Polymers

7581 KiB

Open AccessArticle

Bond Performance of Sand Coated UHM CFRP Tendons in High Performance Concrete

by Tobias Dominik Lämmlein, Francesco Messina, Michele Griffa, Giovanni Pietro Terrasi and Pietro Lura

Polymers 2017, 9(2), 78; https://doi.org/10.3390/polym9020078 - 22 Feb 2017

Cited by 8 | Viewed by 6500

Abstract

The bond behaviour of novel, sand-coated ultra-high modulus (UHM) carbon fibre reinforced polymers (CFRP) tendons to high performance concrete (HPC) was studied by a combined numerical and experimental approach. A series of pull-out tests revealed that the failure type can vary between sudden [...] Read more.

The bond behaviour of novel, sand-coated ultra-high modulus (UHM) carbon fibre reinforced polymers (CFRP) tendons to high performance concrete (HPC) was studied by a combined numerical and experimental approach. A series of pull-out tests revealed that the failure type can vary between sudden and continuous pull-out depending on the chosen sand coating grain size. Measuring the same shear stress vs. tendon draw-in (τ-δ) curves in the same test set-up, for sand coated CFRP tendons with a longitudinal stiffness of 137 and 509 GPa, respectively, indicated that the absolute bond strength in both cases was not influenced by the tendon’s stiffness. However, the τ-δ curves significantly differed in terms of the draw-in rate, showing higher draw-in rate for the UHM CFRP tendon. With the aid of X-ray computed tomography (CT), scanning electron microscopy (SEM) and visual analysis methods, the bond failure interface was located between the CFRP tendon and the surrounding sand-epoxy layer. For further investigation, a simplified finite element analysis (FEA) of the tendon pull-out was performed using a cohesive surface interaction model and the software Abaqus 6.14. A parametric study, varying the tendon-related material properties, revealed the tendon’s longitudinal stiffness to be the only contributor to the difference in the τ-δ curves found in the experiments, thus to the shear stress transfer behaviour between the CFRP tendon and the concrete. In conclusion, the excellent bond of the sand-coated UHM CFRP tendons to HPC as well as the deeper insight in the bond failure mechanism encourages the application of UHM CFRP tendons for prestressing applications. Full article

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4710 KiB

Open AccessArticle

Enhanced Injection Molding Simulation of Advanced Injection Molds

by Béla Zink, Ferenc Szabó, István Hatos, András Suplicz, Norbert Krisztián Kovács, Hajnalka Hargitai, Tamás Tábi and József Gábor Kovács

Polymers 2017, 9(2), 77; https://doi.org/10.3390/polym9020077 - 22 Feb 2017

Cited by 37 | Viewed by 11128

Abstract

The most time-consuming phase of the injection molding cycle is cooling. Cooling efficiency can be enhanced with the application of conformal cooling systems or high thermal conductivity copper molds. The conformal cooling channels are placed along the geometry of the injection-molded product, and [...] Read more.

The most time-consuming phase of the injection molding cycle is cooling. Cooling efficiency can be enhanced with the application of conformal cooling systems or high thermal conductivity copper molds. The conformal cooling channels are placed along the geometry of the injection-molded product, and thus they can extract more heat and heat removal is more uniform than in the case of conventional cooling systems. In the case of copper mold inserts, cooling channels are made by drilling and heat removal is facilitated by the high thermal conductivity coefficient of copper, which is several times that of steel. Designing optimal cooling systems is a complex process; a proper design requires injection molding simulations, but the accuracy of calculations depends on how precise the input parameters and boundary conditions are. In this study, three cooling circuit designs and three mold materials (Ampcoloy 940, 1.2311 (P20) steel, and MS1 steel) were used and compared using numerical methods. The effect of different mold designs and materials on cooling efficiency were examined using calculated and measured results. The simulation model was adjusted to the measurement results by considering the joint gap between the mold inserts. Full article

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1286 KiB

Open AccessArticle

Tailoring Copolymer Properties by Gradual Changes in the Distribution of the Chains Composition Using Semicontinuous Emulsion Polymerization

by Carlos Federico Jasso-Gastinel, Alvaro H. Arnez-Prado, Francisco José Aranda-García, Luis Octavio Sahagún-Aguilar, Fernando A. López-Dellamary Toral, María Elena Hernández-Hernández and Luis Javier González-Ortiz

Polymers 2017, 9(2), 72; https://doi.org/10.3390/polym9020072 - 22 Feb 2017

Cited by 3 | Viewed by 5171

Abstract

To design the properties of a copolymer using free radical polymerization, a semicontinuous process can be applied to vary the instantaneous copolymer composition along the conversion searching for a specific composition spectrum of copolymer chains, which can be termed as weight composition distribution [...] Read more.

To design the properties of a copolymer using free radical polymerization, a semicontinuous process can be applied to vary the instantaneous copolymer composition along the conversion searching for a specific composition spectrum of copolymer chains, which can be termed as weight composition distribution (WCD) of copolymer chains. Here, the styrene-n-butyl acrylate (S/BA) system was polymerized by means of a semicontinuous emulsion process, varying the composition of the comonomer feed to obtain forced composition copolymers (FCCs). Five different feeding profiles were used, searching for a scheme to obtain chains rich in S (looking for considerable modulus), and chains rich in BA (looking for large deformation) as a technique to achieve synergy in copolymer properties; the mechanostatic and dynamic characterization discloses the correspondence between WCD and the bulk properties. ¹H-nuclear magnetic resonance (¹H-NMR) analysis enabled the determination of the cumulative copolymer composition characterization, required to estimate the WCD. The static test (stress-strain) and dynamic mechanical analysis (DMA) were performed following normed procedures. This is the first report that shows very diverse mechanostatic performances of copolymers obtained using the same chemical system and global comonomer composition, forming a comprehensive failure envelope, even though the tests were carried out at the same temperature and cross head speed. The principles for synergic performance can be applied to controlled radical copolymerization, designing the composition variation in individual molecules along the conversion. Full article

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6696 KiB

Open AccessReview

Nanocarbons in Electrospun Polymeric Nanomats for Tissue Engineering: A Review

by Roberto Scaffaro, Andrea Maio, Francesco Lopresti and Luigi Botta

Polymers 2017, 9(2), 76; https://doi.org/10.3390/polym9020076 - 21 Feb 2017

Cited by 80 | Viewed by 10053

Abstract

Electrospinning is a versatile process technology, exploited for the production of fibers with varying diameters, ranging from nano- to micro-scale, particularly useful for a wide range of applications. Among these, tissue engineering is particularly relevant to this technology since electrospun fibers offer topological [...] Read more.

