled delivery of anticancer drugs at the desired lysosomal pH and/or by slightly heating the cells using magnetic hyperthermia. Copyright © 2016 Elsevier Inc. All rights reserved.

Biomedical applications of polymers derived by reversible addition - fragmentation chain-transfer (RAFT).

PubMed

Fairbanks, Benjamin D; Gunatillake, Pathiraja A; Meagher, Laurence

2015-08-30

RAFT- mediated polymerization, providing control over polymer length and architecture as well as facilitating post polymerization modification of end groups, has been applied to virtually every facet of biomedical materials research. RAFT polymers have seen particularly extensive use in drug delivery research. Facile generation of functional and telechelic polymers permits straightforward conjugation to many therapeutic compounds while synthesis of amphiphilic block copolymers via RAFT allows for the generation of self-assembled structures capable of carrying therapeutic payloads. With the large and growing body of literature employing RAFT polymers as drug delivery aids and vehicles, concern over the potential toxicity of RAFT derived polymers has been raised. While literature exploring this complication is relatively limited, the emerging consensus may be summed up in three parts: toxicity of polymers generated with dithiobenzoate RAFT agents is observed at high concentrations but not with polymers generated with trithiocarbonate RAFT agents; even for polymers generated with dithiobenzoate RAFT agents, most reported applications call for concentrations well below the toxicity threshold; and RAFT end-groups may be easily removed via any of a variety of techniques that leave the polymer with no intrinsic toxicity attributable to the mechanism of polymerization. The low toxicity of RAFT-derived polymers and the ability to remove end groups via straightforward and scalable processes make RAFT technology a valuable tool for practically any application in which a polymer of defined molecular weight and architecture is desired. Copyright © 2015. Published by Elsevier B.V.

In vitro synthesis of polyhydroxyalkanoate (PHA) incorporating lactate (LA) with a block sequence by using a newly engineered thermostable PHA synthase from Pseudomonas sp. SG4502 with acquired LA-polymerizing activity.

PubMed

Tajima, Kenji; Han, Xuerong; Satoh, Yasuharu; Ishii, Ayako; Araki, Yuji; Munekata, Masanobu; Taguchi, Seiichi

2012-04-01

Recently, we succeeded in isolating a thermotolerant bacterium, Pseudomonas sp. SG4502, which is capable of accumulating polyhydroxyalkanoate (PHA) even at 55 °C, as a source of thermostable enzymes. In this study, we cloned a pha locus from the bacterium and identified two genes encoding PHA synthases (PhaC1(SG) and PhaC2(SG)). Two mutations, Ser324Thr and Gln480Lys, corresponding to those of a lactate (LA)-polymerizing enzyme (LPE) from mesophilic Pseudomonas sp. 61-3 were introduced into PhaC1(SG) to evaluate the potential of the resulting protein as a "thermostable LPE". The mutated PhaC1(SG) [PhaC1(SG)(STQK)] showed high thermal stability in synthesizing P(LA-co-3HB) in an in vitro reaction system under a range of high temperatures. Requirement of 3HBCoA as a priming unit for LA polymerization by the LPE has been suggested in both of the in vitro and in vivo experiments. Based on the finding, the PhaC1(SG)(STQK)-mediated synthesis of a LA-based copolymer with a block sequence was achieved in the in vitro system by sequential feeding of the corresponding two substrates. This in vitro reaction system using the thermostable LPE provides us with a versatile way to synthesize the various types of LA-based copolymers with desired sequence patterns, random or block, depending on the way of supplying hydroxyalkanoates (mixed or sequential feeding).

Fluid Dynamic Characterization of a Polymeric Heart Valve Prototype (Poli-Valve) tested under Continuous and Pulsatile Flow Conditions

PubMed Central

De Gaetano, Francesco; Serrani, Marta; Bagnoli, Paola; Brubert, Jacob; Stasiak, Joanna; Moggridge, Geoff D.; Costantino, Maria Laura

2016-01-01

Introduction Only mechanical and biological heart valve prostheses are currently commercially available. The former show longer durability but require anticoagulant therapy, the latter display better fluid dynamic behaviour but do not have adequate durability. New Polymeric Heart Valves (PHVs) could potentially combine the haemodynamic properties of biological valves with the durability of mechanical valves. This work presents a hydrodynamic evaluation of two groups of newly developed supra-annular tri-leaflet prosthetic heart valves made from styrenic block copolymers (SBC): Poli-Valves. Methods Two types of Poli-Valves made of SBC differing in polystyrene fraction content were tested under continuous and pulsatile flow conditions as prescribed by ISO 5840 Standard. An ad - hoc designed pulse duplicator allowed the valve prototypes to be tested at different flow rates and frequencies. Pressure and flow were recorded; pressure drops, effective orifice area (EOA), and regurgitant volume were computed to assess the valve’s behaviour. Results Both types Poli-Valves met the minimum requirements in terms of regurgitation and EOA as specified by ISO 5840 Standard. Results were compared with five mechanical heart valves (MHVs) and five tissue heart valves (THVs), currently available on the market. Conclusion Based on these results, polymeric heart valves based on styrenic block copolymers, as Poli-Valves are, can be considered as promising alternative for heart valve replacement in near future. PMID:26689146

Synthesis of well-defined bisbenzoin end-functionalized poly(ε-caprolactone) macrophotoinitiator by combination of ROP and click chemistry and its use in the synthesis of star copolymers by photoinduced free radical promoted cationic polymerization

PubMed Central

Uyar, Zafer; Degirmenci, Mustafa; Genli, Nasrettin; Yilmaz, Ayse

2017-01-01

Abstract A new well-defined bisbenzoin group end-functionalized poly(ε-caprolactone) macrophotoinitiator (PCL-(PI)2) was synthesized by combination of ring opening polymerization (ROP) and click chemistry. The ROP of ε-CL monomer in bulk at 110 °C, by means of a hydroxyl functional initiator namely, 3-cyclohexene-1-methanol in conjunction with stannous-2-ethylhexanoate, (Sn(Oct)2), yielded a well-defined PCL with a cyclohexene end-chain group (PCL-CH). The bromination and subsequent azidation of the cyclohexene end-chain group gave bisazido functionalized poly(ε-caprolactone) (PCL-(N3)2). Separately, an acetylene functionalized benzoin photoinitiator (PI-alkyne) was synthesized by using benzoin and propargyl bromide. Then the click reaction between PCL-(N3)2 and PI-alkyne was performed by Cu(I) catalysis. The spectroscopic studies revealed that poly(ε-caprolactone) with bisbenzoin photoactive functional group at the chain end (PCL-(PI)2) with controlled chain length and low-polydispersity was obtained. This PCL-(PI)2 macrophotoinitiator was used as a precursor in photoinduced free radical promoted cationic polymerization to synthesize an AB2-type miktoarm star copolymer consisting of poly(ε-caprolactone) (PCL, as A block) and poly(cyclohexene oxide) (PCHO, as B block), namely PCL(PCHO)2. PMID:29491778

Organisation and shape of micellar solutions of block copolymers

NASA Astrophysics Data System (ADS)

Gaspard, J. P.; Creutz, S.; Bouchat, Ph.; Jérôme, R.; Cohen Stuart, M.

1997-02-01

Diblock copolymers of polymethacrylic acid sodium salt, forming the hair, and styrene derivatives have been studied in aqueous solutions by SANS and SAXS. The influence of both the chemical nature and the length of the hydrophobic bloxk on the size and shape of micelles have been investigated. The micellar core size is in agreement with the theoretical evaluation for copolymers with a short hydrophobic sequence. In contrast, in case of larger hydrophobic blocks, the measured size is incompatible with a star-like model. Various hypotheses are presented for the latter.

Polymer brushes on nanoparticles: their positioning in and influence on block copolymer morphology.

NASA Astrophysics Data System (ADS)

Kim, Bumjoon

2007-03-01

Polymers brushes grafted to the nanoparticle surface enable the precise positioning of particles within a block copolymer matrix by determining the compatibility of nanoparticles within a polymeric matrix and modifying the interfacial properties between polymers and inorganic nanoparticle. Short thiol terminated polystyrene (PS-SH), poly(2-vinylpyridine) (P2VP-SH) and PS-r-P2VP with the molecular weight (Mn) of 3 kg/mol were used to control the location of Au nanoparticles over PS-b-P2VP diblock copolymer template. We will discuss further the approach of varying the areal chain density (σ) of PS-SH brushes on the PS coated particles, which utilizes the preferential wetting of one block of a copolymer (P2VP) on the Au substrate. Such favorable interaction provides the strong binding of Au particles to the PS/P2VP interface as σ of PS chains on the Au particle decreases. We find that at σ above a certain value, the nanoparticles are segregated to the center of the PS domains while below this value they are segregated to the interface. The transition σ for PS-SH chains (Mn = 3.4 kg/mol) is 1.3 chains/nm^2 but unexpectedly scales as Mn-0.55 as Mn is varied from 1.5 to 13 kg/mol. In addition, we will discuss changes in block copolymer morphology that occur as the nanoparticle volume fraction (φ) is increased for nanoparticles that segregate to the domain center as well as those that segregate to the interface, the latter behaving as nanoparticle surfactants. Small φ of such surfactants added to lamellar diblock copolymers lead initially to a decrease in lamellar thickness, a consequence of decreasing interfacial tension, up to a critical value of φ beyond which the block copolymer adopts a bicontinuous morphology. I thank my collaborators G. H. Fredrickson, J. Bang, C. J. Hawker, and E. J. Kramer as well as funding by the MRL as UCSB from the NSF-MRSEC-Program Award DMR05-20418.

Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

NASA Astrophysics Data System (ADS)

Hoarfrost, Megan Lane

Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there is incredible freedom in designing the block copolymer architecture in order to optimize the mechanical and other properties of the membrane without sacrificing conductivity. The derived scaling relationships are shown to be general for many block copolymer and ionic liquid chemistries. In certain cases, the mechanism of ion conduction in the ionic liquid is affected by block copolymer nanoconfinement. The introduction of excess neutral imidazole to [Im][TFSI] leads to enhanced proton conductivity as well as a high H+ transference number due to facilitated proton hopping between imidazole molecules. We show that there is increased proton hopping when the nonstoichiometric ionic liquid is confined to lamellar block copolymer nanodomains, which we hypothesize is due to changes in the hydrogen bond structure of the ionic liquid under confinement. This, in combination with unique ion aggregation behavior, leads to a lower activation energy for macroscopic ion transport compared to that in a corresponding homopolymer/ionic liquid mixture. Through this work, we further the understanding of the relationship between membrane composition, structure, and ion transport. The findings presented herein portend the rational design of nanostructured membranes having improved mechanical properties and conductivity.

Exploiting Molecular Weight Distribution Shape to Tune Domain Spacing in Block Copolymer Thin Films.

PubMed

Gentekos, Dillon T; Jia, Junteng; Tirado, Erika S; Barteau, Katherine P; Smilgies, Detlef-M; DiStasio, Robert A; Fors, Brett P

2018-04-04

We report a method for tuning the domain spacing ( D sp ) of self-assembled block copolymer thin films of poly(styrene- block-methyl methacrylate) (PS- b-PMMA) over a large range of lamellar periods. By modifying the molecular weight distribution (MWD) shape (including both the breadth and skew) of the PS block via temporal control of polymer chain initiation in anionic polymerization, we observe increases of up to 41% in D sp for polymers with the same overall molecular weight ( M n ≈ 125 kg mol -1 ) without significantly changing the overall morphology or chemical composition of the final material. In conjunction with our experimental efforts, we have utilized concepts from population statistics and least-squares analysis to develop a model for predicting D sp based on the first three moments of the MWDs. This statistical model reproduces experimental D sp values with high fidelity (with mean absolute errors of 1.2 nm or 1.8%) and provides novel physical insight into the individual and collective roles played by the MWD moments in determining this property of interest. This work demonstrates that both MWD breadth and skew have a profound influence over D sp , thereby providing an experimental and conceptual platform for exploiting MWD shape as a simple and modular handle for fine-tuning D sp in block copolymer thin films.

Broadband pH-Sensing Organic Transistors with Polymeric Sensing Layers Featuring Liquid Crystal Microdomains Encapsulated by Di-Block Copolymer Chains.

PubMed

Seo, Jooyeok; Song, Myeonghun; Jeong, Jaehoon; Nam, Sungho; Heo, Inseok; Park, Soo-Young; Kang, Inn-Kyu; Lee, Joon-Hyung; Kim, Hwajeong; Kim, Youngkyoo

2016-09-14

We report broadband pH-sensing organic field-effect transistors (OFETs) with the polymer-dispersed liquid crystal (PDLC) sensing layers. The PDLC layers are prepared by spin-coating using ethanol solutions containing 4-cyano-4'-pentyl-biphenyl (5CB) and a diblock copolymer (PAA-b-PCBOA) that consists of LC-philic block [poly(4-cyano-biphenyl-4-oxyundecyl acrylate) (PCBOA)] and acrylic acid block [poly(acrylic acid) (PAA)]. The spin-coated sensing layers feature of 5CB microdomains (<5 μm) encapsulated by the PAA-b-PCBOA polymer chains. The resulting LC-integrated-OFETs (PDLC-i-OFETs) can detect precisely and reproducibly a wide range of pH with only small amounts (10-40 μL) of analyte solutions in both static and dynamic perfusion modes. The positive drain current change is measured for acidic solutions (pH < 7), whereas basic solutions (pH > 7) result in the negative change of drain current. The drain current trend in the present PDLC-i-OFET devices is explained by the shrinking-expanding mechanism of the PAA chains in the diblock copolymer layers.

Acrylic Triblock Copolymers Incorporating Isosorbide for Pressure Sensitive Adhesives

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

Gallagher, James J.; Hillmyer, Marc A.; Reineke, Theresa M.

A new monomer acetylated acrylic isosorbide (AAI) was prepared in two steps using common reagents without the need for column chromatography. Free radical polymerization of AAI afforded poly(acetylated acrylic isosorbide) (PAAI), which exhibited a glass transition temperature (Tg) = 95 °C and good thermal stability (Td, 5% weight loss; N2 = 331 °C, air = 291 °C). A series of ABA triblock copolymers with either poly(n-butyl acrylate) (PnBA) or poly(2-ethylhexyl acrylate) (PEHA) as the low Tg midblocks and PAAI as the high Tg end blocks were prepared using Reversible Addition–Fragmentation chain Transfer (RAFT) polymerization. The triblock copolymers ranging from 8–24more » wt % PAAI were evaluated as pressure sensitive adhesives by 180° peel, loop tack, and static shear testing. While the PAAI-PEHA-PAAI series exhibited poor adhesive qualities, the PAAI-PnBA-PAAI series of triblock copolymers demonstrated peel forces up to 2.9 N cm–1, tack forces up to 3.2 N cm–1, and no shear failure up to 10000 min. Dynamic mechanical analysis indicated that PAAI-PEHA-PAAI lacked the dissipative qualities needed to form an adhesive bond with the substrate, while the PAAI-PnBA-PAAI series exhibited a dynamic mechanical response consistent with related high performing PSAs.« less

Thermosensitive behavior of poly(ethylene glycol)-based block copolymer (PEG-b-PADMO) controlled via self-assembled microstructure.

PubMed

Cui, Qianling; Wu, Feipeng; Wang, Erjian

2011-05-19

Stimuli-responsive, well-defined diblock copolymers (PEG-b-PADMO) comprising poly(ethylene glycol) (PEG, DP (degree of polymerization)=45) as the hydrophilic and temperature-sensitive part and poly(N-acryloyl-2,2-dimethyl-1,3-oxazolidine) (PADMO, DP=18-47) as the hydrophobic and acid-labile part self-assembled in water into spherical micelles with high aggregation number. The micellar structures and thermally induced phase transitions of the copolymers were investigated with (1)H NMR spectroscopy, light scattering, microscopy, turbidimetry, and fluorescence techniques. Thermoresponsive phase transitions of the copolymers in water were controlled via formation of core-shell-type micelles with densely compact PEG corona. Their lower critical solution temperatures (LCSTs) were modulated within the range 40-72 °C by varying PADMO block length. This unusually low LCST was attributed to the densely packed PEG structure in the polymer micelles, which resulted in strong n-clustering attractive interactions and insufficient hydration of PEG chains in the shell and greatly enhanced the thermosensitivity. The LCST behavior can also be modulated by partial acid hydrolysis of PADMO segments through the resulting change of hydrophobicity. © 2011 American Chemical Society

Amphiphilic multiarm star block copolymer-based multifunctional unimolecular micelles for cancer targeted drug delivery and MR imaging.

PubMed

Li, Xiaojie; Qian, Yinfeng; Liu, Tao; Hu, Xianglong; Zhang, Guoying; You, Yezi; Liu, Shiyong

2011-09-01

We report on the fabrication of multifunctional polymeric unimolecular micelles as an integrated platform for cancer targeted drug delivery and magnetic resonance imaging (MRI) contrast enhancement under in vitro and in vivo conditions. Starting from a fractionated fourth-generation hyperbranched polyester (Boltorn H40), the ring-opening polymerization of ɛ-caprolactone (CL) from the periphery of H40 and subsequent terminal group esterification with 2-bromoisobutyryl bromide afforded star copolymer-based atom transfer radical polymerization (ATRP) macroinitiator, H40-PCL-Br. Well-defined multiarm star block copolymers, H40-PCL-b-P(OEGMA-co-AzPMA), were then synthesized by the ATRP of oligo(ethylene glycol) monomethyl ether methacrylate (OEGMA) and 3-azidopropyl methacrylate (AzPMA). This was followed by the click reaction of H40-PCL-b-P(OEGMA-co-AzPMA) with alkynyl-functionalized cancer cell-targeting moieties, alkynyl-folate, and T(1)-type MRI contrast agents, alkynyl-DOTA-Gd (DOTA is 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakisacetic acid), affording H40-PCL-b-P(OEGMA-Gd-FA). In aqueous solution, the amphiphilic multiarm star block copolymer exists as structurally stable unimolecular micelles possessing a hyperbranched polyester core, a hydrophobic PCL inner layer, and a hydrophilic P(OEGMA-Gd-FA) outer corona. H40-PCL-b-P(OEGMA-Gd-FA) unimolecular micelles are capable of encapsulating paclitaxel, a well-known hydrophobic anticancer drug, with a loading content of 6.67 w/w% and exhibiting controlled release of up to 80% loaded drug over a time period of ∼120 h. In vitro MRI experiments demonstrated considerably enhanced T(1) relaxivity (18.14 s(-1) mM(-1)) for unimolecular micelles compared to 3.12 s(-1) mM(-1) for that of the small molecule counterpart, alkynyl-DOTA-Gd. Further experiments of in vivo MR imaging in rats revealed good accumulation of unimolecular micelles within rat liver and kidney, prominent positive contrast enhancement, and relatively long duration of blood circulation. The reported unimolecular micelles-based structurally stable nanocarriers synergistically integrated with cancer targeted drug delivery and controlled release and MR imaging functions augur well for their potential applications as theranostic systems. Copyright © 2011 Elsevier Ltd. All rights reserved.

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.

Thermo- and pH-Responsive Copolymers Bearing Cholic Acid and Oligo(ethylene glycol) Pendants: Self-Assembly and pH-Controlled Release.

PubMed

Jia, Yong-Guang; Zhu, X X

2015-11-11

A family of block and random copolymers of norbornene derivatives bearing cholic acid and oligo(ethylene glycol) pendants were prepared in the presence of Grubbs' catalyst. The phase transition temperature of the copolymers in aqueous solutions may be tuned by the variation of comonomer ratios and pH values. Both types of copolymers formed micellar nanostructures with a hydrophilic poly(ethylene glycol) shell and a hydrophobic core containing cholic acid residues. The micellar size increased gradually with increasing pH due to the deprotonation of the carboxylic acid groups. These micelles were capable of encapsulating hydrophobic compounds such as Nile Red (NR). A higher hydrophobicity/hydrophilicity ratio in both copolymers resulted in a higher loading capacity for NR. With similar molecular weights and monomer compositions, the block copolymers showed a higher loading capacity for NR than the random copolymers. The NR-loaded micelles exhibited a pH-triggered release behavior. At pH 7.4 within 96 h, the micelles formed by the block and random of copolymers released 56 and 97% NR, respectively. Therefore, these micelles may have promise for use as therapeutic nanocarriers in drug delivery systems.

Preparation, co-assembling and interfacial crosslinking of photocurable and folate-conjugated amphiphilic block copolymers for controlled and targeted drug delivery: smart armored nanocarriers.

PubMed

Khoee, Sepideh; Kavand, Alireza

2014-02-12

Novel pH-sensitive, biodegradable and biocompatible copolymers based on polycaprolactone-poly(ethylene glycol) (PCL/PEG) were synthesized and further modified with folic acid and/or acryloyl chloride. The mixed polymeric micelles were formed by self-assembling of folated-copolymer and non-folated-copolymer with different compositions via nanoprecipitation method. The solubilization of quercetin as anti-cancer drug by the mixed micelle with the optimized composition (folated/non-folated 20/80) was more efficient than those made of each one alone. Nanogels with different crosslinking density were produced in the presence of ethylene glycol dimethacrylate (EGDMA) as the crosslinker via a photochemical method. Interfacial crosslinking of acrylated groups were utilized to produce a core-shell spherical nanoparticle to evaluate their in-vitro drug release and degradation rate. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

Biocompatible Polysiloxane-Containing Diblock Copolymer PEO-b-PγMPS for Coating Magnetic Nanoparticles

PubMed Central

Chen, Hongwei; Wu, Xinying; Duan, Hongwei; Wang, Y. Andrew; Wang, Liya; Zhang, Minming; Mao, Hui

2009-01-01

We report a biocompatible polysiloxane containing amphiphilic diblock copolymer, poly(ethylene oxide)-block-poly(γ-methacryloxypropyltrimethoxysilane) (PEO-b-PγMPS), for coating and stabilizing nanoparticles for biomedical applications. Such amphiphilic diblock copolymer which comprises both a hydrophobic segment with “surface anchoring moiety” (silane group) and a hydrophilic segment with PEO (Mn=5000 g/mol) was obtained by the reversible addition fragmentation chain transfer (RAFT) polymerization using the PEO macromolecular chain transfer agent. When used for coating paramagnetic iron oxide nanoparticles (IONPs), copolymers were mixed with hydrophobic oleic acid coated core size uniformed IONPs (D=13 nm) in co-solvent tetrahydrofuran. After being aged over a period of time, resulting monodispersed IONPs can be transferred into aqueous medium. With proper PγMPS block length (Mn=10,000 g/mol), polysiloxane containing diblock copolymers formed a thin layer of coating (~3 nm) around monocrystalline nanoparticles as measured by transmission electron microscopy (TEM). Magnetic resonance imaging (MRI) experiments showed excellent T2 weighted contrast effect from coated IONPs with a transverse relaxivity r2=98.6 mM−1s−1 (at 1.5 Tesla). Such thin coating layer has little effect on the relaxivity when compared to that of IONPs coated with conventional amphiphilic copolymer. Polysiloxane containing diblock copolymer coated IONPs are stable without aggregation or binding to proteins in serum when incubated for 24 h in culture medium containing 10% serum. Furthermore, much lower level of intracellular uptake by macrophage cells was observed with polysiloxane containing diblock copolymers coated IONPs, suggesting the reduction of non-specific cell uptakes and antibiofouling effect. PMID:20161520

RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers

PubMed Central

2016-01-01

RAFT solution polymerization of N-(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was chain-extended with NMEP using a RAFT aqueous dispersion polymerization formulation at 70 °C. The target PNMEP DP was systematically varied from 100 up to 6000 to generate a series of PGMA63–PNMEPx diblock copolymers. High conversions (≥92%) could be achieved when targeting up to x = 5000. GPC analysis confirmed high blocking efficiencies and a linear evolution in Mn with increasing PNMEP DP. A gradual increase in Mw/Mn was also observed when targeting higher DPs. However, this problem could be minimized (Mw/Mn < 1.50) by utilizing a higher purity grade of NMEP (98% vs 96%). This suggests that the broader molecular weight distributions observed at higher DPs are simply the result of a dimethacrylate impurity causing light branching, rather than an intrinsic side reaction such as chain transfer to polymer. Kinetic studies confirmed that the RAFT aqueous dispersion polymerization of NMEP was approximately four times faster than the RAFT solution polymerization of NMEP in ethanol when targeting the same DP in each case. This is perhaps surprising because both 1H NMR and SAXS studies indicate that the core-forming PNMEP chains remain relatively solvated at 70 °C in the latter formulation. Moreover, dissolution of the initial PGMA63–PNMEPx particles occurs on cooling from 70 to 20 °C as the PNMEP block passes through its LCST. Hence this RAFT aqueous dispersion polymerization formulation offers an efficient route to a high molecular weight water-soluble polymer in a rather convenient low-viscosity form. Finally, the relatively expensive PGMA macro-CTA was replaced with a poly(methacrylic acid) (PMAA) macro-CTA. High conversions were also achieved for PMAA85–PNMEPx diblock copolymers prepared via RAFT aqueous dispersion polymerization for x ≤ 4000. Again, better control was achieved when using the 98% purity NMEP monomer in such syntheses. PMID:27375300

RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers.

PubMed

Cunningham, Victoria J; Derry, Matthew J; Fielding, Lee A; Musa, Osama M; Armes, Steven P

2016-06-28

RAFT solution polymerization of N -(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was chain-extended with NMEP using a RAFT aqueous dispersion polymerization formulation at 70 °C. The target PNMEP DP was systematically varied from 100 up to 6000 to generate a series of PGMA 63 -PNMEP x diblock copolymers. High conversions (≥92%) could be achieved when targeting up to x = 5000. GPC analysis confirmed high blocking efficiencies and a linear evolution in M n with increasing PNMEP DP. A gradual increase in M w / M n was also observed when targeting higher DPs. However, this problem could be minimized ( M w / M n < 1.50) by utilizing a higher purity grade of NMEP (98% vs 96%). This suggests that the broader molecular weight distributions observed at higher DPs are simply the result of a dimethacrylate impurity causing light branching, rather than an intrinsic side reaction such as chain transfer to polymer. Kinetic studies confirmed that the RAFT aqueous dispersion polymerization of NMEP was approximately four times faster than the RAFT solution polymerization of NMEP in ethanol when targeting the same DP in each case. This is perhaps surprising because both 1 H NMR and SAXS studies indicate that the core-forming PNMEP chains remain relatively solvated at 70 °C in the latter formulation. Moreover, dissolution of the initial PGMA 63 -PNMEP x particles occurs on cooling from 70 to 20 °C as the PNMEP block passes through its LCST. Hence this RAFT aqueous dispersion polymerization formulation offers an efficient route to a high molecular weight water-soluble polymer in a rather convenient low-viscosity form. Finally, the relatively expensive PGMA macro-CTA was replaced with a poly(methacrylic acid) (PMAA) macro-CTA. High conversions were also achieved for PMAA 85 -PNMEP x diblock copolymers prepared via RAFT aqueous dispersion polymerization for x ≤ 4000. Again, better control was achieved when using the 98% purity NMEP monomer in such syntheses.

Temperature and pH Dual-Responsive Core-Brush Nanocomposite for Enrichment of Glycoproteins.

PubMed

Jiang, Lingdong; Messing, Maria E; Ye, Lei

2017-03-15

In this report, we present a novel modular approach to the immobilization of a high density of boronic acid ligands on thermoresponsive block copolymer brushes for effective enrichment of glycoproteins via their synergistic multiple covalent binding with the immobilized boronic acids. Specifically, a two-step, consecutive surface-initiated atom transfer radical polymerization (SI-ATRP) was employed to graft a flexible block copolymer brush, pNIPAm-b-pGMA, from an initiator-functionalized nanosilica surface, followed by postpolymerization modification of the pGMA moiety with sodium azide. Subsequently, an alkyne-tagged boronic acid (PCAPBA) was conjugated to the polymer brush via a Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click reaction, leading to a silica-supported polymeric hybrid material, Si@pNIPAm-b-pBA, with a potent glycol binding affinity. The obtained core-brush nanocomposite was systematically characterized with regard to particle size, morphology, organic content, brush density, and number of immobilized boronic acids. We also studied the characteristics of glycoprotein binding of the nanocomposite under different conditions. The nanocomposite showed high binding capacities for ovalbumin (OVA) (98.0 mg g -1 ) and horseradish peroxidase (HRP) (26.8 mg g -1 ) in a basic buffer (pH 9.0) at 20 °C. More importantly, by adjusting the pH and temperature, the binding capacities of the nanocomposite can be tuned, which is meaningful for the separation of biological molecules. In general, the synthetic approach developed for the fabrication of block copolymer brushes in the nanocomposite opened new opportunities for the design of more functional hybrid materials that will be useful in bioseparation and biomedical applications.

Surface and Bulk Phase Separations in Block Copolymers and Their Blends.

DTIC Science & Technology

1984-03-01

research effort in _. the biomedical area to study polymeric surfaces which may be applied where biocompatibility (particularly, blood compatibilty) is...elasticity(thermoplastic) and good biocompatibility . Two such commercially available polyurethanes-, Avcothane and Biomer, have been used in this...the biocompatible properties depended considerably on the rate of evaporation of solvent during the film preparation. ATR-IR spectroscopy showed that

Personal Cooling Fabric Based on Polymeric Thermoelectrics

DTIC Science & Technology

2016-07-28

weight organic materials. Furthermore, p- and n-doped conjugated polymers with high electrical conductivity were discovered over two decades ago...fully conjugated PPV polymer MEH-PPV with SWCNT provided films with the highest conductivity while maintaining relatively unchanged Seebeck...Geise, H. J., Synthesis of Electrically Conducting Copolymers with Short Alternating Conjugated and Non- conjugated Blocks. Polymer 1994, 35, (2), 391-397.

Synthesis of hollow spherical calcium phosphate nanoparticles using polymeric nanotemplates

NASA Astrophysics Data System (ADS)

Tjandra, Wiliana; Ravi, Palaniswamy; Yao, Jia; Tam, Kam C.

2006-12-01

Poly(methylmethacrylate)-block-poly(methacrylic acid) (PMMA-b-PMAA) copolymer was synthesized by an atom transfer radical polymerization (ATRP) technique. The block copolymer was employed as a template for the controlled precipitation of calcium phosphate from aqueous solution at different pH values. A Ca2+ ion selective electrode was used to study the interactions between Ca2+ ions and the polymer, which indicated a possible weak interaction between Ca2+ and un-ionized MAA segments at pH~4.0 in addition to electrostatic interaction between Ca2+ and ionized MAA segments at higher pH. An interesting structure representing that of a superstructure consisting of hybrid nano-filaments was observed by the transmission electron microscope at pH~4.0. The filaments originated from a core of similar size to primary polymer aggregates, suggesting that cooperative interactions at a local level between dissolving calcium phosphate clusters and disassembling polymer segments are responsible for the secondary growth process. A hollow spherical morphology was obtained at pH~7.0 and 9.0. Such calcium phosphate/polymer monohybrids with complex morphologies are interesting and might be useful as novel drug delivery carriers, ceramics precursors, reinforcing fillers or biomedical implants.

Synthesis and Characterization of Comb and Centipede Multigraft Copolymers P nBA- g-PS with High Molecular Weight Using Miniemulsion Polymerization

DOE PAGES

Wang, Wenwen; Wang, Weiyu; Lu, Xinyi; ...

