Supramolecular Dynamics as Origin for Thermally Induced Insoluble‐to‐Soluble‐to‐Insoluble Transitions of Copolymers in Water

The synthesis of cationic mono‐(6‐O‐(1‐vinylimidazolium))‐ß‐cyclodextrin with toluenesulfonate as the corresponding anion is described. Free‐radical copolymerization of the resulting host–guest complex with N‐isopropylacrylamide or N,N‐diethylacrylamide yielded copolymers showing a temperature‐controlled solubility window in water. The impact of different anionic guests and salt concentrations on solubility behavior was investigated via turbidity measurements.

     

Cooperative Self‐Assembly of Nanoparticle Mixtures in Lamellar Diblock Copolymers: A Dissipative Particle Dynamics Study

Summary: Dissipative particle dynamics simulations are performed on the distribution of binary nanoparticle mixtures in lamellar diblock copolymers. The results show that the self‐assembly of nanoparticle mixtures in polymer matrix is a cooperative assembly that is affected by various factors, providing molecular‐level information for the rational design of new polymer nanocomposites with tailored properties.

The simulated polymer nanocomposite structure (the polymer matrix was omitted for clarity; P, gray; Q, black).     

Synthesis of Novel Biomimetic Zwitterionic Phosphorylcholine‐Bound Chitosan Derivative

Summary: Water‐soluble biomimetic chitosan derivative conjugating zwitterionic phosphorylcholine was efficiently prepared through Atherton‐Todd reaction under the mild conditions, and the possible formation mechanism of zwitterionic product was related to the nucleophilic attack of adjacent 3‐hydroxyl on the D ‐glucosamine residue to phosphorus with the help of base. UV absorption and melting behaviors of DNA/phosphorylcholine‐bound chitosan derivative showed that the phosphorylcholine‐bound chitosan derivative could be a new carrier for long‐circulating macromolecular drug delivery.

Structure of zwitterionic PC‐chitosan.     

Temperature Dependence of the Activity of a Late Transition Metal Catalyst by Molecular Modeling

A combination of molecular mechanics and the charge equilibration method was applied and further developed to predicting the catalyst activity of a metal complex. A late transition metal catalyst, {di‐μ‐bromotetra [N,N′‐bis(3,5‐dimethylanil)‐4‐methyl‐2,6‐bis(imino)phenoxy]nickel} bromide (MOL) was dealt with. A modified molecular force field from universal force field was set and validated for this system. Simulations predict that the activity of MOL varies little with temperature. Simulation results were in good agreement with experimental results for ethylene oligomerization with MOL.

Temperature dependence of QEq charge on the Ni central atom of MOL.     

Architecture of Polymeric Superstructures Constructed by Mesoscopically Ordered Cubic Lattices

Highly monodisperse crosslinked core‐shell polymer microspheres could be prepared easily by introducing special crosslinking reagents into the segregated core in block copolymer assembly films. The crosslinked core was stabilized sterically by highly branched shell chains in solution. These microspheres moved like pseudo‐latex. The microspheres formed a lattice with a body‐centered cubic (BCC) structure near the overlap threshold (C*). This structure changed to a face‐centered cubic (FCC) lattice in the bulk region of the films. Photofunctionalized core‐shell microspheres were prepared by introducing dithiocarbamate (DC) groups into shell parts by means of polymer reactions, where DC groups could be propagated using vinyl monomers such as methyl methacrylate (MMA) with living radical mechanism. Polymeric superstructure (three microphase‐separated structure) films were constructed by graft copolymerization of MMA initiated with photofunctionalized microspheres such as macroinitiators under UV irradiation, exhibiting self‐coloring due to Bragg diffraction. These materials can be used for the construction of optical devices such as for the fabrication of light modulators.

Photograph of a solution of the microsphere in MMA.     

Electro‐active Polymer Actuator Based on Sulfonated Polyimide with Highly Conductive Silver Electrodes Via Self‐metallization

We report here a facile synthesis of high performance electro‐active polymer actuator based on a sulfonated polyimide with well‐defined silver electrodes via self‐metallization. The proposed method greatly reduces fabrication time and cost, and obviates a cation exchange process required in the fabrication of ionic polymer‐metal composite actuators. Also, the self‐metallized silver electrodes exhibit outstanding metal‐polymer adhesion with high conductivity, resulting in substantially larger tip displacements compared with Nafion‐based actuators.

     

Chemoenzymatic Synthesis of Amylose‐Grafted Chitosan

An amylose‐grafted chitosan has been synthesized by a chemoenzymatic method according to the following two reactions. First, maltoheptaose is introduced to chitosan by a reductive amination using sodium cyanotrihydroborate in a mixed solvent of 1.0 mol · L⁻¹ aqueous acetic acid and methanol at room temperature to produce a maltoheptaose‐grafted chitosan that has a well‐defined molecular structure. A phosphorylase‐catalyzed enzymatic polymerization of α‐D ‐glucose 1‐phosphate is then performed from the maltoheptaose‐grafted chitosan to obtain the amylose‐grafted chitosan. This material does not dissolve in any solvent, e.g., aqueous acetic acid and dimethyl sufoxide, which are good solvents for chitosan and amylose, respectively.

