Self-oscillation of polymer chains induced by the Belousov-Zhabotinsky reaction under acid-free conditions

A novel self-oscillating polymer was prepared by utilizing the Belousov-Zhabotinsky (BZ) reaction. In this study, a sulfonic acid group was newly introduced as a pH-control site into the copolymer of N-isopropylacrylamide, and the ruthenium complex was introduced as a catalyst site. By introducing the pH-control site, we succeed in causing the soluble-insoluble self-oscillation of the polymer solution under acid-free conditions in which only two BZ substrates, malonic acid and sodium bromate, were present as added agents. The self-oscillating behavior was remarkably influenced by the temperature and polymer concentration, which reflects the intermolecular aggregative capacity of the polymer chains in the reduced state to change the lower critical solution temperature. This achievement of self-oscillation of polymer chains under acid-free conditions may lead to their practical use as novel biomimetic materials under biological conditions.     

Dependence of turbidity oscillations of self-oscillating polymers on the selective recognition of the crown ether receptors contained in the polymer chain

The turbidity oscillations of self-oscillating polymers in the Belousov-Zhabotinsky (BZ) reaction system depending on the crown ether receptors contained in the polymer network have been studied. The three monomers are copolymerized, namely, N-isopropylacrylamide, the metal catalyst monomer for the BZ reaction, and the crown ether receptor monomer, to prepare the self-oscillating polymers used in this study. The turbidity oscillations are characterized by monitoring the transmittance of the polymer solution in the BZ reaction system at a specific wavelength of 570 nm. The oscillations are varied by crown ether receptors used in the polymerization process, i.e., BCAm(6) or BCAm(5), for the selective recognition of specific cations between potassium and sodium ions in the solution. The selective recognition of the BCAm receptors in the polymer chain for the two ions has brought out a variation in the turbidity oscillations by a change in the hydrophilicity of the polymer chain. The oscillations of the polymer solution composed of the BCAm(5) receptor are more influenced by sodium ion, while the polymer solution of BCAm(6) receptor is affected by potassium ion. However, the oscillation patterns of the redox changes obtained by these solution systems look much alike despite the differences in the polymer chain by crown ether receptors and cations of bromate used for the BZ reaction.     

A viscosity self-oscillation of polymer solution induced by the Belousov-Zhabotinsky reaction under acid-free condition

We succeeded in measuring a viscosity self-oscillation induced by the Belousov-Zhabotinsky (BZ) reaction for a polymer solution on the constant temperature condition under acid-free condition. The polymer chain is consisted of N-isopropylacrylamide, ruthenium complex as a catalyst of the BZ reaction, and an acrylamide-2-methylpropanesulfonic acid (AMPS) as a pH and the solubility control site. The viscosity self-oscillation for the AMPS-containing polymer solution was attributed to the difference between viscosities for the polymer solution in the reduced and oxidized states. The effects of the polymer concentration and the temperature of the polymer solution on the viscosity self-oscillation were investigated. As a result, the viscosity self-oscillating behavior significantly depended on the polymer concentration and the temperature of the polymer solution. The period of the viscosity self-oscillation decreased with increasing temperature in accordance with the Arrenius equation.     

Characterization of a self‐oscillating polymer with periodic soluble‐insoluble changes

A copolymer of N‐isopropylacrylamide (NIPAAm), ruthenium‐complex (Ru(bpy)₃), and N‐succinimidyl acrylic acid (NAS) was synthesized to investigate its selfoscillating properties in a solution. This polymer exhibits selfoscillation in turbidity and viscosity synchronized via a Belousov–Zhabotinsky (BZ) reaction. The molecular size of the polymer during oscillation was investigated by dynamic light scattering and electrochemical measurements. Both molecular size and viscosity exhibited periodic changes during the BZ reaction. A simple mechanism accounting for such periodic changes was investigated by numerical calculations. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1578–1588, 2007     

An elegant method to study an isolated spiral wave in a thin layer of a batch Belousov-Zhabotinsky reaction under oxygen-free conditions