2014-10-23

For this study, comb and centipede multigraft copolymers, poly(n-butyl acrylate)-g-polystyrene (PnBA-g-PS) with PnBA backbones and PS side chains, were synthesized via high-vacuum anionic polymerization and miniemulsion polymerization. Single-tailed and double-tailed PS macromonomers were synthesized by anionic polymerization and Steglich esterification. Subsequently, the copolymerization of each macromonomer and nBA was carried out in miniemulsion, and multigraft copolymers were obtained. The latex particles of multigraft copolymers were characterized using dynamic light scattering. The molecular weights of macromonomers and multigraft copolymers were analyzed by size exclusion chromatography. Moreover, the molecular weights and structures of macromonomers were investigated by matrix-assisted laser desorption/ionization time-of-flight massmore » spectrometry and 1H nuclear magnetic resonance spectroscopy. The weight contents of PS in comb and centipede multigraft copolymers were calculated by 1H nuclear magnetic resonance spectroscopy. The thermal properties of multigraft copolymers were characterized by thermogravimetric analysis and differential scanning calorimetry. The microphase separation of multigraft copolymers was observed by atomic force microscopy and transmission electronic microscopy. Rheological measurements showed that comb and centipede multigraft copolymers have elastic properties when the weight content of PS side chains is 26–32 wt %. Centipede multigraft copolymers possess better elastic properties than comb multigraft copolymers with the similar weight content of PS. In conclusion, these findings are similar to previous results on poly(isoprene-g-polystyrene) comb and centipede copolymers made by anionic polymerization.« less

Endocytotic uptake of HPMA-based polymers by different cancer cells: impact of extracellular acidosis and hypoxia

PubMed Central

Gündel, Daniel; Allmeroth, Mareli; Reime, Sarah; Zentel, Rudolf; Thews, Oliver

2017-01-01

Background Polymeric nanoparticles allow to selectively transport chemotherapeutic drugs to the tumor tissue. These nanocarriers have to be taken up into the cells to release the drug. In addition, tumors often show pathological metabolic characteristics (hypoxia and acidosis) which might affect the polymer endocytosis. Materials and methods Six different N-(2-hydroxypropyl)methacrylamide (HPMA)-based polymer structures (homopolymer as well as random and block copolymers with lauryl methacrylate containing hydrophobic side chains) varying in molecular weight and size were analyzed in two different tumor models. The cellular uptake of fluorescence-labeled polymers was measured under hypoxic (pO2 ≈1.5 mmHg) and acidic (pH 6.6) conditions. By using specific inhibitors, different endocytotic routes (macropinocytosis and clathrin-mediated, dynamin-dependent, cholesterol-dependent endocytosis) were analyzed separately. Results The current results revealed that the polymer uptake depends on the molecular structure, molecular weight and tumor line used. In AT1 cells, the uptake of random copolymer was five times stronger than the homopolymer, whereas in Walker-256 cells, the uptake of all polymers was much stronger, but this was independent of the molecular structure and size. Acidosis increased the uptake of random copolymer in AT1 cells but reduced the intracellular accumulation of homopolymer and block copolymer. Hypoxia reduced the uptake of all polymers in Walker-256 cells. Hydrophilic polymers (homopolymer and block copolymer) were taken up by all endocytotic routes studied, whereas the more lipophilic random copolymer seemed to be taken up preferentially by cholesterol- and dynamin-dependent endocytosis. Conclusion The study indicates that numerous parameters of the polymer (structure, size) and of the tumor (perfusion, vascular permeability, pH, pO2) modulate drug delivery, which makes it difficult to select the appropriate polymer for the individual patient. PMID:28831253

Endocytotic uptake of HPMA-based polymers by different cancer cells: impact of extracellular acidosis and hypoxia.

PubMed

Gündel, Daniel; Allmeroth, Mareli; Reime, Sarah; Zentel, Rudolf; Thews, Oliver

2017-01-01

Polymeric nanoparticles allow to selectively transport chemotherapeutic drugs to the tumor tissue. These nanocarriers have to be taken up into the cells to release the drug. In addition, tumors often show pathological metabolic characteristics (hypoxia and acidosis) which might affect the polymer endocytosis. Six different N -(2-hydroxypropyl)methacrylamide (HPMA)-based polymer structures (homopolymer as well as random and block copolymers with lauryl methacrylate containing hydrophobic side chains) varying in molecular weight and size were analyzed in two different tumor models. The cellular uptake of fluorescence-labeled polymers was measured under hypoxic (pO 2 ≈1.5 mmHg) and acidic (pH 6.6) conditions. By using specific inhibitors, different endocytotic routes (macropinocytosis and clathrin-mediated, dynamin-dependent, cholesterol-dependent endocytosis) were analyzed separately. The current results revealed that the polymer uptake depends on the molecular structure, molecular weight and tumor line used. In AT1 cells, the uptake of random copolymer was five times stronger than the homopolymer, whereas in Walker-256 cells, the uptake of all polymers was much stronger, but this was independent of the molecular structure and size. Acidosis increased the uptake of random copolymer in AT1 cells but reduced the intracellular accumulation of homopolymer and block copolymer. Hypoxia reduced the uptake of all polymers in Walker-256 cells. Hydrophilic polymers (homopolymer and block copolymer) were taken up by all endocytotic routes studied, whereas the more lipophilic random copolymer seemed to be taken up preferentially by cholesterol- and dynamin-dependent endocytosis. The study indicates that numerous parameters of the polymer (structure, size) and of the tumor (perfusion, vascular permeability, pH, pO 2 ) modulate drug delivery, which makes it difficult to select the appropriate polymer for the individual patient.

Photonic Resins: Designing Optical Appearance via Block Copolymer Self-Assembly

PubMed Central

2018-01-01

Despite a huge variety of methodologies having been proposed to produce photonic structures by self-assembly, the lack of an effective fabrication approach has hindered their practical uses. These approaches are typically limited by the poor control in both optical and mechanical properties. Here we report photonic thermosetting polymeric resins obtained through brush block copolymer (BBCP) self-assembly. We demonstrate that the control of the interplay between order and disorder in the obtained photonic structure offers a powerful tool box for designing the optical appearance of the polymer resins in terms of reflected wavelength and scattering properties. The obtained materials exhibit excellent mechanical properties with hardness up to 172 MPa and Young’s modulus over 2.9 GPa, indicating great potential for practical uses as photonic coatings on a variety of surfaces. PMID:29681653

Polymersomes from dual responsive block copolymers: drug encapsulation by heating and acid-triggered release.

PubMed

Qiao, Zeng-Ying; Ji, Ran; Huang, Xiao-Nan; Du, Fu-Sheng; Zhang, Rui; Liang, De-Hai; Li, Zi-Chen

2013-05-13

A series of well-defined thermoresponsive diblock copolymers (PEO45-b-PtNEAn, n=22, 44, 63, 91, 172) were prepared by the atom transfer radical polymerization of trans-N-(2-ethoxy-1,3-dioxan-5-yl) acrylamide (tNEA) using a poly(ethylene oxide) (PEO45) macroinitiator. All copolymers are water-soluble at low temperature, but upon quickly heating to 37 °C, laser light scattering (LLS) and transmission electron microscopy (TEM) characterizations indicate that these copolymers self-assemble into aggregates with different morphologies depending on the chain length of PtNEA and the polymer concentration; the morphologies gradually evolved from spherical solid nanoparticles to a polymersome as the degree of polymerization ("n") of PtNEA block increased from 22 to 172, with the formation of clusters with rod-like structure at the intermediate PtNEA length. Both the spherical nanoparticle and the polymersome are stable at physiological pH but susceptible to the mildly acidic medium. Acid-triggered hydrolysis behaviors of the aggregates were investigated by LLS, Nile red fluorescence, TEM, and (1)H NMR spectroscopy. The results revealed that the spherical nanoparticles formed from PEO45-b-PtNEA44 dissociated faster than the polymersomes of PEO45-b-PtNEA172, and both aggregates showed an enhanced hydrolysis under acidic conditions. Both the spherical nanoparticle and polymersome are able to efficiently load the hydrophobic doxorubicin (DOX), and water-soluble fluorescein isothiocyanate-lysozyme (FITC-Lys) can be conveniently encapsulated into the polymersome without using any organic solvent. Moreover, FITC-Lys and DOX could be coloaded in the polymersome. The drugs loaded either in the polymersome or in the spherical nanoparticle could be released by acid triggering. Finally, the DOX-loaded assemblies display concentration-dependent cytotoxicity to HepG2 cells, while the copolymers themselves are nontoxic.

The protection of different Italian marbles with two partially flourinated acrylic copolymers

NASA Astrophysics Data System (ADS)

Poli, T.; Toniolo, L.; Chiantore, O.

Committing stone protection to polymeric materials started in the sixties but the study and knowledge of the complex and multiple interactions between stone and polymers has only been carried out recently. It's important to note that, together with the factors related to the polymeric system itself, intrinsic properties of the stone substrate, like composition, porosity, and crystalline characteristics, play a relevant role. In this paper the issues related to protection of three different Italian marbles have been investigated: Candoglia marble, employed in the building of the Milan Cathedral, Carrara marble, widely used in sculpture and historical architecture, and S. Giuliano marble, used in the building of the Pisa Cathedral and its famous leaning tower. Specimens coming from blocks of the three quarried stones have been characterized, treated with two new partially fluorinated acrylic copolymers, 2,2,2-trifluoroethyl methacrylate/methyl acrylate (TFEMA/MA), and trifluoromethyl-2,2,2-trifluorethyl methacrylate/methyl acrylate (HFIMA/MA), and tested according to UNI-Normal Italian protocol. All the measurements including capillary water absorption, static contact angles, colour variation, water vapour permeability, and SEM morphological analysis have been carried out before and after the polymeric treatment. The aim of this work is to evaluate the protective efficacy of these two new partially fluorinated acrylic copolymers on the three different marbles, and to correlate the different behaviours with the polymers' properties and with the stone substrates characteristics.

Novel alkyd-type coating resins produced using cationic polymerization

DOE PAGES

Chisholm, Bret J.; Kalita, Harjyoti; Alam, Samim; ...

2015-05-06

Novel, partially bio-based poly(vinyl ether) copolymers derived from soybean oil and cyclohexyl vinyl ether (CHVE) were produced by cationic polymerization and investigated for application as alkyd-type surface coatings. Compared to conventional alkyd resins, which are produced by high temperature melt condensation polymerization, the poly(v9nyl ether)s provide several advantages. These advantages include milder, more energy efficient polymer synthesis, elimination of issues associated with gelation during polymer synthesis, production of polymers with well-defined composition and relatively narrow molecular weight distribution, and elimination of film formation and physical property issues associated with entrained monomers, dimers, trimers, etc. The results of the studied showedmore » that the thermal, mechanical, and physical properties of the coatings produced from these novel polymers varied considerably as a function of polymer composition and cure temperature. Overall, the results suggest a good potential for these novel copolymers to be used for coatings cured by autoxidation.« less

Immobilization of Polyoxometalates on Tailored Polymeric Surfaces.

PubMed

Aguado-Ureta, Saioa; Rodríguez-Hernández, Juan; Del Campo, Adolfo; Perez-Álvarez, Leyre; Ruiz-Rubio, Leire; Vilas, José Luis; Artetxe, Beñat; Reinoso, Santiago; Gutiérrez-Zorrilla, Juan M

2018-03-02

Herein we describe the preparation of hybrid polymer-inorganic interfaces by the immobilization of polyoxometalate nanoclusters on functionalized polymer surfaces. The polymeric surfaces were made of polystyrene- b -poly(acrylic acid)/polystyrene (PS- b -PAA/PS) blends by spin coating on a silicon wafer. The functionalization of the polymer film was obtained by interfacial migration of the amphiphilic block copolymer toward the interface upon water vapor annealing. The carboxylic acid functional groups contained in the PAA block were then employed to anchor the [Ln III (α-SiW 11 O 39 )] 5- polyoxometalates (Ln: Ce, Er). This purpose was achieved by immersing the films in aqueous solutions of the in situ-formed inorganic nanoclusters. X-ray photoelectron and confocal Raman spectroscopies, together with atomic force microscopy, confirmed the immobilization of the inorganic species at the interface.

Rethinking Cysteine Protective Groups: S-Alkylsulfonyl-l-Cysteines for Chemoselective Disulfide Formation.

PubMed

Schäfer, Olga; Huesmann, David; Muhl, Christian; Barz, Matthias

2016-12-12

The ability to reversibly cross-link proteins and peptides grants the amino acid cysteine its unique role in nature as well as in peptide chemistry. We report a novel class of S-alkylsulfonyl-l-cysteines and N-carboxy anhydrides (NCA) thereof for peptide synthesis. The S-alkylsulfonyl group is stable against amines and thus enables its use under Fmoc chemistry conditions and the controlled polymerization of the corresponding NCAs yielding well-defined homo- as well as block co-polymers. Yet, thiols react immediately with the S-alkylsulfonyl group forming asymmetric disulfides. Therefore, we introduce the first reactive cysteine derivative for efficient and chemoselective disulfide formation in synthetic polypeptides, thus bypassing additional protective group cleavage steps. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesizing a Trefoil Knotted Block Copolymer via Ring-Expansion Strategy

DOE PAGES

Cao, Pengfei; Rong, Li-Han; Mangadlao, Joey; ...

2017-02-07

We synthesized a synthetic trefoil knotted poly(e-caprolatone) block-poly(L-lactide) (TK-PLA-b-PCL) via a ring expansion strategy from a trefoil knotted tin (Sn) initiator. Ring closing reaction between the bis-copper(I) templated phenanthro line complex and dibutyldimethoxytin results in a templated trefoil knotted initiator. Furthermore, the bis-copper(I) templated trefoil knotted poly(L-lactide) (TK-PLA) can be synthesized by ring-opening polymerization of L-lactide monomer, and decomplexation reaction of the templated TK-PLA will result in a geniune TK-PLA without constraint from the copper template. Subsequent insertion of e caprolactone in the bis-copper(I) templated TK-PLA forms the templated trefoil knotted block copolymer, i.e., TK-PLA-b-PCL, and the copper-free TK-PLA-b-PCL canmore » be obtained by decomplexation reaction. Finally, both TK-PLA and TK-PLA-b-PCL are analyzed by the 1 H NMR, FT-IR, UV-vis, DLS, and GPC.« less

A Critical Appraisal of RAFT-Mediated Polymerization-Induced Self-Assembly

PubMed Central

2016-01-01

Recently, polymerization-induced self-assembly (PISA) has become widely recognized as a robust and efficient route to produce block copolymer nanoparticles of controlled size, morphology, and surface chemistry. Several reviews of this field have been published since 2012, but a substantial number of new papers have been published in the last three years. In this Perspective, we provide a critical appraisal of the various advantages offered by this approach, while also pointing out some of its current drawbacks. Promising future research directions as well as remaining technical challenges and unresolved problems are briefly highlighted. PMID:27019522

Artificial Informational Polymers and Nanomaterials from Ring-Opening Metathesis Polymerization

NASA Astrophysics Data System (ADS)

James, Carrie Rae

Inspired by naturally occurring polymers (DNA, polypeptides, polysaccharides, etc.) that can self-assemble on the nanoscale into complex, information-rich architectures, we have synthesized nucleic acid based polymers using ROMP. These polymers were synthesized using a graft-through strategy, whereby nucleic acids bearing a strained cyclic olefin were directly polymerized. This is the first example of the graft-through polymerization of nucleic acids. Our approach takes advantage of non-charged peptide nucleic acids (PNAs) as elements to incorporate into ROMP polymer backbones. PNA is a synthetic nucleic acid analogue known for its increased affinity and specificity for complementary DNA or RNA. To accomplish the graft-through polymerization of PNA, we conjugated PNA to strained cyclic olefins using solid phase peptide conjugation chemistry. These PNA monomers were then directly polymerized into homo and block copolymers forming brushes, or comb-like arrangements, of information. Block copolymer amphiphiles of these materials, where the PNA brush served as the hydrophilic portion, were capable of self-assembly into spherical nanoparticles (PNA NPs). These PNA NPs were then studied with respect to their ability to hybridize complementary DNA sequences, as well as their ability to undergo cellular internalization. PNA NPs consisting of densely packed brushes of nucleic acids possessed increased thermal stability when mixed with their complementary DNA sequence, indicating a greater DNA binding affinity over their unpolymerized PNA counterparts. In addition, by arranging the PNA into dense brushes at the surface of the nanoparticle, Cy5.5 labeled PNA NPs were able to undergo cellular internalization into HeLa cells without the need for an additional cellular delivery device. Importantly, cellular internalization of PNA has remained a significant challenge in the literature due to the neutrally charged amino-ethyl glycine backbone of PNA. Therefore, this represents a novel way of facilitating cellular uptake of PNA. This materials strategy represents the first direct polymerization of nucleic acids, and presents a novel method for arranging biological information on the nanoscale at high density in order to confer novel attributes.

Rheological Design of Sustainable Block Copolymers

NASA Astrophysics Data System (ADS)

Mannion, Alexander M.

Block copolymers are extremely versatile materials that microphase separate to give rise to a rich array of complex behavior, making them the ideal platform for the development of rheologically sophisticated soft matter. In line with growing environmental concerns of conventional plastics from petroleum feedstocks, this work focuses on the rheological design of sustainable block copolymers--those derived from renewable sources and are degradable--based on poly(lactide). Although commercially viable, poly(lactide) has a number of inherent deficiencies that result in a host of challenges that require both creative and practical solutions that are cost-effective and amenable to large-scale production. Specifically, this dissertation looks at applications in which both shear and extensional rheology dictate performance attributes, namely chewing gum, pressure-sensitive adhesives, and polymers for blown film extrusion. Structure-property relationships in the context of block polymer architecture, polymer composition, morphology, and branching are explored in depth. The basic principles and fundamental findings presented in this thesis are applicable to a broader range of substances that incorporate block copolymers for which rheology plays a pivotal role.

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.

Materials Design for Block Copolymer Lithography

NASA Astrophysics Data System (ADS)

Sweat, Daniel Patrick

Block copolymers (BCPs) have attracted a great deal of scientific and technological interest due to their ability to spontaneously self-assemble into dense periodic nanostructures with a typical length scale of 5 to 50 nm. The use of self-assembled BCP thin-films as templates to form nanopatterns over large-area is referred to as BCP lithography. Directed self-assembly of BCPs is now viewed as a viable candidate for sub-20 nm lithography by the semiconductor industry. However, there are multiple aspects of assembly and materials design that need to be addressed in order for BCP lithography to be successful. These include substrate modification with polymer brushes or mats, tailoring of the block copolymer chemistry, understanding thin-film assembly and developing epitaxial like methods to control long range alignment. The rational design, synthesis and self-assembly of block copolymers with large interaction parameters (chi) is described in the first part of this dissertation. Two main blocks were chosen for introducing polarity into the BCP system, namely poly(4-hydroxystyrene) and poly(2-vinylpyridine). Each of these blocks are capable of ligating Lewis acids which can increase the etch contrast between the blocks allowing for facile pattern transfer to the underlying substrate. These BCPs were synthesized by living anionic polymerization and showed excellent control over molecular weight and dispersity, providing access to sub 5-nm domain sizes. Polymer brushes consist of a polymer chain with one end tethered to the surface and have wide applicability in tuning surface energy, forming responsive surfaces and increasing biocompatibility. In the second part of the dissertation, we present a universal method to grow dense polymer brushes on a wide range of substrates and combine this chemistry with BCP assembly to fabricate nanopatterned polymer brushes. This is the first demonstration of introducing additional functionality into a BCP directing layer and opens up a wide slew of applications from directed self-assembly to biomaterial engineering.

Application of an assay Cascade methodology for a deep preclinical characterization of polymeric nanoparticles as a treatment for gliomas.

PubMed

Fornaguera, Cristina; Lázaro, Miguel Ángel; Brugada-Vilà, Pau; Porcar, Irene; Morera, Ingrid; Guerra-Rebollo, Marta; Garrido, Cristina; Rubio, Núria; Blanco, Jerónimo; Cascante, Anna; Borrós, Salvador

2018-11-01

Glioblastoma multiforme (GBM) is the most devastating primary brain tumor due to its infiltrating and diffuse growth characteristics, a situation compounded by the lack of effective treatments. Currently, many efforts are being devoted to find novel formulations to treat this disease, specifically in the nanomedicine field. However, due to the lack of comprehensive characterization that leads to insufficient data on reproducibility, only a reduced number of nanomedicines have reached clinical phases. In this context, the aim of the present study was to use a cascade of assays that evaluate from physical-chemical and structural properties to biological characteristics, both in vitro and in vivo, and also to check the performance of nanoparticles for glioma therapy. An amphiphilic block copolymer, composed of polyester and poly(ethylene glycol; PEG) blocks, has been synthesized. Using a mixture of this copolymer and a polymer containing an active targeting moiety to the Blood Brain Barrier (BBB; Seq12 peptide), biocompatible and biodegradable polymeric nanoparticles have been prepared and extensively characterized. In vitro studies demonstrated that nanoparticles are safe for normal cells but cytotoxic for cancer cells. In vivo studies in mice demonstrated the ability of the Seq12 peptide to cross the BBB. Finally, in vivo efficacy studies using a human tumor model in SCID mice resulted in a significant 50% life-span increase, as compared with non-treated animals. Altogether, this assay cascade provided extensive pre-clinical characterization of our polymeric nanoparticles, now ready for clinical evaluation.

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

Enzymatic Continuous Flow Synthesis of Thiol-Terminated Poly(δ-Valerolactone) and Block Copolymers.

PubMed

Zhu, Ning; Huang, Weijun; Hu, Xin; Liu, Yihuan; Fang, Zheng; Guo, Kai

2018-04-01

Thiol-terminated poly(δ-valerolactone) is directly synthesized via enzymatic 6-mercapto-1-hexanol initiated ring-opening polymerization in both batch and microreactor. By using Candida antartica Lipase B immobilized tubular reactor, narrowly dispersed poly(δ-valerolactone) with higher thiol fidelity is more efficiently prepared in contrast to the batch reactor. Moreover, the integrated enzyme packed tubular reactor system is established to perform the chain extension experiments. Thiol-terminated poly(δ-valerolactone)-block-poly(ε-caprolactone) and poly(ε-caprolactone)-block-poly(δ-valerolactone) are easily prepared by modulating the monomer introduction sequence. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and Cross-Linking of All-Acrylamide Diblock Copolymer Nano-Objects via Polymerization-Induced Self-Assembly in Aqueous Solution

PubMed Central

2017-01-01

Various carboxylic acid-functionalized poly(N,N-dimethylacrylamide) (PDMAC) macromolecular chain transfer agents (macro-CTAs) were chain-extended with diacetone acrylamide (DAAM) by reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization at 70 °C and 20% w/w solids to produce a series of PDMAC–PDAAM diblock copolymer nano-objects via polymerization-induced self-assembly (PISA). TEM studies indicate that a PDMAC macro-CTA with a mean degree of polymerization (DP) of 68 or higher results in the formation of well-defined spherical nanoparticles with mean diameters ranging from 40 to 150 nm. In contrast, either highly anisotropic worms or polydisperse vesicles are formed when relatively short macro-CTAs (DP = 40–58) are used. A phase diagram was constructed to enable accurate targeting of pure copolymer morphologies. Dynamic light scattering (DLS) and aqueous electrophoresis studies indicated that in most cases these PDMAC–PDAAM nano-objects are surprisingly resistant to changes in either solution pH or temperature. However, PDMAC40–PDAAM99 worms do undergo partial dissociation to form a mixture of relatively short worms and spheres on adjusting the solution pH from pH 2–3 to around pH 9 at 20 °C. Moreover, a change in copolymer morphology from worms to a mixture of short worms and vesicles was observed by DLS and TEM on heating this worm dispersion to 50 °C. Postpolymerization cross-linking of concentrated aqueous dispersions of PDMAC–PDAAM spheres, worms, or vesicles was performed at ambient temperature using adipic acid dihydrazide (ADH), which reacts with the hydrophobic ketone-functionalized PDAAM chains. The formation of hydrazone groups was monitored by FT-IR spectroscopy and afforded covalently stabilized nano-objects that remained intact on exposure to methanol, which is a good solvent for both blocks. Rheological studies indicated that the cross-linked worms formed a stronger gel compared to linear precursor worms. PMID:28260814

Synthesis of Novel μ-Star Copolymers with Poly(N-Octyl Benzamide) and Poly(ε-Caprolactone) Miktoarms through Chain-Growth Condensation Polymerization, Styrenics-Assisted Atom Transfer Radical Coupling, and Ring-Opening Polymerization.

PubMed

Huang, Chih-Feng; Aimi, Junko; Lai, Kuan-Yu

2017-02-01

Star copolymers are known to phase separate on the nanoscale, providing useful self-assembled morphologies. In this study, the authors investigate synthesis and assembly behavior of miktoarm star (μ-star) copolymers. The authors employ a new strategy for the synthesis of unprecedented μ-star copolymers presenting poly(N-octyl benzamide) (PBA) and poly(ε-caprolactone) (PCL) arms: a combination of chain-growth condensation polymerization, styrenics-assisted atom transfer radical coupling, and ring-opening polymerization. Gel permeation chromatography, mass-analyzed laser desorption/ionization mass spectrometry, and 1 H NMR spectroscopy reveal the successful synthesis of a well-defined (PBA 11 ) 2 -(PCL 15 ) 4 μ-star copolymer (M n ,NMR ≈ 12 620; Đ = 1.22). Preliminary examination of the PBA 2 PCL 4 μ-star copolymer reveals assembled nanofibers having a uniform diameter of ≈20 nm. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

“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

Advanced Materials for PEM-Based Fuel Cell Systems

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

James E. McGrath; Donald G. Baird; Michael von Spakovsky

2005-10-26

Proton exchange membrane fuel cells (PEMFCs) are quickly becoming attractive alternative energy sources for transportation, stationary power, and small electronics due to the increasing cost and environmental hazards of traditional fossil fuels. Two main classes of PEMFCs include hydrogen/air or hydrogen/oxygen fuel cells and direct methanol fuel cells (DMFCs). The current benchmark membrane for both types of PEMFCs is Nafion, a perfluorinated sulfonated copolymer made by DuPont. Nafion copolymers exhibit good thermal and chemical stability, as well as very high proton conductivity under hydrated conditions at temperatures below 80 degrees C. However, application of these membranes is limited due tomore » their high methanol permeability and loss of conductivity at high temperatures and low relative humidities. These deficiencies have led to the search for improved materials for proton exchange membranes. Potential PEMs should have good thermal, hydrolytic, and oxidative stability, high proton conductivity, selective permeability, and mechanical durability over long periods of time. Poly(arylene ether)s, polyimides, polybenzimidazoles, and polyphenylenes are among the most widely investigated candidates for PEMs. Poly(arylene ether)s are a promising class of proton exchange membranes due to their excellent thermal and chemical stability and high glass transition temperatures. High proton conductivity can be achieved through post-sulfonation of poly(arylene ether) materials, but this most often results in very high water sorption or even water solubility. Our research has shown that directly polymerized poly(arylene ether) copolymers show important advantages over traditional post-sulfonated systems and also address the concerns with Nafion membranes. These properties were evaluated and correlated with morphology, structure-property relationships, and states of water in the membranes. Further improvements in properties were achieved through incorporation of inorganic fillers, such as phosphotungstic acid and zirconium hydrogen phosphate. Block copolymers were also studied due to the possibility to achieve a desired combination of homopolymer properties as well as the unique morphologies that are possible with block copolymers. Bezoyl substituted poly(p-phenylene) blocks were combined with poly(arylene ether) blocks to merge the structural rigidity of the poly(p-phenylene) with the ductility and high protonic conductivity of the poly(arylene ether)s. As evidenced by our many refereed publications and preprints, the research that we have conducted over the past several years has made a valuable and significant contribution to the literature and to the state of understanding of proton exchange membranes. Our early efforts at scale-up have suggested that the directly polymerized disulfonated poly(arylene ether sulfone) copolymers are commercially viable alternatives for proton exchange membranes. A new process for bipolar plates was developed and is described. An important single domain PEMFC model was developed and is documented in herein.« less

Combining living anionic polymerization with branching reactions in an iterative fashion to design branched polymers.

PubMed

Higashihara, Tomoya; Sugiyama, Kenji; Yoo, Hee-Soo; Hayashi, Mayumi; Hirao, Akira

2010-06-16

This paper reviews the precise synthesis of many-armed and multi-compositional star-branched polymers, exact graft (co)polymers, and structurally well-defined dendrimer-like star-branched polymers, which are synthetically difficult, by a commonly-featured iterative methodology combining living anionic polymerization with branched reactions to design branched polymers. The methodology basically involves only two synthetic steps; (a) preparation of a polymeric building block corresponding to each branched polymer and (b) connection of the resulting building unit to another unit. The synthetic steps were repeated in a stepwise fashion several times to successively synthesize a series of well-defined target branched polymers. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Emulsion Solvent Evaporation-Induced Self-Assembly of Block Copolymers Containing pH-Sensitive Block.

PubMed

Wu, Yuqing; Wang, Ke; Tan, Haiying; Xu, Jiangping; Zhu, Jintao

2017-09-26

A simple yet efficient method is developed to manipulate the self-assembly of pH-sensitive block copolymers (BCPs) confined in emulsion droplets. Addition of acid induces significant variation in morphological transition (e.g., structure and surface composition changes) of the polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) assemblies, due to the hydrophobic-hydrophilic transition of the pH-sensitive P4VP block via protonation. In the case of pH > pKa (P4VP) (pKa (P4VP) = 4.8), the BCPs can self-assemble into pupa-like particles because of the nearly neutral wetting of PS and P4VP blocks at the oil/water interface. As expected, onion-like particles obtained when pH is slightly lower than pKa (P4VP) (e.g., pH = 3.00), due to the interfacial affinity to the weakly hydrophilic P4VP block. Interestingly, when pH was further decreased to ∼2.5, interfacial instability of the emulsion droplets was observed, and each emulsion droplet generated nanoscale assemblies including vesicles, worm-like and/or spherical micelles rather than a nanostructured microparticle. Furthermore, homopolymer with different molecular weights and addition ratio are employed to adjust the interactions among copolymer blocks. By this means, particles with hierarchical structures can be obtained. Moreover, owing to the kinetically controlled processing, we found that temperature and stirring speed, which can significantly affect the kinetics of the evaporation of organic solvent and the formation of particles, played a key role in the morphology of the assemblies. We believe that manipulation of the property for the aqueous phase is a promising strategy to rationally design and fabricate polymeric assemblies with desirable shapes and internal structures.

pH-induced vesicle-to-micelle transition in amphiphilic diblock copolymer: investigation by energy transfer between in situ formed polymer embedded gold nanoparticles and fluorescent dye.

PubMed

Maiti, Chiranjit; Banerjee, Rakesh; Maiti, Saikat; Dhara, Dibakar

2015-01-01

The ability to regulate the formation of nanostructures through self-assembly of amphiphilic block copolymers is of immense significance in the field of biology and medicine. In this work, a new block copolymer synthesized by using reversible addition-fragmentation chain transfer (RAFT) polymerization technique from poly(ethylene glycol) monomethyl ether acrylate (PEGMA) and Boc-l-tryptophan acryloyloxyethyl ester (Boc-l-trp-HEA) was found to spontaneously form pH-responsive water-soluble nanostructures after removal of the Boc group. While polymer vesicles or polymerosomes were formed at physiological pH, the micelles were formed at acidic pH (< 5.2), and this facilitated a pH-induced reversible vesicle-to-micelle transition. Formation of these nanostructures was confirmed by different characterization techniques, viz. transmission electron microscopy, dynamic light scattering, and steady-state fluorescence measurements. Further, these vesicles were successfully utilized to reduce HAuCl4 and stabilize the resulting gold nanoparticles (AuNPs). These AuNPs, confined within the hydrophobic shell of the vesicles, could participate in energy transfer process with fluorescent dye molecules encapsulated in the core of the vesicles, thus forming a nanometal surface energy transfer (NSET) pair. Subsequently, following the efficiency of energy transfer between this pair, it was possible to monitor the process of transition from vesicles to micelles. Thus, in this work, we have successfully demonstrated that NSET can be used to follow the transition between nanostructures formed by amphiphilic block copolymers.

Synthesis of TiO{sub 2} nanoparticles by self-assembling reverse micelle cores of PS-b-PAA for functional textile applications

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

Akpolat, Leyla Budama; Çakır, Burçin Acar; Topel, Önder, E-mail: ondertopel@akdeniz.edu.tr

2015-04-15

Highlights: • TiO{sub 2} nanoparticles were synthesized within poly(styrene)-b-poly(acrylic acid) micelles. • The copolymer solution including nano TiO{sub 2} was coated onto textile fabrics. • UV-protective factor of nano TiO{sub 2} coated fabrics was estimated as 50+. • Nano TiO{sub 2} coated fabrics was found to exhibit a high photocatalytic activity. - Abstract: Titanium dioxide (i.e., titanium(IV) oxide, TiO{sub 2}) nanoparticles have been fabricated using a copolymer templating technique in micellar solution of poly(styrene)-block-poly(acrylic acid), PS(10912)-b-PAA(4842) synthesized by atom transfer radical polymerization (ATRP). The size and morphology of the synthesized TiO{sub 2} nanoparticles have been characterized via TEM and XRDmore » measurements. The average size of TiO{sub 2} nanoparticles was determined as 13 ± 3 and 13 ± 4 nm for titanium:copolymer ratios of 20:1 and 33:1, respectively. The copolymer solution including nano TiO{sub 2} particles has been coated onto textile fabrics to enhance their UV-blocking and self-cleaning properties. It has been determined that nano TiO{sub 2} coated textile fabrics have very good UV-blocking properties with 50+ of the ultraviolet protecting factor (UPF) and high photocatalytic efficiency with 69.2% of the photodegradation of methylene blue.« less

Rapid self-assembly of block copolymers to photonic crystals

DOEpatents

Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.

2016-07-05

The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

Core-shell-corona polymeric micelles as a versatile template for synthesis of inorganic hollow nanospheres.