Electrospinning is a versatile process technology, exploited for the production of fibers with varying diameters, ranging from nano- to micro-scale, particularly useful for a wide range of applications. Among these, tissue engineering is particularly relevant to this technology since electrospun fibers offer topological structure features similar to the native extracellular matrix, thus providing an excellent environment for the growth of cells and tissues. Recently, nanocarbons have been emerging as promising fillers for biopolymeric nanofibrous scaffolds. In fact, they offer interesting physicochemical properties due to their small size, large surface area, high electrical conductivity and ability to interface/interact with the cells/tissues. Nevertheless, their biocompatibility is currently under debate and strictly correlated to their surface characteristics, in terms of chemical composition, hydrophilicity and roughness. Among the several nanofibrous scaffolds prepared by electrospinning, biopolymer/nanocarbons systems exhibit huge potential applications, since they combine the features of the matrix with those determined by the nanocarbons, such as conductivity and improved bioactivity. Furthermore, combining nanocarbons and electrospinning allows designing structures with engineered patterns at both nano- and microscale level. This article presents a comprehensive review of various types of electrospun polymer-nanocarbon currently used for tissue engineering applications. Furthermore, the differences among graphene, carbon nanotubes, nanodiamonds and fullerenes and their effect on the ultimate properties of the polymer-based nanofibrous scaffolds is elucidated and critically reviewed. Full article

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11685 KiB

Open AccessReview

Theoretical Methods for Studying DNA Structural Transitions under Applied Mechanical Constraints

by Artem K. Efremov, Ricksen S. Winardhi and Jie Yan

Polymers 2017, 9(2), 74; https://doi.org/10.3390/polym9020074 - 21 Feb 2017

Cited by 2 | Viewed by 6992

Abstract

Recent progress in single-molecule manipulation technologies has made it possible to exert force and torque on individual DNA biopolymers to probe their mechanical stability and interaction with various DNA-binding proteins. It was revealed in these experiments that the DNA structure and formation of [...] Read more.

Recent progress in single-molecule manipulation technologies has made it possible to exert force and torque on individual DNA biopolymers to probe their mechanical stability and interaction with various DNA-binding proteins. It was revealed in these experiments that the DNA structure and formation of nucleoprotein complexes by DNA-architectural proteins can be strongly modulated by an intricate interplay between the entropic elasticity of DNA and its global topology, which is closely related to the mechanical constraints applied to the DNA. Detailed understanding of the physical processes underlying the DNA behavior observed in single-molecule experiments requires the development of a general theoretical framework, which turned out to be a rather challenging task. Here, we review recent advances in theoretical methods that can be used to interpret single-molecule manipulation experiments on DNA. Full article

(This article belongs to the Special Issue Semiflexible Polymers)

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1069 KiB

Open AccessArticle

Polymer Conformation under Confinement

by Stavros Bollas, Kiriaki Chrissopoulou, Konstantinos S. Andrikopoulos, George A. Voyiatzis and Spiros H. Anastasiadis

Polymers 2017, 9(2), 73; https://doi.org/10.3390/polym9020073 - 20 Feb 2017

Cited by 13 | Viewed by 8156

Abstract

The conformation of polymer chains under confinement is investigated in intercalated polymer/layered silicate nanocomposites. Hydrophilic poly(ethylene oxide)/sodium montmorillonite, PEO/Na⁺-MMT, hybrids were prepared utilizing melt intercalation with compositions where the polymer chains are mostly within the ~1 nm galleries of the inorganic [...] Read more.

The conformation of polymer chains under confinement is investigated in intercalated polymer/layered silicate nanocomposites. Hydrophilic poly(ethylene oxide)/sodium montmorillonite, PEO/Na⁺-MMT, hybrids were prepared utilizing melt intercalation with compositions where the polymer chains are mostly within the ~1 nm galleries of the inorganic material. The polymer chains are completely amorphous in all compositions even at temperatures where the bulk polymer is highly crystalline. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) is utilized to investigate the conformation of the polymer chains over a broad range of temperatures from below to much higher than the bulk polymer melting temperature. A systematic increase of the gauche conformation relatively to the trans is found with decreasing polymer content both for the C–C and the C–O bonds that exist along the PEO backbone indicating that the severe confinement and the proximity to the inorganic surfaces results in a more disordered state of the polymer. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials)

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2495 KiB

Open AccessArticle

Chemical Modification of Butyl Rubber with Maleic Anhydride via Nitroxide Chemistry and Its Application in Polymer Blends

by José Bonilla-Cruz, Brenda Hernández-Mireles, Ricardo Mendoza-Carrizales, Luis A. Ramírez-Leal, Román Torres-Lubián, Luis F. RamosdeValle, Donald R. Paul and Enrique Saldívar-Guerra

Polymers 2017, 9(2), 63; https://doi.org/10.3390/polym9020063 - 20 Feb 2017

Cited by 14 | Viewed by 9800

Abstract

Butyl rubber (isobutylene–isoprene–rubber, IIR) was functionalized in solution with a nitroxide moiety taking advantage of the unsaturations present in the isoprene units of IIR, and was further grafted with maleic anhydride (MA) or styrene–MA (SMA) to produce IIR-g-MA and IIR-g [...] Read more.

Butyl rubber (isobutylene–isoprene–rubber, IIR) was functionalized in solution with a nitroxide moiety taking advantage of the unsaturations present in the isoprene units of IIR, and was further grafted with maleic anhydride (MA) or styrene–MA (SMA) to produce IIR-g-MA and IIR-g-SMA. In one of the functionalization techniques used, the molecular structure of the IIR was preserved as the chain-breaking reactions are prevented from occurring. The resulting graft copolymers were tested as compatiblizers/impact modifiers blended with Nylon-6, and one of them was preliminarily tested as a coupling agent in the preparation of nanocomposites of IIR and an organo-clay. Blends of PA-6/IIR-g-MA exhibited a significant increase in impact resistance at increasing loads of the modified IIR, as well as a good rubber particle dispersion in the polyamide matrix. On the other hand, the performance of IIR-g-SMA as an impact modifier of PA, or as a coupling agent in the preparation of rubber-organoclay nanocomposites, is marginal. Full article

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2278 KiB

Open AccessArticle

Optical Properties and Amplified Spontaneous Emission of Novel MDMO-PPV/C500 Hybrid

by Rasha A. Abumosa, Bandar Ali Al-Asbahi and Mohamad Saleh AlSalhi

Polymers 2017, 9(2), 71; https://doi.org/10.3390/polym9020071 - 17 Feb 2017

Cited by 4 | Viewed by 5394

Abstract

The influence of the solvent nature on optical properties of poly[2-methoxy-5-3,7-dimethyloctyloxy-1,4-phenylenevinylene] (MDMO-PPV)/Coumarine 500 (C500) have been investigated. In addition, the amplified spontaneous emission (ASE) from MDMO-PPV and efficient energy transfer between the MDMO-PPV and C500 has been verified. The MDMO-PPV was dissolved in [...] Read more.

