Concentration‐dependent conformation transition of regenerated silk fibroin induced by graphene oxide nanosheets incorporation

Regenerated silk fibroin (RSF)/graphene oxide (GO) nanocomposite has been substantially investigated due to its significant multifunctional potential. Here, in combination of micromorphology, crystalline conformation, dynamic mechanical property characterization, and Fourier self‐deconvolution (FSD) quantitative analysis, we investigated the RSF molecular chains conformation transition induced by GO nanosheet incorporation, and its influence on the structural and mechanical properties of solution casted RSF/GO composite films. The GO nanosheet promoted the silk fibroin molecular chains conformation transition from random coil to β‐sheet structure, and a correlation between β‐sheet structure fraction and GO concentration was revealed. The β‐sheet structure fraction increases further improved the dynamic mechanical property of composite films. Moreover, based on nucleation‐dependent aggregation of silk fibroin molecular chains, a mechanism considering the competition effect between GO concentration and its total surface area was proposed to explain the observed concentration‐dependent conformation transition phenomenon. The study improves our understanding on silk fibroin conformation transition process in RSF/GO composite and would provide a valuable reference for the rational design of bioinspired multifunctional materials with enhanced mechanical properties. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1506–1515     

Polymerization and self‐assembly of thermally responsive in‐chain functionalized double‐hydrophilic macromonomers

Double‐hydrophilic in‐chain functionalized macromonomers consisting of poly(N‐isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) were prepared by a multistep procedure including esterification of PNIPAM monoester of maleic acid with α‐methoxy‐ω‐hydroxypolyoxyethylene or its amidation with α‐methoxy‐ω‐aminopolyoxyethylene. The polymerization of the macromonomers was carried out in aqueous solutions. The temperature was the key parameter controlling the polymerization process that was performed in the organized domains formed by the macromonomers below and above the phase transition temperature (T_tr). Polymacromonomers with higher degrees of polymerization were prepared at temperatures just below the T_tr. Static light scattering measurements on dilute aqueous solutions of thermally‐responsive macromonomers and their polymerization products demonstrated that they formed aggregates below the T_tr. Supramolecular structures with low density cores, formed by the polymacromonomers at room temperature, were imaged by SEM. Morphological tuning was achieved by varying both the composition of the copolymer and the concentration of the aqueous solution. The rheological behavior of the polymacromonomers in 25 wt % aqueous solution was compared to that of the respective macromonomers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4720–4732, 2007     

Brownian dynamics simulation of polyelectrolyte dilute solutions: Relaxation time and elongational flow

The authors used the bead‐and‐spring model and the Brownian dynamics simulation technique including hydrodynamic interaction to study the behavior of dilute polyelectrolyte solutions under elongational flow. First they carried out simulations to determine the longest relaxation time of a polyelectrolyte, finding that the relaxation time depends on the ionic strength of the solution. Then, they studied the coil‐stretch transition of polyelectrolyte molecules in elongational flow and determined the critical value of the elongational rate necessary in order this transition to occur. In this way, they could compute the value of the Deborah number at which coil‐stretch transition sets in for polyelectrolyte dilute solutions. Finally, they studied the power law relationship that relates the critical elongational rate with the molecular weight of the polyelectrolyte. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 714–722, 2007     

Influence of the draw ratio on the tensile and fracture behavior of NMMO regenerated silk fibers

The tensile properties and fracture surfaces of N‐methylmorpholine‐N‐oxide (NMMO) regenerated silk fibroin fibers produced with a range of draw ratios has been characterized and related to their microstructure with data obtained from Raman spectroscopy and birefringence measurements. The spinning process allows control of two different draw ratios, coagulation, and postspinning, and it has been found that the microstructure and the properties of the fibers can be modified by the proper combination of both draw ratios. NMMO regenerated silk fibroin fibers subjected to postspinning drawing yield tensile properties comparable to other regenerated fibers and strain at breaking comparable to natural Bombyx mori silk fibers. Tensile strength; however, is still significantly lower than that of natural fibers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2568–2579, 2007     