PubMed

Sasidharan, Manickam; Nakashima, Kenichi

2014-01-21

Hollow, inorganic nanoscale capsules have many applications, from the delivery of encapsulated products for cosmetic and medicinal purposes to use as lightweight composite materials. Early methods for producing inorganic hollow nanospheres using hard templates suffered from low product yield and shell weakness upon template removal. In the past decade, researchers have turned to amphiphilic copolymers to synthesize hollow nanostructures and ordered mesoporous materials. Amphiphilic molecules self-assemble into well-defined nanostructures including spherical micelles. Micelles formed from simple, two-component AB diblock and ABA triblock copolymers, however, have been difficult to work with to construct inorganic hollow nanoparticles, because the corona of the micelle, which serves as the template for the shell, becomes unstable as it absorbs inorganic shell precursors, causing aggregates to form. Newly developed, three-component ABC triblock copolymers may solve this problem. They provide nanoassemblies with more diverse morphological and functional features than AB diblock and ABA triblock copolymers. Micelles formed from ABC triblock copolymers in selective solvents that dissolve only one or two of the blocks provide templates for these improved nanoassemblies. By manipulating individual polymer blocks, one can "encode" additional features at the molecular level. For instance, modifying the functional groups or substitution patterns of the blocks allows better morphological and size control. Insights into polymer self-assembly gained over years of work in our group have set the stage to systematically engineer inorganic spherical hollow nanoparticles using ABC triblock copolymers. In this Account, we report our recent progress in producing diverse, inorganic hollow spherical nanospheres from asymmetric triblock copolymeric micelles with core-shell-corona architecture as templates. We discuss three classes of polymeric micelles-with neutral, cationic, and anionic shell structures-that allow fabrication of a variety of hollow nanoparticles. Importantly, we synthesized all of these particles in water, avoiding use of hazardous organic solvents. We have designed the precursor of the inorganic material to be selectively sorbed into the shell domain, leaving the corona free from the inorganic precursors that would destabilize the micelle. The core, meanwhile, is the template for the formation of the hollow void. By rationally tailoring experimental parameters, we readily and selectively obtained a variety of hollow nanoparticles including silica, hybrid silicas, metal-oxides, metal-carbonates, metal-sulfates, metal-borates, and metal-phosphates. Finally, we highlight the state-of-the-art techniques we used to characterize these nanoparticles, and describe experiments that demonstrate the potential of these hollow particles in drug delivery, and as anode and cathode materials for lithium-ion batteries.

Immobilization of Polyoxometalates on Tailored Polymeric Surfaces

PubMed Central

Aguado-Ureta, Saioa; Rodríguez-Hernández, Juan; del Campo, Adolfo; Perez-Álvarez, Leyre

2018-01-01

Herein we describe the preparation of hybrid polymer–inorganic interfaces by the immobilization of polyoxometalate nanoclusters on functionalized polymer surfaces. The polymeric surfaces were made of polystyrene-b-poly(acrylic acid)/polystyrene (PS-b-PAA/PS) blends by spin coating on a silicon wafer. The functionalization of the polymer film was obtained by interfacial migration of the amphiphilic block copolymer toward the interface upon water vapor annealing. The carboxylic acid functional groups contained in the PAA block were then employed to anchor the [LnIII(α-SiW11O39)]5− polyoxometalates (Ln: Ce, Er). This purpose was achieved by immersing the films in aqueous solutions of the in situ-formed inorganic nanoclusters. X-ray photoelectron and confocal Raman spectroscopies, together with atomic force microscopy, confirmed the immobilization of the inorganic species at the interface. PMID:29498656

Sustainable thermoplastic elastomers derived from cellulose, fatty acid and furfural via ATRP and click chemistry.

PubMed

Yu, Juan; Lu, Chuanwei; Wang, Chunpeng; Wang, Jifu; Fan, Yimin; Chu, Fuxiang

2017-11-15

Cellulose-based thermoplastic elastomers (TPEs) have attracted considerable attention because of their rigid backbone, good mechanical properties, renewable nature and abundance. In the present study, sustainable TPEs based on ethyl cellulose (EC), fatty acid and furfural were generated by the combination of ATRP and "click chemistry". To fabricate sustainable TPEs with higher toughness, a range of polymers, including mono random-copolymer poly(tetrahydrofurfuryl methacrylate-co-lauryl methacrylate) (P(THFMA-co-LMA), dual polymer side chains PTHFMA and PLMA, and mono-block copolymer PTHFMA-b-PLMA, were designed as side chains to fabricate EC brush copolymers with random, dual or block side chain architectures using the "grafting from" and "grafting onto" methods. The multi-armed structures, chemical compositions and phase separation of these EC brush copolymers were confirmed by FT-IR, 1 H NMR, GPC, DSC, TEM and SEM. Overall, three types of EC brush copolymers all exhibited the desired mechanical properties of TPEs. In addition, the EC brush copolymers with dual/block side chain architectures showed higher tensile strength than that of the random polymers with similar compositions. Copyright © 2017. Published by Elsevier Ltd.

Design, synthesis, and characterization of new phosphazene related materials, and study the structure property correlations

NASA Astrophysics Data System (ADS)

Tian, Zhicheng

The work described in this thesis is divided into three major parts, and all of which involve the exploration of the chemistry of polyphosphazenes. The first part (chapters 2 and 3) of my research is synthesis and study polyphoshazenes for biomedical applications, including polymer drug conjugates and injectable hydrogels for drug or biomolecule delivery. The second part (chapters 4 and 5) focuses on the synthesis of several organic/inorganic hybrid polymeric structures, such as diblock, star, brush and palm tree copolymers using living cationic polymerization and atom transfer radical polymerization techniques. The last part (chapters 6 and 7) is about exploratory synthesis of new polymeric structures with fluorinated side groups or cycloaliphatic side groups, and the study of new structure property relationships. Chapter 1 is an outline of the fundamental concepts for polymeric materials, as such the history, important definitions, and some introductory material for to polymer chemistry and physics. The chemistry and applications of phopshazenes is also briefly described. Chapter 2 is a description of the design, synthesis, and characterization of development of a new class of polymer drug conjugate materials based on biodegradable polyphosphazenes and antibiotics. Poly(dichlorophosphazene), synthesized by a thermal ring opening polymerization, was reacted with up to 25 mol% of ciprofloxacin or norfloxacin and three different amino acid esters (glycine, alanine, or phenylalanine) as cosubstituents via macromolecular substitutions. Nano/microfibers of several selected polymers were prepared by an electrospinning technique. Chapter 3 is concerned with the development of a class of injectable and biodegradable hydrogels based on water-soluble poly(organophosphazenes) containing oligo(ethylene glycol) methyl ethers and glycine ethyl esters. The hydrogels can be obtained by mixing alpha-cyclodextrin aqueous solution and poly(organophosphazenes) aqueous solution in various gelation rates depending on the polymer structures and the concentrations. The rheological measurements of the supramolecular hydrogels indicate a fast gelation process and flowable character under a large stain. Chapter 4 outlines the preparation of a number of amphiphilic diblock copolymers based on poly[bis(trifluoroethoxy)phosphazene] (TFE) as the hydrophobic block and poly(dimethylaminoethylmethacrylate) (PDMAEMA) as the hydrophilic block. The TFE block was synthesized first by the controlled living cationic polymerization of a phosphoranimine, followed by replacement of all the chlorine atoms using sodium trifluoroethoxide. To allow for the growth of the PDMAEMA block, 3-azidopropyl-2-bromo-2-methylpropanoate, an atom transfer radical polymerization (ATRP) initiator, was grafted onto the endcap of the TFE block via the 'click' reaction followed by the ATRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA). Chapter 5 is a report on the design and assembly of polyphosphazene materials based on the non-covalent "host--guest" interactions either at the terminus of the polymeric main-chains or the pendant side-chains. The supramolecular interaction at the main chain terminus was used to produce amphiphilic palm-tree like pseudo-block copolymers via host-guest interactions between an adamantane end-functionalized polyphosphazene and a 4-armed beta-cyclodextrin (beta-CD) initiated poly[poly(ethylene glycol) methyl ether methacylate] branched-star type polymer. The formation of micelles of the obtained amphiphiles was analyzed by fluorescence technique, dynamic light scattering, transmission electron microscopy, and atomic force microscopy. Chapter 6 is an investigation of the influence of bulky fluoroalkoxy side groups on the properties of polyphosphazenes. A new series of mixed-substituent high polymeric poly(fluoroalkoxyphosphazenes) containing trifluoroethoxy and branched fluoroalkoxy side groups was synthesized and characterized by NMR and GPC methods. These polymers contained 19--29 mol% of di-branched hexafluoropropoxy groups or 4mol% of tri-branched tert-perfluorobutoxy groups, which serve as regio-irregularities to reduce the macromolecular microcrystallinity. The structure--property correlations of the polymers were then analyzed and interpreted by several techniques: specifically by the thermal behavior by DSC and TGA methods, the crystallinity by wide-angle X-ray diffraction, and the surface hydrophobicity/oleophobicity by contact angle measurements. (Abstract shortened by UMI.). Chapter 7 is an outline of the exploratory synthesis of a new series of phosphazene model cyclic trimers and single- and mixed- substituent high polymers containing cyclic aliphatic rings, --CnH2n-1 (where n = 4--8). The cylco-aliphatic side group containing phosphazenes expand the structural and property boundaries of phosphazene chemistry, and suggest additional approaches for studying slow macromolecular substitution reactions and substituent exchange reactions.

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.

Controlled protein adsorption on PMOXA/PAA based coatings by thermally induced immobilization

NASA Astrophysics Data System (ADS)

Mumtaz, Fatima; Chen, Chaoshi; Zhu, Haikun; Pan, Chao; Wang, Yanmei

2018-05-01

In this work, poly(2-methyl-2-oxazoline-random-glycidyl methacrylate) (PMOXA-r-GMA) and poly(acrylic acid)-block-poly(glycidyl methacrylate) (PAA-b-PGMA) copolymers were synthesized via cationic ring-opening polymerization (CROP) of 2-methyl-2-oxazoline (MOXA) and reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylic acid (AA) followed by their random and block copolymerization with glycidyl methacrylate (GMA), respectively, and then characterized carefully. PMOXA/PAA based coatings were then prepared by simply spin coating the mixture of PMOXA-r-GMA and PAA-b-PGMA copolymer solutions onto silicon/glass substrates followed by annealing at 110 °C. The coatings were rigorously characterized by using X-ray photoelectron spectroscopy (XPS), the static water contact angle (WCA) test, ellipsometry and atomic force microscopy (AFM). The results demonstrated that the coating based mixed PMOXA/PAA brushes with desired surface composition could be attained by simply maintaining their percentage in the mixture of PMOXA-r-GMA and PAA-b-PGMA copolymer solutions. Finally, the switchable behavior of PMOXA/PAA based coatings toward bovine serum albumin (BSA) adsorption was investigated by fluorescein isothiocyanate-labelled BSA (FITC-BSA) assay and quartz crystal microbalance with dissipation monitoring (QCM-D), which indicated that the coating based mixed PMOXA/PAA brushes could control BSA adsorption/desorption from very low to high amount (>90% desorption) through adjusting the composition of PMOXA-r-GMA and PAA-b-PGMA solution used in preparing PMOXA/PAA based coatings upon pH and ionic strength change. Furthermore, PMOXA/PAA based coatings displayed efficient repeatability of reversible BSA adsorption/desorption cycles.

Unusual kinetics of poly(ethylene glycol) oxidation with cerium(IV) ions in sulfuric acid medium and implications for copolymer synthesis.

PubMed

Szymański, Jan K; Temprano-Coleto, Fernando; Pérez-Mercader, Juan

2015-03-14

The cerium(IV)-alcohol couple in an acidic medium is an example of a redox system capable of initiating free radical polymerization. When the alcohol has a polymeric nature, the outcome of such a process is a block copolymer, a member of a class of compounds possessing many useful properties. The most common polymer with a terminal -OH group is poly(ethylene glycol) (PEG); however, the detailed mechanism of its reaction with cerium(IV) remains underexplored. In this paper, we report our findings for this reaction based on spectrophotometric measurements and kinetic modeling. We find that both the reaction order and the net rate constant for the oxidation process depend strongly on the nature of the acidic medium used. In order to account for the experimental observations, we postulate that protonation of PEG decreases its affinity for some of the cerium(IV)-sulfate complexes formed in the system.

Synthesis and self-assembly of four-armed star copolymer based on poly(ethylene brassylate) hydrophobic block as potential drug carries

NASA Astrophysics Data System (ADS)

Chen, Jiucun; Li, Junzhi; Liu, Jianhua; Weng, Bo; Xu, Liqun

2016-05-01

A novel well-defined four-armed star poly(ethylene brassylate)- b-poly(poly(ethylene glycol)methyl ether methacrylate) (s-PEB- b-P(PEGMA)) was synthesized and self-assembled via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer polymerization (RAFT) in this work. It proceeded firstly with the synthesis of hydrophobic four-armed star homopolymer of ethylene brassylate (EB) via ROP with organic catalyst, followed by the esterification reaction of s-PEB with chain transfer agent. Afterward, RAFT polymerization of PEGMA monomer was initialed using PEB-based macro-RAFT agent, resulting in the target amphiphilic four-armed star copolymer. The obtained s-PEB- b-P(PEGMA) can assemble into micelles with PEB segments as core and P(PEGMA) segments as shell in aqueous solution. The self-assembly behavior was studied by dynamic light scattering and transmission electron microscope. The micelles of s-PEB- b-P(PEGMA) exhibited higher loading capacity of the anticancer drug doxorubicin (DOX). The investigation of DOX release from the micelles demonstrated that the release rate of the hydrophobic drug could be effectively controlled.

Methacrylic Zwitterionic, Thermoresponsive, and Hydrophilic (Co)Polymers via Cu(0)-Polymerization: The Importance of Halide Salt Additives.

PubMed

Simula, Alexandre; Anastasaki, Athina; Haddleton, David M

2016-02-01

The synthesis of hydrophilic, thermoresponsive, and zwitterionic polymethacrylates is reported by Cu(0)-mediated reversible deactivation radical polymerization in water and/or water/alcohol mixtures. The predisproportionation of [Cu(I) (PMDETA)Cl] in water prior to initiator and monomer addition is exploited to yield well-defined polymethacrylates with full monomer conversions in 30 min. The addition of supplementary halide salts (NaCl) enables the synthesis of various molecular weight poly[poly(ethylene glycol) methyl ether methacrylate] (PEGMA475) (DPn = 10-80, Mn ≈ 10,000-40 000 g mol(-1)) with full monomer conversion and narrow molecular weight distributions attained in all cases (Đ ≈ 1.20-1.30). A bifunctional PEG initiator (average Mn ≈ 1000 g mol(-1)) is utilized for the polymerization of a wide range of methacrylates including 2-dimethylaminoethyl methacrylate, 2-morpholinoethyl methacrylate, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, and 2-methacryloyloxyethyl phosphorylcholine. Despite the high water content, high end group fidelity is demonstrated by in situ chain extensions and block copolymerizations with PEGMA475 yielding well-defined functional telechelic pentablock copolymers within 2.5 h. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer therapeutics: Top 10 selling pharmaceuticals - what next?

PubMed

Duncan, Ruth

2014-09-28

At the time of the first issue of the Journal of Controlled Release (JCR), polymeric drugs, polymer-drug and protein conjugates and block copolymer micelles carrying bound drugs, i.e. polymer therapeutics, were still regarded as scientific curiosities with little or no prospect of generating practical to use medicines. How this perception has changed. Many major Pharma now have R&D programmes in this area and in 2013 two polymer therapeutics, Copaxone and Neulasta, are featured in the Top 10 US pharmaceutical sales list. Although there are a growing number of marketed products (e.g. PEGylated proteins, a PEG-aptamer and oral polymeric sequestrants), and the first follow-on (generic products) are emerging, the first polymer-drug conjugates and block copolymer micelle products (as covalent conjugates) have yet to enter routine clinical use. Industrial familiarity and recent advances in the underpinning scientific disciplines will no doubt accelerate the transfer of polymer therapeutics into clinically useful medicines and imaging agents. This short personal perspective reflects on the current status of polymer therapeutics and the future opportunities to improve their successful translation. It adds to recent and historical reviews that comprehensively document the evolution of the field since JCR was born. Copyright © 2014 Elsevier B.V. All rights reserved.

Stereo-, Temporal and Chemical Control through Photoactivation of Living Radical Polymerization: Synthesis of Block and Gradient Copolymers.

PubMed

Shanmugam, Sivaprakash; Boyer, Cyrille

2015-08-12

Nature has developed efficient polymerization processes, which allow the synthesis of complex macromolecules with a perfect control of tacticity as well as molecular weight, in response to a specific stimulus. In this contribution, we report the synthesis of various stereopolymers by combining a photoactivated living polymerization, named photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) with Lewis acid mediators. We initially investigated the tolerance of two different photoredox catalysts, i.e., Ir(ppy)3 and Ru(bpy)3, in the presence of a Lewis acid, i.e., Y(OTf)3 and Yb(OTf)3, to mediate the polymerization of N,N-dimethyl acrylamide (DMAA). An excellent control of tacticity as well as molecular weight and dispersity was observed when Ir(ppy)3 and Y(OTf)3 were employed in a methanol/toluene mixture, while no polymerization or poor control was observed with Ru(bpy)3. In comparison to a thermal system, a lower amount of Y(OTf)3 was required to achieve good control over the tacticity. Taking advantage of the temporal control inherent in our system, we were able to design complex macromolecular architectures, such as atactic block-isotactic and isotactic-block-atactic polymers in a one-pot polymerization approach. Furthermore, we discovered that we could modulate the degree of tacticity through a chemical stimulus, by varying [DMSO]0/[Y(OTf)3]0 ratio from 0 to 30 during the polymerization. The stereochemical control afforded by the addition of a low amount of DMSO in conjunction with the inherent temporal control enabled the synthesis of stereogradient polymer consisting of five different stereoblocks in one-pot polymerization.

Applications of polymeric micelles with tumor targeted in chemotherapy

NASA Astrophysics Data System (ADS)

Ding, Hui; Wang, Xiaojun; Zhang, Song; Liu, Xinli

2012-11-01

Polymeric micelles (PMs) have gained more progress as a carrier system with the quick development of biological and nanoparticle techniques. In particular, PMs with smart targeting can deliver anti-cancer drugs directly into tumor cells at a sustained rate. PMs with core-shell structure (with diameters of 10 100 nm) have been prepared by a variety of biodegradable and biocompatible polymers via a self-assembly process. The preparation of polymeric micelles with stimuli-responsive block copolymers or modification of target molecules on polymeric micelles' surface are able to significantly improve the efficiency of drug delivery. Polymeric micelles, which have been considered as a novel promising drug carrier for cancer therapeutics, are rapidly evolving and being introduced in an attempt to overcome several limitations of traditional chemotherapeutics, including water solubility, tumor-specific accumulation, anti-tumor efficacy, and non-specific toxicity. This review describes the preparation of polymeric micelles and the targeted modification which greatly enhance the effects of chemotherapeutic agents.

Advanced Materials by Atom Transfer Radical Polymerization.

PubMed

Matyjaszewski, Krzysztof

2018-06-01

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

Butadiene-Isoprene Block Copolymers and Their Hydrogenated Derivatives.

DTIC Science & Technology

1981-04-01

polyethylene, LDPE. The crystallinity, density and AHf for all of the block copolymers were found to be linearly de - pendent on HB content indicating...etc. It is known for example, that carbanions can exist in "tight", "loose", or even "free" structures as a function of counterion and solvent. (5,6...is then observed for the styrene segment. Thus in these systems , there is an apparent "reversal of reactivity" of styrene and the diene, since for the

One-step synthesis of titania nanoparticles from PS-P4VP diblock copolymer solution

NASA Astrophysics Data System (ADS)

Song, Lixin; Lam, Yeng Ming; Boothroyd, Chris; Teo, Puat Wen

2007-04-01

Polymeric films containing titania nanoparticles have potential as dielectric films for flexible electronic applications. For this purpose, the nanoparticles must be homogeneously distributed. Self-assembly is emerging as a neat, elegant method for fabricating such nanostructured hybrid materials with well-distributed nanoparticles. In this work, we report a micellar solution approach for the assembly of copolymer-titanium precursor nanostructures in which titania nanoparticles were synthesized. The ratio of the amount of titanium precursor, titanium isopropoxide, to the blocks forming the micellar core, poly(4-vinylpyridine), was found to play a key role in controlling film morphology. A sphere-to-ribbon transition was observed when the amount of titanium isopropoxide was increased. The thin film morphology can be tuned using the precursor-copolymer interaction rather than just the polymer-polymer interaction or the polymer-solution interaction. This method provides yet another way to control the morphology of nanostructures.

Nanocomposites based on self-assembly poly(hydroxypropyl methacrylate)-block-poly(N-phenylmaleimide) and Fe3O4-NPs. Thermal stability, morphological characterization and optical properties

NASA Astrophysics Data System (ADS)

Pizarro, Guadalupe del C.; Marambio, Oscar G.; Jeria-Orell, Manuel; Sánchez, Julio; Oyarzún, Diego P.

2018-02-01

The current work presents the synthesis, characterization and preparation of organic-inorganic hybrid polymer films that contain inorganic magnetic nanoparticles (NPs). The block copolymer, prepared by Atom-Transfer Radical Polymerization (ATRP), was used as a nanoreactor for iron oxide NPs. The NPs were embedded in poly(hydroxypropyl methacrylate)-block-poly(N-phenylmaleimide) matrix. The following topographical modifications of the surface of the film were specially analyzed: control of pore features and changes in surface roughness. Finally, the NPs functionality inside the polymer matrix and how it may affect the thermal and optical properties of the films were assessed.

Construction of Hierarchical Polymer Brushes on Upconversion Nanoparticles via NIR-Light-Initiated RAFT Polymerization.

PubMed

Xie, Zhongxi; Deng, Xiaoran; Liu, Bei; Huang, Shanshan; Ma, Pingan; Hou, Zhiyao; Cheng, Ziyong; Lin, Jun; Luan, Shifang

2017-09-13

Photoinduced reversible addition-fragmentation chain transfer (RAFT) polymerization generally adopts high-energy ultraviolet (UV) or blue light. In combination with photoredox catalyst, the excitation light wavelength was extended to the visible and even near-infrared (NIR) region for photoinduced electron transfer RAFT polymerization. In this report, we introduce for the first time a surface NIR-light-initiated RAFT polymerization on upconversion nanoparticles (UCNPs) without adding any photocatalyst and construct a functional inorganic core/polymer shell nanohybrid for application in cancer theranostics. The multilayer core-shell UCNPs (NaYF 4 :Yb/Tm@NaYbF 4 :Gd@NaNdF 4 :Yb@NaYF 4 ), with surface anchorings of chain transfer agents, can serve as efficient NIR-to-UV light transducers for initiating the RAFT polymerization. A hierarchical double block copolymer brush, consisting of poly(acrylic acid) (PAA) and poly(oligo(ethylene oxide)methacrylate-co-2-(2-methoxy-ethoxy)ethyl methacrylate) (PEG for short), was grafted from the surface in sequence. The targeting arginine-glycine-aspartic (RGD) peptide was modified at the end of the copolymer through the trithiolcarbonate end group. After loading of doxorubicin, the UCNPs@PAA-b-PEG-RGD exhibited an enhanced U87MG cancer cell uptake efficiency and cytotoxicity. Besides, the unique upconversion luminescence of the nanohybrids was used for the autofluoresence-free cell imaging and labeling. Therefore, our strategy verified that UCNPs could efficiently activate RAFT polymerization by NIR photoirradiation and construct the complex nanohybrids, exhibiting prospective biomedical applications due to the low phototoxicity and deep penetration of NIR light.

Effects of Cationic Pendant Groups on Ionic Conductivity for Anion Exchange Membranes: Structure Conductivity Relationships

NASA Astrophysics Data System (ADS)

Kim, Sojeong; Choi, Soo-Hyung; Lee, Won Bo

Anion exchange membranes(AEMs) have been widely studied due to their various applications, especially for Fuel cells. Previous proton exchange membranes(PEMs), such as Nafions® have better conductivity than AEMs so far. However, technical limitations such as slow electrode kinetics, carbon monoxide (CO) poisoning of metal catalysts, high methanol crossover and high cost of Pt-based catalyst detered further usages. AEMs have advantages to supplement its drawbacks. AEMs are environmentally friendly and cost-efficient. Based on the well-defined block copolymer, self-assembled morphology is expected to have some relationship with its ionic conductivity. Recently AEMs based on various cations, including ammonium, phosphonium, guanidinium, imidazolium, metal cation, and benzimidazolium cations have been developed and extensively studied with the aim to prepare high- performance AEMs. But more fundamental approach, such as relationships between nanostructure and conductivity is needed. We use well-defined block copolymer Poly(styrene-block-isoprene) as a backbone which is synthesized by anionic polymerization. Then we graft various cationic functional groups and analysis the relation between morphology and conductivity. Theoretical and computational soft matter lab.

Functionalization of Cellulose Nanocrystals with PEG-Metal-Chelating Diblock Copolymers via Controlled Conjugation in Aqueous Medium

NASA Astrophysics Data System (ADS)

Guo, Melinda

The surface of cellulose nanocrystals (CNCs) was successfully functionalized with metal chelating diblock copolymers via HyNic-4FB conjugation. Two types of PEG-metal-chelating block polymers with hydrazinonicotinate acetone hydrazine (HyNic) end groups were synthesized: mPEG-PGlu(DTPA) 18-HyNic and mPEG-PGlu(DTPA)25-HyNic. These two polymers both had a methoxy PEG (M ˜ 2000 Da) block that differed in the mean degree of polymerization of the metal-chelating block. They were characterized by 1H NMR spectroscopy and gel-permeation chromatography (GPC). 4-Formylbenzamide (4FB) groups were introduced onto the surface of CNCs and quantified through their reaction with 2-hydrazinopyridine. The polymers were grafted onto the surface of CNCs via bis-aryl hydrazone bond formation, and the kinetics of this reaction was explored by UV/Vis spectroscopy. The CNCs were also labeled with rhodamine and Alexa FluorRTM 488 dyes. Students in our collaborator's group in Pharmacy are examining applications of these materials as radiotherapeutic agents for cancer treatment.

Method of forming oriented block copolymer line patterns, block copolymer line patterns formed thereby, and their use to form patterned articles

DOEpatents

Russell, Thomas P.; Hong, Sung Woo; Lee, Doug Hyun; Park, Soojin; Xu, Ting

2015-10-13

A block copolymer film having a line pattern with a high degree of long-range order is formed by a method that includes forming a block copolymer film on a substrate surface with parallel facets, and annealing the block copolymer film to form an annealed block copolymer film having linear microdomains parallel to the substrate surface and orthogonal to the parallel facets of the substrate. The line-patterned block copolymer films are useful for the fabrication of magnetic storage media, polarizing devices, and arrays of nanowires.

Method of forming oriented block copolymer line patterns, block copolymer line patterns formed thereby, and their use to form patterned articles

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

Russell, Thomas P.; Hong, Sung Woo; Lee, Dong Hyun

A block copolymer film having a line pattern with a high degree of long-range order is formed by a method that includes forming a block copolymer film on a substrate surface with parallel facets, and annealing the block copolymer film to form an annealed block copolymer film having linear microdomains parallel to the substrate surface and orthogonal to the parallel facets of the substrate. The line-patterned block copolymer films are useful for the fabrication of magnetic storage media, polarizing devices, and arrays of nanowires.

The effects of non-ionic polymeric surfactants on the cleaning of biofouled hydrogel materials.

PubMed

Guan, Allan; Li, Zhenyu; Phillips, K Scott

2015-01-01

Block co-polymer surfactants have been used for cleaning hydrogel medical devices that contact the body (e.g., contact lenses) because of their biocompatibility. This work examined the relationship between concentration and detergency of two non-ionic polymeric surfactants (Pluronic F127 and Triton X-100) for cleaning protein soil, with anionic surfactants (sodium dodecyl sulfate and sodium laureth sulfate) as positive controls. Surface plasmon resonance was used to quantify removal of simulated tear soil from self-assembled monolayer surfaces, and a microplate format was used to study the removal of fluorescently labeled soil proteins from contact lenses. While detergency increased as a function of concentration for anionic surfactants, it decreased with concentration for the two polymeric surfactants. The fact that the protein detergency of some non-ionic polymeric surfactants did not increase with concentration above the critical micelle concentration could have implications for optimizing the tradeoff between detergency and biocompatibility.

Photoisomerization study of p-phenylazoacrylanilide and its homo- and copolymers

NASA Astrophysics Data System (ADS)

Rachkov, A.; Minoura, N.; Shimizu, T.

2003-01-01

To develop materials possessing intrinsic photoresponsive properties, a polymerizable derivative of azobenzene was synthesized. Condensation of acryloyl chloride with 4-phenylazoaniline was performed in THF with 100% conversion to the final product p-phenylazoacrylanilide. Its homopolymers and copolymers with methacrylic acid were prepared by free radical polymerization using 2,2 '-azobis (2,4-dimethylvaleronitrile) as an initiator. Copolymerization reactivity ratios showed clear preference to form short sequences of polymethacrylic acid alternated by individual p-phenylazoacrylanilide residues. Photochemical interconversion between trans and cis isomers of p-phenylazoacrylanilide under UV or visible light irradiation was shown to be reversible and reproducible for the monomer as well as for the homopolymers and the copolymers with methacrylic acid.

Preparation of epoxy-acrylate copolymer/nano-silica via Pickering emulsion polymerization and its application as printing binder

NASA Astrophysics Data System (ADS)

Gao, Dangge; Chang, Rui; Lyu, Bin; Ma, Jianzhong; Duan, Xiying

2018-03-01

This paper presents a facile and efficient synthesis method to fabricate epoxy-acrylate copolymer/nano-silica latex via Pickering emulsion polymerization stabilized by silica sol. The effects of solid contents, silica concentration and polymerization time on emulsion polymerization were studied. The core-shell epoxy-acrylate copolymer/nano-silica was obtained with average diameter 690 nm, was observed by Transmission Electron Microscopy (TEM) and Dynamic Light Scattering (DLS). The formation mechanism of epoxy-acrylate copolymer/nano-silica emulsion polymerization was proposed through observing the morphology of latex particles at different polymerization time. Fourier Transformation Infrared (FT-IR) and Thermogravimetric Analysis (TGA) were used to study structure and thermostability of the composites. Morphology of the latex film was characterized by Scanning Electron Microscope (SEM). The results indicated that nano-silica particles existed in the composite emulsion and could improve the thermal stability of the film. The epoxy-acrylate copolymer/nano-silica latex was used as binder applied to cotton fabric for pigment printing. The application results demonstrated that Pickering emulsion stabilized by silica sol has good effects in the pigment printing binder without surfactant. Compared with commodity binder, the resistance to wet rubbing fastness and soaping fastness were improved half grade.

Dimensional control of block copolymer nanofibers with a π-conjugated core: crystallization-driven solution self-assembly of amphiphilic poly(3-hexylthiophene)-b-poly(2-vinylpyridine).

PubMed

Gwyther, Jessica; Gilroy, Joe B; Rupar, Paul A; Lunn, David J; Kynaston, Emily; Patra, Sanjib K; Whittell, George R; Winnik, Mitchell A; Manners, Ian

2013-07-08

With the aim of accessing colloidally stable, fiberlike, π-conjugated nanostructures of controlled length, we have studied the solution self-assembly of two asymmetric crystalline-coil, regioregular poly(3-hexylthiophene)-b-poly(2-vinylpyridine) (P3HT-b-P2VP) diblock copolymers, P3HT23-b-P2VP115 (block ratio=1:5) and P3HT44-b-P2VP115 (block ratio=ca. 1:3). The self-assembly studies were performed under a variety of solvent conditions that were selective for the P2VP block. The block copolymers were prepared by using Cu-catalyzed azide-alkyne cycloaddition reactions of azide-terminated P2VP and alkyne end-functionalized P3HT homopolymers. When the block copolymers were self-assembled in a solution of a 50% (v/v) mixture of THF (a good solvent for both blocks) and an alcohol (a selective solvent for the P2VP block) by means of the slow evaporation of the common solvent; fiberlike micelles with a P3HT core and a P2VP corona were observed by transmission electron microscopy (TEM). The average lengths of the micelles were found to increase as the length of the hydrocarbon chain increased in the P2VP-selective alcoholic solvent (MeOH3 μm) fiberlike micelles were prepared by the dialysis of solutions of the block copolymers in THF against iPrOH. Furthermore the widths of the fibers were dependent on the degree of polymerization of the chain-extended P3HT blocks. The crystallinity and π-conjugated nature of the P3HT core in the fiberlike micelles was confirmed by a combination of UV/Vis spectroscopy, photoluminescence (PL) measurements, and wide-angle X-ray scattering (WAXS). Intense sonication (iPrOH, 1 h, 0 °C) of the fiberlike micelles formed by P3HT23-b-P2VP115 resulted in small (ca. 25 nm long) stublike fragments that were subsequently used as initiators in seeded growth experiments. Addition of P3HT23-b-P2VP115 unimers to the seeds allowed the preparation of fiberlike micelles with narrow length distributions (L(w)/L(n) < 1.11) and lengths from about 100-300 nm, that were dependent on the unimer-to-seed micelle ratio. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DISPERSION POLYMERIZATION OF STYRENE IN SUPERCRITICAL CARBON DIOXIDE UTILIZING RANDOM COPOLYMERS INCLUDING FLUORINATED ACRYLATE FOR PREPARING MICRON-SIZE POLYSTYRENE PARTICLES. (R826115)

EPA Science Inventory

The dispersion polymerization of styrene in supercritical CO₂ utilizing CO₂-philic random copolymers was investigated. The resulting high yield of polystyrene particles in the micron-size range was formed using various random copolymers as stabilizers. The p...