The influence of the solvent nature on optical properties of poly[2-methoxy-5-3,7-dimethyloctyloxy-1,4-phenylenevinylene] (MDMO-PPV)/Coumarine 500 (C500) have been investigated. In addition, the amplified spontaneous emission (ASE) from MDMO-PPV and efficient energy transfer between the MDMO-PPV and C500 has been verified. The MDMO-PPV was dissolved in aromatic and nonaromatic solvents, while the solution blending method was employed to prepare the MDMO-PPV:C500 hybrid. The quantum yield of the MDMO-PPV was found to increase with the reduction of a few factors such as polarity index of the solvent, absorption cross section (σ_a), emission cross section (σ_e), and extinction coefficient (ε_max). The fluorescence spectra of the MDMO-PPV appears from two vibronic band transitions (0-0, 0-1) and the ASE occurs at 0-1 transition, which was verified by the ASE from MDMO-PPV. The MDMO-PPV in toluene exhibited the best ASE efficiency due to its high quantum yield compared with other solvents. Strong overlap between the absorption spectrum of MDMO-PPV and emission spectrum of C500 confirmed the efficient energy transfer between them. Moreover, the ASE for energy transfer of the MDMO-PPV:C500 hybrid was proved. Full article

(This article belongs to the Special Issue Polymer Blends 2017)

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2080 KiB

Open AccessReview

Bio-Based Adhesives and Evaluation for Wood Composites Application

by Fatemeh Ferdosian, Zihe Pan, Guchuhan Gao and Boxin Zhao

Polymers 2017, 9(2), 70; https://doi.org/10.3390/polym9020070 - 17 Feb 2017

Cited by 162 | Viewed by 23785

Abstract

There has been a rapid growth in research and innovation of bio-based adhesives in the engineered wood product industry. This article reviews the recent research published over the last few decades on the synthesis of bio-adhesives derived from such renewable resources as lignin, [...] Read more.

There has been a rapid growth in research and innovation of bio-based adhesives in the engineered wood product industry. This article reviews the recent research published over the last few decades on the synthesis of bio-adhesives derived from such renewable resources as lignin, starch, and plant proteins. The chemical structure of these biopolymers is described and discussed to highlight the active functional groups that are used in the synthesis of bio-adhesives. The potentials and drawbacks of each biomass are then discussed in detail; some methods have been suggested to modify their chemical structures and to improve their properties including water resistance and bonding strength for their ultimate application as wood adhesives. Moreover, this article includes discussion of techniques commonly used for evaluating the petroleum-based wood adhesives in terms of mechanical properties and penetration behavior, which are expected to be more widely applied to bio-based wood adhesives to better evaluate their prospect for wood composites application. Full article

(This article belongs to the Special Issue Renewable Polymeric Adhesives)

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1639 KiB

Open AccessArticle

Synthesis of Aggregation-Induced Emission-Active Conjugated Polymers Composed of Group 13 Diiminate Complexes with Tunable Energy Levels via Alteration of Central Element

by Shunichiro Ito, Amane Hirose, Madoka Yamaguchi, Kazuo Tanaka and Yoshiki Chujo

Polymers 2017, 9(2), 68; https://doi.org/10.3390/polym9020068 - 16 Feb 2017

Cited by 26 | Viewed by 6212

Abstract

Conjugated polymers containing boron and gallium diiminate complexes were prepared with various electron-donating comonomers via pre- and post-complexation methods, respectively. From a comparison of emission quantum yields between solution and film states, it was seen that all polymers containing group 13 elements possessed [...] Read more.

Conjugated polymers containing boron and gallium diiminate complexes were prepared with various electron-donating comonomers via pre- and post-complexation methods, respectively. From a comparison of emission quantum yields between solution and film states, it was seen that all polymers containing group 13 elements possessed an aggregation-induced emission property. Additionally, the frontier orbital energies and the optical and electrochemical properties of the polymers can be tuned by altering a central element at the complex moieties as well as by changing a comonomer unit. In particular, it was demonstrated that the gallium atom can contribute to stabilizing the energy levels of the lowest unoccupied molecular orbitals, resulting in narrow band gaps of the conjugated polymers. This study presents the potential of gallium not only for preparing solid-state emissive conjugated polymers but also for fabricating low-band gap materials by employing the conjugated ligand. Full article

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4608 KiB

Open AccessReview

Polymers in Carbon Dots: A Review

by Yiqun Zhou, Shiv K. Sharma, Zhili Peng and Roger M. Leblanc

Polymers 2017, 9(2), 67; https://doi.org/10.3390/polym9020067 - 16 Feb 2017

Cited by 119 | Viewed by 18315

Abstract

Carbon dots (CDs) have been widely studied since their discovery in 2004 as a green substitute of the traditional quantum dots due to their excellent photoluminescence (PL) and high biocompatibility. Meanwhile, polymers have increasingly become an important component for both synthesis and modification [...] Read more.

Carbon dots (CDs) have been widely studied since their discovery in 2004 as a green substitute of the traditional quantum dots due to their excellent photoluminescence (PL) and high biocompatibility. Meanwhile, polymers have increasingly become an important component for both synthesis and modification of CDs to provide polymeric matrix and enhance their PL property. Furthermore, critical analysis of composites of CDs and polymers has not been available. Herein, in this review, we summarized the use of polymers in the synthesis and functionalization of CDs, and the applications of these CDs in various fields. Full article

(This article belongs to the Special Issue Renewable Polymeric Adhesives)

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1240 KiB

Open AccessArticle

Characterization of Responsive Hydrogel Nanoparticles upon Polyelectrolyte Complexation

by Su-Kyoung Lee, Gyuri Hwang, Jihyun Woo, Joseph Park and Jongseong Kim

Polymers 2017, 9(2), 66; https://doi.org/10.3390/polym9020066 - 16 Feb 2017

Cited by 6 | Viewed by 4670

Abstract

Characterization of responsive hydrogels and their interaction with other molecules have significantly expanded our understanding of the functional materials. We here report on the response of poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAm-co-AAc) nanogels to the addition of the poly(allylamine hydrochloride) [...] Read more.