Synthesis and properties of fluorine‐containing poly(aryl ether oxadiazole)s

Fluorine‐containing poly(aryl ether 1,3,4‐ozadiazole)s were synthesized by the nucleophilic aromatic substitution reaction of 2,5‐bis(2,3,4,5,6‐pentafluorophenyl)‐1,3,4‐oxadiazole and various bisphenols in the presence of potassium carbonate. The polymerizations were carried out at 30 °C in 1‐methyl‐2‐pyrrolidinone to avoid the gelation caused by a crosslinking reaction at para and ortho carbons to the 1,3,4‐oxidiazole ring. The obtained polymers were all para‐connected linear structures. The obtained fluorine‐containing poly(aryl ether 1,3,4‐ozadiazole)s showed excellent solubility and afforded tough, transparent films by the solution‐casting method. They also exhibited a high glass transition temperature depending on the molecular structure, and the glass transition temperature could be controlled by the bisphenols in the range of 157–257 °C. They showed good thermal stability and excellent hydrophobicity due to the incorporation of the 2,3,5,6‐tetrafluoro‐1,4‐phenylene moiety. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2855–2866, 2007     

Modulating light‐tunable acid sensitivity of a bioinspired polymer simply by adjusting the position of a single methoxy substituent

This article describes a rhodopsin‐inspired photosensitive polymer whose light‐tunable acid sensitivity can be widely modulated simply by adjusting the position of a single methoxy substituent in the aromatic rings of cinnamyl groups. The well‐defined poly(5‐ethyl‐5‐methacryloyloxymethyl‐2‐(p‐methoxystyryl)‐[1,3]dioxane) (PEMpMSD) and poly(5‐ethyl‐5‐methacryloyloxymethyl‐2‐(o‐methoxystyryl)‐[1,3]dioxane) (PEMoMSD) as well as poly(5‐ethyl‐5‐methacryloyloxymethyl‐2‐styryl‐[1,3]dioxane) were synthesized via reversible addition‐fragmentation chain transfer (RAFT) process. The results demonstrated that the para‐methoxy substitution of EMpMSD monomer led to the more shortened initialization period and rapid chain propagation of RAFT process than 5‐ethyl‐5‐methacryloyloxymethyl‐2‐styryl‐[1,3]dioxane monomer under mild visible light radiation at 25 °C. The ortho‐methoxy substitution of PEMoMSD led to high degree of photoinduced Z‐isomerization over 80%. Moreover, the para‐methoxy substitution of PEMpMSD led to the rapid hydrolysis of the cyclic acetal linkages in ambient acid media, while the ortho‐methoxy substitution of PEMoMSD slowed down this hydrolysis. This hydrolysis slowed down on Z‐isomerization particularly in PEMoMSD. These effects widely broadened the tunability of the light‐modulated acid sensitivity. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Morphological development and rheological changes of phenoxy/SAN blends during in‐situ polymerization

This article reports the results of an investigation into the time‐dependent morphological and rheological changes that accompany the in‐situ polymerization of blends composed of poly(hydroxyether of bisphenol A) (phenoxy) and poly(styrene‐co‐acrylonitrile) (SAN). The rheological behavior was monitored continuously during the in‐situ polymerization, whereas the miscibility and phase structure of blends formed in situ were examined at discrete stages of polymerization by differential scanning calorimetry and transmission electron microscopy. In the blend with 30 wt % SAN, a co‐continuous blend morphology was associated with gradual changes in the dynamic moduli, suggesting that phase separation proceeded by spinodal decomposition (SD). In contrast, phenoxy‐rich dispersions were uniformly dispersed in a continuous SAN‐rich matrix in the blend with 50 wt % SAN, and the corresponding rheological signature revealed a sharp initial increase in the dynamic moduli, followed by slower growth after long times, indicative of phase separation via nucleation and growth (NG). The rheological property changes are closely related to morphology development and mechanisms of phase separation induced duringin‐situ polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2614–2619, 2007     

