Signaling Recognition Events with Fluorescent Sensors and Switches.

Electrochemical energy storage systems (batteries) have a tremendous role in technical applications In this review the authors examine the prospects of electroactive polymers in view of the properties required for such batteries Conducting organic polymers are considered here in the light of their rugged chemical environment: organic solvents, acids, and alkalis The goal of the present article is to provide, first of all in tabular form, a survey of electroactive polymers in view of potential applications in rechargeable batteries It reviews the preparative methods and the electrochemical performance of polymers as rechargeable battery electrodes The theoretical values of specific charge of the polymers are comparable to those of metal oxide electrodes, but are not as high as those of most of the metal electrodes normally used in batteries Therefore, it is an advantage in conventional battery designs to use the conducting polymer as a positive electrode material in combination with a negative electrode such as Li, Na, Mg, Zn, MeH{sub x}, etc 504 refs

Electrochemically Active Polymers for Rechargeable Batteries.

A methacrylate monomer having the phospholipid polar group, 2-methacryloyloxyethyl phosphorylcholine (MPC) was prepared by an improved method with good yield. MPC was copolymerized with n-butyl methacrylate (BMA). The polymer membranes were prepared from the poly(MPC-co-BMA) by a solution casting method. The membrane adsorbed water well and became a hydrogel structure even MPC mole fraction in the copolymer was 0.04. The water content of the hydrogel membrane increased with increase of MPC units and rise of temperature. These properties of the hydrogel membrane were attributed to the highly hydrophilic phospholipid polar group in the copolymer. Water soluble organic compounds and proteins whose molecular weights were below 104 permeated through the hydrogel membrane. However, the protein could not permeate when the molecular weight was higher than 105.

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Preparation of phospholipid polymers and their properties as polymer hydrogel membranes.

In this work, we show the strong resistance of zwitterionic phosphorylcholine (PC) self-assembled monolayers (SAMs) to protein adsorption and examine key factors leading to their nonfouling behavior using both experimental and molecular simulation techniques. Zwitterions with a balanced charge and minimized dipole are excellent candidates as nonfouling materials due to their strong hydration capacity via electrostatic interactions.

Strong resistance of phosphorylcholine self-assembled monolayers to protein adsorption: insights into nonfouling properties of zwitterionic materials.

Synthesis and solution properties of zwitterionic polymers.

The synthesis of N-vinyluracil, N-vinylthymine, and N-vinyladenine is described. The general procedure consists of the conversion of the corresponding nucleric acid bases to their N-hydroxyethyl compounds, followed by chlorination to the N-chloroethyl compounds and dehydrochlorination to the N-vinyl derivaties.



Die Synthese von N-Vinyluracil, N-Vinylthymin sowie N-vinyladenin warde beschrieben. Diese drei N-Vinylverbindungen wurden ausgehend von den entsprechenden Nucleinsaurebasen uber die N-Hydroxyathylderivate und die durch Chlorierung erhaltenen N-Chlorathylderivate dargestellt.

Vinyl polymerization. 217. Vinyl compounds of nucleic acid basis. I. Synthesis of N-vinylthymine, and N-vinyladenine†

The radical polymerization of styrene and of the p-substituted styrenes p-methoxy-, p-methyl-, p-fluoro-, p-chloro-, p-bromo-, and p-cyanostyrene, was kinetically studied. The styrenes with more electron-attracting substituents show a greater overall rate of polymerization. At 30,0°C., the individual rate constants of propagation (kp) and termination (kt) were determined by a rotating sector and by usual inhibitor method using diphenylpicrylhydrazyl (DPPH) or p-benzoquinone. It was found that the following HAMMETT relationship is established in the homopolymerization of p-substituted styrenes: 






where σ is the HAMMETT constant, and ρ′ is a reaction constant which was calculated as +0.6. This relation is interpreted from a participation of ionic structures in the transition state of the propagation reaction. For confirmation, MULLIKEN's electronegativity of the p-substituted styrene and the p-substituted benzyl radical was calculated by simple LCAO MO method. The relationship between the rate constants of termination, kt, and the σ-values is expressed by two lines, crossing at p-fluorostyrene which is at the maximum point. These two lines are explained by two ways; one is the diffusion controlled termination and the other is the recombination of the two polarized radical ends.