     

Controlled Synthesis of a Chitosan‐Based Graft Copolymer Having Polysarcosine Side Chains Using the NCA Method with a Carboxylic Acid Additive

Summary: A novel chitosan derivative with polysarcosine side chains, i.e., chitosan‐graft‐polysarcosine [chitosan‐graft‐poly(N‐methylglycine)], was synthesized by ring‐opening polymerization of sarcosine N‐carboxyanhydride (NCA) with chitosan as a macroinitiator in the presence of carboxylic acids in dimethyl sulfoxide at 27 °C. Degree of substitution ( ) for polysarcosine side chains introduced to chitosan was controlled successfully by the feed amount of the additive nicotinic acid ( = 0.21–0.71). Independent of control, degree of polymerization ( ) for polysarcosine side chains was controlled by adjusting feed ratios of NCA monomer to chitosan ( = 14–43). Kinetic analysis of the propagation of sarcosine NCA was conducted by measuring CO₂ evolution. Apparent k_p values decreased with increased feed amounts of nicotinic acid, supporting the theory that propagation of NCA in the presence of nicotinic acid proceeds via equilibrium between active amine and dormant ammonium species.

Propagation mechanism of carboxylic acid‐mediated polymerization of sarcosine N‐carboxyanhydride.     

Oriented Synthesis of One‐Dimensional Polypyrrole Molecule Chains in a Metal‐Organic Framework

We report for the first time the preparation of single polypyrrole (PPy) molecule chains using a “metal‐organic framework” with 1 nm channels as a template. The obtained one‐dimensional (1‐D) PPy has highly structure order and excellent conductivity, which has improved by as much as five orders of magnitude in comparison with that of 2‐D PPy.

     

Novel Cross‐Linked Films Prepared from Hyperbranched Poly(amine‐ester)

Summary: Novel hyperbranched poly(amine‐ester) (HPAE) cross‐linked films were prepared by cross‐linking the terminal hydroxyl groups of HPAE using glutaraldehyde (GA). Atom force microscope and scanning electron microscope revealed their smooth surfaces, dense and homogenous matrices. Property characterizations indicated that these cross‐linked films had good hydrophilicity, relative low protein adsorption, and high tensile strength. Also, their swelling behavior varied with the solvent.

Structure of the hyperbranched poly(amine‐ester).     

Poly(cyclooctene)s with Pendant Fluorescent and Phosphorescent Metal Complexes

Poly(cyclooctene)s with pendant Alq₃ and fac‐Ir(ppy)₃ were synthesized. Carbazole‐based comonomers were used to increase the solubility of the polymers and to transfer the energy into metal complexes. Excitation spectra of all polymers provided evidence of energy transfer. We established that the polymer backbone does not interfere with the optical properties of the metal complexes. All copolymers retained the optical properties of their small molecule metal complex analogs in solution and the solid state, making these polymers promising materials for potential electro‐optical applications.

     

Polysorbate 80 as a Tool: Synthesis of Gold Nanoparticles

The preparation of metal nanoparticles generally requires the use of mostly toxic reducing agents according to state‐of‐the‐art procedures. Here, we report that polysorbate 80, a polymeric nonionic surfactant, when reacted with a gold salt in water at room temperature, yields well‐dispersed gold nanoparticles. Furthermore, we could control the particle size by simply altering concentration or temperature. The synthetic procedure presented here is easy, inexpensive, straightforward, and user‐friendly.

     

Chitosan‐Hydroxybenzotriazole Aqueous Solution: A Novel Water‐Based System for Chitosan Functionalization

Summary: A chitosan‐hydroxybenzotriazole (HOBt) aqueous solution prepared by simply mixing chitosan and HOBt in water provides an effective system to functionalize chitosan in an aqueous environment. This aqueous solution in combination with water‐soluble carbodiimide (WSC) allows the conjugation of functional groups onto chitosan under mild conditions without requiring any organic solvents or acid and heat. In this contribution, a series of model reactions that use a novel water‐based system of chitosan to functionalize the polymer with boc‐L ‐phenylalanine, poly(ethylene glycol) methyl ether, and dicarboxylated poly(ethylene glycol) is demonstrated.

Chitosan‐HOBt is effectively conjugated with R‐COOH via a water‐soluble carbodiimide (WSC) conjugating agent.     

Preparation of Functionalized Polysilsesquioxane and Polysilsesquioxane‐Metal Nanoparticle Composite Spheres

Summary: Network polysilsesquioxane spheres made solely of poly(vinylsilsesquioxane) (PVSQ) and poly(3‐mercaptopropylsilsesquioxane) (PMPSQ) were prepared from heterogeneous mixtures of triethylamine (TEA), water, and either vinyltrimethoxysilane (VTMS), or 3‐mercaptopropyltrimethoxysilane (MPTMS). The microscopic, macroscopic observations, and the relationship between the diameters of spheres and the amount of each ingredient in the reaction system, showed that spheres formed via a mechanism similar to emulsion polymerization and suspension polymerization, depending on the reaction conditions. Diameters of spheres could be controlled from tens of nanometers to a few micrometers by adjusting the amounts of TEA, water, and a surfactant. Heating aqueous solutions of metal ions with these spheres produced polysilsesquioxanes (PSQ)‐metal nanoparticle composite spheres. The spheres prepared in this study were characterized by scanning electron microscopy, transmission electron microscopy, solid state NMR spectroscopy, IR spectroscopy, elemental analysis, and differential thermal analysis. These spheres would be useful in recovering metals from their ionic solutions and probes after chemical modifications.