Characterization of responsive hydrogels and their interaction with other molecules have significantly expanded our understanding of the functional materials. We here report on the response of poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAm-co-AAc) nanogels to the addition of the poly(allylamine hydrochloride) (PAH) in aqueous dispersions. We find that the hydrodynamic radius and stability of nanogels are dependent on the PAH/nanogel stoichiometry. If the nanogel solution is titrated with very small aliquots of PAH, the nanogels decrease in radius until the equivalence point, followed by aggregation at suprastoichiometric PAH additions. Conversely, when titrated with large aliquots, the nanogel charge switches rapidly from anionic to cationic, and no aggregation is observed. This behavior correlates well with electrophoretic mobility measurements, which shows the nanogel charge transitioning from negative to positive upon PAH addition. The volume phase transition temperature (VPTT) of the nanogels is also measured to discover the effect of polyelectrolyte complexation on the deswelling thermodynamics. These data show that charge neutralization upon PAH addition decreases the VPTT of the nanogel at pH 6.5. However, if an excess amount of PAH is added to the nanogel solution, the VPTT shifts back to higher temperatures due to the formation of a net positive charge in the nanogel network. Full article

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3268 KiB

Open AccessArticle

Degradation of Polyester Polyurethane by Bacterial Polyester Hydrolases

by Juliane Schmidt, Ren Wei, Thorsten Oeser, Lukas Andre Dedavid e Silva, Daniel Breite, Agnes Schulze and Wolfgang Zimmermann

Polymers 2017, 9(2), 65; https://doi.org/10.3390/polym9020065 - 16 Feb 2017

Cited by 106 | Viewed by 16656

Abstract

Polyurethanes (PU) are widely used synthetic polymers. The growing amount of PU used industrially has resulted in a worldwide increase of plastic wastes. The related environmental pollution as well as the limited availability of the raw materials based on petrochemicals requires novel solutions [...] Read more.

Polyurethanes (PU) are widely used synthetic polymers. The growing amount of PU used industrially has resulted in a worldwide increase of plastic wastes. The related environmental pollution as well as the limited availability of the raw materials based on petrochemicals requires novel solutions for their efficient degradation and recycling. The degradation of the polyester PU Impranil DLN by the polyester hydrolases LC cutinase (LCC), TfCut2, Tcur1278 and Tcur0390 was analyzed using a turbidimetric assay. The highest hydrolysis rates were obtained with TfCut2 and Tcur0390. TfCut2 also showed a significantly higher substrate affinity for Impranil DLN than the other three enzymes, indicated by a higher adsorption constant K. Significant weight losses of the solid thermoplastic polyester PU (TPU) Elastollan B85A-10 and C85A-10 were detected as a result of the enzymatic degradation by all four polyester hydrolases. Within a reaction time of 200 h at 70 °C, LCC caused weight losses of up to 4.9% and 4.1% of Elastollan B85A-10 and C85A-10, respectively. Gel permeation chromatography confirmed a preferential degradation of the larger polymer chains. Scanning electron microscopy revealed cracks at the surface of the TPU cubes as a result of enzymatic surface erosion. Analysis by Fourier transform infrared spectroscopy indicated that the observed weight losses were a result of the cleavage of ester bonds of the polyester TPU. Full article

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5395 KiB

Open AccessArticle

Sustainable and Low Viscous 1-Allyl-3-methylimidazolium Acetate + PEG Solvent for Cellulose Processing

by Airong Xu and Quan Li

Polymers 2017, 9(2), 54; https://doi.org/10.3390/polym9020054 - 16 Feb 2017

Cited by 9 | Viewed by 5080

Abstract

Developing sustainable, low viscous and efficient solvents are always advantageous to the processing/fabricating of cellulose materials in practical applications. To this end, in this work novel solvents were developed; ([Amim][CH₃COO]/PEG) by dissolving polyethylene glycol 200 (PEG-200) in 1-allyl-3-methylimidazolium acetate ([Amim][CH₃ [...] Read more.

Developing sustainable, low viscous and efficient solvents are always advantageous to the processing/fabricating of cellulose materials in practical applications. To this end, in this work novel solvents were developed; ([Amim][CH₃COO]/PEG) by dissolving polyethylene glycol 200 (PEG-200) in 1-allyl-3-methylimidazolium acetate ([Amim][CH₃COO]). The solubilities of cellulose in [Amim][CH₃COO]/PEG solvents were determined as a function of temperature, and the possible dissolution mechanism of cellulose in [Amim][CH₃COO]/PEG solvent was investigated. The novel solvent exhibits outstanding advantages for good dissolution capacity of cellulose, such as low viscosity, negligible vapor pressure, and recycling capability. The [CH₃COO]⁻ anion and the [Amim]⁺ cation of [Amim][CH₃COO] in [Amim][CH₃COO]/PEG-10 are the driving force for cellulose dissolution verified by the ¹³C NMR spectra. In addition, the regenerated cellulose films from [Amim][CH₃COO]/PEG solvent were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and thermogravimetric analysis (TGA) to estimate their morphologies and structures. Full article

(This article belongs to the Collection Polysaccharides)

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2615 KiB

Open AccessArticle

Enhancement of Curcumin Bioavailability Using Nanocellulose Reinforced Chitosan Hydrogel

by Thennakoon M. Sampath Udeni Gunathilake, Yern Chee Ching and Cheng Hock Chuah

Polymers 2017, 9(2), 64; https://doi.org/10.3390/polym9020064 - 15 Feb 2017

Cited by 110 | Viewed by 12336

Abstract

A unique biodegradable, superporous, swellable and pH sensitive nanocellulose reinforced chitosan hydrogel with dynamic mechanical properties was prepared for oral administration of curcumin. Curcumin, a less water-soluble drug was used due to the fact that the fast swellable, superporous hydrogel could release a [...] Read more.

A unique biodegradable, superporous, swellable and pH sensitive nanocellulose reinforced chitosan hydrogel with dynamic mechanical properties was prepared for oral administration of curcumin. Curcumin, a less water-soluble drug was used due to the fact that the fast swellable, superporous hydrogel could release a water-insoluble drug to a great extent. CO₂ gas foaming was used to fabricate hydrogel as it eradicates using organic solvents. Field emission scanning electron microscope images revealed that the pore size significantly increased with the formation of widely interconnected porous structure in gas foamed hydrogels. The maximum compression of pure chitosan hydrogel was 25.9 ± 1 kPa and it increased to 38.4 ± 1 kPa with the introduction of 0.5% cellulose nanocrystals. In vitro degradation of hydrogels was found dependent on the swelling ratio and the amount of CNC of the hydrogel. All the hydrogels showed maximum swelling ratios greater than 300%. The 0.5% CNC-chitosan hydrogel showed the highest swelling ratio of 438% ± 11%. FTIR spectrum indicated that there is no interaction between drug and ingredients present in hydrogels. The drug release occurred in non-Fickian (anomalous) manner in simulated gastric medium. The drug release profiles of hydrogels are consistent with the data obtained from the swelling studies. After gas foaming of the hydrogel, the drug loading efficiency increased from 41% ± 2.4% to 50% ± 2.0% and release increased from 0.74 to 1.06 mg/L. The drug release data showed good fitting to Ritger-Peppas model. Moreover, the results revealed that the drug maintained its chemical activity after in vitro release. According to the results of this study, CNC reinforced chitosan hydrogel can be suggested to improve the bioavailability of curcumin for the absorption from stomach and upper intestinal tract. Full article

(This article belongs to the Collection Polysaccharides)

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9794 KiB

Open AccessArticle

Mechanical and Electrical Properties of Sulfur-Containing Polymeric Materials Prepared via Inverse Vulcanization

by Sergej Diez, Alexander Hoefling, Patrick Theato and Werner Pauer

Polymers 2017, 9(2), 59; https://doi.org/10.3390/polym9020059 - 15 Feb 2017

Cited by 56 | Viewed by 10252

Abstract

Recently, new methods have been developed for the utilization of elemental sulfur as a feedstock for novel polymeric materials. One promising method is the inverse vulcanization, which is used to prepare polymeric structures derived from sulfur and divinyl comonomers. However, the mechanical and [...] Read more.