A method to prepare a uniform thin layer of a batch Belousov-Zhabotinsky (BZ) reaction under oxygen-free conditions for the study of an isolated spiral wave is presented. After a first layer of gel soaked with the BZ solution has been delivered into the reactor, a single spiral wave was initiated, and finally the remaining reactor volume was filled with gel and BZ medium. The completely filled reactor is sealed gas-tightly, yielding oxygen-free, and thus more controlled, reaction conditions. A systematic study of the behaviour of an isolated spiral wave in a ferroin-catalyzed BZ reaction under batch conditions has been performed. Recipes for BZ media that support a slowly rotating meandering spiral were developed. In cases of extremely low excitability (i.e., relative large stimuli are required to induce a propagating wave), the number of petals in the trajectory of a spiral tip decreased due to aging of the reaction system. Since oxygen-free conditions are necessary for the study of the dynamics in three-dimensional excitable media, and the wave velocities of a spiral are sufficiently low, the developed chemical recipes are suitable for studies of the behaviour of scroll waves in three-dimensional systems by optical tomography.     

二维高聚物振动谱的研究

聚乙炔和聚苯胺通常由于链间耦合比较弱 ,具有一维特性 .但在增加压力的条件下可以使其链间距b减少 ,当达到与晶格常数a相近的程度时 ,这时应考虑其晶格链间耦合作用 ,它们就具有二维复式晶格结构 ,由此会带来新的物理效应 .本文考虑了由于增压作用可以使高聚物晶格链间耦合作用增强 ,并使链间距b减少 ,当b达到与晶格常数a相比拟时 ,它们可以被看作具有二维晶格结构 .基于这种情况建立了理想的二维复式晶格链模型 ,利用晶格动力学的方法 ,计算其晶格链间及原子次近邻间的相互作用 ,借助计算机计算分别在几种晶格链耦合作用下和不同质量比时的色散关系 ,模拟色散曲线 ,讨论第一布里渊区BrillouinZone(BZ)中格波高对称线上频谱的变化 ,分析了由此会带来的新的物理效应 .     

基于Belousov-Zhabotinsky自振荡反应的智能高分子

自振荡高分子是基于Belousov-Zhabotinsky自振荡反应(BZ反应)设计的一类新型智能高分子,其物理、化学性质可以在相对封闭且无外界刺激的BZ反应溶液中发生自主、可逆和循环的变化。本文从概念、设计原理、设计方法及潜在应用4个方面系统介绍了自振荡高分子,其中重点结合自振荡高分子的化学结构设计与物理结构设计介绍了这一领域的研究进展:详细归纳了目前已成功制备的具有不同化学结构或物理结构的自振荡高分子或凝胶,阐述了不同的设计方法的优点、存在的问题及可能的解决办法,最后介绍了自振荡高分子在自动运输智能表面、凝胶机器人、自主转动马达等方面的设计实例,并分析了该领域面临的问题及今后发展趋势。     

Self-oscillating polymer gel as novel biomimetic materials exhibiting spatiotemporal structure

As a novel biomimetic polymer gel, we have been studying polymer gel with an autonomous self-oscillating function since it was firstly reported in 1996. For developing the polymer gels, we utilized an oscillating chemical reaction, called the Belousov?CZhabotinsky (BZ) reaction, which is recognized as a chemical model for understanding several autonomous phenomena in biological systems. The self-oscillating polymer gel is composed of a poly(N-isopropylacrylamide) network in which the metal catalyst for the BZ reaction is covalently immobilized. Under the coexistence of the reactants, the polymer undergoes spontaneous swelling?Cdeswelling changes (in the case of gel) or cyclic soluble?Cinsoluble changes (in the case of uncross-linked polymer) without any on?Coff switching of external stimuli. Several kinds of functional material systems utilizing the self-oscillating polymer and gel such as biomimetic actuators, mass transport surface, etc. are expected. Here, these recent progress on the self-oscillating polymer and gels and the design of functional material systems are summarized.     