Creating surfactant nanoparticles for block copolymer composites through surface chemistry.

PubMed

Kim, Bumjoon J; Bang, Joona; Hawker, Craig J; Chiu, Julia J; Pine, David J; Jang, Se Gyu; Yang, Seung-Man; Kramer, Edward J

2007-12-04

A simple strategy to tailor the surface of nanoparticles for their specific adsorption to and localization at block copolymer interfaces was explored. Gold nanoparticles coated by a mixture of low molecular weight thiol end-functional polystyrene (PS-SH) (Mn = 1.5 and 3.4 kg/mol) and poly(2-vinylpyridine) homopolymers (P2VP-SH) (Mn = 1.5 and 3.0 kg/mol) were incorporated into a lamellar poly(styrene-b-2-vinylpyridine) diblock copolymer (PS-b-P2VP) (Mn = 196 kg/mol). A library of nanoparticles with varying PS and P2VP surface compositions (FPS) and high polymer ligand areal chain densities was synthesized. The location of the nanoparticles in the PS-b-P2VP block copolymer was determined by transmission electron microscopy. Sharp transitions in particle location from the PS domain to the PS/P2VP interface, and subsequently to the P2VP domain, were observed at FPS = 0.9 and 0.1, respectively. This extremely wide window of FPS values where the polymer-coated gold nanoparticles adsorb to the interface suggests a redistribution of PS and P2VP polymers on the Au surface, inducing the formation of amphiphilic nanoparticles at the PS/P2VP interface. In a second and synthetically more challenging approach, gold nanoparticles were covered with a thiol terminated random copolymer of styrene and 2-vinylpyridine synthesized by RAFT polymerization. Two different random copolymers were considered, where the molecular weight was fixed at 3.5 kg/mol and the relative incorporation of styrene and 2-vinylpyridine repeat units varied (FPS = 0.52 and 0.40). The areal chain density of these random copolymers on Au is unfortunately not high enough to preclude any contact between the P2VP block of the block copolymer and the Au surface. Interestingly, gold nanoparticles coated by the random copolymer with FPS = 0.4 were dispersed in the P2VP domain, while those with FPS = 0.52 were located at the interface. A simple calculation for the adsorption energy to the interface of the nanoparticles with different surface arrangements of PS and P2VP ligands supports evidence for the rearrangement of thiol terminated homopolymers. An upper limit estimate of the adsorption energy of nanoparticles uniformly coated with a random arrangement of PS and P2VP ligands where a 10% surface area was occupied by P2VP -mers or chains was approximately 1 kBT, which indicates that such nanoparticles are unlikely to be segregated along the interface, in contrast to the experimental results for nanoparticles with mixed ligand-coated surfaces.

HPMA-based block copolymers promote differential drug delivery kinetics for hydrophobic and amphiphilic molecules.

PubMed

Tomcin, Stephanie; Kelsch, Annette; Staff, Roland H; Landfester, Katharina; Zentel, Rudolf; Mailänder, Volker

2016-04-15

We describe a method how polymeric nanoparticles stabilized with (2-hydroxypropyl)methacrylamide (HPMA)-based block copolymers are used as drug delivery systems for a fast release of hydrophobic and a controlled release of an amphiphilic molecule. The versatile method of the miniemulsion solvent-evaporation technique was used to prepare polystyrene (PS) as well as poly-d/l-lactide (PDLLA) nanoparticles. Covalently bound or physically adsorbed fluorescent dyes labeled the particles' core and their block copolymer corona. Confocal laser scanning microscopy (CLSM) in combination with flow cytometry measurements were applied to demonstrate the burst release of a fluorescent hydrophobic drug model without the necessity of nanoparticle uptake. In addition, CLSM studies and quantitative calculations using the image processing program Volocity® show the intracellular detachment of the amphiphilic block copolymer from the particles' core after uptake. Our findings offer the possibility to combine the advantages of a fast release for hydrophobic and a controlled release for an amphiphilic molecule therefore pointing to the possibility to a 'multi-step and multi-site' targeting by one nanocarrier. We describe thoroughly how different components of a nanocarrier end up in cells. This enables different cargos of a nanocarrier having a consecutive release and delivery of distinct components. Most interestingly we demonstrate individual kinetics of distinct components of such a system: first the release of a fluorescent hydrophobic drug model at contact with the cell membrane without the necessity of nanoparticle uptake. Secondly, the intracellular detachment of the amphiphilic block copolymer from the particles' core after uptake occurs. This offers the possibility to combine the advantages of a fast release for a hydrophobic substance at the time of interaction of the nanoparticle with the cell surface and a controlled release for an amphiphilic molecule later on therefore pointing to the possibility to a 'multi-step and multisite' targeting by one nanocarrier. We therefore feel that this could be used for many cellular systems where the combined and orchestrated delivery of components is prerequisite in order to obtain the highest efficiency. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Distribution of short block copolymer chains in Binary Blends of Block Copolymers Having Hydrogen Bonding

NASA Astrophysics Data System (ADS)

Kwak, Jongheon; Han, Sunghyun; Kim, Jin Kon

2014-03-01

A binary mixture of two block copolymers whose blocks are capable of forming the hydrogen bonding allows one to obtain various microdomains that could not be expected for neat block copolymer. For instance, the binary blend of symmetric polystyrene-block-poly(2-vinylpyridine) copolymer (PS-b-P2VP) and polystyrene-block-polyhydroxystyrene copolymer (PS-b-PHS) blends where the hydrogen bonding occurred between P2VP and PHS showed hexagonally packed (HEX) cylindrical and body centered cubic (BCC) spherical microdomains. To know the exact location of short block copolymer chains at the interface, we synthesized deuterated polystyrene-block-polyhydroxystyrene copolymer (dPS-b-PHS) and prepared a binary mixture with PS-b-P2VP. We investigate, via small angle X-ray scattering (SAXS) and neutron reflectivity (NR), the exact location of shorter dPS block chain near the interface of the microdomains.

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

Bioinspired mineralization of inorganics from aqueous media controlled by synthetic polymers.

PubMed

Gorna, Katarzyna; Muñoz-Espí, Rafael; Gröhn, Franziska; Wegner, Gerhard

2007-02-12

The formation of inorganic structures in nature is commonly controlled by biogenic macromolecules. The understanding of mineralization phenomena and the nucleation and growth mechanisms involved is still a challenge in science but also of great industrial interest. This article focuses on the formation and mineralization of two archetypical inorganic materials: zinc oxide and amorphous calcium carbonate (ACC). Zinc oxide is selected as a model compound to investigate the role that polymers play in mineralization. Most of the effort has been devoted to the investigation of the effects of double-hydrophilic block and graft copolymers. Recent work has demonstrated that latex particles synthesized by miniemulsion polymerization, properly functionalized by various chemical groups, have similar effects to conventional block copolymers and are excellently suited for morphology control of ZnO crystals. Latex particles might serve as analogues of natural proteins in biomineralization. The second example presented, ACC, addresses the issue of whether this amorphous phase is an intermediate in the biomineralization of calcite, vaterite, or aragonite. Conditions under which amorphous calcium carbonate can be obtained as nanometer-sized spheres as a consequence of a liquid-liquid phase segregation are presented. Addition of specific block copolymers allows control of the particle size from the micrometer to the submicrometer length scale. The physical properties of novel materials synthesized from concentrated solution and their potential applications as a filler of polymers are also discussed.

Periodic nanostructures from self assembled wedge-type block-copolymers

DOEpatents

Xia, Yan; Sveinbjornsson, Benjamin R.; Grubbs, Robert H.; Weitekamp, Raymond; Miyake, Garret M.; Piunova, Victoria; Daeffler, Christopher Scot

2015-06-02

The invention provides a class of wedge-type block copolymers having a plurality of chemically different blocks, at least a portion of which incorporates a wedge group-containing block providing useful properties. For example, use of one or more wedge group-containing blocks in some block copolymers of the invention significantly inhibits chain entanglement and, thus, the present block copolymers materials provide a class of polymer materials capable of efficient molecular self-assembly to generate a range of structures, such as periodic nanostructures and microstructures. Materials of the present invention include copolymers having one or more wedge group-containing blocks, and optionally for some applications copolymers also incorporating one or more polymer side group-containing blocks. The present invention also provides useful methods of making and using wedge-type block copolymers.

Passive targeting of thermosensitive diblock copolymer micelles to the lungs: synthesis and characterization of poly(N-isopropylacrylamide)-block-poly(ε-caprolactone).

PubMed

Lee, Ren-Shen; Lin, Chih-Hung; Aljuffali, Ibrahim A; Hu, Kai-Yin; Fang, Jia-You

2015-06-18

Amphiphilic poly(N-isopropylacrylamide)-block-poly(ε-caprolactone) (PNiPAAm-b-PCL) copolymers were synthesized by ring-opening polymerization to form thermosensitive micelles as nanocarriers for bioimaging and carboplatin delivery. The critical micelle concentration increased from 1.8 to 3.5 mg/l following the decrease of the PNiPAAm chain length. The copolymers revealed a lower critical solution temperature (LCST) between 33 and 40°C. The copolymers self-assembled to form spherical particles of 146-199 nm in diameter. Carboplatin in micelles exhibited a slower release at 37°C relative to that at 25°C due to the gel layer formation on the micellar shell above the LCST. The micelles containing dye or carboplatin were intravenously injected into the rats for in vivo bioimaging and drug biodistribution. The bioimaging profiles showed a significant accumulation of micelles in the lungs. The micelles could minimize the reticuloendothelial system (RES) recognition of the dye. In vivo biodistribution demonstrated an improved pulmonary accumulation of carboplatin from 2.5 to 3.4 μg/mg by the micelles as compared to the control solution. Carboplatin accumulation in the heart and kidneys was reduced after encapsulation by the micelles. This study supports the potential of PNiPAAm-b-PCL micelles to passively target the lungs and attenuate RES uptake and possible side effects.

Hydroperoxide Traces in Common Cyclic Ethers as Initiators for Controlled RAFT Polymerizations.

PubMed

Eggers, Steffen; Abetz, Volker

2018-04-01

Herein, a reversible addition-fragmentation chain transfer (RAFT) polymerization is introduced for reactive monomers like N-acryloylpyrrolidine or N,N-dimethylacrylamide working without a conventional radical initiator. As a very straightforward proof of principle, the method takes advantage of the usually inconvenient radical-generating hydroperoxide contaminations in cyclic ethers like tetrahydrofuran or 1,4-dioxane, which are very common solvents in polymer sciences. The polymerizations are surprisingly well controlled and the polymers can be extended with a second block, indicating their high livingness. "Solvent-initiated" RAFT polymerizations hence prove to be a feasible access to tailored materials with minimal experimental effort and standard laboratory equipment, only requiring the following ingredients: hydroperoxide-contaminated solvent, monomer, and RAFT agent. In other respects, however, the potential coinitiating ability of the used solvent is to be considered when investigating the kinetics of RAFT polymerizations or aiming for the synthesis of high-livingness polymers, e.g., multiblock copolymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of the hydrophilic/hydrophobic ratio of polymeric micelles on their endocytosis pathways into cells.

PubMed

Zhang, Zhao; Qu, Qianqian; Li, Jinrong; Zhou, Shaobing

2013-06-01

Fluorescein isothiocyanate (FITC), a fluorescent probe, is coupled to amphiphilic monomethoxy poly(ethylene glycol)-block-poly(ε-caprolactone) (mPEG-PCL) copolymers. FITC-labeled mPEG-PCL copolymers self-assemble into micelles through the solvent evaporation method. The cellular internalization is examined using fluorescence microscopy on incubation of NIH-3T3 fibroblasts with micelles or free FITC solution. The effect of the hydrophilic/hydrophobic ratio on the endocytosis mechanisms is evaluated by fluorescence microscopy on culturing of human hepatoblastoma cells and human umbilical vein endothelial cells, individually, mixed with the micelles holding the same parameters including micelle size, shape, and surface charges. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Elaboration of thermoresponsive supramolecular diblock copolymers in water from complementary CBPQT4+ and TTF end-functionalized polymers.

PubMed

Sambe, Léna; Stoffelbach, François; Poltorak, Katarzyna; Lyskawa, Joël; Malfait, Aurélie; Bria, Marc; Cooke, Graeme; Woisel, Patrice

2014-02-01

A well-defined poly(N-isopropyl acrylamide) 1 incorporating at one termini a cyclobis(paraquat-p-phenylene) (CBPQT(4+)) recognition unit is prepared via a RAFT polymerization followed by a copper-catalyzed azide-alkyne cycloaddition (CuAAC). (1)H NMR (1D, DOSY), UV-vis and ITC experiments reveal that polymer 1 is able of forming effective host-guest complexes with tetrathiafulvalene (TTF) end-functionalized polymers in water, thereby leading to the formation of non-covalently-linked double-hydrophilic block copolymers. The effect of the temperature on both the LCST phase transition of 1 and its complexes and on CBPQT(4+)/TTF host-guest interactions is investigated. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamics of coil-hyperbranched poly(styrene-b-acrylated epoxidized soybean oil) block copolymers

NASA Astrophysics Data System (ADS)

Lin, Fang-Yi; Hohmann, Austin; Hernández, Nacú; Cochran, Eric

Here we present the phase behavior of a new type of coil-hyperbranched diblock copolymer: poly(styrene- b-acrylated epoxidized soybean oil), or PS-PAESO. PS-PAESO is an example of a biorenewable thermoplastic elastomer (bio-TPE). To date, we have shown that bio-TPEs can be economical commercial substitutes for their petrochemically derived analogues--such as poly(styrene- b-butadiene- b-styrene) (SBS)--in a range of applications including pressure sensitive adhesives and bitumen modification. From a polymer physics perspective, PS-PAESO is an interesting material in that it couples a linear coil-like block with a highly branched block. Thus in contrast to the past five decades of studies on linear AB diblock copolymers, coil-hyperbranched block copolymers are relatively unknown to the community and can be expected to deviate substantially from the standard ``universal'' phase behavior in the AB systems. To explore these new materials, we have constructed a library of PS-PAESO materials spanning a range of molecular weight and composition values. The phase transition behavior and the morphology information will be interpreted by isochronal temperature scanning in dynamic shear rheology, small angle X-ray scattering and the corresponding transmission electron microscopy.

Tertiary-amine-containing thermo- and pH-sensitive hydrophilic ABA triblock copolymers: effect of different tertiary amines on thermally induced sol-gel transitions.

PubMed

Henn, Daniel M; Wright, Roger A E; Woodcock, Jeremiah W; Hu, Bin; Zhao, Bin

2014-03-11

This Article reports on the synthesis of a series of well-defined, tertiary-amine-containing ABA triblock copolymers, composed of a poly(ethylene oxide) (PEO) central block and thermo- and pH-sensitive outer blocks, and the study of the effect of different tertiary amines on thermally induced sol-gel transition temperatures (T(sol-gel)) of their 10 wt % aqueous solutions. The doubly responsive ABA triblock copolymers were prepared from a difunctional PEO macroinitiator by atom transfer radical polymerization of methoxydi(ethylene glycol) methacrylate and ethoxydi(ethylene glycol) methacrylate at a feed molar ratio of 30:70 with ∼5 mol % of either N,N-diethylaminoethyl methacrylate (DEAEMA), N,N-diisopropylaminoethyl methacrylate, or N,N-di(n-butyl)aminoethyl methacrylate. The chain lengths of thermosensitive outer blocks and the molar contents of tertiary amines were very similar for all copolymers. Using rheological measurements, we determined the pH dependences of T(sol-gel) of 10 wt % aqueous solutions of these copolymers in a phosphate buffer. The T(sol-gel) versus pH curves of all polymers exhibited a sigmoidal shape. The T(sol-gel) increased with decreasing pH; the changes were small on both high and low pH sides. At a specific pH, the T(sol-gel) decreased with increasing the hydrophobicity of the tertiary amine, and upon decreasing pH the onset pH value for the T(sol-gel) to begin to increase noticeably was lower for the more hydrophobic tertiary amine-containing copolymer. In addition, we studied the effect of different tertiary amines on the release behavior of FITC-dextran from 10 wt % micellar gels in an acidic medium at 37 and 27 °C. The release profiles for three studied hydrogels at 37 °C were essentially the same, suggesting that the release was dominated by the diffusion of FITC-dextran. At 27 °C, the release was significantly faster for the DEAEMA-containing copolymer, indicating that both diffusion and gel dissolution contributed to the release at this temperature.

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.

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

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.

Drug delivery using novel nanoplexes against a Salmonella mouse infection model

NASA Astrophysics Data System (ADS)

Ranjan, A.; Pothayee, N.; Seleem, M.; Jain, N.; Sriranganathan, N.; Riffle, J. S.; Kasimanickam, R.

2010-03-01

A novel methodology for incorporating gentamicin into macromolecular complexes with anionic homo- and block copolymers via cooperative electrostatic interactions is described. Block copolymers of poly(ethylene oxide- b-sodium acrylate) (PEO- b-PAA- +Na) or poly(ethylene oxide- b-sodium methacrylate) (PEO- b-PMA- +Na) were blended with PAA- Na+ and complexed with the polycationic antibiotic gentamicin. Gentamicin nanoplexes made with PEO- b-PMA- +Na/PAA- +Na (PMPG) and analogous nanoplexes with PEO- b-PAA- +Na/PAA- +Na (PAPG) had mean intensity average diameters of 120 and 90 nm, zeta potentials of -17 and -11 mv, and incorporated 26% and 23% by weight of gentamicin, respectively. Gentamicin release rates at physiological pH from nanoplexes were relatively slow. PAPG and PMPG as drug delivery systems for treating murine salmonellosis at doses similar to the free gentamicin experiments resulted in reduced numbers of viable bacteria in the liver and spleen. Polymeric nanoplexes developed by this methodology can potentially improve targeting of intracellular pathogens.

Molecular basis of cooperativity in pH-triggered supramolecular self-assembly

NASA Astrophysics Data System (ADS)

Li, Yang; Zhao, Tian; Wang, Chensu; Lin, Zhiqiang; Huang, Gang; Sumer, Baran D.; Gao, Jinming

2016-10-01

Supramolecular self-assembly offers a powerful strategy to produce high-performance, stimuli-responsive nanomaterials. However, lack of molecular understanding of stimulated responses frequently hampers our ability to rationally design nanomaterials with sharp responses. Here we elucidated the molecular pathway of pH-triggered supramolecular self-assembly of a series of ultra-pH sensitive (UPS) block copolymers. Hydrophobic micellization drove divergent proton distribution in either highly protonated unimer or neutral micelle states along the majority of the titration coordinate unlike conventional small molecular or polymeric bases. This all-or-nothing two-state solution is a hallmark of positive cooperativity. Integrated modelling and experimental validation yielded a Hill coefficient of 51 in pH cooperativity for a representative UPS block copolymer, by far the largest reported in the literature. These data suggest hydrophobic micellization and resulting positive cooperativity offer a versatile strategy to convert responsive nanomaterials into binary on/off switchable systems for chemical and biological sensing, as demonstrated in an additional anion sensing model.

Thermally Induced Structural Evolution and Performance of Mesoporous Block Copolymer-Directed Alumina Perovskite Solar Cells

PubMed Central

2015-01-01

Structure control in solution-processed hybrid perovskites is crucial to design and fabricate highly efficient solar cells. Here, we utilize in situ grazing incidence wide-angle X-ray scattering and scanning electron microscopy to investigate the structural evolution and film morphologies of methylammonium lead tri-iodide/chloride (CH3NH3PbI3–xClx) in mesoporous block copolymer derived alumina superstructures during thermal annealing. We show the CH3NH3PbI3–xClx material evolution to be characterized by three distinct structures: a crystalline precursor structure not described previously, a 3D perovskite structure, and a mixture of compounds resulting from degradation. Finally, we demonstrate how understanding the processing parameters provides the foundation needed for optimal perovskite film morphology and coverage, leading to enhanced block copolymer-directed perovskite solar cell performance. PMID:24684494

Environmentally stable polymers and coatings for space application: CH-5, supplement 10

NASA Technical Reports Server (NTRS)

Sykes, G.

1986-01-01

High molecular weight, randomly coupled poly(imide siloxane) soluble block copolymers were synthesized from bis(amino propyl) polydimethylsiloxane equilibrates of various molecular weights, aromatic metalinked diamines, and 3,3'-4,4'-benzophenone tetracarboxylic dianhydride (BTDA). Two synthetic procedures were successfully used to synthesize the poly(amic acid siloxane) intermediates. For both synthetic procedures, a cosolvent system was employed to achieve complete solvation of all components throughout the polymerization. Physical property characterization is continuing.

Nucleation in Polymers and Soft Matter

NASA Astrophysics Data System (ADS)

Xu, Xiaofei; Ting, Christina L.; Kusaka, Isamu; Wang, Zhen-Gang

2014-04-01

Nucleation is a ubiquitous phenomenon in many physical, chemical, and biological processes. In this review, we describe recent progress on the theoretical study of nucleation in polymeric fluids and soft matter, including binary mixtures (polymer blends, polymers in poor solvents, compressible polymer-small molecule mixtures), block copolymer melts, and lipid membranes. We discuss the methodological development for studying nucleation as well as novel insights and new physics obtained in the study of the nucleation behavior in these systems.

Fluid dynamic characterization of a polymeric heart valve prototype (Poli-Valve) tested under continuous and pulsatile flow conditions.

PubMed

De Gaetano, Francesco; Serrani, Marta; Bagnoli, Paola; Brubert, Jacob; Stasiak, Joanna; Moggridge, Geoff D; Costantino, Maria Laura

2015-11-01

Only mechanical and biological heart valve prostheses are currently commercially available. The former show longer durability but require anticoagulant therapy; the latter display better fluid dynamic behavior but do not have adequate durability. New Polymeric Heart Valves (PHVs) could potentially combine the hemodynamic properties of biological valves with the durability of mechanical valves. This work presents a hydrodynamic evaluation of 2 groups of newly developed supra-annular, trileaflet prosthetic heart valves made from styrenic block copolymers (SBC): Poli-Valves. 2 types of Poli-Valves made of SBC and differing in polystyrene fraction content were tested under continuous and pulsatile flow conditions as prescribed by ISO 5840 Standard. A pulse duplicator designed ad hoc allowed the valve prototypes to be tested at different flow rates and frequencies. Pressure and flow were recorded; pressure drops, effective orifice area (EOA), and regurgitant volume were computed to assess the behavior of the valve. Both types of Poli-Valves met the minimum requirements in terms of regurgitation and EOA as specified by the ISO 5840 Standard. Results were compared with 5 mechanical heart valves (MHVs) and 5 tissue heart valves (THVs), currently available on the market. Based on these results, PHVs based on styrenic block copolymers, as are Poli-Valves, can be considered a promising alternative for heart valve replacement in the near future.

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

PubMed

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

2012-05-30

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

Patterning by area selective oxidation

DOEpatents

Nam, Chang-Yong; Kamcev, Jovan; Black, Charles T.; Grubbs, Robert

2015-12-29

Technologies are described for methods for producing a pattern of a material on a substrate. The methods may comprise receiving a patterned block copolymer on a substrate. The patterned block copolymer may include a first polymer block domain and a second polymer block domain. The method may comprise exposing the patterned block copolymer to a light effective to oxidize the first polymer block domain in the patterned block copolymer. The method may comprise applying a precursor to the block copolymer. The precursor may infuse into the oxidized first polymer block domain and generate the material. The method may comprise applying a removal agent to the block copolymer. The removal agent may be effective to remove the first polymer block domain and the second polymer block domain from the substrate, and may not be effective to remove the material in the oxidized first polymer block domain.

Preparation and characterization of poly(acrylic acid)-hydroxyethyl cellulose graft copolymer.

PubMed

Abdel-Halim, E S

2012-10-01

Poly(acrylic acid) hydroxyethyl cellulose [poly(AA)-HEC] graft copolymer was prepared by polymerizing acrylic acid (AA) with hydroxyethyl cellulose (HEC) using potassium bromate/thiourea dioxide (KBrO(3)/TUD) as redox initiation system. The polymerization reaction was carried out under a variety of conditions including concentrations of AA, KBrO(3) and TUD, material to liquor ratio and polymerization temperature. The polymerization reaction was monitored by withdrawing samples from the reaction medium and measuring the total conversion. The rheological properties of the poly(AA)-HEC graft copolymer were investigated. The total conversion and rheological properties of the graft copolymer depended on the ratio of KBrO(3) to TUD and on acrylic acid concentration as well as temperature and material to liquor ratio. Optimum conditions of the graft copolymer preparation were 30 mmol KBrO(3) and 30 mmol TUD/100g HEC, 100% AA (based on weight of HEC), duration 2h at temperature 50 °C using a material to liquor ratio of 1:10. Copyright © 2012. Published by Elsevier Ltd.

Enzyme-Cleavable Polymeric Micelles for the Intracellular Delivery of Proapoptotic Peptides.

PubMed

Kern, Hanna B; Srinivasan, Selvi; Convertine, Anthony J; Hockenbery, David; Press, Oliver W; Stayton, Patrick S

2017-05-01

Peptides derived from the third Bcl-2 homology domain (BH3) renormalize apoptotic signaling by antagonizing prosurvival Bcl-2 family members. These potential peptide drugs exhibit therapeutic activities but are limited by barriers including short circulation half-lives and poor penetration into cells. A diblock polymeric micelle carrier for the BIM BH3 peptide was recently described that demonstrated antitumor activity in a B-cell lymphoma xenograft model [Berguig et al., Mol. Ther. 2015, 23, 907-917]. However, the disulfide linkage used to conjugate the BIM peptide was shown to have nonoptimal blood stability. Here we describe a peptide macromonomer composed of BIM capped with a four amino acid cathepsin B substrate (FKFL) that possesses high blood stability and is cleaved to release the drug inside of target cells. Employing RAFT polymerization, the peptide macromonomer was directly integrated into a multifunctional diblock copolymer tailored for peptide delivery. The first polymer block was made as a macro-chain transfer agent (CTA) and composed of a pH-responsive endosomolytic formulation of N,N-diethylaminoethyl methacrylate (DEAEMA) and butyl methacrylate (BMA). The second polymer block was a copolymer of the peptide and polyethylene glycol methacrylate (PEGMA). PEGMA monomers of two sizes were investigated (300 Da and 950 Da). Protein gel analysis, high performance liquid chromatography, and coupled mass spectrometry (MS) showed that incubation with cathepsin B specifically cleaved the FKFL linker and released active BIM peptide with PEGMA 300 but not with PEGMA 950 . MALDI-TOF MS showed that incubation of the peptide monomers alone in human serum resulted in partial cleavage at the FKFL linker after 12 h. However, formulation of the peptides into polymers protected against serum-mediated peptide degradation. Dynamic light scattering (DLS) demonstrated pH-dependent micelle disassembly (25 nm polymer micelles at pH 7.4 versus 6 nm unimers at pH 6.6), and a red blood cell lysis assay showed a corresponding increase in membrane destabilizing activity (<1% lysis at pH 7.4 versus 95% lysis at pH 6.6). The full carrier-drug system successfully induced apoptosis in SKOV3 ovarian cancer cells in a dose-dependent manner, in comparison to a control polymer containing a scrambled BIM peptide sequence. Mechanistic analysis verified target-dependent activation of caspase 3/7 activity (8.1-fold increase), and positive annexin V staining (72% increase). The increased blood stability of this enzyme-cleavable peptide polymer design, together with the direct polymerization approach that eliminated postsynthetic conjugation steps, suggests that this new carrier design could provide important benefits for intracellular peptide drug delivery.

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.

Amphiphilic block copolymer membrane for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Wang, Fei; Sylvia, James M.; Jacob, Monsy M.; Peramunage, Dharmasena

2013-11-01

An amphiphilic block copolymer comprised of hydrophobic polyaryletherketone (PAEK) and hydrophilic sulfonated polyaryletherketone (SPAEK) blocks has been synthesized and characterized. A membrane prepared from the block copolymer is used as the separator in a single cell vanadium redox flow battery (VRB). The proton conductivity, mechanical property, VO2+ permeability and single VRB cell performance of this block copolymer membrane are investigated and compared to Nafion™ 117. The block copolymer membrane showed significantly improved vanadium ion selectivity, higher mechanical strength and lower conductivity than Nafion™ 117. The VRB containing the block copolymer membrane exhibits higher coulombic efficiency and similar energy efficiency compared to a VRB using Nafion™ 117. The better vanadium ion selectivity of the block copolymer membrane has led to a much smaller capacity loss during 50 charge-discharge cycles for the VRB.

Polymeric micelles from poly(ethylene glycol)–poly(amino acid) block copolymer for drug and gene delivery

PubMed Central

Osada, Kensuke; Christie, R. James; Kataoka, Kazunori

2009-01-01

Dramatic advances in biological research have revealed the mechanisms underlying many diseases at the molecular level. However, conventional techniques may be inadequate for direct application of this new knowledge to medical treatments. Nanobiotechnology, which integrates biology with the rapidly growing field of nanotechnology, has great potential to overcome many technical problems and lead to the development of effective therapies. The use of nanobiotechnology in drug delivery systems (DDS) is attractive for advanced treatment of conditions such as cancer and genetic diseases. In this review paper for a special issue on biomaterial research in Japan, we discuss the development of DDS based on polymeric micelles mainly in our group for anti-cancer drug and gene delivery, and also address our challenges associated with developing polymeric micelles as super-functionalized nanodevices with intelligent performance. PMID:19364722

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.

Poly(cyclohexylethylene)- block-poly(ethylene oxide) block polymers for metal oxide templating

DOE PAGES

Schulze, Morgan W.; Sinturel, Christophe; Hillmyer, Marc A.

2015-09-01

A series of poly(cyclohexylethylene)- block-poly(ethylene oxide) (CEO) diblock copolymers were synthesized through tandem anionic polymerizations and heterogeneous catalytic hydrogenation. Solvent-annealed CEO diblock films were used to template dense arrays of inorganic oxide nanodots via simple spin coating of an inorganic precursor solution atop the ordered film. The substantial chemical dissimilarity of the two blocks enables (i) selective inclusion of the inorganic precursor within the PEO domain and (ii) the formation of exceptionally small feature sizes due to a relatively large interaction parameter estimated from mean-field analysis of the order–disorder transition temperatures of compositionally symmetric samples. UV/ozone treatment following incorporation producesmore » an ordered arrangement of oxide nanodots and simultaneously removes the block polymer template. However, we report the smallest particles (6 ± 1 nm) templated from a selective precursor insertion method to date using a block polymer scaffold.« less

Synthesis of ethylene-propylene rubber graft copolymers by borane approach

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

Chung, T.C.; Janvikul, W.; Bernard, R.

1994-01-01

This paper describes a new method to prepare graft copolymers which have an EP rubber backbone and several free radical polymerized polymers grafted thereto. The process involves hydroboration of commercial EPDM rubbers, such as poly(ethylene-co-propylene-co-1,4-hexadiene) and poly(ethylene-co-propylene-co-5-ethylidene-2-norbornene), with 9-borabicyclononane (9-BBN). The resulting secondary alkyl-9-BBN moieties in the EPDM copolymer were then exposed to oxygen in the presence of free radical polymerizable monomers. Under certain conditions, the selective autoxidation reaction of secondary alkyl-9-BBN took place to create desirable polymeric radicals which can in situ initiate free radical polymerization. High graft efficiency was observed with controllable copolymer compositions. The graft copolymer ofmore » EP-g-PMMA is used to show the chemistry as well as some of the physical properties.« less

Hemicellulose block copolymers made from woods for wide-range directed self-assembly lithography enabling wider range of applicable patterning size

NASA Astrophysics Data System (ADS)

Morita, Kazuyo; Yamamoto, Kimiko

2017-03-01

Xylan, one of hemicellulose family, block copolymer was newly developed for wide-range directed self-assembly lithography (DSA). Xylan is higher hydrophilic material because of having many hydroxy groups in one molecule. It means that xylan block copolymer has a possibility of high-chi block copolymer. Generally, DSA is focused on microphase separation for smaller size with high-chi block copolymer and not well known for larger size. In this study, xylan block copolymer was confirmed enabling wider range of patterning size, from smaller size to larger size. The key of xylan block copolymer is a new molecular structure of block copolymer and sugar chain control technology. Sugar content is the important parameter for not only micro-phase separation property but also line edge roughness (LER) and defects. Based on the sugar control technology, wide-range (hp 8.3nm to 26nm L/S and CD 10nm to 51nm hole) DSA patterning was demonstrated. Additionally it was confirmed that xylan block copolymer is suitable for sequential infiltration synthesis (SIS) process.