Recently, new methods have been developed for the utilization of elemental sulfur as a feedstock for novel polymeric materials. One promising method is the inverse vulcanization, which is used to prepare polymeric structures derived from sulfur and divinyl comonomers. However, the mechanical and electrical properties of the products are virtually unexplored. Hence, in the present study, we synthesized a 200 g scale of amorphous, hydrophobic as well as translucent, hyperbranched polymeric sulfur networks that provide a high thermal resistance (>220 °C). The polymeric material properties of these sulfur copolymers can be controlled significantly by varying the monomers as well as the feed content. The investigated comonomers are divinylbenzene (DVB) and 1,3-diisopropenylbenzene (DIB). Plastomers with low elastic content and high shape retention containing 12.5%–30% DVB as well as low viscose waxy plastomers with a high flow behavior containing a high DVB content of 30%–35% were obtained. Copolymers with 15%–30% DIB act, on the one hand, as thermoplastics and, on the other hand, as vitreous thermosets with a DIB of 30%–35%. Results of the thermogravimetric analysis (TGA), the dynamic scanning calorimetry (DSC) and mechanical characterization, such as stress–strain experiments and dynamic mechanical thermal analysis, are discussed with the outcome that they support the assumption of a polymeric cross-linked network structure in the form of hyper-branched polymers. Full article

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1390 KiB

Open AccessArticle

Wide-Range Magnetoelectric Response on Hybrid Polymer Composites Based on Filler Type and Content

by Pedro Martins, Marco Silva, Silvia Reis, Nélson Pereira, Harvey Amorín and Senentxu Lanceros-Mendez

Polymers 2017, 9(2), 62; https://doi.org/10.3390/polym9020062 - 14 Feb 2017

Cited by 20 | Viewed by 5838

Abstract

In order to obtain a wide-range magnetoelectric (ME) response on a ME nanocomposite that matches industry requirements, Tb0.3Dy0.7Fe1.92 (Terfenol-D)/CoFe₂O₄/P(VDF-TrFE) flexible films were produced by the solvent casting technique and their morphologic, piezoelectric, magnetic and magnetoelectric properties were investigated. The [...] Read more.

In order to obtain a wide-range magnetoelectric (ME) response on a ME nanocomposite that matches industry requirements, Tb0.3Dy0.7Fe1.92 (Terfenol-D)/CoFe₂O₄/P(VDF-TrFE) flexible films were produced by the solvent casting technique and their morphologic, piezoelectric, magnetic and magnetoelectric properties were investigated. The obtained composites revealed a high piezoelectric response (≈−18 pC·N⁻¹) that is independent of the weight ratio between the fillers. In turn, the magnetic properties of the composites were influenced by the composite composition. It was found that the magnetization saturation values decreased with the increasing CoFe₂O₄ content (from 18.5 to 13.3 emu·g⁻¹) while the magnetization and coercive field values increased (from 3.7 to 5.5 emu·g⁻¹ and from 355.7 to 1225.2 Oe, respectively) with the increasing CoFe₂O₄ content. Additionally, the films showed a wide-range dual-peak ME response at room temperature with the ME coefficient increasing with the weight content of Terfenol-D, from 18.6 to 42.3 mV·cm⁻¹·Oe⁻¹. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials)

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2038 KiB

Open AccessArticle

Characterization of Comb-Shaped Copolymers by Multidetection SEC, DLS and SANS

by Giulia Gelardi, Nicolas Sanson, Gergely Nagy and Robert J. Flatt

Polymers 2017, 9(2), 61; https://doi.org/10.3390/polym9020061 - 14 Feb 2017

Cited by 27 | Viewed by 7710

Abstract

PolyCarboxylate ether-based superplasticizers (PCEs) are a type of comb-shaped copolymers used as polymeric dispersants in cementitious materials. PCEs have a high degree of dispersity, which limits the suitability of conventional characterization techniques, such as Size Exclusion Chromatography (SEC). Properties of PCEs strongly depend [...] Read more.

PolyCarboxylate ether-based superplasticizers (PCEs) are a type of comb-shaped copolymers used as polymeric dispersants in cementitious materials. PCEs have a high degree of dispersity, which limits the suitability of conventional characterization techniques, such as Size Exclusion Chromatography (SEC). Properties of PCEs strongly depend on their molecular structure and a comprehensive characterization is needed to fully understand the structure–property relationships. PCEs with well-defined molecular structures were synthesized to study their solution conformation by SEC and scattering techniques. The combined use of SEC, dynamic light scattering and small-angle neutron scattering allowed us to demonstrate the validity of a scaling law describing the radius of gyration of comb-shaped copolymers as a function of their molecular structure. Moreover, we show that the use of SEC with standard calibration, although widely spread, is not adequate for PCEs. Full article

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5813 KiB

Open AccessArticle

Novel Melt-Spun Polymer-Optical Poly(methyl methacrylate) Fibers Studied by Small-Angle X-ray Scattering

by Markus Beckers, Thomas Vad, Benjamin Mohr, Benjamin Weise, Wilhelm Steinmann, Thomas Gries, Gunnar Seide, Emmanuel Kentzinger and Christian-Alexander Bunge

Polymers 2017, 9(2), 60; https://doi.org/10.3390/polym9020060 - 13 Feb 2017

Cited by 9 | Viewed by 9008

Abstract

The structural properties of novel melt-spun polymer optical fibers (POFs) are investigated by small-angle X-ray scattering. The amorphous PMMA POFs were subjected to a rapid cooling in a water quench right after extrusion in order to obtain a radial refractive index profile. Four [...] Read more.