Capturing of acidic macromolecules from biological samples using a temperature-responsive polymer modified with poly-l-lysine

We synthesized a temperature-responsive polymer, N-(isopropylacrylamide)-methacrylic acid copolymer, to which poly-l-lysine was introduced. The synthesized polymer as well as the parent polymer showed reversible soluble-insoluble changes in response to temperature changes across the lower critical solution temperature at 32 degree C in an aqueous solution. We found that the polymer efficiently captured acidic bio-macromolecules such as RNA, glycosaminoglycans and mucin-type glycoproteins in biological samples, and the captured molecules were recovered using aqueous NaCl solutions at high concentration. The target acidic molecules thus obtained will be employed for further studies such as structural analysis after brief desalting procedure. The proposed method does not require any chromatographic separations, but only needs a small volume of an aqueous salt solution for releasing captured molecules. Overall procedures are quite easy and simple, and are completed at least within 1 h. We show a few examples for capturing RNA and glycosaminoglycans from cultured cells using the polymer.     

Macroscopic and mesoscopic patterns observed in thin films formed due to polymerization of aniline at the air-water interface

We report two-dimensional mesoscopic and macroscopic patterns observed in thin films formed due to polymerization of aniline at the air-water interface. The polymerization at the interface was coupled to a reaction in the bulk medium that was either an iron (ferroin)-catalyzed Belousov-Zhabotinsky (BZ) reaction or another reaction condition where the ferroin component of BZ reaction was replaced by FeSO(4) or Mohr's salt [(NH(4))(2)SO(4).FeSO(4).6H(2)O]. Also, a simple mixture of KBrO(3) and KBr in aqueous acidic solution produced patterned polymers at the interface, observed with aniline introduced from both the vapor phase and the bulk phase (by dissolving in H(2)SO(4)). Observation under an optical microscope revealed that the macroscopic patterns consisted of mesoscopic patterns of various geometrical shapes. In one case, regular circular mesoscopic patterned polymer growth was observed when the reaction was carried out in the presence of 2.02 mM sodium dodecyl sulfate. On the other hand, when the film was grown in an ultrasonicator bath there were no observable mesoscopic or macroscopic patterns in the film.     

A comparative study of temperature dependence of induction time and oscillatory frequency in polymer‐immobilized and free catalyst Belousov‐Zhabotinsky reactions

Environment‐sensitive poly(N‐isopropylacrylamide) (PNIPAM) microgel particles with covalently bonded ruthenium(4‐vinyl‐4′‐methyl‐2,2′‐bipyridine) bis (2,2′‐bipyridine) [Ru(vmbipy)(bipy)₂] display periodic size changes when placed in Belousov‐Zhabotinsky (BZ) reaction substrates. The temperature dependency of the induction time and oscillatory frequency of the BZ reaction in this polymer‐immobilized catalyst system were compared to the bulk BZ reaction with the catalyst in the solution phase. Prolonged induction times are observed for the immobilized catalyst, compared with free catalyst, while little difference is observed on the oscillation frequency. The Arrhenius frequency factor calculated using the induction time for the immobilized catalyst BZ reaction is about seven times smaller than that for the free catalyst Ru(bipy) case. On the other hand, the Arrhenius frequency factors calculated using the oscillatory frequency are almost the same, showing similar reaction kinetics during the BZ oscillations. The tunability of the induction time using a polymer matrix, as we observed here, while maintaining similar oscillatory behavior, should provide a new dimension to control the self‐assembling of BZ active particles. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 847–854, 2009     

Theoretical and computational modeling of self-oscillating polymer gels

The authors model wave propagation in swollen, chemoresponsive polymer gels that are undergoing the oscillatory Belousov-Zhabotinsky (BZ) reaction. To carry out this study, they first modify the Oregonator model for BZ reactions in simple solutions to include the effect of the polymer on the reaction kinetics. They then describe the gel dynamics through the framework of the two-fluid model. The polymer-solvent interactions that are introduced through the BZ reaction are captured through a coupling term, which is added to the Flory-Huggins model for polymer-solvent mixtures. The resulting theoretical model is then used to develop the gel lattice spring model (gLSM), which is a computationally efficient approach for simulating large-scale, two-dimensional (2D) deformations and chemical reactions within a swollen polymer network. The 2D calculations allow the authors to probe not only volume changes but also changes in the sample's shape. Using the gLSM, they determine the pattern formation and shape changes in 2D rectangular BZ gels that are anchored to a solid wall. They demonstrate that the dynamic patterns depend on whether the gel is expanded or contracted near the wall, and on the sample's dimensions. Finally, they isolate a scenario where the detachment of the gel from the wall leads to macroscopic motion of the entire sample.     