Nonlinear optical properties of regioregular main‐chain polyesters

We have prepared new polyesters containing quadratic, nonlinear optical (NLO) active chromophores covalently incorporated into the main chain. In these polymers, the sequence of the chromophore units along the main chain is rigorously head to tail. All the polyesters are processable, both in the melt and in solution. For one polyester, a full second‐order NLO characterization has been performed. An out‐of‐resonance d₃₃ coefficient of 21 pm/V at 1368 nm has been measured. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2719–2725, 2007     

Fracture surfaces and tensile properties of UV‐irradiated spider silk fibers

A study of the influence of UV radiation on the tensile properties of spider silk has shown that the shape of the stress–strain curves is not affected by 254‐nm irradiation, except for a significant decrease in the tensile strength and strain at breaking. This decrease has been found in both forcibly silked and maximum‐supercontracted fibers, despite the different initial alignments of the protein chains. Local damage is also induced by UV radiation. With this procedure, it is possible to recover and analyze fracture surfaces. These show different granular microstructures that are characteristic of fibers spun from a solution. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 786–793, 2007     

Rheology and morphology change with temperature of SEBS/hydrocarbon oil blends

The effect of hydrocarbon oil incorporation on the rheological and phase behaviors of poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) (SEBS) has been investigated. SEBS‐A1 (neat SEBS) shows a presence of very long relaxation time mode even at the highest temperature carried out here. On the other hand, G′ of SEBS‐A3 (oil concentration = 50 wt %) drastically decreases with increase of temperature at a critical temperature, which can be assigned to be order–disorder transition (ODT). The critical temperature was determined by two rheological criteria. Incorporation of hydrocarbon oil affects the ODT temperature. The rheological response is very sensitive to a few temperature increases around the ODT temperature. Above the critical temperature, G′ finally yields the terminal flow in the low frequency range. The morphological observation at various temperatures was determined using atomic force microscopy (AFM) equipped with environmental controller. This enabled in situ observation of structural change of SEBS induced by temperature and phase transition. We found that the layered texture, mostly aligned along the surface can be seen for SEBS‐A1 ranging from room temperature to 230 °C, though the image contrast reduced by an increase of temperature. SEBS‐A3 showed sphere domains at room temperature and also remains the structure at a critical temperature. The phase separated structure disappeared almost completely above ODT temperature, which was confirmed by the rheologial criteria. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 955–965, 2009     

Novel route to styrene/p‐aminostyrene copolymers

A novel route to styrene/p‐aminostyrene copolymers is described that involves the introduction of amino functionality into the structure of pure monodisperse polystyrene. The simple two‐step synthesis involves the introduction of a bromo group into the aromatic ring by electrophilic substitution and then a palladium‐catalyzed reaction with LiN(SiMe₃)₂ followed by an acid and base treatment to release the free amine. All reactions are carried out at room temperature. This approach avoids the difficulties often associated with the preparation of copolymers from incompatible monomers. The technique also gives a product with a precisely known molecular weight and polydispersity, important parameters governing many physical properties. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1282–1286, 2007     

Synthesis and properties of fluorene‐based fluorinated polymers

Fluorene‐based polymers containing various fluorinated benzene (fluorobenzene, p‐difluorobenzene, and tetrafluorobenzene) moieties were synthesized. In addition, perfluorooctylation of poly‐[(9,9‐dioctylfluorene‐2,7‐diyl)‐co‐(fluorene‐2,7‐diyl)] was carried out to afford fluorene‐based polymers with perfluorooctyl moiety at the 9‐position on the fluorene ring. To evaluate the effect of fluorine moiety, polymers containing nonfluorinated benzene moieties and nonfluorinated octyl groups were synthesized. The photoluminescence measurements indicated that all these polymers exhibited blue emission in solution, but a polymer containing a perfluorooctyl group did not emit in the film state. Polymers containing various fluorinated benzene moieties showed higher fluorescence quantum yields and thermal stability than those containing nonfluorinated benzene. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3143–3150, 2001     

Study of the phase transition of poly(N,N‐diethylacrylamide) in water by rheology and dynamic light scattering