Heat resistant polymers of oxidized styrylphosphine

NASA Technical Reports Server (NTRS)

Paciorek, K. J. L. (Inventor)

1978-01-01

Homopolymers, copolymers and terpolymers of a styrene based monomer are prepared by polymerizing at least one oxidized styrylphosphine monomer or by polymerizing p-diphenylphosphinestyrene and then oxidizing the polymerized monomer with an organoazide. Copolymers can also be prepared by copolymerizing styrene with at least one oxidized styrylphosphine monomer. Flame resistant vinyl based polymers whose degradation products are non toxic and non corrosive are obtained.

Microphase separation in random multiblock copolymers

NASA Astrophysics Data System (ADS)

Govorun, E. N.; Chertovich, A. V.

2017-01-01

Microphase separation in random multiblock copolymers is studied with the mean-field theory assuming that long blocks of a copolymer are strongly segregated, whereas short blocks are able to penetrate into "alien" domains and exchange between the domains and interfacial layer. A bidisperse copolymer with blocks of only two sizes (long and short) is considered as a model of multiblock copolymers with high polydispersity in the block size. Short blocks of the copolymer play an important role in the microphase separation. First, their penetration into the "alien" domains leads to the formation of joint long blocks in their own domains. Second, short blocks localized at the interface considerably change the interfacial tension. The possibility of penetration of short blocks into the "alien" domains is controlled by the product χ Nsh (χ is the Flory-Huggins interaction parameter and Nsh is the short block length). At not very large χ Nsh , the domain size is larger than that for a regular copolymer consisting of the same long blocks as in the considered random copolymer. At a fixed mean block size, the domain size grows with an increase in the block size dispersity, the rate of the growth being dependent of the more detailed parameters of the block size distribution.

Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization

DOE PAGES

Wang, Wenwen; Wang, Weiyu; Li, Hui; ...

2015-01-14

In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermalmore » analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 10 5 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.« less

Near-infrared fluorescent aza-BODIPY dye-loaded biodegradable polymeric nanoparticles for optical cancer imaging

NASA Astrophysics Data System (ADS)

Hamon, Casey L.; Dorsey, Christopher L.; Özel, Tuğba; Barnes, Eugenia M.; Hudnall, Todd W.; Betancourt, Tania

2016-07-01

Nanoparticles are being readily investigated as carriers for the delivery of imaging and therapeutic agents for the detection, monitoring, and treatment of cancer and other diseases. In the present work, the preparation of biodegradable polymeric nanoparticles loaded with a near-infrared fluorescent aza-boron dipyrromethene (NIR-BODIPY ) derivative, and their use as contrast agents for optical imaging in cancer are described. Nanoparticles were prepared by nanoprecipitation of amphiphilic block copolymers of poly(lactic acid) and poly(ethylene glycol). The size, morphology, dye loading, spectral properties, quantum yield, cytocompatibility, and in vitro NIR imaging potential of the nanoparticles in breast and ovarian cancer cells were evaluated. Spherical nanoparticles of 30-70 nm in diameter were loaded with 0.73 w/w% BODIPY derivative. At this loading, the dye presented a fluorescence quantum yield in the same order of magnitude as in solution. Nanoparticle suspensions at concentrations up to 580 μg/mL were cytocompatible to breast (MDA-MB-231) and ovarian (SKOV-3 and Caov-3) cancer cells after a four-hour incubation period. Fluorescence microscopy images demonstrated the ability of the nanoparticles to act as imaging agents in all three cell lines in as little as 1 hour. The results shown indicate the potential of these NIR-BODIPY-loaded nanoparticles as contrast agents for near-infrared optical imaging in cancer.

Synthesis of amphiphilic tadpole-shaped linear-cyclic diblock copolymers via ring-opening polymerization directly initiating from cyclic precursors and their application as drug nanocarriers.

PubMed

Wan, Xuejuan; Liu, Tao; Liu, Shiyong

2011-04-11

We report on the facile synthesis of well-defined amphiphilic and thermoresponsive tadpole-shaped linear-cyclic diblock copolymers via ring-opening polymerization (ROP) directly initiating from cyclic precursors, their self-assembling behavior in aqueous solution, and the application of micellar assemblies as controlled release drug nanocarriers. Starting from a trifunctional core molecule containing alkynyl, hydroxyl, and bromine moieties, alkynyl-(OH)-Br, macrocyclic poly(N-isopropylacrylamide) (c-PNIPAM) bearing a single hydroxyl functionality was prepared by atom transfer radical polymerization (ATRP), the subsequent end group transformation into azide functionality, and finally the intramacromolecular ring closure reaction via click chemistry. The target amphiphilic tadpole-shaped linear-cyclic diblock copolymer, (c-PNIPAM)-b-PCL, was then synthesized via the ROP of ε-caprolactone (CL) by directly initiating from the cyclic precursor. In aqueous solution at 20 °C, (c-PNIPAM)-b-PCL self-assembles into spherical micelles consisting of hydrophobic PCL cores and well-solvated coronas of cyclic PNIPAM segments. For comparison, linear diblock copolymer with comparable molecular weight and composition, (l-PNIPAM)-b-PCL, was also synthesized. It was found that the thermoresponsive coronas of micelles self-assembled from (c-PNIPAM)-b-PCL exhibit thermoinduced collapse and aggregation at a lower critical thermal phase transition temperature (T(c)) compared with those of (l-PNIPAM)-b-PCL. Temperature-dependent drug release profiles from the two types of micelles of (c-PNIPAM)-b-PCL and (l-PNIPAM)-b-PCL loaded with doxorubicin (Dox) were measured, and the underlying mechanism for the observed difference in releasing properties was proposed. Moreover, MTT assays revealed that micelles of (c-PNIPAM)-b-PCL are almost noncytotoxic up to a concentration of 1.0 g/L, whereas at the same polymer concentration, micelles loaded with Dox lead to ∼60% cell death. Overall, chain topologies of thermoresponsive block copolymers, that is, (c-PNIPAM)-b-PCL versus (l-PNIPAM)-b-PCL, play considerable effects on the self-assembling and thermal phase transition properties and their functions as controlled release drug nanocarriers.

pH-sensitive polymeric nanoparticles with antioxidant and anti-inflammatory properties against cisplatin-induced hearing loss.

PubMed

Martín-Saldaña, Sergio; Palao-Suay, Raquel; Aguilar, María Rosa; García-Fernández, Luis; Arévalo, Humberto; Trinidad, Almudena; Ramírez-Camacho, Rafael; San Román, Julio

2018-01-28

Polymeric nanoparticles (NPs) based on smart synthetic amphiphilic copolymers are used to transport and controlled release dexamethasone in the inner ear to protect against the ototoxic effect of cisplatin. The NPs were based on a mixture of two pseudo-block polymer drugs obtained by free radical polymerization: poly(VI-co-HEI) and poly(VP-co-MVE) or poly(VP-co-MTOS), being VI 1-vinylimidazole, VP N-vinylpyrrolidone, and HEI, MVE and MTOS the methacrylic derivatives of ibuprofen, α-tocopherol and α-tocopheryl succinate, respectively. The NPs were obtained by nanoprecipitation with appropriate hydrodynamic properties, and isoelectric points that matched the pH of inflamed tissue. The NPs were tested both in vitro (using HEI-OC1 cells) and in vivo (using a murine model) with good results. Although the concentration of dexamethasone administered in the NPs is around two orders of magnitude lower that the conventional treatment for intratympanic administration, the NPs protected from the cytotoxic effect of cisplatin when the combination of the appropriate properties in terms of size, zeta potential, encapsulation efficiency and isoelectric point were achieved. To the best of our knowledge this is the first time that pH sensitive NPs are used to protect from cisplatin-induced hearing loss by intratympanic administration. Copyright © 2017 Elsevier B.V. All rights reserved.

Highχ block copolymers for directed self-assembly patterning without the need for topcoat or solvent annealing

NASA Astrophysics Data System (ADS)

Xu, Kui; Hockey, Mary Ann; Calderas, Eric; Guerrero, Douglas; Sweat, Daniel; Fiehler, Jeffrey

2017-03-01

High-χ block copolymers for directed self-assembly (DSA) patterning that do not need topcoat or solvent annealing have been developed. A variety of functionalities have been successfully added into the block copolymers, such as balanced surface energy between the polymer blocks, outstandingly high χ, tunable glass transition temperature (Tg), and selective crosslinking. Perpendicular orientation control, as desired for patterning, of the block copolymers can be simply achieved by thermal annealing due to the equal surface energy of the polymer blocks at the annealing temperatures, which allows avoiding solvent annealing or top-coat. The χ value can be tuned up to achieve L0 as low as 8-10 nm for lamellar-structured block copolymers and hole/pillar size as small as 5-6 nm for cylinder-structured block copolymers. The Tg of the block copolymers can be tuned to improve the kinetics of thermal annealing by enhancing the polymer chain mobility. Block-selective crosslinking facilitates the pattern transfer by mitigating pattern collapse during wet etching and improving oxygen plasma etching selectivity between the polymer blocks. This paper provides an introductory review of our high-χ block copolymer materials with various functionalities for achieving improved DSA performance.

Method of producing nanopatterned articles, and articles produced thereby

DOEpatents

Russell, Thomas P; Park, Soojin; Xu, Ting

2013-11-12

A nanopatterned surface is prepared by forming a block copolymer film on a miscut crystalline substrate, annealing the block copolymer film, then reconstructing the surface of the annealed block copolymer film. The method creates a well-ordered array of voids in the block copolymer film that is maintained over a large area. The nanopatterned block copolymer films can be used ina variety of different applications, including the fabrication of high density data storage media.

Resilient self-assembling hydrogels from block copolypeptide amphiphiles

NASA Astrophysics Data System (ADS)

Nowak, Andrew Paul

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

Polymeric micelle for tumor pH and folate-mediated targeting.

PubMed

Lee, Eun Seong; Na, Kun; Bae, You Han

2003-08-28

Novel pH-sensitive polymeric mixed micelles composed of poly(L-histidine) (polyHis; M(w) 5000)/PEG (M(n) 2000) and poly(L-lactic acid) (PLLA) (M(n) 3000)/PEG (M(n) 2000) block copolymers with or without folate conjugation were prepared by diafiltration. The micelles were investigated for pH-dependent drug release, folate receptor-mediated internalization and cytotoxicity using MCF-7 cells in vitro. The polyHis/PEG micelles showed accelerated adriamycin release as the pH decreased from 8.0. When the cumulative release for 24 h was plotted as a function of pH, the gradual transition in release rate appeared in a pH range from 8.0 to 6.8. In order to tailor the triggering pH of the polymeric micelles to the more acidic extracellular pH of tumors, while improving the micelle stability at pH 7.4, the PLLA/PEG block copolymer was blended with polyHis/PEG to form mixed micelles. Blending shifted the triggering pH to a lower value. Depending on the amount of PLLA/PEG, the mixed micelles were destabilized in the pH range of 7.2-6.6 (triggering pH for adriamycin release). When the mixed micelles were conjugated with folic acid, the in vitro results demonstrated that the micelles were more effective in tumor cell kill due to accelerated drug release and folate receptor-mediated tumor uptake. In addition, after internalization polyHis was found to be effective for cytosolic ADR delivery by virtue of fusogenic activity. This approach is expected to be useful for treatment of solid tumors in vivo.

Living supramolecular polymerization achieved by collaborative assembly of platinum(II) complexes and block copolymers

PubMed Central

Zhang, Kaka; Yeung, Margaret Ching-Lam; Leung, Sammual Yu-Lut; Yam, Vivian Wing-Wah

2017-01-01

An important feature of biological systems to achieve complexity and precision is the involvement of multiple components where each component plays its own role and collaborates with other components. Mimicking this, we report living supramolecular polymerization achieved by collaborative assembly of two structurally dissimilar components, that is, platinum(II) complexes and poly(ethylene glycol)-b-poly(acrylic acid) (PEG-b-PAA). The PAA blocks neutralize the charges of the platinum(II) complexes, with the noncovalent metal–metal and π–π interactions directing the longitudinal growth of the platinum(II) complexes into 1D crystalline nanostructures, and the PEG blocks inhibiting the transverse growth of the platinum(II) complexes and providing the whole system with excellent solubility. The ends of the 1D crystalline nanostructures have been found to be active during the assembly and remain active after the assembly. One-dimensional segmented nanostructures with heterojunctions have been produced by sequential growth of two types of platinum(II) complexes. The PAA blocks act as adapters at the heterojunctions for lattice matching between chemically and crystallographically different platinum(II) complexes, achieving heterojunctions with a lattice mismatch as large as 21%. PMID:29078381

Statistical Ring Opening Metathesis Copolymerization of Norbornene and Cyclopentene by Grubbs' 1st-Generation Catalyst.

PubMed

Nikovia, Christiana; Maroudas, Andreas-Philippos; Goulis, Panagiotis; Tzimis, Dionysios; Paraskevopoulou, Patrina; Pitsikalis, Marinos

2015-08-27

Statistical copolymers of norbornene (NBE) with cyclopentene (CP) were prepared by ring-opening metathesis polymerization, employing the 1st-generation Grubbs' catalyst, in the presence or absence of triphenylphosphine, PPh₃. The reactivity ratios were estimated using the Finemann-Ross, inverted Finemann-Ross, and Kelen-Tüdos graphical methods, along with the computer program COPOINT, which evaluates the parameters of binary copolymerizations from comonomer/copolymer composition data by integrating a given copolymerization equation in its differential form. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length, which were derived using the monomer reactivity ratios. The kinetics of thermal decomposition of the copolymers along with the respective homopolymers was studied by thermogravimetric analysis within the framework of the Ozawa-Flynn-Wall and Kissinger methodologies. Finally, the effect of triphenylphosphine on the kinetics of copolymerization, the reactivity ratios, and the kinetics of thermal decomposition were examined.

Using Dynamic Covalent Chemistry To Drive Morphological Transitions: Controlled Release of Encapsulated Nanoparticles from Block Copolymer Vesicles

PubMed Central

2017-01-01

Dynamic covalent chemistry is exploited to drive morphological order–order transitions to achieve the controlled release of a model payload (e.g., silica nanoparticles) encapsulated within block copolymer vesicles. More specifically, poly(glycerol monomethacrylate)–poly(2-hydroxypropyl methacrylate) (PGMA–PHPMA) diblock copolymer vesicles were prepared via aqueous polymerization-induced self-assembly in either the presence or absence of silica nanoparticles. Addition of 3-aminophenylboronic acid (APBA) to such vesicles results in specific binding of this reagent to some of the pendent cis-diol groups on the hydrophilic PGMA chains to form phenylboronate ester bonds in mildly alkaline aqueous solution (pH ∼ 10). This leads to a subtle increase in the effective volume fraction of this stabilizer block, which in turn causes a reduction in the packing parameter and hence induces a vesicle-to-worm (or vesicle-to-sphere) morphological transition. The evolution in copolymer morphology (and the associated sol–gel transitions) was monitored using dynamic light scattering, transmission electron microscopy, oscillatory rheology, and small-angle X-ray scattering. In contrast to the literature, in situ release of encapsulated silica nanoparticles is achieved via vesicle dissociation at room temperature; moreover, the rate of release can be fine-tuned by varying the solution pH and/or the APBA concentration. Furthermore, this strategy also works (i) for relatively thick-walled vesicles that do not normally exhibit stimulus-responsive behavior and (ii) in the presence of added salt. This novel molecular recognition strategy to trigger morphological transitions via dynamic covalent chemistry offers considerable scope for the design of new stimulus-responsive copolymer vesicles (and hydrogels) for targeted delivery and controlled release of cargoes. In particular, the conditions used in this new approach are relevant to liquid laundry formulations, whereby enzymes require protection to prevent their deactivation by bleach. PMID:28497960

Microstructural study of a nitroxide-mediated poly(ethylene oxide)/polystyrene block copolymer (PEO-b-PS) by electrospray tandem mass spectrometry.

PubMed

Girod, Marion; Phan, Trang N T; Charles, Laurence

2008-08-01

Electrospray ionization tandem mass spectrometry has been used to characterize the microstructure of a nitroxide-mediated poly(ethylene oxide)/polystyrene block copolymer, called SG1-capped PEO-b-PS. The main dissociation route of co-oligomers adducted with lithium or silver cation was observed to proceed via the homolytic cleavage of a C-ON bond, aimed at undergoing reversible homolysis during nitroxide mediated polymerization. This cleavage results in the elimination of the terminal SG1 end-group as a radical, inducing a complete depolymerization process of the PS block from the so-formed radical cation. These successive eliminations of styrene molecules allowed a straightforward determination of the PS block size. An alternative fragmentation pathway of the radical cation was shown to provide structural information on the junction group between the two blocks. Proposed dissociation mechanisms were supported by accurate mass measurements. Structural information on the SG1 end-group could be reached from weak abundance fragment ions detected in the low m/z range of the MS/MS spectrum. Amongst fragments typically expected from PS dissociation, only beta ions were produced. Moreover, specific dissociation of the PEO block was not observed to occur in MS/MS, suggesting that these rearrangement reactions do not compete effectively with dissociations of the odd-electron fragment ions. Information about the PEO block length and the initiated end-group were obtained in MS(3) experiments.

Method of producing nanopatterned articles, and articles produced thereby

DOEpatents

Russell, Thomas P; Park, Soojin; Xu, Ting

2015-04-28

A nanopatterned surface is prepared by forming a block copolymer film on a miscut crystalline substrate, annealing the block copolymer film, then reconstructing the surface of the annealed block copolymer film The method creates a well-ordered array of voids in the block copolymer film that is maintained over a large area. The nanopatterned block copolymer films can be used in a variety of different applications, including the fabrication of high density data storage media.

Modeling random methyl branching in ethylene/ propylene copolymers using metathesis chemistry: synthesis and thermal behavior.

PubMed

Sworen, John C; Smith, Jason A; Wagener, Kenneth B; Baugh, Lisa S; Rucker, Steven P

2003-02-26

The structure of random ethylene/propylene (EP) copolymers has been modeled using step polymerization chemistry. Six ethylene/propylene model copolymers have been prepared via acyclic diene metathesis (ADMET) polymerization and characterized for primary and higher level structure using in-depth NMR, IR, DSC, WAXD, and GPC analysis. These copolymers possess 1.5, 7.1, 13.6, 25.0, 43.3, and 55.6 methyl branches per 1000 carbons. Examination of these macromolecules by IR and WAXD analysis has demonstrated the first hexagonal phase in EP copolymers containing high ethylene content (90%) without the influence of sample manipulation (temperature, pressure, or radiation). Thermal behavior studies have shown that the melting point and heat of fusion decrease as the branch content increases. Further, comparisons have been made between these random ADMET EP copolymers, random EP copolymers made by typical chain addition techniques, and precisely branched ADMET EP copolymers.

Interfacial activity of polymeric surfactants at the polystyrene-carbon dioxide interface

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

Harrison, K.L.; Rocha, S.R.P. da; Yates, M.Z.

1998-11-24

The reduction of the interfacial tension at the polystyrene (PS, M{sub n} = 1850)-supercritical CO{sub 2} interface is reported for poly(1,1-dihydroperfluorooctyl acrylate)(PFOA) and the block copolymers PS-b-PFOA(3.7K/27K) and PS-b-poly(dimethylsiloxane) (PDMS) (2K/16K, 500/10K) at 45 C. PS-b-PDMS (2K/16K) lowers the interfacial tension to 0.5 dyn/cm at 45 C and 238 bar, more than that of any of the other copolymers. On the basis of the dynamics of the lowering of the interfacial tension, the apparent diffusion coefficient of PS-b-PDMS (2K/16K) is 8 {times} 10{sup {minus}6} cm{sup 2}/s. The critical micelle concentration of PS-b-PFOA (3.7K/27K) is 9 {times} 10{sup {minus}4} wt %.more » Whereas both the PDMS- and PFOA-based copolymers studied adsorb on the PS surface, PS-b-PFOA is much more effective in stabilizing the PS emulsions. The difference in stabilization is discussed in terms of the surfactant adsorption and the interactions of the anchor and buoy blocks with CO{sub 2} and the PS surface.« less

A series of poly(butylimidazolium) ionic liquid functionalized copolymers for anion exchange membranes

NASA Astrophysics Data System (ADS)

Ouadah, Amina; Xu, Hulin; Luo, Tianwei; Gao, Shuitao; Wang, Xing; Fang, Zhou; Jing, Chaojun; Zhu, Changjin

2017-12-01

A new series of ionic liquid functionalized copolymers for anion exchange membranes (AEM) is prepared. Poly(butylvinylimidazolium)(b-VIB) is copolymerized with para-methyl styrene (p-MS) by the radical polymerization formed block copolymers b-VIB/p-MS, which is crosslinked with poly(diphenylether bibenzimidazole) (DPEBI) providing the desired materials b-VIB/p-MS/DPEBI. Structures are characterized via H1NMR, FTIR spectra and elemental analysis. The b-VIB blocks offer the anion conduction function while DPEBI moieties contribute to enhancing other properties. The prepared membranes display chloride conductivity as high as 19.5 mS/cm at 25 °C and 69.2 mS/cm at 100 °C-higher than that of the commercial membrane tokuyuama A201-. Their hydroxide conductivity reaches 35.7 Scm-1 at 25 °C and 73.1 Scm-1 at 100 °C. The membranes showed a linear Arrhenius behavior in the anion conduction, low activation energies and distinguished nanophase separation of hydrophilic/hydrophobic regions by the transmission electron microscopy (TEM) studies. Thermal investigations using TGA and DSC confirm that the membranes are stable up to 250 °C. Particularly, drastically alkaline stability due to no decrease in the hydroxide conductivity after 168 h of treatment with 2M KOH.

Small-angle-neutron-scattering from giant water-in-oil microemulsion droplets. II. Polymer-decorated droplets in a quaternary system

NASA Astrophysics Data System (ADS)

Foster, Tobias; Sottmann, Thomas; Schweins, Ralf; Strey, Reinhard

2008-02-01

Amphiphilic block copolymers of the type poly(ethylenepropylene)-co-poly(ethyleneoxide) dramatically enhance the solubilisation efficiency of non-ionic surfactants in microemulsions that contain equal volumes of water in oil. Consequently, the length scale of the microstructure of such bicontinuous microemulsions is dramatically increased up to the order of a few 100nm. In this paper, we show that this so-called efficiency boosting effect can also be applied to water-in-oil microemulsions with droplet microstructure. Such giant water-in-oil microemulsions would provide confined compartments in which chemical reactions of biological macromolecules can be performed on a single molecule level. With this motivation we investigated the phase behavior and the microstructure of oil-rich microemulsions containing D2O, n-decane(d22), C10E4 and the amphiphilic block copolymer PEP5-PEO5 [poly(ethylenepropylene)-co-poly(ethyleneoxide), weight per block of 5000g/mol]. We found that 15wt% of water can be solubilised by 5wt% of surfactant and block copolymer when about 6wt% of surfactant is replaced by the block copolymer. Small-angle-neutron-scattering experiments were performed to determine the length scales and microstructure topologies of the oil-rich microemulsions. To analyze the scattering data, we derived a novel form factor that also takes into account the scattering contribution of the hydrophobic part of the block copolymer molecules that reside in the surfactant shell. The quantitative analysis of the scattering data with this form factor shows that the radius of the largest droplets amounts up to 30nm. The novel form factor also yielded qualitative information on the stretching of the polymer chains in dependence on the polymer surface density and the droplet radius.

Palladium (Ii) Catalyzed Polymerization Of Norbornene And Acrylates

DOEpatents

Sen, Ayusman; Kacker, Smita; Hennis, April; Polley, Jennifer D.

2001-10-09

Homopolymers or copolymers of acrylates, homopolymers or copolymers of norbornenes, and copolymers of acrylates with norbornenes, may be prepared by contacting acrylate and/or norbornene monomer reactant under polymerization conditions and in the presence of a solvent with a catalyst system consisting essentially of a Pd(II) dimer component having the formula: where L is a monodentate phosphorus or nitrogen ligand, X is an anionic group, and R is an alkyl or aryl group.

Crystalline imide/arylene ether copolymers

NASA Technical Reports Server (NTRS)

Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor)

1995-01-01

Crystalline imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly)arylene ethers) in polar aprotic solvents and chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The block copolymers of the invention have one glass transition temperature or two, depending on the particular structure and/or the compatibility of the block units. Most of these crystalline block copolymers for tough, solvent resistant films with high tensile properties. While all of the copolymers produced by the present invention are crystalline, testing reveals that copolymers with longer imide blocks or higher imide content have increased crystallinity.

Protein based Block Copolymers

PubMed Central

Rabotyagova, Olena S.; Cebe, Peggy; Kaplan, David L.

2011-01-01

Advances in genetic engineering have led to the synthesis of protein-based block copolymers with control of chemistry and molecular weight, resulting in unique physical and biological properties. The benefits from incorporating peptide blocks into copolymer designs arise from the fundamental properties of proteins to adopt ordered conformations and to undergo self-assembly, providing control over structure formation at various length scales when compared to conventional block copolymers. This review covers the synthesis, structure, assembly, properties, and applications of protein-based block copolymers. PMID:21235251

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.

Chain Reaction Polymerization.

ERIC Educational Resources Information Center

McGrath, James E.

1981-01-01

The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

Backbone degradable multiblock N-(2-hydroxypropyl)methacrylamide copolymer conjugates via reversible addition-fragmentation chain transfer polymerization and thiol-ene coupling reaction.

PubMed

Pan, Huaizhong; Yang, Jiyuan; Kopecková, Pavla; Kopecek, Jindrich

2011-01-10

Telechelic water-soluble HPMA copolymers and HPMA copolymer-doxorubicin (DOX) conjugates have been synthesized by RAFT polymerization mediated by a new bifunctional chain transfer agent (CTA) that contains an enzymatically degradable oligopeptide sequence. Postpolymerization aminolysis followed by chain extension with a bis-maleimide resulted in linear high molecular weight multiblock HPMA copolymer conjugates. These polymers are enzymatically degradable; in addition to releasing the drug (DOX), the degradation of the polymer backbone resulted in products with molecular weights similar to the starting material and below the renal threshold. The new multiblock HPMA copolymers hold potential as new carriers of anticancer drugs.

Generation of Synthetic Copolymer Libraries by Combinatorial Assembly on Nucleic Acid Templates.

PubMed

Kong, Dehui; Yeung, Wayland; Hili, Ryan

2016-07-11

Recent advances in nucleic acid-templated copolymerization have expanded the scope of sequence-controlled synthetic copolymers beyond the molecular architectures witnessed in nature. This has enabled the power of molecular evolution to be applied to synthetic copolymer libraries to evolve molecular function ranging from molecular recognition to catalysis. This Review seeks to summarize different approaches available to generate sequence-defined monodispersed synthetic copolymer libraries using nucleic acid-templated polymerization. Key concepts and principles governing nucleic acid-templated polymerization, as well as the fidelity of various copolymerization technologies, will be described. The Review will focus on methods that enable the combinatorial generation of copolymer libraries and their molecular evolution for desired function.

Performance impact of dynamic surface coatings on polymeric insulator-based dielectrophoretic particle separators.

PubMed

Davalos, Rafael V; McGraw, Gregory J; Wallow, Thomas I; Morales, Alfredo M; Krafcik, Karen L; Fintschenko, Yolanda; Cummings, Eric B; Simmons, Blake A

2008-02-01

Efficient and robust particle separation and enrichment techniques are critical for a diverse range of lab-on-a-chip analytical devices including pathogen detection, sample preparation, high-throughput particle sorting, and biomedical diagnostics. Previously, using insulator-based dielectrophoresis (iDEP) in microfluidic glass devices, we demonstrated simultaneous particle separation and concentration of various biological organisms, polymer microbeads, and viruses. As an alternative to glass, we evaluate the performance of similar iDEP structures produced in polymer-based microfluidic devices. There are numerous processing and operational advantages that motivate our transition to polymers such as the availability of numerous innate chemical compositions for tailoring performance, mechanical robustness, economy of scale, and ease of thermoforming and mass manufacturing. The polymer chips we have evaluated are fabricated through an injection molding process of the commercially available cyclic olefin copolymer Zeonor 1060R. This publication is the first to demonstrate insulator-based dielectrophoretic biological particle differentiation in a polymeric device injection molded from a silicon master. The results demonstrate that the polymer devices achieve the same performance metrics as glass devices. We also demonstrate an effective means of enhancing performance of these microsystems in terms of system power demand through the use of a dynamic surface coating. We demonstrate that the commercially available nonionic block copolymer surfactant, Pluronic F127, has a strong interaction with the cyclic olefin copolymer at very low concentrations, positively impacting performance by decreasing the electric field necessary to achieve particle trapping by an order of magnitude. The presence of this dynamic surface coating, therefore, lowers the power required to operate such devices and minimizes Joule heating. The results of this study demonstrate that iDEP polymeric microfluidic devices with surfactant coatings provide an affordable engineering strategy for selective particle enrichment and sorting.

Improved block copolymer domain dispersity on chemical patterns via homopolymer-blending and molecular transfer printing

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

Liu, Guoliang; Nealey, Paul F.

Herein we have investigated the domain width distributions of block copolymers and their ternary blends after directed assembly on chemically patterned surfaces with and without density multiplication. On chemical patterns with density multiplication, the width of the interpolated block copolymer domains was bimodal. Once blended with the corresponding homopolymers, the block copolymers exhibited unimodal distributions of domain width due to the redistribution of homopolymers in the block copolymer domains. When the block copolymers were blended with hydroxyl-terminated homopolymers, the homopolymers with functional end-groups healed the chemical patterns and facilitated the formation of nanostructures with further improved domain width distributions. Lastly,more » it is demonstrated that the block copolymers achieved the most improved domain width distributions when directed to assemble without density multiplication on one-to-one chemical patterns generated by molecular transfer printing.« less

Fluorescent polymeric micelles with aggregation-induced emission properties for monitoring the encapsulation of doxorubicin.

PubMed

Chen, Jen-Ing; Wu, Wen-Chung

2013-05-01

A new type of fluorescent polymeric micelles is developed by self-assembly from a series of amphiphilic block copolymers, poly(ethylene glycol)-b-poly[styrene-co-(2-(1,2,3,4,5-pentaphenyl-1H-silol-1-yloxy)ethyl methacrylate)] [PEG-b-P(S-co-PPSEMA)]. Their capability of loading doxorubicin (DOX) is investigated by monitoring the loading content, encapsulation efficiency, and photophysical properties of micelles. Förster resonance energy transfer from PPSEMA to DOX is observed in DOX-loaded micelles, which can serve as an indication of successful encapsulation of DOX in these micelles. The application of this new type of fluorescent polymeric micelles as a fluorescent probe and an anticancer drug carrier simultaneously is explored by studying the intracellular uptake of DOX-loaded micelles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct Synthesis of Polymer Nanotubes by Aqueous Dispersion Polymerization of a Cyclodextrin/Styrene Complex.

PubMed

Chen, Xi; Liu, Lei; Huo, Meng; Zeng, Min; Peng, Liao; Feng, Anchao; Wang, Xiaosong; Yuan, Jinying

2017-12-22

A one-step synthesis of nanotubes by RAFT dispersion polymerization of cyclodextrin/styrene (CD/St) complexes directly in water is presented. The resulted amphiphilic PEG-b-PS diblock copolymers self-assemble in situ into nanoparticles with various morphologies. Spheres, worms, lamellae, and nanotubes were controllably obtained. Because of the complexation, the swelling degree of polystyrene (PS) blocks by free St is limited, resulting in limited mobility of PS chains. Consequently, kinetically trapped lamellae and nanotubes were obtained instead of spherical vesicles. During the formation of nanotubes, small vesicles first formed at the ends of the tape-like lamellae, then grew and fused into nanotubes with a limited chain rearrangement. The introduction of a host-guest interaction based on CDs enables the aqueous dispersion polymerization of water-immiscible monomers, and produces kinetically trapped nanostructures, which could be a powerful technique for nanomaterials synthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

PubMed Central

Yeow, Jonathan; Xu, Jiangtao; Boyer, Cyrille

2016-01-01

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (λ = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology. PMID:27340940

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst.

PubMed

Yeow, Jonathan; Xu, Jiangtao; Boyer, Cyrille

2016-06-08

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (λ = 460 nm, 0.7 mW/cm(2)), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

21 CFR 175.210 - Acrylate ester copolymer coating.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylate ester copolymer coating. 175.210 Section... COATINGS Substances for Use as Components of Coatings § 175.210 Acrylate ester copolymer coating. Acrylate...) The acrylate ester copolymer is a fully polymerized copolymer of ethyl acrylate, methyl methacrylate...