The structural properties of novel melt-spun polymer optical fibers (POFs) are investigated by small-angle X-ray scattering. The amorphous PMMA POFs were subjected to a rapid cooling in a water quench right after extrusion in order to obtain a radial refractive index profile. Four fiber samples were investigated with small-angle X-ray scattering (SAXS). The resulting distance-distribution functions obtained from the respective equatorial and meridional SAXS data exhibit a real-space correlation peak indicative of periodic cross-sectional and axial variations in the scattering density contrast. Simple model calculations demonstrate how the structural information contained particularly in the equatorial distance distribution function can be interpreted. The respective results are qualitatively verified for one of the fiber samples by comparison of the model curve with the measured SAXS data. Eventually, the study confirms that the cross-sectional variation of the (scattering-) density is the main reason for the formation of radial refractive-index profiles in the POFs. Full article

(This article belongs to the Special Issue Polymeric Fibers)

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1955 KiB

Open AccessArticle

Hydrophilic Polyelectrolyte Multilayers Improve the ELISA System: Antibody Enrichment and Blocking Free

by Xing Lai, Gan Gao, Junji Watanabe, Huiyu Liu and Heyun Shen

Polymers 2017, 9(2), 51; https://doi.org/10.3390/polym9020051 - 12 Feb 2017

Cited by 13 | Viewed by 7003

Abstract

In this study, polyelectrolyte multilayers were fabricated on a polystyrene (PS) plate using a Layer-by-Layer (LbL) self-assembly technique. The resulting functional platform showed improved performance compared with conventional enzyme-linked immunosorbent assay (ELISA) systems. Poly(diallyldimethylammonium chloride) (PDDA) and poly(acrylic acid) (PAA) were used as [...] Read more.

In this study, polyelectrolyte multilayers were fabricated on a polystyrene (PS) plate using a Layer-by-Layer (LbL) self-assembly technique. The resulting functional platform showed improved performance compared with conventional enzyme-linked immunosorbent assay (ELISA) systems. Poly(diallyldimethylammonium chloride) (PDDA) and poly(acrylic acid) (PAA) were used as cationic and anionic polyelectrolytes. On the negatively-charged (PDDA/PAA)₃ polyelectrolyte multilayers the hydrophilic PAA surface could efficiently decrease the magnitude of the noise signal, by inhibiting nonspecific adsorption even without blocking reagent adsorption. Moreover, the (PDDA/PAA)₃ substrate covalently immobilized the primary antibody, greatly increasing the amount of primary antibody adsorption and enhancing the specific detection signal compared with a conventional PS plate. The calibration curve of the (PDDA/PAA)₃ substrate showed a wide linear range, for concentrations from 0.033 to 33 nM, a large specific signal change, and a detection limit of 33 pM, even though the conventional blocking reagent adsorption step was omitted. The (PDDA/PAA)₃ substrate provided a high-performance ELISA system with a simple fabrication process and high sensitivity; the system presented here shows potential for a variety of immunosensor applications. Full article

(This article belongs to the Collection Polyelectrolytes)

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2667 KiB

Open AccessArticle

Visible Light-Induced Metal Free Surface Initiated Atom Transfer Radical Polymerization of Methyl Methacrylate on SBA-15

by Liang Ma, Na Li, Jian Zhu and Xiaodong Chen

Polymers 2017, 9(2), 58; https://doi.org/10.3390/polym9020058 - 10 Feb 2017

Cited by 24 | Viewed by 7538

Abstract

Surface-initiated atom transfer radical polymerization (SI-ATRP) is one of the most versatile techniques to modify the surface properties of materials. Recent developed metal-free SI-ATRP makes such techniques more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide, [...] Read more.

Surface-initiated atom transfer radical polymerization (SI-ATRP) is one of the most versatile techniques to modify the surface properties of materials. Recent developed metal-free SI-ATRP makes such techniques more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide, and N,N-dimethylaminoethyl methacrylate, on the surface of SBA-15 was reported to fabricate organic-inorganic hybrid materials. A SBA-15-based polymeric composite with an adjustable graft ratio was obtained. The structure evolution during the SI-ATRP modification of SBA-15 was monitored and verified by FT-IR, XPS, TGA, BET, and TEM. The obtained polymeric composite showed enhanced adsorption ability for the model compound toluene in aqueous conditions. This procedure provides a low-cost, readily available, and easy modification method to synthesize polymeric composites without the contamination of metal. Full article

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8701 KiB

Open AccessArticle

Trapping a Knot into Tight Conformations by Intra-Chain Repulsions

by Liang Dai and Patrick S. Doyle

Polymers 2017, 9(2), 57; https://doi.org/10.3390/polym9020057 - 10 Feb 2017

Cited by 13 | Viewed by 5438

Abstract

Knots can occur in biopolymers such as DNA and peptides. In our previous study, we systematically investigated the effects of intra-chain interactions on knots and found that long-range repulsions can surprisingly tighten knots. Here, we use this knowledge to trap a knot into [...] Read more.

Knots can occur in biopolymers such as DNA and peptides. In our previous study, we systematically investigated the effects of intra-chain interactions on knots and found that long-range repulsions can surprisingly tighten knots. Here, we use this knowledge to trap a knot into tight conformations in Langevin dynamics simulations. By trapping, we mean that the free energy landscape with respect to the knot size exhibits a potential well around a small knot size in the presence of long-range repulsions, and this potential can well lead to long-lived tight knots when its depth is comparable to or larger than thermal energy. We tune the strength of intra-chain repulsion such that a knot is weakly trapped. Driven by thermal fluctuations, the knot can escape from the trap and is then re-trapped. We find that the knot switches between tight and loose conformations—referred to as “knot breathing”. We use a Yukawa potential to model screened electrostatic interactions to explore the relevance of knot trapping and breathing in charged biopolymers. We determine the minimal screened length and the minimal strength of repulsion for knot trapping. We find that Coulomb-induced knot trapping is possible to occur in single-stranded DNA and peptides for normal ionic strengths. Full article

(This article belongs to the Special Issue Semiflexible Polymers)

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3984 KiB

Open AccessArticle

Entropic Interactions between Two Knots on a Semiflexible Polymer

by David Richard, Stefanie Stalter, Jonathan Tammo Siebert, Florian Rieger, Benjamin Trefz and Peter Virnau

Polymers 2017, 9(2), 55; https://doi.org/10.3390/polym9020055 - 09 Feb 2017

Cited by 7 | Viewed by 6427

Abstract

Two knots on a string can either be separated or intertwined, and may even pass through each other. At the microscopic scale, such transitions may occur spontaneously, driven by thermal fluctuations, and can be associated with a topological free energy barrier. In this [...] Read more.

Two knots on a string can either be separated or intertwined, and may even pass through each other. At the microscopic scale, such transitions may occur spontaneously, driven by thermal fluctuations, and can be associated with a topological free energy barrier. In this manuscript, we study the respective location of a trefoil (

3_{1}

) and a figure-eight (

4_{1}

) knot on a semiflexible polymer, which is parameterized to model dsDNA in physiological conditions. Two cases are considered: first, end monomers are grafted to two confining walls of varying distance. Free energy profiles and transition barriers are then compared to a subset of free chains, which contain exactly one

3_{1}

and one

4_{1}

knot. For the latter, we observe a small preference to form an intertwined state, which can be associated with an effective entropic attraction. However, the respective free energy barrier is so small that we expect transition events to occur spontaneously and frequently in polymers and DNA, which are highly knotted for sufficient strain lengths. Full article

(This article belongs to the Special Issue Semiflexible Polymers)

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9234 KiB

Open AccessArticle

A Biodegradable Microneedle Cuff for Comparison of Drug Effects through Perivascular Delivery to Balloon-Injured Arteries

by Dae-Hyun Kim, Eui Hwa Jang, Kang Ju Lee, Ji Yong Lee, Seung Hyun Park, Il Ho Seo, Kang Woog Lee, Seung Hyun Lee, WonHyoung Ryu and Young-Nam Youn

Polymers 2017, 9(2), 56; https://doi.org/10.3390/polym9020056 - 08 Feb 2017

Cited by 12 | Viewed by 7210

Abstract

Restenosis at a vascular anastomosis site is a major cause of graft failure and is difficult to prevent by conventional treatment. Perivascular drug delivery has advantages as drugs can be diffused to tunica media and subintima while minimizing the direct effect on endothelium. [...] Read more.