Poly(N,N‐diethylacrylamide) (PDEA) possesses a lower critical solution temperature (LCST) in aqueous media. The solution properties of PDEA at various temperatures have been characterized with techniques such as rheology and dynamic light scattering. There is a decrease in the coil size before the phase transition due to a coil‐to‐globule transition. At the LCST, rheological and dynamic light scattering studies have also confirmed an aggregation phenomenon. This aggregation modifies the rheological properties of the polymer solutions. High frequencies hinder the phase‐transition process and reduce the LCST of the polymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1627–1637, 2003     

A novel silk‐based segmented block copolymer containing GlyAlaGlyAla β‐sheets templated by phenoxathiin

A novel segmented block copolymer, containing polyethylene glycol segment and GlyAlaGlyAla sequence derived from B. mori silk, has been prepared as a model for silk‐based materials using both solution and interfacial techniques. Inherent viscosity, size exclusion chromatography, and light‐scattering measurements gave molecular weight between M_w 34,000–39,000. Evidence for phase separation was provided by differential scanning calorimetry, which gave two T_g's at −57 °C and 111 °C, and transmission electron microscopy, which showed a morphology in which the peptide domain, estimated to be about 20–50 nm, was dispersed in the continuous polyether phase. Solid‐state FTIR spectroscopic results showed that the polymer contained both parallel and antiparallel β‐sheet stacks, and that the solution‐polymerized material has the higher β‐sheet content. This was further confirmed by ¹³C NMR, which gave about 80% total β‐sheet content for the solution‐polymerized product and about 40% for the polymer obtained by interfacial polymerization. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 352–366, 2000     

Structural analysis of polyethene prepared with rac‐dimethylsilylbis(indenyl)zirconium dichloride/methylaluminoxane in a high‐temperature,continuously stirred tank reactor

A study of ethene solution polymerization with the rac‐dimethylsilylbis(indenyl)‐zirconium dichloride/methylaluminoxane catalyst system in a high‐temperature (140 °C), continuously stirred tank reactor system was carried out. ¹³C NMR, gel permeation chromatography, Fourier transform infrared, and rheological measurements were used for polymer analyses. Polyethylenes with low molecular weights (weight‐average molecular weight ≈ 35–55 kg/mol) and small amounts of methyl, ethyl, and long‐chain branching were produced. ¹³C NMR measurements showed that the long‐chain and methyl branches increased and that the ethyl branch contents decreased with decreasing monomer concentrations. At high monomer concentrations, the chain transfer to the coordinated monomer was concluded to be the predominant chain termination mechanism, whereas the chain transfer to aluminum was dominant at low monomer concentrations, which was evidenced by the fact that the selectivity of end groups was reduced to about 50%. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3292–3301, 2002     

Morphological change of a diblock copolymer film induced by selective doping of a photoactive chromophore

Tetrakis‐5,10,15,20‐(4‐carboxyphenyl)porphyrine (TCPP) was position‐selectively introduced into a diblock copolymer film of polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) with a sea–island microphase structure. By immersing the PS‐b‐P4VP film into a solution of TCPP/methanol, TCPP was introduced into the island parts comprising P4VP phase. The morphology of the island parts depended on the immersion time and TCPP concentration. A schematic model for the morphological change caused by the phase‐selective introduction of TCPP was proposed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 368–375, 2007     

Preparation of carboxyl‐end‐group polyacrylamide with low polydispersity by ATRP initiated with chloroacetic acid

Atom transfer radical polymerization (ATRP) of acrylamide was successfully carried out with chloroacetic acid as initiator and CuCl/N,N,N′,N′‐tetramethylethylenediamine (TMEDA) as catalyst either in water at 80 °C or in glycerol–water (1:1 v/v) medium at 130 °C. In both cases, carboxyl‐end‐group polyacrylamide was obtained with lower polydispersity ranging from 1.03 to 1.44 depending on the polymerization condition. Polymerization kinetics showed that the polymerizations proceeded with a living/controlled nature and accelerated at a higher temperature. The effect of pH in the reaction system on the polymerizations was further studied, revealing that chloroacetic acid not only served as a functional initiator for the ATRP of acrylamde but also provided the acidic polymerization condition, which effectively protected the ATRP of acrylamide from the unexpected complexation and cyclization side‐reactions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3956–3965, 2007     