Benzil Photoperoxidations in Polymer Films and Crosslinking by the Resultant Benzoyl Peroxides in Polystyrene and Other Polymers

Benzil (BZ) can be converted almost quantitatively to benzoyl peroxide (BP) in aerated polymer films upon irradiation at >400 nm (i.e., the long-wavelength edge of the n→π* absorption band of BZ, where BP does not absorb). Here, we summarize results for the photoperoxidation of BZ structures with molecular oxygen, principally in glassy polymer matrices. Some of the polymers are doped directly with BZ or its derivatives, and others, contain covalently attached BZ pendant groups from which BP groups are derived. While the decomposition of low-molecular-weight BP doped into polymer films (such as those of polystyrene (PS)) results in a net decrease in polymer molecular weight, thermal decomposition of pendant BP groups is an efficient method for chain crosslinking. Crosslinking of PS films doped with a molecule containing two covalently linked BZ or BP groups proceeds in a similar fashion. Free radicals from the covalently attached BP allow grafting of new monomers, as well. Additionally, the use of radiation filtered through masks has been used to create patterns of polymers on solid surfaces. Crosslinking of photodegradable poly(phenyl vinyl ketone) with BP structures obtained by photoperoxidation of BZ structures for the preparation of photodegradable polymer networks is described as well. In sum, the use of BZ and BP and their derivatives offers simple and convenient routes for modifying polymer chains and, especially, for crosslinking them. Specific applications of each use and process are provided. Although applications with PS are featured here, the methodologies described are amenable to a wide variety of other polymers.     

Design of a Tunable Self‐Oscillating Polymer with Ureido and Ru(bpy)3 Moieties

An upper critical solution temperature (UCST)‐type self‐oscillating polymer was designed that exhibited rhythmic soluble–insoluble changes induced by the Belousov–Zhabotinsky (BZ) reaction. The target polymers were prepared by conjugating Ru(bpy)₃, a catalyst for the BZ reaction, to ureido‐containing poly(allylamine‐co‐allylurea) (PAU) copolymers. The Ru(bpy)₃‐conjugated PAUs exhibited a UCST‐type phase‐transition behavior, and the solubility of the polymer changed in response to the alternation in the valency of Ru(bpy)₃. The ureido content influences the temperature range of self‐oscillation, and the oscillation occurred at higher temperatures than conventional LCST‐type self‐oscillating polymers. Furthermore, the self‐oscillating behavior of the Ru‐PAU could be regulated by addition of urea, which is a unique tuning strategy. We envision that novel self‐oscillating polymers with widely tunable soluble‐insoluble behaviors can be rationally designed based these UCST‐type polymers.     

Modeling of the optical anisotropy of a dye polarizer

A new model has been developed to account for the dependence of the optical anisotropy of a dye polarizer on the dye concentration. The effect of the dye concentration has been studied through an examination of the changes in the orientation distribution of the polymer. The model takes into account the intrinsic optical anisotropy of the dichroic dye, the polymer orientation, the polymer orientation distribution, and the dye orientation with respect to the polymer. It is assumed that (1) the orientation distribution function of the polymer segments can be expressed as an elliptical distribution function and that (2) the free rotation of each dye molecule on its axis is suppressed because of the attraction force between the dye molecules and the polymer chains. The pseudo‐order parameter, which takes into account the aforementioned assumptions, determines the relation between single‐piece transmittance and polarizing efficiency. The orientation distribution of the polymer molecules in the experiment and its effect on the optical performance of a polarizer are quantitatively determined. The model predicts that the effect of the orientation distribution becomes more significant as the polymer chains are oriented more highly. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1363–1370, 2002     