Restenosis at a vascular anastomosis site is a major cause of graft failure and is difficult to prevent by conventional treatment. Perivascular drug delivery has advantages as drugs can be diffused to tunica media and subintima while minimizing the direct effect on endothelium. This in vivo study investigated the comparative effectiveness of paclitaxel, sirolimus, and sunitinib using a perivascular biodegradable microneedle cuff. A total of 31 New Zealand white rabbits were used. Rhodamine was used to visualize drug distribution (n = 3). Sirolimus- (n = 7), sunitinib- (n = 7), and paclitaxel-loaded (n = 7) microneedle cuffs were placed at balloon-injured abdominal aortae and compared to drug-free cuffs (n = 7). Basic histological structures were not affected by microneedle devices, and vascular wall thickness of the device-only group was similar to that of normal artery. Quantitative analysis revealed significantly decreased neointima formation in all drug-treated groups (p < 0.001). However, the tunica media layer of the paclitaxel-treated group was significantly thinner than that of other groups and also showed the highest apoptotic ratio (p < 0.001). Proliferating cell nuclear antigen (PCNA)-positive cells were significantly reduced in all drug-treated groups. Sirolimus or sunitinib appeared to be more appropriate for microneedle devices capable of slow drug release because vascular wall thickness was minimally affected. Full article

(This article belongs to the Special Issue Advance of Polymers Applied to Biomedical Applications: Cell Scaffolds)

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5403 KiB

Open AccessArticle

Improvement of Dielectric, Magnetic and Thermal Properties of OPEFB Fibre–Polycaprolactone Composite by Adding Ni–Zn Ferrite

by Ahmad F. Ahmad, Zulkifly Abbas, Suzan J. Obaiys and Daw M. Abdalhadi

Polymers 2017, 9(2), 12; https://doi.org/10.3390/polym9020012 - 08 Feb 2017

Cited by 21 | Viewed by 5892

Abstract

The dielectric and magnetic behaviour and thermal properties of composites based on nickel–zinc ferrite (NZF) filler can be improved by the addition of various types of materials. Amongst others, ferrite–polymer composites have been subjected to a wide range of research, due to their [...] Read more.

The dielectric and magnetic behaviour and thermal properties of composites based on nickel–zinc ferrite (NZF) filler can be improved by the addition of various types of materials. Amongst others, ferrite–polymer composites have been subjected to a wide range of research, due to their extensive applications: electromagnetic interference shielding, microwave absorption, electrodes and sensors. Currently, the interest in scientific and technical searches for the potential outcomes of ferrite–polymer materials due to their different uses in applications such as telecommunication applications, microwave devices and electromagnetic interference shielding has been growing stronger. The dielectric and magnetic behaviour and thermal properties for such composite materials depend on size, shape and the amount of filler addition. Nickel–zinc ferrite material was prepared using the conventional solid-state reaction technique. This study highlights the development of microwave-absorbing material from NZF by adding natural fibres, Oil Palm Empty Fruit Bunch (OPEFB) and polycaprolactone (PCL). OPEFB is considered in this study because it is a solid waste product of the oil palm milling process which is widely and cheaply available. The use of OPEFB in this product may save the environment from oil palm solid waste. A Thermal Hake blending machine was used in blending the powder structure of NZF + OPEFB + PCL, which made it homogeneous. These composites were characterized by the use of Fourier transform infrared (FTIR) spectrometry and scanning electron microscopy (SEM). The thermal degradation behaviour of the composites was analyzed using thermogravimetric analysis (TGA) and differential thermogravimetric (DTG) thermograms. The effective permittivity and effective permeability was obtained over a broad frequency range from 8 to 12 GHz at room temperature. It was observed that the values of effective permittivity and permeability increased as the content of NZF content increased. A rectangular waveguide connected to a microwave vector network analyser (PNA) (HP/Agilent model PNA E8364B) was employed in measuring the reflection coefficient S₁₁ and transmission coefficient S₂₁ parameters of composites for different percentages of NZF filler. This parameter was then used in calculating the microwave absorbing properties (dB). Full article

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3053 KiB

Open AccessArticle

DFT Studies on cis-1,4-Polymerization of Dienes Catalyzed by a Cationic Rare-Earth Metal Complex Bearing an Ancillary PNP Ligand

by Xingbao Wang, Xiaohui Kang, Guangli Zhou, Jingping Qu, Zhaomin Hou and Yi Luo

Polymers 2017, 9(2), 53; https://doi.org/10.3390/polym9020053 - 07 Feb 2017

Cited by 15 | Viewed by 7775

Abstract

Dnsity functional theory (DFT) calculations have been carried out for the highly selective cis-1,4-polymerization of butadiene catalyzed by a cationic rare-earth metal complex bearing an ancillary PNP ligand. It has been found that the chain initiation and propagation of butadiene polymerization occurs [...] Read more.

Dnsity functional theory (DFT) calculations have been carried out for the highly selective cis-1,4-polymerization of butadiene catalyzed by a cationic rare-earth metal complex bearing an ancillary PNP ligand. It has been found that the chain initiation and propagation of butadiene polymerization occurs via the favorable cis-1,4-insertion route. The trans-1,4 and 1,2-insertion are unfavorable both kinetically and thermodynamically. The chain growth follows the π-allyl-insertion mechanism. The analyses of energy decomposition of transition states indicate that the likelihood of rival insertion pathways is predominantly controlled by the interaction energy of butadiene with a metal center and the deformation energy of butadiene moiety. The electronic factor of the central metal has a decisive influence on the cis- vs. trans-insertion and the regioselectivity (cis-1,4- vs. cis-1,2-insertion) is mainly determined by steric hindrance. Tetrahydrofuran (THF) coordination made monomer insertion less favorable compared with THF-free case and had more noticeable impact on the trans-monomer insertion compared with the cis case. During the chain propagation, cis-insertion of monomer facilitates THF de-coordination and the THF molecule could therefore dissociate from the central metal. Full article

(This article belongs to the Special Issue Metal Complexes-Mediated Catalysis in Polymerization)

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2639 KiB

Open AccessReview

Theory of Semiflexible Filaments and Networks

by Fanlong Meng and Eugene M. Terentjev

Polymers 2017, 9(2), 52; https://doi.org/10.3390/polym9020052 - 05 Feb 2017

Cited by 44 | Viewed by 8423

Abstract

We briefly review the recent developments in the theory of individual semiflexible filaments, and of a crosslinked network of such filaments, both permanent and transient. Starting from the free energy of an individual semiflexible chain, models on its force-extension relation and other mechanical [...] Read more.