Advanced Materials for PEM-Based Fuel Cell Systems

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

James E. McGrath

2005-10-26

Proton exchange membrane fuel cells (PEMFCs) are quickly becoming attractive alternative energy sources for transportation, stationary power, and small electronics due to the increasing cost and environmental hazards of traditional fossil fuels. Two main classes of PEMFCs include hydrogen/air or hydrogen/oxygen fuel cells and direct methanol fuel cells (DMFCs). The current benchmark membrane for both types of PEMFCs is Nafion, a perfluorinated sulfonated copolymer made by DuPont. Nafion copolymers exhibit good thermal and chemical stability, as well as very high proton conductivity under hydrated conditions at temperatures below 80 °C. However, application of these membranes is limited due to theirmore » high methanol permeability and loss of conductivity at high temperatures and low relative humidities. These deficiencies have led to the search for improved materials for proton exchange membranes. Potential PEMs should have good thermal, hydrolytic, and oxidative stability, high proton conductivity, selective permeability, and mechanical durability over long periods of time. Poly(arylene ether)s, polyimides, polybenzimidazoles, and polyphenylenes are among the most widely investigated candidates for PEMs. Poly(arylene ether)s are a promising class of proton exchange membranes due to their excellent thermal and chemical stability and high glass transition temperatures. High proton conductivity can be achieved through post-sulfonation of poly(arylene ether) materials, but this most often results in very high water sorption or even water solubility. Our research has shown that directly polymerized poly(arylene ether) copolymers show important advantages over traditional post-sulfonated systems and also address the concerns with Nafion membranes. These properties were evaluated and correlated with morphology, structure-property relationships, and states of water in the membranes. Further improvements in properties were achieved through incorporation of inorganic fillers, such as phosphotungstic acid and zirconium hydrogen phosphate. Block copolymers were also studied due to the possibility to achieve a desired combination of homopolymer properties as well as the unique morphologies that are possible with block copolymers. Bezoyl substituted poly(p-phenylene) blocks were combined with poly(arylene ether) blocks to merge the structural rigidity of the poly(p-phenylene) with the ductility and high protonic conductivity of the poly(arylene ether)s. As evidenced by our many refereed publications and preprints, the research that we have conducted over the past several years has made a valuable and significant contribution to the literature and to the state of understanding of proton exchange membranes. Our early efforts at scale-up have suggested that the directly polymerized disulfonated poly(arylene ether sulfone) copolymers are commercially viable alternatives for proton exchange membranes. A new process for bipolar plates was developed and is described. An important single domain PEMFC model was developed and is documented in this final report.« less

Block copolymer micelles with acid-labile ortho ester side-chains: Synthesis, characterization, and enhanced drug delivery to human glioma cells.

PubMed

Tang, Rupei; Ji, Weihang; Panus, David; Palumbo, R Noelle; Wang, Chun

2011-04-10

A new type of block copolymer micelles for pH-triggered delivery of poorly water-soluble anticancer drugs has been synthesized and characterized. The micelles were formed by the self-assembly of an amphiphilic diblock copolymer consisting of a hydrophilic poly(ethylene glycol) (PEG) block and a hydrophobic polymethacrylate block (PEYM) bearing acid-labile ortho ester side-chains. The diblock copolymer was synthesized by atom transfer radical polymerization (ATRP) from a PEG macro-initiator to obtain well-defined polymer chain-length. The PEG-b-PEYM micelles assumed a stable core-shell structure in aqueous buffer at physiological pH with a low critical micelle concentration as determined by proton NMR and pyrene fluorescence spectroscopy. The hydrolysis of the ortho ester side-chain at physiological pH was minimal yet much accelerated at mildly acidic pHs. Doxorubicin (Dox) was successfully loaded into the micelles at pH 7.4 and was released at a much higher rate in response to slight acidification to pH 5. Interestingly, the release of Dox at pH 5 followed apparently a biphasic profile, consisting of an initial fast phase of several hours followed by a sustained release period of several days. Dox loaded in the micelles was rapidly taken up by human glioma (T98G) cells in vitro, accumulating in the endolysosome and subsequently in the nucleus in a few hours, in contrast to the very low uptake of free drug at the same dose. The dose-dependent cytotoxicity of the Dox-loaded micelles was determined by the MTT assay and compared with that of the free Dox. While the empty micelles themselves were not toxic, the IC(50) values of the Dox-loaded micelles were approximately ten-times (by 24h) and three-times (by 48h) lower than the free drug. The much enhanced potency in killing the multi-drug-resistant human glioma cells by Dox loaded in the micelles could be attributed to high intracellular drug concentration and the subsequent pH-triggered drug release. These results establish the PEG-b-PEYM block copolymer with acid-labile ortho ester side-chains as a novel and effective pH-responsive nano-carrier for enhancing the delivery of drugs to cancer cells. Copyright © 2010 Elsevier B.V. All rights reserved.

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.

Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization of 4-Vinylbenzaldehyde

PubMed Central

Sun, Guorong; Cheng, Chong; Wooley, Karen L.

2008-01-01

The direct reversible addition fragmentation chain transfer (RAFT) polymerization of 4-vinylbenzaldehyde (VBA) was established as a new synthetic method for the preparation of well-defined poly(vinylbenzaldehyde) (PVBA), a polymer having reactive aldehyde side chain substiuents. RAFT polymerization of VBA was investigated using S-1-dodecyl-S’-(α,α’-dimethyl-α”-acetic acid)trithiocarbonate (DDMAT) as chain transfer agent (CTA) and 2,2′-azobis(isobutyronitrile) (AIBN) as initiator in 1,4-dioxane or 2-butanone at 70-75 °C for 7.5-22.5 h. With 45-76% of monomer conversion, the resulting PVBA had well controlled number-average molecular weight (Mn) and low polydispersity (PDI < 1.17). The living characteristic of the RAFT polymerization process was confirmed by the linearity between the Mn values of PVBA and monomer conversions. Well-defined PVBA was further used as a macromolecular chain transfer agent (macro-CTA) in RAFT polymerization of styrene (St), and a block copolymer PVBA-b-PSt with relatively low polydispersity (PDI = 1.20) was successfully synthesized. PMID:19066633

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.

Non-Surface Activity of Cationic Amphiphilic Diblock Copolymers

NASA Astrophysics Data System (ADS)

Ranjan Nayak, Rati; Yamada, Tasuku; Matsuoka, Hideki

2011-09-01

Cationic amphiphilic diblock copolymers containing quaternized poly (2-vinylpyridine) chain as a hydrophilic segment (PIp-b-PNMe2VP) were synthesized by living anionic polymerization. By IR measurement, we confirmed the quaternization of the polymer (PIp-b-PNMe2VP), and determined the degree of quaternization by conductometric titration. The surface tension experiment showed that the polymers are non-surface active in nature. The foam formation of the polymer solutions was also investigated with or without added salt. Almost no foam formation behavior was observed without added salt, while a little foam was observed in the presence of 1M NaCl. The critical micelle concentration (cmc) of the diblock copolymers with 3 different chain lengths was measured by the static light scattering method. The cmc values obtained in this study were much lower than the values obtained for anionic non-surface active diblock polymers studied previously. The hydrodynamic radii of the polymer micelle increased slightly in the presence of 1 M NaCl. The transmission electron microscopic images revealed spherical micelles in pure water. In the presence of salt, the cmc values increased as was the case for anionic polymers, which is unlike conventional surfactant systems but consistent with non-surface active anionic block copolymers. The microviscosity of the micelle core was evaluated using Coumarin-153 as a fluorescent anisotropy probe using steady-sate fluorescence depolarization. Non-surface activity has been proved to be universal for ionic amphiphilic block copolymers both for anionic and cationic. Hence, the origin of non-surface activity is not the charged state of water surface itself, but should be an image charge repulsion at the air/water interface.

Targeted polymeric micelles for siRNA treatment of experimental cancer by intravenous injection.

PubMed

Christie, R James; Matsumoto, Yu; Miyata, Kanjiro; Nomoto, Takahiro; Fukushima, Shigeto; Osada, Kensuke; Halnaut, Julien; Pittella, Frederico; Kim, Hyun Jin; Nishiyama, Nobuhiro; Kataoka, Kazunori

2012-06-26

Small interfering ribonucleic acid (siRNA) cancer therapies administered by intravenous injection require a delivery system for transport from the bloodstream into the cytoplasm of diseased cells to perform the function of gene silencing. Here we describe nanosized polymeric micelles that deliver siRNA to solid tumors and elicit a therapeutic effect. Stable multifunctional micelle structures on the order of 45 nm in size formed by spontaneous self-assembly of block copolymers with siRNA. Block copolymers used for micelle formation were designed and synthesized to contain three main features: a siRNA binding segment containing thiols, a hydrophilic nonbinding segment, and a cell-surface binding peptide. Specifically, poly(ethylene glycol)-block-poly(L-lysine) (PEG-b-PLL) comprising lysine amines modified with 2-iminothiolane (2IT) and the cyclo-Arg-Gly-Asp (cRGD) peptide on the PEG terminus was used. Modification of PEG-b-PLL with 2IT led to improved control of micelle formation and also increased stability in the blood compartment, while installation of the cRGD peptide improved biological activity. Incorporation of siRNA into stable micelle structures containing the cRGD peptide resulted in increased gene silencing ability, improved cell uptake, and broader subcellular distribution in vitro and also improved accumulation in both the tumor mass and tumor-associated blood vessels following intravenous injection into mice. Furthermore, stable and targeted micelles inhibited the growth of subcutaneous HeLa tumor models and demonstrated gene silencing in the tumor mass following treatment with antiangiogenic siRNAs. This new micellar nanomedicine could potentially expand the utility of siRNA-based therapies for cancer treatments that require intravenous injection.

Preparation and in vitro characterization of SN-38-loaded, self-forming polymeric depots as an injectable drug delivery system.

PubMed

Manaspon, Chawan; Hongeng, Suradej; Boongird, Atthaporn; Nasongkla, Norased

2012-10-01

This work describes the preparation and characterization of anticancer-loaded injectable polymeric depots that consisted of D,L-lactide (LA), ε-caprolactone (CL), and poly(ethylene glycol) (PEG) or [poly(ε-caprolactone)-random-poly(D,L-lactide)]-block-poly(ethylene glycol)-block-[poly(ε-caprolactone)-random-poly(D,L-lactide)] (PLEC) copolymers for malignant gliomas treatment. PLECs were polymerized with different percentages of LA to deliver 7-ethyl-10-hydroxycamptothecin (SN-38), a highly potent anticancer drug. SN-38-loaded depots could form directly in phosphate buffer saline with more than 98% encapsulation efficiency. The release rate of SN-38 from depots was found to depend on the amount of LA in PLECs, loading content of SN-38 in the depots, and depot weight. Encapsulation of SN-38 inside depots could enhance the stability of SN-38 where all of SN-38 released after 60 days was in an active form. Depots without SN-38 were evaluated as noncytotoxic against U-87MG, whereas SN-38-loaded depots showed cytotoxic effect as a function of concentration. Copyright © 2012 Wiley Periodicals, Inc.

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

PubMed Central

2012-01-01

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

Adsorption of Small Cationic Nanoparticles onto Large Anionic Particles from Aqueous Solution: A Model System for Understanding Pigment Dispersion and the Problem of Effective Particle Density.

PubMed

North, S M; Jones, E R; Smith, G N; Mykhaylyk, O O; Annable, T; Armes, S P

2017-02-07

The present study focuses on the use of copolymer nanoparticles as a dispersant for a model pigment (silica). Reversible addition-fragmentation chain transfer (RAFT) alcoholic dispersion polymerization was used to synthesize sterically stabilized diblock copolymer nanoparticles. The steric stabilizer block was poly(2-(dimethylamino)ethyl methacrylate) (PDMA) and the core-forming block was poly(benzyl methacrylate) (PBzMA). The mean degrees of polymerization for the PDMA and PBzMA blocks were 71 and 100, respectively. Transmission electron microscopy (TEM) studies confirmed a near-monodisperse spherical morphology, while dynamic light scattering (DLS) studies indicated an intensity-average diameter of 30 nm. Small-angle X-ray scattering (SAXS) reported a volume-average diameter of 29 ± 0.5 nm and a mean aggregation number of 154. Aqueous electrophoresis measurements confirmed that these PDMA 71 -PBzMA 100 nanoparticles acquired cationic character when transferred from ethanol to water as a result of protonation of the weakly basic PDMA chains. Electrostatic adsorption of these nanoparticles from aqueous solution onto 470 nm silica particles led to either flocculation at submonolayer coverage or steric stabilization at or above monolayer coverage, as judged by DLS. This technique indicated that saturation coverage was achieved on addition of approximately 465 copolymer nanoparticles per silica particle, which corresponds to a fractional surface coverage of around 0.42. These adsorption data were corroborated using thermogravimetry, UV spectroscopy and X-ray photoelectron spectroscopy. TEM studies indicated that the cationic nanoparticles remained intact on the silica surface after electrostatic adsorption, while aqueous electrophoresis confirmed that surface charge reversal occurred below pH 7. The relatively thick layer of adsorbed nanoparticles led to a significant reduction in the effective particle density of the silica particles from 1.99 g cm -3 to approximately 1.74 g cm -3 , as judged by disk centrifuge photosedimentometry (DCP). Combining the DCP and SAXS data suggests that essentially no deformation of the PBzMA cores occurs during nanoparticle adsorption onto the silica particles.

Directed self assembly of block copolymers using chemical patterns with sidewall guiding lines, backfilled with random copolymer brushes.

PubMed

Pandav, Gunja; Durand, William J; Ellison, Christopher J; Willson, C Grant; Ganesan, Venkat

2015-12-21

Recently, alignment of block copolymer domains has been achieved using a topographically patterned substrate with a sidewall preferential to one of the blocks. This strategy has been suggested as an option to overcome the patterning resolution challenges facing chemoepitaxy strategies, which utilize chemical stripes with a width of about half the period of block copolymer to orient the equilibrium morphologies. In this work, single chain in mean field simulation methodology was used to study the self assembly of symmetric block copolymers on topographically patterned substrates with sidewall interactions. Random copolymer brushes grafted to the background region (space between patterns) were modeled explicitly. The effects of changes in pattern width, film thicknesses and strength of sidewall interaction on the resulting morphologies were examined and the conditions which led to perpendicular morphologies required for lithographic applications were identified. A number of density multiplication schemes were studied in order to gauge the efficiency with which the sidewall pattern can guide the self assembly of block copolymers. The results indicate that such a patterning technique can potentially utilize pattern widths of the order of one-two times the period of block copolymer and still be able to guide ordering of the block copolymer domains up to 8X density multiplication.

21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Poly-1-butene resins and butene/ethylene copolymers... resins and butene/ethylene copolymers. The poly-1-butene resins and butene/ethylene copolymers identified... the catalytic polymerization of 1-butene liquid monomer. Butene/ethylene copolymers are produced by...

Polymeric microcapsules assembled from a cationic/zwitterionic pair of responsive block copolymer micelles.

PubMed

Addison, Timothy; Cayre, Olivier J; Biggs, Simon; Armes, Steven P; York, David

2010-05-04

Using a layer-by-layer (LbL) approach, this work presents the preparation of hollow microcapsules with a membrane constructed entirely from a cationic/zwitterionic pair of pH-responsive block copolymer micelles. Our previous work with such systems highlighted that, in order to retain the responsive nature of the individual micelles contained within the multilayer membranes, it is important to optimize the conditions required for the selective dissolution of the sacrificial particulate templates. Consequently, here, calcium carbonate particles have been employed as colloidal templates as they can be easily dissolved in aqueous environments with the addition of chelating agents such as ethylenediaminetetraacetic acid (EDTA). Furthermore, the dissolution can be carried out in solutions buffered to a desirable pH so not to adversely affect the pH sensitive micelles forming the capsule membranes. First, we have deposited alternating layers of anionic poly[2-(dimethylamino)ethyl methacrylate-block-poly(2-(diethylamino)ethyl methacrylate)] (PDMA-PDEA) and cationic poly(2-(diethylamino)ethyl)methacrylate-block-poly(methacrylic acid) (PDEA-PMAA) copolymer micelles onto calcium carbonate colloidal templates. After deposition of five micelle bilayers, addition of dilute EDTA solution resulted in dissolution of the calcium carbonate and formation of hollow polymer capsules. The capsules were imaged using atomic force microscopy (AFM) and scanning electron microscopy (SEM), which shows that the micelle/micelle membrane is sufficiently robust to withstand dissolution of the supporting template. Quartz crystal microbalance studies were conducted and provide good evidence that the micelle multilayer structure is retained after EDTA treatment. In addition, a hydrophobic dye was incorporated into the micelle cores prior to adsorption. After dissolution of the particle template, the resulting hollow capsules retained a high concentration of dye, suggesting that the core/shell structure of the micelles remains intact. Finally, thermogravimetric analysis (TGA) of dried capsules confirmed complete removal of the sacrificial inorganic template. As far as we are aware, this is the first demonstration of LbL assembled capsules composed entirely from responsive block copolymer micelles. The results presented here when combined with our previous findings demonstrate that such systems have potential application in the encapsulation and triggered release of actives.

RAFT Dispersion Alternating Copolymerization of Styrene with N-Phenylmaleimide: Morphology Control and Application as an Aqueous Foam Stabilizer

PubMed Central

2016-01-01

We report a new nonaqueous polymerization-induced self-assembly (PISA) formulation based on the reversible addition–fragmentation chain transfer (RAFT) dispersion alternating copolymerization of styrene with N-phenylmaleimide using a nonionic poly(N,N-dimethylacrylamide) stabilizer in a 50/50 w/w ethanol/methyl ethyl ketone (MEK) mixture. The MEK cosolvent is significantly less toxic than the 1,4-dioxane cosolvent reported previously [YangP.; Macromolecules2013, 46, 8545−8556]. The core-forming alternating copolymer block has a relatively high glass transition temperature (Tg), which leads to vesicular morphologies being observed during PISA, as well as the more typical sphere and worm phases. Each of these copolymer morphologies has been characterized by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies. TEM studies reveal micrometer-sized elliptical particles with internal structure, with SAXS analysis suggesting an oligolamellar vesicle morphology. This structure differs from that previously reported for a closely related PISA formulation utilizing a poly(methacrylic acid) stabilizer block for which unilamellar platelet-like particles are observed by TEM and SAXS. This suggests that interlamellar interactions are governed by the nature of the steric stabilizer layer. Moreover, using the MEK cosolvent also enables access to a unilamellar vesicular morphology, despite the high Tg of the alternating copolymer core-forming block. This was achieved by simply conducting the PISA synthesis at a higher temperature for a longer reaction time (80 °C for 24 h). Presumably, MEK solvates the core-forming block more than the previously utilized 1,4-dioxane cosolvent, which leads to greater chain mobility. Finally, preliminary experiments indicate that the worms are much more efficient stabilizers for aqueous foams than either the spheres or the oligolamellar elliptical vesicles. PMID:27708458

Palladium (II) catalyized polymerization of norbornene and acrylates

DOEpatents

Sen, Ayusman; Kacker, Smita; Hennis, April; Polley, Jennifer D.

2000-08-29

Homopolymers or copolymers of acrylates, homopolymers or copolymers of norbornenes, and copolymers of acrylates with norbornenes, may be prepared by contacting acrylate and/or norbornene monomer reactant under polymerization conditions and in the presence of a solvent with a catalyst system consisting essentially of a Pd(II) dimer component having the formula: [(L)Pd(R)(X)].sub.2, where L is a monodentate phosphorus or nitrogen ligand, X is an anionic group, and R is an alkyl or aryl group.

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.

Synthesis and Characterization of a Poly(ethylene glycol)-Poly(simvastatin) Diblock Copolymer

PubMed Central

Asafo-Adjei, Theodora A.; Dziubla, Thomas D.; Puleo, David A.

2014-01-01

Biodegradable polyesters are commonly used as drug delivery vehicles, but their role is typically passive, and encapsulation approaches have limited drug payload. An alternative drug delivery method is to polymerize the active agent or its precursor into a degradable polymer. The prodrug simvastatin contains a lactone ring that lends itself to ring-opening polymerization (ROP). Consequently, simvastatin polymerization was initiated with 5 kDa monomethyl ether poly(ethylene glycol) (mPEG) and catalyzed via stannous octoate. Melt condensation reactions produced a 9.5 kDa copolymer with a polydispersity index of 1.1 at 150 °C up to a 75 kDa copolymer with an index of 6.9 at 250 °C. Kinetic analysis revealed first-order propagation rates. Infrared spectroscopy of the copolymer showed carboxylic and methyl ether stretches unique to simvastatin and mPEG, respectively. Slow degradation was demonstrated in neutral and alkaline conditions. Lastly, simvastatin, simvastatin-incorporated molecules, and mPEG were identified as the degradation products released. The present results show the potential of using ROP to polymerize lactone-containing drugs such as simvastatin. PMID:25431653

Determining the Effective Density and Stabilizer Layer Thickness of Sterically Stabilized Nanoparticles

PubMed Central

2016-01-01

A series of model sterically stabilized diblock copolymer nanoparticles has been designed to aid the development of analytical protocols in order to determine two key parameters: the effective particle density and the steric stabilizer layer thickness. The former parameter is essential for high resolution particle size analysis based on analytical (ultra)centrifugation techniques (e.g., disk centrifuge photosedimentometry, DCP), whereas the latter parameter is of fundamental importance in determining the effectiveness of steric stabilization as a colloid stability mechanism. The diblock copolymer nanoparticles were prepared via polymerization-induced self-assembly (PISA) using RAFT aqueous emulsion polymerization: this approach affords relatively narrow particle size distributions and enables the mean particle diameter and the stabilizer layer thickness to be adjusted independently via systematic variation of the mean degree of polymerization of the hydrophobic and hydrophilic blocks, respectively. The hydrophobic core-forming block was poly(2,2,2-trifluoroethyl methacrylate) [PTFEMA], which was selected for its relatively high density. The hydrophilic stabilizer block was poly(glycerol monomethacrylate) [PGMA], which is a well-known non-ionic polymer that remains water-soluble over a wide range of temperatures. Four series of PGMAx–PTFEMAy nanoparticles were prepared (x = 28, 43, 63, and 98, y = 100–1400) and characterized via transmission electron microscopy (TEM), dynamic light scattering (DLS), and small-angle X-ray scattering (SAXS). It was found that the degree of polymerization of both the PGMA stabilizer and core-forming PTFEMA had a strong influence on the mean particle diameter, which ranged from 20 to 250 nm. Furthermore, SAXS was used to determine radii of gyration of 1.46 to 2.69 nm for the solvated PGMA stabilizer blocks. Thus, the mean effective density of these sterically stabilized particles was calculated and determined to lie between 1.19 g cm–3 for the smaller particles and 1.41 g cm–3 for the larger particles; these values are significantly lower than the solid-state density of PTFEMA (1.47 g cm–3). Since analytical centrifugation requires the density difference between the particles and the aqueous phase, determining the effective particle density is clearly vital for obtaining reliable particle size distributions. Furthermore, selected DCP data were recalculated by taking into account the inherent density distribution superimposed on the particle size distribution. Consequently, the true particle size distributions were found to be somewhat narrower than those calculated using an erroneous single density value, with smaller particles being particularly sensitive to this artifact. PMID:27478250

The influence of chain rigidity and the degree of sulfonation on the morphology of block copolymers as nano reactor

NASA Astrophysics Data System (ADS)

Hong, K.; Zhang, X.

2005-03-01

Polyelectrolyte block copolymer was used to form an ordered domain of ionic block as a ``nanoreactor'' due to its ability to bind oppositely charged metal ion, Zn^2+, Fe^2+ etc. The purpose of our research is to investigate the controllability of the size and morphology of domains (inorganic nano particles) by changing backbone stiffness, the charge density and the volume fraction of ionic block. Poly(styrene sulfonate) (PSS), which backbone is flexible, and poly(cyclohexadiene sulfonate) (PCHDS), which backbone is ``semiflexible'', were used as ionic blocks. We synthesized PtBS-PSS and PS-PCHDS with various degree of sulfonation and the volume fraction. Zinc oxide (ZnO) nano particles successfully formed in the ionic domain of microphase separated block copolymers. We used SANS to characterize the morphology of block copolymers and TEM for block copolymer containing ZnO nano particles. Our experimental results show that the chemistry of ``sulfonation'' of block copolymers can be successfully used to synthesize nano composite materials.

Polyazidoesters as Energetic Polymers and Copolymer Components with Fluoro Derivatives.

DTIC Science & Technology

1988-04-13

i. 0, ’C b" U’. I’. ’- Unclasifie 4)1II FILE COP~Y 4 S’ 9 2 . 1E 0_ UMENTATION PAGE Unclassified _____________________ AD-A 194 236 ER’ESQRDtX. 8S - 0...TASK WORK jNir Bolling AFB, D.C. 2033 2 -6448 a LEMINT NO NO. No NO is riri E’ /,elun~de Sircu..I Clomllti~oI Pol azidon ters as 2303 B2 Emrgf Pol mr...which undergoes polymerization. Specifically 4,4’- diazidodiphenylkelene (1) was ozonized at -780 C to yield 2 , which spontaneously polymerized to yield

Maltopentaose-conjugated CTA for RAFT polymerization generating nanostructured bioresource-block copolymer.

PubMed

Togashi, Daichi; Otsuka, Issei; Borsali, Redouane; Takeda, Koichi; Enomoto, Kazushi; Kawaguchi, Seigou; Narumi, Atsushi

2014-12-08

We now describe the synthesis of a new family of oligosaccharide-conjugated functional molecules, which act as chain transfer agents (CTAs) for the reversible addition-fragmentation chain transfer (RAFT) polymerization. The synthesis was started from the catalyst-free direct N-glycosyl reaction of 5-azidopentylamine onto maltopentaose (Mal5) in dry methanol at room temperature and subsequent N-protected reaction with acetic anhydride, producing a stable oligosaccharide-building block, such as Mal5 with an azidopentyl group (Mal5-N3). The azido group was hydrogenated using platinum dioxide (PtO2) as a catalyst to give Mal5 with aminopentyl group (Mal5-NH2), which was then reacted with CTA molecules bearing activated ester moieties. These reactions produced Mal5-modified macro-CTAs (Mal5-CTAs, 1), which were used for the RAFT polymerizations of styrene (St) and methyl methacrylate (MMA) in DMF. The polymerizations were performed using the [M]0/[1]0 values ranging from 50 to 600, affording the Mal5-hybrid amphiphilic block copolymers (BCPs), such as Mal5-polystyrene (2) and Mal5-poly(methyl methacrylate) (3), with a quantitative end-functionality and the controlled molecular weights between 4310 and 20 300 g mol(-1). The small-angle X-ray scattering (SAXS) measurements were accomplished for 2 and 3 to ensure their abilities to form phase separated structures in their bulk states with the increasing temperatures from 30 to 190 °C. The featured results were observed for 2 (ϕMal5 = 0.14) and 3 (ϕMal5 = 0.16) at temperatures above 100 °C, where ϕMal5 denotes the volume fraction of the Mal5 unit in the BCP sample. For both BCP samples, the primary scattering peaks q* were clearly observed together with the higher-ordered scattering peaks √2q* and √3q*. Thus, these Mal5-hybrid amphiphilic BCP samples have a body centered cubic (BCC) phase morphology. The domain spacing (d) values of the BCC morphology for 2 (ϕMal5 = 0.14) and 3 (ϕMal5 = 0.16) were 10.4 and 9.55 nm, respectively, which were determined using Bragg's relation (d = 2π/q*). The present RAFT agents were shown to eventually provide the phase separated structural polymeric materials in which 5.4 nm bioresource-spherical domains were periodically arrayed at the interval of about 10 nm.

Stereoregular polyacrylamide and its copolymer brushes: Preparation and surface characters

NASA Astrophysics Data System (ADS)

Jiang, Jianguo; Wang, Xiaoshu; Lu, Xiaoyan; Lu, Yun

2008-12-01

Two kinds of polymer brushes, the single one with stereospecific polyacrylamide (PAAM) chains and the dual-component one with random poly(methyl methacrylate) (PMMA) segments grafting from stereospecific PAAM chains, were prepared on silicon wafer for the first time by combining the immobilization of initiator and the stereospecific living radical in situ polymerization. With the addition of the Lewis acid AlCl 3 into the polymerization system, the PAAM brushes obtained exhibited an increased stereospecificity as well as a decreased hydrophilicity, which might attribute to the reduced thickness of PAAM brushes on the silicon wafer and the handicap of the free rotation of the stereospecific molecular chain. The smoother surface morphology of the stereospecific PAAM brushes shown in AFM images was in good agreement with the experimental data of water contact angle. Also, block amphiphilic copolymer brushes were prepared with the stereospecific PAAM formed first on silicon wafer as the anchored-initiator and revealed a novel surface self-assembly behavior after being treated with different solvent such as toluene or water. The stereospecificity of PAAM chains in the polymer brushes could be modulated by adjusting reaction conditions according to the requirement of applications for surface hydrophilicity.

Synthesis and Characterization of Stimuli-Responsive Star-Like Polypept(o)ides: Introducing Biodegradable PeptoStars.

PubMed

Holm, Regina; Weber, Benjamin; Heller, Philipp; Klinker, Kristina; Westmeier, Dana; Docter, Dominic; Stauber, Roland H; Barz, Matthias

2017-06-01

Star-like polymers are one of the smallest systems in the class of core crosslinked polymeric nanoparticles. This article reports on a versatile, straightforward synthesis of three-arm star-like polypept(o)ide (polysarcosine-block-polylysine) polymers, which are designed to be either stable or degradable at elevated levels of glutathione. Polypept(o)ides are a recently introduced class of polymers combining the stealth-like properties of the polypeptoid polysarcosine with the functionality of polypeptides, thus enabling the synthesis of materials completely based on endogenous amino acids. The star-like homo and block copolymers are synthesized by living nucleophilic ring opening polymerization of the corresponding N-carboxyanhydrides (NCAs) yielding polymeric stars with precise control over the degree of polymerization (X n = 25, 50, 100), Poisson-like molecular weight distributions, and low dispersities (Đ = 1.06-1.15). Star-like polypept(o)ides display a hydrodynamic radius of 5 nm (μ 2 < 0.05) as determined by dynamic light scattering (DLS). While star-like polysarcosines and polypept(o)ides based on disulfide containing initiators are stable in solution, degradation occurs at 100 × 10 -3 m glutathione concentration. The disulfide cleavage yields the respective polymeric arms, which possess Poisson-like molecular weight distributions and low dispersities (Đ = 1.05-1.12). Initial cellular uptake and toxicity studies reveal that PeptoStars are well tolerated by HeLa, HEK 293, and DC 2.4 cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tailoring charge density and hydrogen bonding of imidazolium copolymers for efficient gene delivery.

PubMed

Allen, Michael H; Green, Matthew D; Getaneh, Hiwote K; Miller, Kevin M; Long, Timothy E

2011-06-13

Conventional free radical polymerization with subsequent postpolymerization modification afforded imidazolium copolymers with controlled charge density and side chain hydroxyl number. Novel imidazolium-containing copolymers where each permanent cation contained one or two adjacent hydroxyls allowed precise structure-transfection efficiency studies. The degree of polymerization was identical for all copolymers to eliminate the influence of molecular weight on transfection efficiency. DNA binding, cytotoxicity, and in vitro gene transfection in African green monkey COS-7 cells revealed structure-property-transfection relationships for the copolymers. DNA gel shift assays indicated that higher charge densities and hydroxyl concentrations increased DNA binding. As the charge density of the copolymers increased, toxicity of the copolymers also increased; however, as hydroxyl concentration increased, cytotoxicity remained constant. Changing both charge density and hydroxyl levels in a systematic fashion revealed a dramatic influence on transfection efficiency. Dynamic light scattering of the polyplexes, which were composed of copolymer concentrations required for the highest luciferase expression, showed an intermediate DNA-copolymer binding affinity. Our studies supported the conclusion that cationic copolymer binding affinity significantly impacts overall transfection efficiency of DNA delivery vehicles, and the incorporation of hydroxyl sites offers a less toxic and effective alternative to more conventional highly charged copolymers.

In-situ Polymerization of Polyaniline/Polypyrrole Copolymer using Different Techniques

NASA Astrophysics Data System (ADS)

Hammad, A. S.; Noby, H.; Elkady, M. F.; El-Shazly, A. H.