Synthesis and characterization of arborescent (hyperbranched) polyisobutylenes from the 4‐(1,2‐oxirane‐isopropyl)styrene inimer

The synthesis of the novel inimer (initiator‐monomer) 4‐(1,2‐oxirane‐isopropyl)styrene EPOIM and the copolymerization of this inimer with isobutylene (IB) to form arborescent polyisobutylene (PIB) is described. Polymerizations were accomplished by use of TiCl₄ coinitiator and the effect of reaction conditions was investigated. Size exclusion chromatography (SEC) was used demonstrate EPOIM incorporation across the whole molecular weight distribution. The average number of branch points (B) per chain measured by use of selective link destruction increased with increasing EPOIM/IB ratio and decreased with [TiCl₄]. Large scale polymerizations were carried out based on results from small scale polymerizations. Architecture analysis carried out through use of branching parameters based on the radii of gyration R_g and hydrodynamic radii R_h measured by multidetector SEC corroborated the proposed arborescent architecture. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5847–5856, 2007     

Effects of elastomer on morphology,flammability and rheological properties of HIPS/PS‐encapsulated Mg(OH)2 composites

The effects of elastomer type on morphology, flammability and rheological properties of high‐impact polystyrene/Mg(OH)₂ based on encapsulated by polystyrene have been investigated. The ternary composites characterized by cone calorimetry, horizontal burning rate, limiting oxygen index (LOI), rheology and SEM. Morphology was controlled using poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] triblock copolymer (SEBS) or the corresponding maleinated SEBS (SEBS‐g‐MA). As revealed by SEM observations, composites of HIPS/SEBS/Mg(OH)₂ exhibit separation of the filler and elastomer and good adhesion between SEBS and the filler, whereas composites of HIPS/SEBS‐g‐MA/Mg(OH)₂ exhibit encapsulation of the filler by SEBS‐g‐MA. The flame retardant and rheological properties of ternary composites were strongly dependent on microstructure. The rheological test showed that the composites with encapsulation structure exhibit a stronger solid‐like response at low frequency than those of the composites with separate dispersion structure. The combustion tests showed that the composites with encapsulation structure showed higher flame retardant properties than those of separate dispersion structure at optimum use level of SEBS‐g‐MA. However, with the increase of the content of SEBS‐g‐MA, the flame retardancy of the composite declined somewhat which can be explained that the SEBS‐g‐MA coating acts as a heat and mass transfer barrier due to the formation of encapsulation structure. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2023–2030, 2007     

Exploring rheological properties of aqueous polyaniline‐PVP dispersion

Stable aqueous dispersion of polyaniline (PAn) stabilized by a hydrophilic polymer poly(vinyl pyrrolidone) (PVP) exhibits interesting rheological properties different from its components. Shear thinning observed for both PVP and PAn–PVP colloid (PP) indicates partially entangled nature of the later. Linear viscoelastic response of PVP solution exhibit strong frequency dependence of elastic (G′) and viscous (G″) modulus over the whole frequency range (0.1–100 ras/s) where G′ never exceeds G″ indicating the applicability of the Rouse‐Zimm model to this system. On the other hand, there is a crossover of G′ and G″ in the rheological profile of PP dispersion so that a single relaxation time model can be applicable. Therefore, PVP presents an entangled polymeric system and supposed to have a spectrum of relaxation times, whereas PP resembles to a physically crosslinked system with a single relaxation time. Increasing the extent of hydrogen bonding within the system (by raising the fraction of PAn or by leaving the solution undisturbed for long) relaxation time also becomes longer. The large difference in values of steady and complex shear viscosity (η and η*) within LVE regime reflects that original Cox‐Merz rule is obviously inapplicable to these systems. But at larger strain amplitude, η and η* are satisfactorily coincident that indicates a broader applicability of the modified Cox‐Merz rule. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2443–2455, 2008