We briefly review the recent developments in the theory of individual semiflexible filaments, and of a crosslinked network of such filaments, both permanent and transient. Starting from the free energy of an individual semiflexible chain, models on its force-extension relation and other mechanical properties such as Euler buckling are discussed. For a permanently crosslinked network of filaments, theories on how the network responds to deformation are provided, with a focus on continuum approaches. Characteristic features of filament networks, such as nonlinear stress-strain relation, negative normal stress, tensegrity, and marginal stability are discussed. In the new area of transient filament network, where the crosslinks can be dynamically broken and re-formed, we show some recent attempts for understanding the dynamics of the crosslinks, and the related rheological properties, such as stress relaxation, yield stress and plasticity. Full article

(This article belongs to the Special Issue Semiflexible Polymers)

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2024 KiB

Open AccessArticle

The Effect of Molar Mass and Charge Density on the Formation of Complexes between Oppositely Charged Polyelectrolytes

by Feriel Meriem Lounis, Joseph Chamieh, Laurent Leclercq, Philippe Gonzalez and Hervé Cottet

Polymers 2017, 9(2), 50; https://doi.org/10.3390/polym9020050 - 04 Feb 2017

Cited by 13 | Viewed by 6197

Abstract

The interactions between model polyanions and polycations have been studied using frontal continuous capillary electrophoresis (FACCE) which allows the determination of binding stoichiometry and binding constant of the formed polyelectrolyte complex (PEC). In this work, the effect of the poly(l-lysine) (PLL) [...] Read more.

The interactions between model polyanions and polycations have been studied using frontal continuous capillary electrophoresis (FACCE) which allows the determination of binding stoichiometry and binding constant of the formed polyelectrolyte complex (PEC). In this work, the effect of the poly(l-lysine) (PLL) molar mass on the interaction with statistical copolymers of acrylamide and 2-acrylamido-2-methyl-1-propanesulfonate (PAMAMPS) has been systematically investigated for different PAMAMPS chemical charge densities (15% and 100%) and different ionic strengths. The study of the ionic strength dependence of the binding constant allowed the determination of the total number of released counter-ions during the formation of the PEC, which can be compared to the total number of counter-ions initially condensed on the individual polyelectrolyte partners before the association. Interestingly, this fraction of released counter-ions, which was strongly dependent on the PLL molar mass, was almost independent of the PAMAMPS charge density. These findings are useful to predict the binding constant according to the molar mass and charge density of the polyelectrolyte partners. Full article

(This article belongs to the Collection Polyelectrolytes)

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3860 KiB

Open AccessArticle

Polyion Complex Vesicles with Solvated Phosphobetaine Shells Formed from Oppositely Charged Diblock Copolymers

by Keita Nakai, Kazuhiko Ishihara, Michael Kappl, Syuji Fujii, Yoshinobu Nakamura and Shin-ichi Yusa

Polymers 2017, 9(2), 49; https://doi.org/10.3390/polym9020049 - 04 Feb 2017

Cited by 23 | Viewed by 6834

Abstract

Diblock copolymers consisting of a hydrophilic poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) block and either a cationic or anionic block were prepared from (3-(methacrylamido)propyl)trimethylammonium chloride (MAPTAC) or sodium 2-(acrylamido)-2-methylpropanesulfonate (AMPS). Polymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) radical polymerization using a PMPC macro-chain transfer [...] Read more.

Diblock copolymers consisting of a hydrophilic poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) block and either a cationic or anionic block were prepared from (3-(methacrylamido)propyl)trimethylammonium chloride (MAPTAC) or sodium 2-(acrylamido)-2-methylpropanesulfonate (AMPS). Polymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) radical polymerization using a PMPC macro-chain transfer agent. The degree of polymerization for PMPC, cationic PMAPTAC, and anionic PAMPS blocks was 20, 190, and 196, respectively. Combining two solutions of oppositely charged diblock copolymers, PMPC-b-PMAPTAC and PMPC-b-PAMPS, led to the spontaneous formation of polyion complex vesicles (PICsomes). The PICsomes were characterized using ¹H NMR, static abd dynamic light scattering, transmittance electron microscopy (TEM), and atomic force microscopy. Maximum hydrodynamic radius (R_h) for the PICsome was observed at a neutral charge balance of the cationic and anionic diblock copolymers. The R_h value and aggregation number (N_agg) of PICsomes in 0.1 M NaCl was 78.0 nm and 7770, respectively. A spherical hollow vesicle structure was observed in TEM images. The hydrodynamic size of the PICsomes increased with concentration of the diblock copolymer solutions before mixing. Thus, the size of the PICsomes can be controlled by selecting an appropriate preparation method. Full article

(This article belongs to the Collection Polyelectrolytes)

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1194 KiB

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Thermodynamics of a Compressible Maier-Saupe Model Based on the Self-Consistent Field Theory of Wormlike Polymer

by Ying Jiang, Cristina Greco, Kostas Ch. Daoulas and Jeff Z. Y. Chen

Polymers 2017, 9(2), 48; https://doi.org/10.3390/polym9020048 - 04 Feb 2017

Cited by 5 | Viewed by 5922

Abstract

This paper presents a theoretical formalism for describing systems of semiflexible polymers, which can have density variations due to finite compressibility and exhibit an isotropic-nematic transition. The molecular architecture of the semiflexible polymers is described by a continuum wormlike-chain model. The non-bonded interactions [...] Read more.

This paper presents a theoretical formalism for describing systems of semiflexible polymers, which can have density variations due to finite compressibility and exhibit an isotropic-nematic transition. The molecular architecture of the semiflexible polymers is described by a continuum wormlike-chain model. The non-bonded interactions are described through a functional of two collective variables, the local density and local segmental orientation tensor. In particular, the functional depends quadratically on local density-variations and includes a Maier–Saupe-type term to deal with the orientational ordering. The specified density-dependence stems from a free energy expansion, where the free energy of an isotropic and homogeneous homopolymer melt at some fixed density serves as a reference state. Using this framework, a self-consistent field theory is developed, which produces a Helmholtz free energy that can be used for the calculation of the thermodynamics of the system. The thermodynamic properties are analysed as functions of the compressibility of the model, for values of the compressibility realizable in mesoscopic simulations with soft interactions and in actual polymeric materials. Full article

(This article belongs to the Special Issue Semiflexible Polymers)

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