2018-01-01

The morphology and surface area of the poly(aniline-co-pyrrole) copolymer (PANPY) are important properties which improve the efficiency of the copolymer in various applications. In this investigation, different techniques were employed to produce PANPY in different morphologies. Aniline and pyrrole were used as monomers, and ammonium peroxydisulfate (APS) was used as an oxidizer with uniform molar ratio. Rapid mixing, drop-wise mixing, and supercritical carbon dioxide (ScCO2) polymerization techniques were appointed. The chemical structure, crystallinity, porosity, and morphology of the composite were distinguished by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Brunauer, Emmett and Teller (BET) analysis, and transmission electron microscopy (TEM) respectively. The characterization tests indicated that the polyaniline/polypyrrole copolymer was successfully prepared with different morphologies. Based on the obtained TEM, hollow nanospheres were formed using rapid mixing technique with acetic acid that have a diameter of 75 nm and thickness 26 nm approximately. Also, according to the XRD, the produced structures have a semi- crystalline structure. The synthesized copolymer with ScCO2-assisted polymerization technique showed improved surface area (38.1 m2/g) with HCl as dopant.

Development of zwitterionic sulfobetaine block copolymer conjugation strategies for reduced platelet deposition in respiratory assist devices.

PubMed

Malkin, Alexander D; Ye, Sang-Ho; Lee, Evan J; Yang, Xiguang; Zhu, Yang; Gamble, Lara J; Federspiel, William J; Wagner, William R

2018-02-09

Respiratory assist devices, that utilize ∼2 m 2 of hollow fiber membranes (HFMs) to achieve desired gas transfer rates, have been limited in their adoption due to such blood biocompatibility limitations. This study reports two techniques for the functionalization and subsequent conjugation of zwitterionic sulfobetaine (SB) block copolymers to polymethylpentene (PMP) HFM surfaces with the intention of reducing thrombus formation in respiratory assist devices. Amine or hydroxyl functionalization of PMP HFMs (PMP-A or PMP-H) was accomplished using plasma-enhanced chemical vapor deposition. The generated functional groups were conjugated to low molecular weight SB block copolymers with N-hydroxysuccinimide ester or siloxane groups (SBNHS or SBNHSi) that were synthesized using reversible addition fragmentation chain transfer polymerization. The modified HFMs (PMP-A-SBNHS or PMP-H-SBNHSi) showed 80-95% reduction in platelet deposition from whole ovine blood, stability under the fluid shear of anticipated operating conditions, and uninhibited gas exchange performance relative to non-modified HFMs (PMP-C). Additionally, the functionalization and SBNHSi conjugation technique was shown to reduce platelet deposition on polycarbonate and poly(vinyl chloride), two other materials commonly found in extracorporeal circuits. The observed thromboresistance and stability of the SB modified surfaces, without degradation of HFM gas transfer performance, indicate that this approach is promising for longer term pre-clinical testing in respiratory assist devices and may ultimately allow for the reduction of anticoagulation levels in patients being supported for extended periods. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2018. © 2018 Wiley Periodicals, Inc.

Imide/arylene ether copolymers

NASA Technical Reports Server (NTRS)

Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor)

1992-01-01

Imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly(arylene ethers) in polar aprotic solvents and by chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The resulting block copolymers have one glass transition temperature or two, depending upon the particular structure and/or the compatibility of the block units. Most of these block copolymers form tough, solvent resistant films with high tensile properties.

Salt-Induced Block Copolymer Micelles as Nanoreactors for the Formation of CdS Nanoparticles

DTIC Science & Technology

2001-11-01

or corona of micelles is presented. Poly(styrene-block-2-vinylpyridine) ( PS - b - P2VP ) and cadmium ions form aggregates of single micelles, called...ratio and block copolymer concentration in THF etc. EXPERIMENTAL DETAILS The synthesis of the PS - b - P2VP block copolymer was performed using sequential...nanoparticles: PS - b - P2VP block copolymer was dissolved in THF at different concentrations under vigorous stirring for 1 hour. Cd(Ac)2.2H 20 dissolved in a

Fast annealing DSA materials designed for sub-5 nm resolution

NASA Astrophysics Data System (ADS)

Deng, Hai; Li, Xuemiao; Peng, Yu; Zhou, Jianuo

2018-03-01

In recent years, high-χ block copolymers (BCPs) have been reported to achieve sub-5 nm resolution. These BCPs always require long annealing time at high annealing temperature, which may limit their implementation into semiconductor process. Since hot baking time in conventional semiconductor process is normally less than 3 minutes, how to shorter the thermal annealing time at lower temperature becomes a new topic for the sub-5 nm high-χ BCPs. In this manuscript, various fluoro-containing BCPs are synthesized by living anionic polymerization or atom transfer radical polymerization. The best BCP formed thermal equilibrium sub-5 nm nano domains after mere 1 min annealing at temperature lower than 100 °C, which is the fastest thermal annealing process reported so far. BCPs with various morphology and domain size are obtained by precise control of both the length and the molar ratio of the two blocks. The resulted smallest half-pitch of the BCPs are less than 5 nm in lamella and hexagonal morphologies. Linear and starshaped BCPs containing PMMA and fluoro-block are also synthesized, which also shows best phase separation into ca. 6 nm half-pitch, however, the annealing time is 1 hour at 180 °C.

Grafting of poly[(methyl methacrylate)-block-styrene] onto cellulose via nitroxide-mediated polymerization, and its polymer/clay nanocomposite.

PubMed

Karaj-Abad, Saber Ghasemi; Abbasian, Mojtaba; Jaymand, Mehdi

2016-11-05

For the first time, nitroxide-mediated polymerization (NMP) was used for synthesis of graft and block copolymers using cellulose (Cell) as a backbone, and polystyrene (PSt) and poly(methyl metacrylate) (PMMA) as the branches. For this purpose, Cell was acetylated by 2-bromoisobutyryl bromide (BrBiB), and then the bromine group was converted to 4-oxy-2,2,6,6-tetramethylpiperidin-1-oxyl group by a substitution nucleophilic reaction to afford a macroinitiator (Cell-TEMPOL). The macroinitiator obtained was subsequently used in controlled graft and block copolymerizations of St and MMA monomers to yield Cell-g-PSt and Cell-g-(PMMA-b-PSt). The chemical structures of all samples as representatives were characterized by FTIR and (1)H NMR spectroscopies. In addition, Cell-g-(PMMA-b-PSt)/organophilic montmorillonite nanocomposite was prepared through a solution intercalation method. TEM was used to evaluate the morphological behavior of the polymer-clay system. It was demonstrated that the addition of small percent of organophilic montmorillonite (O-MMT; 3wt.%) was enough to improve the thermal stability of the nanocomposite. Copyright © 2016 Elsevier Ltd. All rights reserved.

Microbial production of polyhydroxyalkanoate block copolymer by recombinant Pseudomonas putida.

PubMed

Li, Shi Yan; Dong, Cui Ling; Wang, Shen Yu; Ye, Hai Mu; Chen, Guo-Qiang

2011-04-01

Polyhydroxyalkanoate (PHA) synthesis genes phaPCJ(Ac) cloned from Aeromonas caviae were transformed into Pseudomonas putida KTOY06ΔC, a mutant of P. putida KT2442, resulting in the ability of the recombinant P. putida KTOY06ΔC (phaPCJ(A.c)) to produce a short-chain-length and medium-chain-length PHA block copolymer consisting of poly-3-hydroxybutyrate (PHB) as one block and random copolymer of 3-hydroxyvalerate (3HV) and 3-hydroxyheptanoate (3HHp) as another block. The novel block polymer was studied by differential scanning calorimetry (DSC), nuclear magnetic resonance, and rheology measurements. DSC studies showed the polymer to possess two glass transition temperatures (T(g)), one melting temperature (T(m)) and one cool crystallization temperature (T(c)). Rheology studies clearly indicated a polymer chain re-arrangement in the copolymer; these studies confirmed the polymer to be a block copolymer, with over 70 mol% homopolymer (PHB) of 3-hydroxybutyrate (3HB) as one block and around 30 mol% random copolymers of 3HV and 3HHp as the second block. The block copolymer was shown to have the highest tensile strength and Young's modulus compared with a random copolymer with similar ratio and a blend of homopolymers PHB and PHVHHp with similar ratio. Compared with other commercially available PHA including PHB, PHBV, PHBHHx, and P3HB4HB, the short-chain- and medium-chain-length block copolymer PHB-b-PHVHHp showed differences in terms of mechanical properties and should draw more attentions from the PHA research community. © Springer-Verlag 2010

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.

Nanocomposites from Stable Dispersions of Carbon Nanotubes in Polymeric Matrices Using Dispersion Interaction

NASA Technical Reports Server (NTRS)

Wise, Kristopher Eric (Inventor); Park, Cheol (Inventor); Kang, Jin Ho (Inventor); Siochi, Emilie J. (Inventor); Harrison, Joycelyn S. (Inventor)

2016-01-01

Stable dispersions of carbon nanotubes (CNTs) in polymeric matrices include CNTs dispersed in a host polymer or copolymer whose monomers have delocalized electron orbitals, so that a dispersion interaction results between the host polymer or copolymer and the CNTs dispersed therein. Nanocomposite products, which are presented in bulk, or when fabricated as a film, fiber, foam, coating, adhesive, paste, or molding, are prepared by standard means from the present stable dispersions of CNTs in polymeric matrices, employing dispersion interactions, as presented hereinabove.

Renormalization of the one-loop theory of fluctuations in polymer blends and diblock copolymer melts.

PubMed

Grzywacz, Piotr; Qin, Jian; Morse, David C

2007-12-01

Attempts to use coarse-grained molecular theories to calculate corrections to the random-phase approximation (RPA) for correlations in polymer mixtures have been plagued by an unwanted sensitivity to the value of an arbitrary cutoff length, i.e., by an ultraviolet (UV) divergence. We analyze the UV divergence of the inverse structure factor S(-1)(k) predicted by a "one-loop" approximation similar to that used in several previous studies. We consider both miscible homopolymer blends and disordered diblock copolymer melts. We show, in both cases, that all UV divergent contributions can be absorbed into a renormalization of the values of the phenomenological parameters of a generalized self-consistent field theory (SCFT). This observation allows the construction of an UV convergent theory of corrections to SCFT phenomenology. The UV-divergent one-loop contribution to S(-1)(k) is shown to be the sum of (i) a k -independent contribution that arises from a renormalization of the effective chi parameter, (ii) a k-dependent contribution that arises from a renormalization of monomer statistical segment lengths, (iii) a contribution proportional to k(2) that arises from a square-gradient contribution to the one-loop fluctuation free energy, and (iv) a k-dependent contribution that is inversely proportional to the degree of polymerization, which arises from local perturbations in fluid structure near chain ends and near junctions between blocks in block copolymers.

Imide/arylene ether block copolymers

NASA Technical Reports Server (NTRS)

Jensen, B. J.; Hergenrother, P. M.; Bass, R. G.

1991-01-01

Two series of imide/arylene either block copolymers were prepared using an arylene ether block and either an amorphous or semi-crystalline imide block. The resulting copolymers were characterized and selected physical and mechanical properties were determined. These results, as well as comparisons to the homopolymer properties, are discussed.

Molecular origin of photovoltaic performance in donor- block-acceptor all-conjugated block copolymers

DOE PAGES

Smith, Kendall A.; Lin, Yen -Hao; Mok, Jorge W.; ...

2015-11-03

All-conjugated block copolymers may be an effective route to self-assembled photovoltaic devices, but we lack basic information on the relationship between molecular characteristics and photovoltaic performance. Here, we synthesize a library of poly(3-hexylthiophene) (P3HT) block poly((9,9-dialkylfluorene)-2,7-diyl-alt-[4,7-bis(alkylthiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT) donor- block-acceptor all-conjugated block copolymers and carry out a comprehensive study of processing conditions, crystallinity, domain sizes, and side-chain structure on photovoltaic device performance. We find that all block copolymers studied exhibit an out-of-plane crystal orientation after deposition, and on thermal annealing at high temperatures the crystal orientation flips to an in-plane orientation. By varying processing conditions on polymer photovoltaic devices, we showmore » that the crystal orientation has only a modest effect (15-20%) on photovoltaic performance. The addition of side-chains to the PFTBT block is found to decrease photovoltaic power conversion efficiencies by at least an order of magnitude. Through grazing-incidence X-ray measurements we find that the addition of side-chains to the PFTBT acceptor block results in weak segregation and small (< 10 nm) block copolymer self-assembled donor and acceptor domains. This work is the most comprehensive to date on all-conjugated block copolymer systems and suggests that photovoltaic performance of block copolymers depends strongly on the miscibility of donor and acceptor blocks, which impacts donor and acceptor domain sizes and purity. Lastly, strategies for improving the device performance of block copolymer photovoltaics should seek to increase segregation between donor and acceptor polymer domains.« less

Molecular origin of photovoltaic performance in donor- block-acceptor all-conjugated block copolymers

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

Smith, Kendall A.; Lin, Yen -Hao; Mok, Jorge W.

All-conjugated block copolymers may be an effective route to self-assembled photovoltaic devices, but we lack basic information on the relationship between molecular characteristics and photovoltaic performance. Here, we synthesize a library of poly(3-hexylthiophene) (P3HT) block poly((9,9-dialkylfluorene)-2,7-diyl-alt-[4,7-bis(alkylthiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT) donor- block-acceptor all-conjugated block copolymers and carry out a comprehensive study of processing conditions, crystallinity, domain sizes, and side-chain structure on photovoltaic device performance. We find that all block copolymers studied exhibit an out-of-plane crystal orientation after deposition, and on thermal annealing at high temperatures the crystal orientation flips to an in-plane orientation. By varying processing conditions on polymer photovoltaic devices, we showmore » that the crystal orientation has only a modest effect (15-20%) on photovoltaic performance. The addition of side-chains to the PFTBT block is found to decrease photovoltaic power conversion efficiencies by at least an order of magnitude. Through grazing-incidence X-ray measurements we find that the addition of side-chains to the PFTBT acceptor block results in weak segregation and small (< 10 nm) block copolymer self-assembled donor and acceptor domains. This work is the most comprehensive to date on all-conjugated block copolymer systems and suggests that photovoltaic performance of block copolymers depends strongly on the miscibility of donor and acceptor blocks, which impacts donor and acceptor domain sizes and purity. Lastly, strategies for improving the device performance of block copolymer photovoltaics should seek to increase segregation between donor and acceptor polymer domains.« less

Automated Defect and Correlation Length Analysis of Block Copolymer Thin Film Nanopatterns

PubMed Central

Murphy, Jeffrey N.; Harris, Kenneth D.; Buriak, Jillian M.

2015-01-01

Line patterns produced by lamellae- and cylinder-forming block copolymer (BCP) thin films are of widespread interest for their potential to enable nanoscale patterning over large areas. In order for such patterning methods to effectively integrate with current technologies, the resulting patterns need to have low defect densities, and be produced in a short timescale. To understand whether a given polymer or annealing method might potentially meet such challenges, it is necessary to examine the evolution of defects. Unfortunately, few tools are readily available to researchers, particularly those engaged in the synthesis and design of new polymeric systems with the potential for patterning, to measure defects in such line patterns. To this end, we present an image analysis tool, which we have developed and made available, to measure the characteristics of such patterns in an automated fashion. Additionally we apply the tool to six cylinder-forming polystyrene-block-poly(2-vinylpyridine) polymers thermally annealed to explore the relationship between the size of each polymer and measured characteristics including line period, line-width, defect density, line-edge roughness (LER), line-width roughness (LWR), and correlation length. Finally, we explore the line-edge roughness, line-width roughness, defect density, and correlation length as a function of the image area sampled to determine each in a more rigorous fashion. PMID:26207990

Characterization of ultrahigh-molecular weight cationic polyacrylamide using frit-inlet asymmetrical flow field-flow fractionation and multi-angle light scattering.

PubMed

Woo, Sohee; Lee, Ju Yong; Choi, Woonjin; Moon, Myeong Hee

2016-01-15

In this study, frit inlet asymmetrical flow field-flow fractionation (FlFFF) with multi-angle light scattering (MALS) and differential refractive index (DRI) detection is utilized for size separation, determination of molecular weight (MW), and conformation of ultrahigh-MW (10(7)-10(9) g/mol) cationic polyacrylamides (C-PAMs), a class of water-soluble copolymers based on acrylamide and vinyl-type comonomers with quaternary ammonium cations that are widely used in wastewater treatment and in paper industries. Linear and branched C-PAM copolymers prepared in two different polymerization methods (solution and emulsion) from varying amounts of crosslinking agent and initiator were size fractionated by FlFFF with field-programming. It was found experimentally that the linear copolymers from both polymerization methods were less than 10(8) g/mol in MW with compact, nearly spherical structures, while the branched C-PAM copolymers from the emulsion polymerization showed a significant increase in average MW up to ∼ 10(9)g/mol, which was about 20-fold greater than those from the solution method, and the branched copolymers had more compact or shrunken conformations. While both linear and branched copolymers less than 10(8) g/mol MW were well resolved in an increasing order of MW (normal mode), it was noted that branched copolymers prepared through emulsion polymerization exhibited significantly larger MWs of 10(8-)10(9) g/mol and eluted in the steric/hyperlayer mode, in which the elution order is reversed in an extreme run condition (strong initial field strength followed by a fast field decay during programming). Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Separation of Poly(styrene-block-t-butyl methacrylate) Copolymers by Various Liquid Chromatography Techniques

PubMed Central

Šmigovec Ljubič, Tina; Pahovnik, David; Žigon, Majda; Žagar, Ema

2012-01-01

The separation of a mixture of three poly(styrene-block-t-butyl methacrylate) copolymers (PS-b-PtBMA), consisting of polystyrene (PS) blocks of similar length and t-butyl methacrylate (PtBMA) blocks of different lengths, was performed using various chromatographic techniques, that is, a gradient liquid chromatography on reversed-phase (C18 and C8) and normal-phase columns, a liquid chromatography under critical conditions for polystyrene as well as a fully automated two-dimensional liquid chromatography that separates block copolymers by chemical composition in the first dimension and by molar mass in the second dimension. The results show that a partial separation of the mixture of PS-b-PtBMA copolymers can be achieved only by gradient liquid chromatography on reversed-phase columns. The coelution of the two block copolymers is ascribed to a much shorter PtBMA block length, compared to the PS block, as well as a small difference in the length of the PtBMA block in two of these copolymers, which was confirmed by SEC-MALS and NMR spectroscopy. PMID:22489207

Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides

PubMed Central

Görl, Daniel; Zhang, Xin; Stepanenko, Vladimir; Würthner, Frank

2015-01-01

New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (AmBB)n. The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating. PMID:25959777

Fabrication routes for one-dimensional nanostructures via block copolymers

NASA Astrophysics Data System (ADS)

Tharmavaram, Maithri; Rawtani, Deepak; Pandey, Gaurav

2017-05-01

Nanotechnology is the field which deals with fabrication of materials with dimensions in the nanometer range by manipulating atoms and molecules. Various synthesis routes exist for the one, two and three dimensional nanostructures. Recent advancements in nanotechnology have enabled the usage of block copolymers for the synthesis of such nanostructures. Block copolymers are versatile polymers with unique properties and come in many types and shapes. Their properties are highly dependent on the blocks of the copolymers, thus allowing easy tunability of its properties. This review briefly focusses on the use of block copolymers for synthesizing one-dimensional nanostructures especially nanowires, nanorods, nanoribbons and nanofibers. Template based, lithographic, and solution based approaches are common approaches in the synthesis of nanowires, nanorods, nanoribbons, and nanofibers. Synthesis of metal, metal oxides, metal oxalates, polymer, and graphene one dimensional nanostructures using block copolymers have been discussed as well.

13C and 15N Solid State MMR Characterization of Aramid-Containing Nylon-6 by In Situ Polymerization with Benzoyl Caprolactam Derivatives.

DTIC Science & Technology

1987-12-01

areas consistant with the alternating copolymer structure. Comparison with the model acetanilide (-241.9) indicates the downfield resonance is due to the...Deguchi, l.; Ando, 1. Macromclecule’-, 1987, 20, 2441. 4 S..:! TABLE I CP-NIAS u N-methyl benzainide -23. 3 2 Acetanilide -241.9 ’iC poly(p-benzamide

Neutral Polymeric Micelles for RNA Delivery

PubMed Central

Lundy, Brittany B.; Convertine, Anthony; Miteva, Martina; Stayton, Patrick S.

2013-01-01

RNA interference (RNAi) drugs have significant therapeutic potential but delivery systems with appropriate efficacy and toxicity profiles are still needed. Here, we describe a neutral, ampholytic polymeric delivery system based on conjugatable diblock polymer micelles. The diblock copolymer contains a hydrophilic poly[N-(2-hydroxypropyl) methacrylamide-co-N-(2-(pyridin-2- yldisulfanyl)ethyl)methacrylamide) (poly[HPMA-co-PDSMA]) segment to promote aqueous stability and facilitate thiol-disulfide exchange reactions, and a second ampholytic block composed of propyl acrylic acid (PAA), dimethylaminoethyl methacrylate (DMAEMA), and butyl methacrylate (BMA). The poly[(HPMA-co-PDSMA)-b-(PAA-co-DMAEMA-co-BMA)] was synthesized using Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization with an overall molecular weight of 22,000 g/mol and a PDI of 1.88. Dynamic light scattering and fluorescence measurements indicated that the diblock copolymers self-assemble under aqueous conditions to form polymeric micelles with a hydrodynamic radius and critical micelle concentration of 25 nm and 25 μg/mL respectively. Red blood cell hemolysis experiments show that the neutral hydrophilic micelles have potent membrane destabilizing activity at endosomal pH values. Thiolated siRNA targeting glyceraldehyde 3-phosphate dehydrogenase (GAPDH) was directly conjugated to the polymeric micelles via thiol exchange reactions with the pyridal disulfide groups present in the micelle corona. Maximum silencing activity in HeLa cells was observed at a 1:10 molar ratio of siRNA to polymer following a 48 h incubation period. Under these conditions 90 % mRNA knockdown and 65 % and protein knockdown of at 48 h was achieved with negligible toxicity. In contrast the polymeric micelles lacking a pH-responsive endosomalytic segment demonstrated negligible mRNA and protein knockdown under these conditions. The potent mRNA knockdown and excellent biocompatibility of the neutral siRNA conjugates demonstrate the potential utility if this carrier design for delivering therapeutic siRNA drugs. PMID:23360541

Pulsed recording of anisotropy and holographic polarization gratings in azo-polymethacrylates with different molecular architectures

NASA Astrophysics Data System (ADS)

Forcén, Patricia; Oriol, Luis; Sánchez, Carlos; Alcalá, Rafael; Jankova, Katja; Hvilsted, Søren

2008-06-01

Recording of anisotropy and holographic polarization gratings using 532nm, 4ns light pulses has been carried out in thin films of polymers with the same azobenzene content (20wt%) and different molecular architectures. Random and block copolymers comprising azobenzene and methylmethacrylate (MMA) moieties as well as statistical terpolymers with azobenzene, biphenyl, and MMA units have been compared in terms of recording sensitivity and stability upon pulsed excitation. Photoinduced anisotropy just after the pulse was significantly higher in the case of the block copolymers than in the two statistical copolymers. The stability of the recorded anisotropy has also been studied. While a stationary value of the photoinduced anisotropy (approximately 50% of the initial photoinduced value) is reached for the block copolymer, photoinduced anisotropy almost vanished after a few hours in the statistical copolymers. Polarization holographic gratings have been registered using two orthogonally circularly polarized light beams. The results are qualitatively similar to those of photoinduced anisotropy, that is, stability of the registered grating and larger values of diffraction efficiency for the block copolymer as compared with the random copolymers. The recording of holographic gratings with submicron period in films several microns thick, showing both polarization and angular selectivity, has also been demonstrated. Block copolymers showed a lamellar block nanosegregated morphology. The interaction among azo chromophores within the nanosegregated azo blocks seems to be the reason for the stability and the photoresponse enhancement in the block copolymer as compared with the statistical ones.

Hg2+-reactive double hydrophilic block copolymer assemblies as novel multifunctional fluorescent probes with improved performance.

PubMed

Hu, Jinming; Li, Changhua; Liu, Shiyong

2010-01-19

We report on novel type of responsive double hydrophilic block copolymer (DHBC)-based multifunctional chemosensors to Hg(2+) ions, pH, and temperatures and investigate the effects of thermo-induced micellization on the detection sensitivity. Well-defined DHBCs bearing rhodamine B-based Hg(2+)-reactive moieties (RhBHA) in the thermo-responsive block, poly(ethylene oxide)-b-poly(N-isopropylacrylamide-co-RhBHA) (PEO-b-P(NIPAM-co-RhBHA)), were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Nonfluorescent RhBHA moieties are subjected to selective ring-opening reaction upon addition of Hg(2+) ions or lowering solution pH, producing highly fluorescent acyclic species. Thus, at room temperature PEO-b-P(NIPAM-co-RhBHA) DHBCs can serve as water-soluble multifunctional and efficient fluorescent chemosensors to Hg(2+) ions and pH. Upon heating above the lower critical solution temperature (approximately 36 degrees C) of the PNIPAM block, they self-assemble into micelles possessing P(NIPAM-co-RhBHA) cores and well-solvated PEO coronas, which were fully characterized by dynamic and static laser light scattering. It was found that the detection sensitivity to Hg(2+) ions and pH could be dramatically improved at elevated temperatures due to fluorescence enhancement of RhBHA residues in the acyclic form, which were embedded within hydrophobic cores of thermo-induced micellar aggregates. This work represents a proof-of-concept example of responsive DHBC-based multifunctional fluorescent chemosensors for the highly efficient detection of Hg(2+) ions, pH, and temperatures with tunable detection sensitivity. Compared to reaction-based small molecule Hg(2+) probes in previous literature reports, the integration of stimuli-responsive block copolymers with well-developed small molecule-based selective sensing moieties in the current study are expected to exhibit preferred advantages including enhanced detection sensitivity, water dispersibility, biocompatibility, facile incorporation into devices, and the ability of further functionalization for targeted imaging and detection.

Sustainable Triblock Copolymers for Application as Thermoplastic Elastomers

NASA Astrophysics Data System (ADS)

Ding, Wenyue; Wang, Shu; Ganewatta, Mitra; Tang, Chuanbing; Robertson, Megan

Thermoplastic elastomers (TPEs), combining the processing advantages of thermoplastics with the flexibility and extensibility of elastomeric materials, have found versatile applications in industry, including electronics, clothing, adhesives, and automotive components. ABA triblock copolymers, in which A represents glassy endblocks and B the rubbery midblock, are commercially available as TPEs, such as poly(styrene-b-butadiene-b-styrene) (SBS) or poly(styrene-b-isoprene-b-styrene) (SIS). However, the commercial TPEs are derived from fossil fuels. The finite availability of fossil fuels and the environmental impact of the petroleum manufacturing have led to the increased interest in the development of alternative polymeric materials from sustainable sources. Rosin acids are promising replacement for the petroleum source due to their abundance in conifers, rigid molecular structures, and ease of functionalization. In this study, we explored the utilization of a rosin acid derivative, poly(dehydroabietic ethyl methacrylate) (PDAEMA), as a sustainable alternative for the glassy domain. The triblock copolymer poly(dehydroabietic ethyl methacrylate-b-n-butyl acylate-b-dehydroabietic ethyl methacrylate) (DnBD) was synthesized and characterized. DnBD exhibited tunable morphological and thermal properties. Tensile testing revealed elastomeric behavior.

In situ UV-visible spectroelectrochemical evidences for conducting copolymer formation between diphenylamine and m-methoxyaniline.

PubMed

Thanneermalai, M; Jeyaraman, T; Sivakumar, C; Gopalan, A; Vasudevan, T; Wen, T C

2003-07-01

Electrochemical copolymerization of diphenylamine (DPA) with m-methoxy aniline (MA) was carried out in 4 M H(2)SO(4) by cyclic voltammetry (CV). Cyclic voltammograms (CVs) of the copolymer films were recorded in monomer-free background electrolyte. In situ sepectroelectrochemical studies were carried out on an optically transparent electrode (Indium tin oxide (ITO) coated glass) in 4 M H(2)SO(4) for different feed ratios of the comonomers. Constant potential and potential sweep methods were employed for performing polymerization. UV-visible absorption spectra were collected continuously and concurrently during the copolymerization in both the cases. The results from constant potential electropolymerisation indicated the formation of an intermediate with an absorption peak at 576 nm. Derivative cyclic voltabsorptogram (DCVA) was deduced from the results of cyclic spectrovoltammetry. The DCVA derived at 576 nm confirms the intermediates formed during the electrochemical copolymerization. The compositional changes of the two monomers in the copolymers with changes in feed composition of two monomers as predicted from in situ spectro electrochemical studies are evident from elemental analysis. A plausible copolymerization mechanism is suggested.

Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties

PubMed Central

Boufflet, Pierre; Wood, Sebastian; Wade, Jessica; Fei, Zhuping; Kim, Ji-Seon

2016-01-01

Summary The microstructure of the active blend layer has been shown to be a critically important factor in the performance of organic solar devices. Block copolymers provide a potentially interesting avenue for controlling this active layer microstructure in solar cell blends. Here we explore the impact of backbone fluorination in block copolymers of poly(3-octyl-4-fluorothiophene)s and poly(3-octylthiophene) (F-P3OT-b-P3OT). Two block co-polymers with varying block lengths were prepared via sequential monomer addition under Kumada catalyst transfer polymerisation (KCTP) conditions. We compare the behavior of the block copolymer to that of the corresponding homopolymer blends. In both types of system, we find the fluorinated segments tend to dominate the UV–visible absorption and molecular vibrational spectral features, as well as the thermal behavior. In the block copolymer case, non-fluorinated segments appear to slightly frustrate the aggregation of the more fluorinated block. However, in situ temperature dependent Raman spectroscopy shows that the intramolecular order is more thermally stable in the block copolymer than in the corresponding blend, suggesting that such materials may be interesting for enhanced thermal stability of organic photovoltaic active layers based on similar systems. PMID:27829922

New self-assembly strategies for next generation lithography

NASA Astrophysics Data System (ADS)

Schwartz, Evan L.; Bosworth, Joan K.; Paik, Marvin Y.; Ober, Christopher K.

2010-04-01

Future demands of the semiconductor industry call for robust patterning strategies for critical dimensions below twenty nanometers. The self assembly of block copolymers stands out as a promising, potentially lower cost alternative to other technologies such as e-beam or nanoimprint lithography. One approach is to use block copolymers that can be lithographically patterned by incorporating a negative-tone photoresist as the majority (matrix) phase of the block copolymer, paired with photoacid generator and a crosslinker moiety. In this system, poly(α-methylstyrene-block-hydroxystyrene)(PαMS-b-PHOST), the block copolymer is spin-coated as a thin film, processed to a desired microdomain orientation with long-range order, and then photopatterned. Therefore, selfassembly of the block copolymer only occurs in select areas due to the crosslinking of the matrix phase, and the minority phase polymer can be removed to produce a nanoporous template. Using bulk TEM analysis, we demonstrate how the critical dimension of this block copolymer is shown to scale with polymer molecular weight using a simple power law relation. Enthalpic interactions such as hydrogen bonding are used to blend inorganic additives in order to enhance the etch resistance of the PHOST block. We demonstrate how lithographically patternable block copolymers might fit in to future processing strategies to produce etch-resistant self-assembled features at length scales impossible with conventional lithography.

Effect of cationic monomer content on polyacrylamide copolymers by frit-inlet asymmetrical flow field-flow fractionation/multi-angle light scattering.

PubMed

Lee, Hyejin; Kim, Jin Yong; Choi, Woonjin; Moon, Myeong Hee

2017-06-23

In this study, ultrahigh-molecular-weight (MW) (>10 7 Da) cationic polyacrylamides (C-PAMs), which are water-soluble polymers used in waste water treatment, were characterized using frit-inlet asymmetrical flow field-flow fractionation coupled with multi-angle light scattering and differential refractive detection. C-PAMs copolymerized with acryloxyethyltrimethyl ammonium chloride (DAC) were prepared by varying the feed amount of cationic monomer, polymerization method (solution vs. emulsion), and degree of branching. The MW of the copolymers prepared using emulsion polymerization (10 7 -10 9 Da) was generally larger than that of copolymers prepared using solution polymerization (4×10 7 -10 8 Da). When the amount of cationic monomer was increased from 10 to 55mol% in solution polymerization, hydrophobic contraction of the core induced formation of more compact C-PAMs. The copolymers prepared using emulsion polymerization formed highly aggregated or supercoil structures owing to increased intermolecular hydrophobic interaction when less cationic monomer was used. However, the MW decreased with increased cationic group content. In addition, C-PAMs larger than ∼10 8 Da prepared using the emulsion method were separated by steric/hyperlayer elution mode while those in the 10 7 -10 8 Da range were analyzed in either normal or steric/hyperlayer mode depending on the decay patterns of field programming. Moreover, branched copolymers were found to be resolved with different elution modes under the same field decay pattern depending on the degree of branching: steric/hyperlayer for low-branching and normal for high-branching C-PAMs. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Inhomogeneity of block copolymers at the interface of an immiscible polymer blend

NASA Astrophysics Data System (ADS)

Ryu, Ji Ho; Kim, YongJoo; Lee, Won Bo

2018-04-01

We present the effects of structure and stiffness of block copolymers on the interfacial properties of an immiscible homopolymer blend. Diblock and two-arm grafted copolymers with variation in stiffness are modeled using coarse-grained molecular dynamics to compare the compatibilization efficiency, i.e., reduction of interfacial tension. Overall, grafted copolymers are located more compactly at the interface and show better compatibilization efficiency than diblock copolymers. In addition, an increase in the stiffness for one of the blocks of the diblock copolymers causes unusual inhomogeneous interfacial coverage due to bundle formation. However, an increase in the stiffness for one of blocks of the grafted copolymers prevents the bundle formation due to the branched chain. As a result, homogeneous interfacial coverage of homopolymer blends is realized with significant reduction of interfacial tension which makes grafted copolymer a better candidate for the compatibilizer of immiscible homopolymer blend.