An image of the spheres of poly(vinylsilsesquioxane)‐gold nanoparticle composite.     

Cu Crystal Growth on a Chelating Fiber with Different Amine Chain Lengths

Summary: Poly(acryloamidino ethyleneamine) (PAEA) and poly(acryloamidino diethylene diamine) (PADD) have been synthesized for the observation of Cu^II complex and Cu(OH)₂ crystal‐growth on the surface of different numbers of amino groups immobilized on polyacrylonitrile (PAN) fibers. The shape of Cu^II crystal growth depends on the amine chain length of the chelating fiber; Cu(OH)₂ crystals grow on the surface of the chelating fiber after Cu^II adsorption.

     

Ethylene and Ethylene/Propylene Polymerization Behavior of Bis(phenoxy‐imine) Zr and Hf Complexes with Perfluorophenyl Substituents

The catalytic properties of bis(phenoxy‐imine) Zr and Hf complexes incorporating perfluorophenyl groups with methylaluminoxane were investigated. The fluorinated complexes produced far higher‐molecular‐weight polyethylenes and ethylene/propylene copolymers with increased activities compared with the non‐fluorinated congeners. Moreover, the fluorinated complexes displayed a higher incorporation ability for propylene.

Structures of complexes 1 – 4 .     

Controlled Chemical Modifications of Chitosan. Characterization and Investigation of Original Properties

The main techniques developed to characterize chitosan are recalled. The interaction of chitosan with oppositely charged surfactants was investigated giving very important surface activity effects. A few chemical modifications are described and the new properties obtained are mentioned: alkylation gives amphiphilic polymers having interesting thickening behavior; grafting cyclodextrin (chit‐CD) gives a polymer able to include hydrophobic molecules; grafting adamantane gives an amphiphilic polymer able to specifically interact with chit‐CD forming a temporary network with gel‐like behavior.

The viscosities of adamantane‐chitosan, cyclodextrin‐chitosan, and unmodified chitosan solutions studied here.     

Noble Metal Decoration and Alignment of Carbon Nanotubes in Carboxymethyl Cellulose

A facile microwave method (MW) is described that accomplishes alignment and decoration of noble metals on carbon nanotubes (CNT) wrapped with carboxymethyl cellulose (CMC). Carbon nanotubes such as single‐ and multi‐walled, and Buckminsterfullerene (C‐60) are well dispersed using the sodium salt of CMC under sonication. Addition of respective noble metal salts then generates noble metal‐decorated CNT composites at room temperature. However, aligned nanocomposites of CNTs could only be generated by exposing the above nanocomposites to MW irradiation. The CNT composites are characterized using scanning electron microscopy, energy dispersive X‐ray analysis, X‐ray mapping, transmission electron microscopy, and UV‐visible spectroscopy. The general preparative procedure is versatile and provides a simple route to manufacturing useful metal‐coated CNT nanocomposites.

     

Tunability of Fluorescence Property of a Terbium‐Complex‐Containing Polymer via Incorporation of a Transition‐Metal Complex

Summary: In this study, a terbium‐complex monomer and transition‐metal‐complex monomers (Fe^III, Mn^II, and Ni^II complex monomers) are synthesized, and novel acrylate copolymers are then obtained through covalent attachment of the terbium complex and the transition‐metal complex onto the macromolecular chain simultaneously. The copolymers developed herein present the characteristic fluorescence properties of the terbium(III ) ion, The incorporation of an Mn^II complex into a Tb^III‐containing polymer leads to greater fluorescence enhancement compared with the Ni^II complex, while the incorporation of the Fe^III complex results in fluorescence quenching, thus the incorporation of different transition‐metal complexes into the copolymers ensures tunability of the copolymer's fluorescence property.

Fluorescence emission spectra of the copolymer solid films. Solid: P‐Tb; dash‐dot: P‐Tb‐Mn^II; dash: P‐Tb‐Ni^II; and dot: P‐Tb‐Fe^III.     

Uniform Sub‐Micron Polymer Spheres Coated with Ag Nanoparticles

Summary: The synthesis of well‐defined uniform and spherical sub‐micron polymeric spheres, specifically poly[styrene‐co‐(glycidyl methacrylate)] (PSGMA) with a uniform size distribution and surface chemical functionality, is described. It is shown that the surface can be modified with a multi‐amine functional polymer, polyethyleneimine (PEI), most likely through covalent bonding in addition to electrostatic attraction. The PEI acts both as a stabilizing agent and a complexation agent for the deposition of noble metal Ag nanoparticles.

Reaction of PSGMA samples with excess PEI, and its TEM image.