Thermo-responsive chitosan-graft-poly(N-isopropylacrylamide) injectable hydrogel for cultivation of chondrocytes and meniscus cells

A thermo-responsive comb-like polymer with chitosan as the backbone and pendant poly(N-isopropylacrylamide) (PNIPAM) groups has been synthesized by grafting PNIPAM-COOH with a single carboxy end group onto chitosan through amide bond linkages. The copolymer exhibits reversible temperature-responsive soluble-insoluble characteristics with the lower critical solution temperature (LCST) being at around 30 degrees C. Results from SEM observations confirm a porous 3D hydrogel structure with interconnected pores ranging from 10 to 40 microm at physiological temperature. A preliminary in vitro cell culture study has demonstrated the usefulness of this hydrogel as an injectable cell-carrier material for entrapping chondrocytes and meniscus cells. The hydrogel not only preserves the viability and phenotypic morphology of the entrapped cells but also stimulates the initial cell-cell interactions.     

Nuclear magnetic resonance relaxation studies of polyacrylamide solution

 The cohesive interaction among polymer chains in a polyacrylamide (PAAm)–D₂O solution has been studied by NMR relaxation. The NMR relaxation times of PAAm in the good solvent D₂O were measured at different temperatures. The results show that the solution system has a high local viscosity and that its relaxation characteristic is soft-solid-like. The temperature dependence of the relaxation behavior of the solution is obviously different from that of ordinary polymer solutions. The difference lies in the relaxation behavior of the methylene protons in the main chain of PAAm, as shown by analyzing the relaxation process with single exponential and biexponential decays. As the temperature increases, the solvation is weakened, leading polymer chains to form curling coils, thus hindering the movement of the methylene protons among the main chains. It can be expected from the existence of 80% fast-relaxing protons that there are a zhigh number of entanglements among the polymer chains in PAAm solution. The information about entanglements among the polymer chains can be deduced from the biexponential dependence of the spin–spin relaxation on the concentration of the polymer solutions. Received: 14 April 1999/Accepted in revised form: 12 October 1999     

Parallel synthesis of strongly fluorescent polysubstituted 2,6-dicyanoanilines via microwave-promoted multicomponent reaction

[reaction: see text] A facile parallel synthesis of polysubstituted 2,6-dicyanoanilines via microwave-promoted three-component reaction of aldehydes, ketones, and propanedinitrile in solution and also on polymer support has been developed. The screening for optical properties identified two new compounds with high fluorescence quantum yields.     

On the relationship of optical absorption energy and conversion during the polymerization of a crystalline diacetylene

Shifts in the optical absorption energy of polymer chains during polymerization of microcrystalline bis(p-toluene sulphonate) diacetylene are shown to be in accord with changes in the strain imposed on the chains by the mismatch of the monomer and polymer crystal lattices.     

Photo-grafting Poly(acrylic acid) onto Poly(lactic acid) Chains in Solution

Poly(lactic acid)(PLA)is one of the most important bio-plastics,and chemical modification of the already-polymerized poly(lactic acid)chains may enable optimization of its material properties and expand its application areas.In this study,we demonstrated that poly(lactic acid)can be readily dissolved in acrylic acid at room temperature,and acrylic acid can be graft-polymerized onto poly(lactic acid)chains in solution with the help of photoinitiator benzophenone under 254 nm ultraviolet(UV)irradiation.Similar photo-grafting polymerization of acrylic acid(PAA)has only been studied before in the surface modification of polymer films.The graft ratio could be controlled by various reaction parameters,including irradiation time,benzophenone content,and monomer/polymer ratios.This photo-grafting reaction resulted in high graft ratio(graft ratio PAA/PLA up to 180%)without formation of homopolymers of acrylic acid.When the PAA/PLA graft ratio was higher than 100%,the resulting PLA-g-PAA polymer was found dispersible in water.The pros and cons of the photo-grafting reaction were also discussed.