Nanopatterned articles produced using surface-reconstructed block copolymer films

DOEpatents

Russell, Thomas P.; Park, Soojin; Wang, Jia-Yu; Kim, Bokyung

2016-06-07

Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred to the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.

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

USDA-ARS?s Scientific Manuscript database

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

Functionalized and graft copolymers of chitosan and its pharmaceutical applications.

PubMed

Bhavsar, Chintan; Momin, Munira; Gharat, Sankalp; Omri, Abdelwahab

2017-10-01

Chitosan is the second most abundant natural polysaccharide. It belongs a family of polycationic polymers comprised of repetitive units of glucosamine and N-acetylglucosamine. Its biodegradability, nontoxicity, non-immunogenicity and biocompatibility along with properties like mucoadhesion, fungistatic and bacteriogenic have made chitosan an appreciated polymer with numerous applications in the pharmaceutical, comestics and food industry. However, the limited solubility of chitosan at alkaline and neutral pH limits its widespread commercial use. This can be circumvented by fabrication of chitosan by graft copolymerization with acyl, alkyl, monomeric and polymeric moieties. Areas covered: Modifications like quarterization, thiolation, acylation and grafting result in copolymers with higher mucoadhesion strength, increased hydrophobic interactions (advantageous in hydrophobic drug entrapment), and increased solubility in alkaline pH, the ability for adsorption of metal ions, protein and peptide delivery and nutrient delivery. Insights on methods of polymerization, including atomic transfer radical polymerization and click chemistry are discussed. Applications of such modified chitosan copolymers in medical and surgical, and drug delivery, including nasal, oral and buccal delivery have also been covered. Expert opinion: Despite a number of successful investigations, commercialization of chitosan copolymers still remains a challenge. Further advancements in polymerization techniques may address the unmet needs of the healthcare industry.

Amphiphilic polymeric micelles as the nanocarrier for peroral delivery of poorly soluble anticancer drugs.

PubMed

Tian, Ye; Mao, Shirui

2012-06-01

Many amphiphilic copolymers have recently been synthesized as novel promising micellar carriers for the delivery of poorly water-soluble anticancer drugs. Studies on the formulation and oral delivery of such micelles have demonstrated their efficacy in enhancing drug uptake and absorption, and exhibit prolonged circulation time in vitro and in vivo. In this review, literature on hydrophobic modifications of several hydrophilic polymers, including polyethylene glycol, chitosan, hyaluronic acid, pluronic and tocopheryl polyethylene glycol succinate, is summarized. Parameters influencing the properties of polymeric micelles for oral chemotherapy are discussed and strategies to overcome main barriers for polymeric micelles peroral absorption are proposed. During the design of polymeric micelles for peroral chemotherapy, selecting or synthesizing copolymers with good compatibility with the drug is an effective strategy to increase drug loading and encapsulation efficiency. Stability of the micelles can be improved in different ways. It is recommended to take permeability, mucoadhesion, sustained release, and P-glycoprotein inhibition into consideration during copolymer preparation or to consider adding some excipients in the formulation. Furthermore, both the copolymer structure and drug loading methods should be controlled in order to get micelles with appropriate particle size for better absorption.

Controlled self-assembly of conjugated rod-coil block copolymers for applications in organic optoelectronics

NASA Astrophysics Data System (ADS)

Tao, Yuefei

Organic electronics are of great interest in manufacturing light weight, mechanical flexible, and inexpensive large area devices. While significant improvements have been made over the last several years and it is now clear that morphology on the lengthscale of exciton diffusion (10nm) is of crucial importance, a clear relationship between structure and device properties has not emerged. This lack of understanding largely emerges from an inability to control morphology on this lengthscale. This thesis will center around an approach, based on block copolymer self-assembly, to generate equilibrium nanostructures on the 10 nm lengthscale of exciton diffusion and study their effects on device performance. Self-assembly of semiconducting block copolymers is complicated by the non-classical chain shape of conjugated polymers. Unlike classical polymers, the chains do not assume a Gaussian coil shape which is stretched near block copolymer interfaces, instead the chains are elongated and liquid crystalline. Previous work has demonstrated how these new molecular interactions and shapes control the phase diagram of so-called rod-coil block copolymers. Here, we will focus on controlling domain size, orientation, and chemical structure. While domain size can be controlled directly through molecular weight, this requires significant additional synthesis of domain size is to be varied. Here, the domain size is controlled by blending homopolymers into a self-assembling rod-coil block copolymer. When coil-like blocks are incorporated, the domains swell, as expected. When rod-like blocks are incorporated, they interdigitate with the rods of the block copolymers. This results in an increase in interfacial area which forces the coils to rearrange and an overall decrease in domain size with increasing rod content. Control over lamellar orientation is crucial in order to design and control charge transport pathways and exciton recombination or separation interfaces. While numerous techniques have been demonstrated for classical block copolymers, the pi conjugation in the rod blocks allow for additional control mechanisms. Liquid crystals are traditionally aligned in magnetic fields. Here, it is demonstrated that if the rod-like blocks are aligned unidirectionally, the block copolymer interfaces follow to create macroscopic alignment of the nanostructures. Organic Light Emitting Diodes (OLEDs) are generally composed of electron transporting and hole transporting moieties to balance charge recombination. Here, a new multifunctional bipolar rod-coil block copolymer containing the hole transporting and electron transporting materials is synthesized. Self-assembly of this new block copolymer results in 15nm lamellae oriented in grains both parallel and perpendicula to the anode. The self-assembled block copolymer shows superior device performance to controls consisting of a luminescent, analogous homopolymer, and a blend of the two component homopolymers. The effects of the morphologies and chemical structure on photovoltaics is explored with a rod-coil block copolymer, (poly(3-hexylthiophene-b-acrylic perylene)). By varying the kinetics of self-assembly through processing, the block copolymer can be disordered, ordered with only short range registry between the nanodomains, or with long-range order. The short range ordered samples showed the best device performance suggesting that the connectivity that is a biproduct of poor order is beneficial for device performance.

Uniformly sized gold nanoparticles derived from PS-b-P2VP block copolymer templates for the controllable synthesis of Si nanowires.

PubMed

Lu, Jennifer Q; Yi, Sung Soo

2006-04-25

A monolayer of gold-containing surface micelles has been produced by spin-coating solution micelles formed by the self-assembly of the gold-modified polystyrene-b-poly(2-vinylpyridine) block copolymer in toluene. After oxygen plasma removed the block copolymer template, highly ordered and uniformly sized nanoparticles have been generated. Unlike other published methods that require reduction treatments to form gold nanoparticles in the zero-valent state, these as-synthesized nanoparticles are in form of metallic gold. These gold nanoparticles have been demonstrated to be an excellent catalyst system for growing small-diameter silicon nanowires. The uniformly sized gold nanoparticles have promoted the controllable synthesis of silicon nanowires with a narrow diameter distribution. Because of the ability to form a monolayer of surface micelles with a high degree of order, evenly distributed gold nanoparticles have been produced on a surface. As a result, uniformly distributed, high-density silicon nanowires have been generated. The process described herein is fully compatible with existing semiconductor processing techniques and can be readily integrated into device fabrication.

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

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.

Low-Dielectric Constant Polyimide Nanoporous Films: Synthesis and Properties

NASA Astrophysics Data System (ADS)

Mehdipour-Ataei, S.; Rahimi, A.; Saidi, S.

2007-08-01

Synthesis of high temperature polyimide foams with pore sizes in the nanometer range was developed. Foams were prepared by casting graft copolymers comprising a thermally stable block as the matrix and a thermally labile material as the dispersed phase. Polyimides derived from pyromellitic dianhydride with new diamines (4BAP and BAN) were used as the matrix material and functionalized poly(propylene glycol) oligomers were used as a thermally labile constituent. Upon thermal treatment the labile blocks were subsequently removed leaving pores with the size and shape of the original copolymer morphology. The polyimides and foamed polyimides were characterized by some conventional methods including FTIR, H-NMR, DSC, TGA, SEM, TEM, and dielectric constant.

Amphiphilic copolymers based on polyoxazoline and grape seed vegetable oil derivatives: self-assemblies and dynamic light scattering

NASA Astrophysics Data System (ADS)

Travelet, Christophe; Stemmelen, Mylène; Lapinte, Vincent; Dubreuil, Frédéric; Robin, Jean-Jacques; Borsali, Redouane

2013-06-01

The self-assembly in solution of original structures of amphiphilic partially natural copolymers based on polyoxazoline [more precisely poly(2-methyl-2-oxazoline) (POx)] and grape seed vegetable oil derivatives (linear, T-, and trident-structure) is investigated. The results show that such systems are found, using dynamic light scattering (DLS), to spontaneously self-organize into monomodal, narrow-size, and stable nanoparticles in aqueous medium. The obtained hydrodynamic diameters ( D h) range from 8.6 to 32.5 nm. Specifically, such size increases strongly with increasing natural block (i.e., lipophilic species) length due to higher hydrophobic interactions (from 10.1 nm for C19 to 19.2 nm for C57). Furthermore, increasing the polyoxazoline (i.e., hydrophilic block) length leads to a moderate linear increase of the D h-values. Therefore, the first-order size effect comes from the natural lipophilic block, whereas the characteristic size can be tuned more finely (i.e., in a second-order) by choosing appropriately the polyoxazoline length. The DLS results in terms of characteristic size are corroborated using nanoparticle tracking analysis (NTA), and also by atomic force microscopy (AFM) and transmission electron microscopy (TEM) imaging where well-defined spherical and individual nanoparticles exhibit a very good mechanical resistance upon drying. Moreover, changing the lipophilic block architecture from linear to T-shape, while keeping the same molar mass, generates a branching and thus a shrinking by a factor of 2 of the nanoparticle volume, as observed by DLS. In this paper, it is clearly shown that the self-assemblies of amphiphilic block copolymer obtained from grape seed vegetable oil derivatives (sustainable renewable resources) as well as their tunability are of great interest for biomass valorization at the nanoscale level [continuation of the article by Stemmelen et al. (Polym Chem 4:1445-1458, 2013)].

Rapid and annealing-free self-assembly of DNA building blocks for 3D hydrogel chaperoned by cationic comb-type copolymers.

PubMed

Zhang, Zheng; Wu, Yuyang; Yu, Feng; Niu, Chaoqun; Du, Zhi; Chen, Yong; Du, Jie

2017-10-01

The construction and self-assembly of DNA building blocks are the foundation of bottom-up development of three-dimensional DNA nanostructures or hydrogels. However, most self-assembly from DNA components is impeded by the mishybridized intermediates or the thermodynamic instability. To enable rapid production of complicated DNA objects with high yields no need for annealing process, herein different DNA building blocks (Y-shaped, L- and L'-shaped units) were assembled in presence of a cationic comb-type copolymer, poly (L-lysine)-graft-dextran (PLL-g-Dex), under physiological conditions. The results demonstrated that PLL-g-Dex not only significantly promoted the self-assembly of DNA blocks with high efficiency, but also stabilized the assembled multi-level structures especially for promoting the complicated 3D DNA hydrogel formation. This study develops a novel strategy for rapid and high-yield production of DNA hydrogel even derived from instable building blocks at relatively low DNA concentrations, which would endow DNA nanotechnology for more practical applications.

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.

Reduction-responsive interlayer-crosslinked micelles prepared from star-shaped copolymer via click chemistry for drug controlled release

NASA Astrophysics Data System (ADS)

Dai, Yu; Wang, Hongquan; Zhang, Xiaojin

2017-12-01

To improve the stability of polymeric micelles, here we describe interlayer-crosslinked micelles prepared from star-shaped copolymer via click chemistry. The formation of interlayer-crosslinked micelles was investigated and confirmed by proton nuclear magnetic resonance, Fourier-transform infrared spectroscopy, and fluorescence spectroscopy. The morphology of un-crosslinked micelles and crosslinked micelles observed by transmission electron microscope is both uniform nano-sized spheres (approximately 20 nm). The crosslinking enhances the stability of polymeric micelles and improves the drug loading capacity of polymeric micelles. The interlayer-crosslinked micelles prepared from star-shaped copolymer and a crosslinker containing a disulfide bond are reduction-responsive and can release the drug quickly in the presence of the reducing agents such as glutathione (GSH).

Synthesis of Diblock copolymer poly-3-hydroxybutyrate -block-poly-3-hydroxyhexanoate [PHB-b-PHHx] by a β-oxidation weakened Pseudomonas putida KT2442.

PubMed

Tripathi, Lakshmi; Wu, Lin-Ping; Chen, Jinchun; Chen, Guo-Qiang

2012-04-05

Block polyhydroxyalkanoates (PHA) were reported to be resistant against polymer aging that negatively affects polymer properties. Recently, more and more attempts have been directed to make PHA block copolymers. Diblock copolymers PHB-b-PHHx consisting of poly-3-hydroxybutyrate (PHB) block covalently bonded with poly-3-hydroxyhexanoate (PHHx) block were for the first time produced successfully by a recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. The chloroform extracted polymers were characterized by nuclear magnetic resonance (NMR), thermo- and mechanical analysis. NMR confirmed the existence of diblock copolymers consisting of 58 mol% PHB as the short chain length block with 42 mol% PHHx as the medium chain length block. The block copolymers had two glass transition temperatures (Tg) at 2.7°C and -16.4°C, one melting temperature (Tm) at 172.1°C and one cool crystallization temperature (Tc) at 69.1°C as revealed by differential scanning calorimetry (DSC), respectively. This is the first microbial short-chain-length (scl) and medium-chain-length (mcl) PHA block copolymer reported. It is possible to produce PHA block copolymers of various kinds using the recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. In comparison to a random copolymer poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P(HB-co-HHx)) and a blend sample of PHB and PHHx, the PHB-b-PHHx showed improved structural related mechanical properties.

Controlled Pd(0)/t Bu3P Catalyzed Suzuki Cross-Coupling Polymerization of AB-Type Monomers with ArPd(t Bu3P)X or Pd2(dba)3/t Bu3P/ArX as the Initiator

DOE PAGES

Zhang, Honghai; Xing, Chun-Hui; Hu, Qiao-Sheng; ...

2015-02-05

The synthesis of well-defined and functionalized conjugated polymers, which are essential in the development of efficient organic electronics, through Suzuki cross-coupling polymerizations has been a challenging task. We developed controlled Pd(0)/t-Bu3P-catalyzed Suzuki cross-coupling polymerizations of AB-type monomers via the chain-growth mechanism with a series of in situ generated ArPd(t-Bu3P)X (X = I, Br, Cl) complexes as initiators. Among them, the combinations of Pd2(dba)3/t-Bu3P/p-BrC6H4I, Pd2(dba)3/t-Bu3P/p-BrC6H4CH2OH and Pd2(dba)3/t-Bu3P/p-PhCOC6H4Br were identified as highly robust initiator systems, resulting in polymers with predictable molecular weight and narrow polydispersity (PDI~1.13-1.20). In addition, Pd2(dba)3/t-Bu3P/p-BrC6H4CH2OH and Pd2(dba)3/t-Bu3P/p-PhCOC6H4Br initiator systems afforded functional polymers with >95% fidelity. Our results pavedmore » the road to access well-defined conjugated polymers, including conjugated polymers with complex polymer architectures such as block copolymers and branch copolymers.« less

Effect of Hyaluronic Acid on the Self Assembling Behaviour of PEO-PPO Copolymers in Aqueous Solution

NASA Astrophysics Data System (ADS)

Mayol, L.; Borzacchiello, A.; Quaglia, F.; La Rotonda, M. I.; Ambrosio, L.

2008-07-01

The influence of hyaluronic acid (HA) on the self assembling properties of pluronic (PEO-PPO-PEO block copolymers) blends has been studied with the aim of engineering thermosensitive and mucoadhesive polymeric platforms for drug delivery. The gelation temperature (Tgel), viscoelastic properties and mucoadhesive force of the systems were investigated and optimised by means of rheological analyses. Pluronic micellar radius was evaluated by Photon Correlation Spectroscopy (PCS). The addition of Low Molecular Weight HA did not hamper the self assembling process of pluronics just delaying the gelation temperature of few Celsius degrees. Furthermore, HA presence led to a strong increase of the pluronics gel rheological properties. PCS results show, in formulations containing HA, aggregates with hydrodynamic diameters values much higher than those of pluronic micelles. Mucoadhesive experiments indicate the possibility of interactions between the pluronic/HA gel and mucus glycoproteins.

Confined crystallization, crystalline phase deformation and their effects on the properties of crystalline polymers

NASA Astrophysics Data System (ADS)

Wang, Haopeng

With the recent advances in processing and catalyst technology, novel morphologies have been created in crystalline polymers and they are expected to substantially impact the properties. To reveal the structure-property relationships of some of these novel polymeric systems becomes the primary focus of this work. In the first part, using an innovative layer-multiplying coextrusion process to obtain assemblies with thousands of polymer nanolayers, dominating "in-plane" lamellar crystals were created when the confined poly(ethylene oxide) (PEO) layers were made progressively thinner. When the thickness was confined to 25 nanometers, the PEO crystallized as single, high-aspect-ratio lamellae that resembled single crystals. This crystallization habit imparted more than two orders of magnitude reduction in the gas permeability. The dramatic decrease in gas permeability was attributed to the reduced diffusion coefficient, because of the increase in gas diffusion path length through the in-plane lamellae. The temperature dependence of lamellar orientation and the crystallization kinetics in the confined nanolayers were also investigated. The novel olefinic block copolymer (OBC) studied in the second part consisted of long crystallizable sequences with low comonomer content alternating with rubbery amorphous blocks with high comonomer content. The crystallizable blocks formed lamellae that organized into space-filling spherulites even when the fraction of crystallizable block was so low that the crystallinity was only 7%. These unusual spherulites were highly elastic and recovered from strains as high as 300%. These "elastic spherulites" imparted higher strain recovery and temperature resistance than the conventional random copolymers that depend on isolated, fringed micellar-like crystals to provide the junctions for the elastomeric network. In the third part, positron annihilation lifetime spectroscopy (PALS) was used to obtain the temperature dependence of the free volume hole size in propylene/ethylene copolymers over a range in comonomer content. Above the glass transition temperature (Tg), the reduced free volume hole size and the densification of the amorphous phase were attributed to constraint imposed on rubbery amorphous chain segments by attached chain segments in crystals. However constant free volume fraction was found at Tg, across the crystallinity range of the copolymers, in agreement with the iso-free volume concept of glass transition.

A Research Project on the Emulsifying and Homogenizing Properties of Block Copolymers in Polymer Blends.

DTIC Science & Technology

1987-06-15

Chain C.V. Berney Scattering in Heterogeneous P. Kofinas Block Copolymers R.E. Cohen 18. SANS Studies of the Configu- C.V. Berney rations of Single...Studies of the Configuratins C.V. Berney Single Chains in Heterogeneous Block P. Cheng Copolymers, J. Materials Research, P. Dofinas in press (1987) R.E...Cohen 2. A Reexamination of the Configurations C.V. Berney of Single-Chain Scattering in Hetero- P. Kofinas geneous Block Copolymers, R.E. Cohen

Tunable Encapsulation Structure of Block Copolymer Coated Single-Walled Carbon Nanotubes in Aqueous Solution

DOE PAGES

Han, Youngkyu; Ahn, Suk-Kyun; Zhang, Zhe; ...

2015-05-15

The nano-sized and shape-tunable molecular building blocks can provide great opportunities for the fabrication of precisely controlled nanostructures. In this work, we have fabricated a molecular building block of single-walled carbon nanotubes (SWNTs) coated by PPO-PEO-PPO block copolymers whose encapsulation structure can be controlled via temperature or addition of small molecules. The structure and optical properties of SWNT-block copolymers have been investigated by small angle neutron scattering (SANS), ultraviolet-visible (UV-vis) spectroscopy, atomic force microscopy (AFM), and molecular dynamics (MD) simulation. The structure of the hydrated block copolymer layer surrounding SWNT can be controlled reversibly by varying temperature as well asmore » by irreversibly adding 5-methylsalicylic acid (5MS). Increasing hydrophobicity of the polymers with temperature and strong tendency of 5MS to interact with both block copolymers and orbitals of the SWNTs are likely to be responsible for the significant structural change of the block copolymer encapsulation layer, from loose corona shell to tightly encapsulating compact shell. These result shows an efficient and simple way to fabricate and manipulate carbon-based nano building blocks in aqueous systems with tunable structure.« less

Proton-transfer lasers based on solid copolymers of modified 2-(2'-hydroxyphenyl)benzimidazoles with methacrylate monomers

NASA Astrophysics Data System (ADS)

Costela, A.; García-Moreno, I.; Mallavia, Ricardo; Amat-Guerri, F.; Barroso, J.; Sastre, R.

1998-06-01

We report on the lasing action of two newly synthesized 2-(2'-hydroxyphenyl) benzimidazole derivatives copolymerized with methyl methacrylate. The laser samples were transversely pumped with a N 2 laser at 337 nm. The influence on the proton-transfer laser performance of the distance between the chromophore group and the polymeric main chain and of the rigidity of the polymeric host matrix, were studied. Significant increases in lasing efficiency and photostability are demonstrated for some of the new materials, as compared to those previously obtained with related proton-transfer dyes also covalently bound to methacrylic monomers.

Drug Combination Synergy in Worm-like Polymeric Micelles Improves Treatment Outcome for Small Cell and Non-Small Cell Lung Cancer.

PubMed

Wan, Xiaomeng; Min, Yuanzeng; Bludau, Herdis; Keith, Andrew; Sheiko, Sergei S; Jordan, Rainer; Wang, Andrew Z; Sokolsky-Papkov, Marina; Kabanov, Alexander V

2018-03-27

Nanoparticle-based systems for concurrent delivery of multiple drugs can improve outcomes of cancer treatments, but face challenges because of differential solubility and fairly low threshold for incorporation of many drugs. Here we demonstrate that this approach can be used to greatly improve the treatment outcomes of etoposide (ETO) and platinum drug combination ("EP/PE") therapy that is the backbone for treatment of prevalent and deadly small cell lung cancer (SCLC). A polymeric micelle system based on amphiphilic block copolymer poly(2-oxazoline)s (POx) poly(2-methyl-2-oxazoline- block-2-butyl-2-oxazoline- block-2-methyl-2-oxazoline) (P(MeOx- b-BuOx- b-MeOx) is used along with an alkylated cisplatin prodrug to enable co-formulation of EP/PE in a single high-capacity vehicle. A broad range of drug mixing ratios and exceptionally high two-drug loading of over 50% wt. drug in dispersed phase is demonstrated. The highly loaded POx micelles have worm-like morphology, unprecedented for drug loaded polymeric micelles reported so far, which usually form spheres upon drug loading. The drugs co-loading in the micelles result in a slowed-down release, improved pharmacokinetics, and increased tumor distribution of both drugs. A superior antitumor activity of co-loaded EP/PE drug micelles compared to single drug micelles or their combination as well as free drug combination was demonstrated using several animal models of SCLC and non-small cell lung cancer.

Antimicrobial Peptide Mimicking Primary Amine and Guanidine Containing Methacrylamide Copolymers Prepared by Raft Polymerization

PubMed Central

Exley, Sarah E.; Paslay, Lea C.; Sahukhal, Gyan S.; Abel, Brooks A.; Brown, Tyler D.; McCormick, Charles L.; Heinhorst, Sabine; Koul, Veena; Choudhary, Veena; Elasri, Mohamed O.; Morgan, Sarah E.

2016-01-01

Naturally occurring antimicrobial peptides (AMPs) display the ability to eliminate a wide variety of bacteria, without toxicity to the host eukaryotic cells. Synthetic polymers containing moieties mimicking lysine and arginine components found in AMPs have been reported to show effectiveness against specific bacteria, with the mechanism of activity purported to depend on the nature of the amino acid mimic. In an attempt to incorporate the antimicrobial activity of both amino acids into a single water-soluble copolymer, a series of copolymers containing lysine mimicking aminopropyl methacrylamide (APMA) and arginine mimicking guanadinopropyl methacrylamide (GPMA) were prepared via aqueous RAFT polymerization. Copolymers were prepared with varying ratios of the comonomers, with degree of polymerization of 35–40 and narrow molecular weight distribution to simulate naturally occurring AMPs. Antimicrobial activity was determined against Gram-negative and Gram-positive bacteria under conditions with varying salt concentration. Toxicity to mammalian cells was assessed by hemolysis of red blood cells and MTT assays of MCF-7 cells. Antimicrobial activity was observed for APMA homopolymer and copolymers with low concentrations of GPMA against all bacteria tested, with low toxicity toward mammalian cells. PMID:26558609

Nanopatterned articles produced using reconstructed block copolymer films

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

Russell, Thomas P.; Park, Soojin; Wang;, Jia-Yu

Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred tomore » the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.« less

Method of producing nanopatterned articles using surface-reconstructed block copolymer films

DOEpatents

Russell, Thomas P; Park, Soojin; Wang, Jia-Yu; Kim, Bokyung

2013-08-27

Nanopatterned surfaces are prepared by a method that includes forming a block copolymer film on a substrate, annealing and surface reconstructing the block copolymer film to create an array of cylindrical voids, depositing a metal on the surface-reconstructed block copolymer film, and heating the metal-coated block copolymer film to redistribute at least some of the metal into the cylindrical voids. When very thin metal layers and low heating temperatures are used, metal nanodots can be formed. When thicker metal layers and higher heating temperatures are used, the resulting metal structure includes nanoring-shaped voids. The nanopatterned surfaces can be transferred to the underlying substrates via etching, or used to prepare nanodot- or nanoring-decorated substrate surfaces.

Widely Tunable Morphologies in Block Copolymer Thin Films Through Solvent Vapor Annealing Using Mixtures of Selective Solvents

PubMed Central

Chavis, Michelle A.; Smilgies, Detlef-M.; Wiesner, Ulrich B.; Ober, Christopher K.

2015-01-01

Thin films of block copolymers are extremely attractive for nanofabrication because of their ability to form uniform and periodic nanoscale structures by microphase separation. One shortcoming of this approach is that to date the design of a desired equilibrium structure requires synthesis of a block copolymer de novo within the corresponding volume ratio of the blocks. In this work, we investigated solvent vapor annealing in supported thin films of poly(2-hydroxyethyl methacrylate)-block-poly(methyl methacrylate) [PHEMA-b-PMMA] by means of grazing incidence small angle X–ray scattering (GISAXS). A spin-coated thin film of lamellar block copolymer was solvent vapor annealed to induce microphase separation and improve the long-range order of the self-assembled pattern. Annealing in a mixture of solvent vapors using a controlled volume ratio of solvents (methanol, MeOH, and tetrahydrofuran, THF), which are chosen to be preferential for each block, enabled selective formation of ordered lamellae, gyroid, hexagonal or spherical morphologies from a single block copolymer with a fixed volume fraction. The selected microstructure was then kinetically trapped in the dry film by rapid drying. To our knowledge, this paper describes the first reported case where in-situ methods are used to study the transition of block copolymer films from one initial disordered morphology to four different ordered morphologies, covering much of the theoretical diblock copolymer phase diagram. PMID:26819574

Highly Efficient One-Pot Synthesis of COS-Based Block Copolymers by Using Organic Lewis Pairs.

PubMed

Yang, Jia-Liang; Cao, Xiao-Han; Zhang, Cheng-Jian; Wu, Hai-Lin; Zhang, Xing-Hong

2018-01-31

A one-pot synthesis of block copolymer with regioregular poly(monothiocarbonate) block is described via metal-free catalysis. Lewis bases such as guanidine, quaternary onium salts, and Lewis acid triethyl borane (TEB) were equivalently combined and used as the catalysts. By using polyethylene glycol (PEG) as the macromolecular chain transfer agent (CTA), narrow polydispersity block copolymers were obtained from the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO). The block copolymers had a poly(monothiocarbonate) block with perfect alternating degree and regioregularity. Unexpectedly, the addition of CTA to COS/PO copolymerization system could dramatically improve the turnover frequency (TOF) of PO (up to 240 h -1 ), higher than that of the copolymerization without CTA. In addition, the conversion of CTA could be up to 100% in most cases, as revealed by ¹H NMR spectra. Of consequence, the number-average molecular weights ( M n s) of the resultant block copolymers could be regulated by varying the feed ratio of CTA to PO. Oxygen-sulfur exchange reaction (O/S ER), which can generate randomly distributed thiocarbonate and carbonate units, was effectively suppressed in all of the cases in the presence of CTA, even at 80 °C. This work presents a versatile method for synthesizing sulfur-containing block copolymers through a metal-free route, providing an array of new block copolymers.

Step Transfer-Addition and Radical-Termination (START) Polymerization of α,ω-Unconjugated Dienes under Irradiation of Blue LED Light.

PubMed

Xu, Tianchi; Yin, Hongnan; Li, Xiaohong; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2017-07-01

A new polymerization method, termed as step transfer-addition and radical-termination, is developed for the step-growth radical polymerization of α,ω-unconjugated dienes under irradiation of visible light at room temperature (25 °C) for the first time. α,ω-Diiodoperfluoroalkane monomers (signified as A) are added onto α,ω-unconjugated dienes (signified as B) alternatively and efficiently with the generation of perfluorocarbon-containing alternating copolymers (AB) n . Based on the combined analyses of polymerization kinetics and NMR spectra ( 1 H and 19 F), the mechanism of the novel polymerization method, including the side reaction, is proposed. This novel polymerization method provides a new strategy not only for the step-growth radical polymerization of α,ω-unconjugated dienes but also for the construction of high molecular weight perfluorocarbon-containing alternating copolymers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Orientation Control in Thin Films of a High-χ Block Copolymer with a Surface Active Embedded Neutral Layer.

PubMed

Zhang, Jieqian; Clark, Michael B; Wu, Chunyi; Li, Mingqi; Trefonas, Peter; Hustad, Phillip D

2016-01-13

Directed self-assembly (DSA) of block copolymers (BCPs) is an attractive advanced patterning technology being considered for future integrated circuit manufacturing. By controlling interfacial interactions, self-assembled microdomains in thin films of polystyrene-block-poly(methyl methacrylate), PS-b-PMMA, can be oriented perpendicular to surfaces to form line/space or hole patterns. However, its relatively weak Flory interaction parameter, χ, limits its capability to pattern sub-10 nm features. Many BCPs with higher interaction parameters are capable of forming smaller features, but these "high-χ" BCPs typically have an imbalance in surface energy between the respective blocks that make it difficult to achieve the required perpendicular orientation. To address this challenge, we devised a polymeric surface active additive mixed into the BCP solution, referred to as an embedded neutral layer (ENL), which segregates to the top of the BCP film during casting and annealing and balances the surface tensions at the top of the thin film. The additive comprises a second BCP with a "neutral block" designed to provide matched surface tensions with the respective polymers of the main BCP and a "surface anchoring block" with very low surface energy that drives the material to the air interface during spin-casting and annealing. The surface anchoring block allows the film to be annealed above the glass transition temperature of the two materials without intermixing of the two components. DSA was also demonstrated with this embedded neutral top layer formulation on a chemical patterned template using a single step coat and simple thermal annealing. This ENL technology holds promise to enable the use of high-χ BCPs in advanced patterning applications.

13C and 14N Solid State NMR Characterization of Aramid-Containing Nylon-6 Polymers Synthesized by In Situ Polymerization of Caprolactam with Benzoyl Caprolactam Derivatives.

DTIC Science & Technology

1987-12-01

261.3 show equivalent areas consistant with tiie alternating copolymer structure. Comparison with the model acetanilide (-241.5) indicates the...T.; Fujito, T.; Deguchi. 1\\.; Ando, 1. Macromolecules. 1987, 2?0, 2441. 4 TABLE I CP MNAS ,_’ii N-methyl benzamide -2-o3.3 -226. Acetanilide -241.9

Copolymers of fluorinated polydienes and sulfonated polystyrene

DOEpatents

Mays, Jimmy W [Knoxville, TN; Gido, Samuel P [Hadley, MA; Huang, Tianzi [Knoxville, TN; Hong, Kunlun [Knoxville, TN

2009-11-17

Copolymers of fluorinated polydienes and sulfonated polystyrene and their use in fuel cell membranes, batteries, breathable chemical-biological protective materials, and templates for sol-gel polymerization.