Die radikalische Polymerisation von Styrol und p-substituierten Styrolen, und zwar p-Methoxy-, p-Methyl-, p-Fluor-, p-Chlor-, p-Brom- und p-Cyanostyrol, wurde kinetisch untersucht. Die Bruttogeschwindigkeit der Polymerisation war bei elektronenanziehenden Substituenten groser als bei elektronenabstosenden. Fur 30,0°C wurden die Absolutwerte der Geschwindigkeitskonstanten des Kettenwachstums (kp) und des Abbruchs (kt) mit Hilfe des rotierenden Sektors und mit Inhibitoren (DPPH oder p-Benzochinon) bestimmt. Es ergab sich, das die folgende HAMMETT-Beziehung erfullt ist: 






wobei σ die HAMMETTsche Substituentenkonstante ist und ρ′ eine Reaktionskonstante, die in diesem Falle zu +0,6 gefunden wurde. Diese Beziehung wird durch die Annahme erklart, das beim Wachstumsschritt ionische (polare) Strukturen am Ubergangszustand beteiligt sind. Um diese Anschauung zu stutzen, wurde die MULLIKENsche Elektronegativitat der substituierten Styrole und der substituierten Benzylradikale nach der einfachen LCAO-MO-Methode berechnet. Die Beziehung zwischen den Geschwindigkeitskonstanten der Abbruchsreaktion (kt) und den σ-Werten wird durch zwei Geraden dargestellt, die sich beim p-Fluorstyrol in einem Maximalpunkt kreuzen. Dieser Befund last sich durch die Annahme eines difussionskontrollierten Abbruchs einerseits und eines Abbruchs durch Kombination polarisierter Radikale andrerseits deuten.

Vinyl polymerization. 93. Polar effects in radical polymerization of p‐substituted styrenes

The Syntheses and the Reactions of 9-Anthryldiazomethane and α-Naphthyldiazomethane

The polymerization of methyl methacrylate (MMA) initiated by α,α′-azobiisobutyronitrile (AIBN) in the presence of zinc chloride at 60°C. was investigated kinetically. Zinc chloride increased the rate of polymerization. Since ZnCl2 dissolved in MMA to form a complex, such a complex was considered to have a close relation to the acceleration effect. It was found from the result of a copolymerization experiment with vinylidene chloride that the reactivity of MMA monomer increased in the presence of ZnCl2. A complex of MMA with ZnCl2 could be easily isolated by removing an excess of MMA from the MMA-ZnCl2 solution. The MMA-ZnCl2 complex polymerized to a high molecular weight polymer.



Die Polymerisation von Methylmethacrylat (MMA) mit Azoisobuttersaurenitril (AIBN) in Gegenwart von ZnCl2 bei 60°C wurde kinetisch untersucht. ZnCl2 bewirkte eine Polymerisationsbeschleunigung. Es bildet mit MMA in Losung einen Komplex, der wahrscheinlich fur den Beschleunigungseffekt verantwortlich ist. Ein Komplex von MMA mit ZnCl2 lies sich durch Entfernen des MMA-Uberschusses aus einer MMA-ZnCl2-Losung isolieren. Der MMA-ZnCl2-Komplex wurde zu einem hochmolekularen Produkt polymerisiert.

Vinyl polymerization. LXVIII. The polymerization of methyl methacrylate in the presence of zinc chloride

A study of the effect of zinc chloride on the radical polymerization of various vinyl monomers has been made. It was observed that zinc chloride could accelerate the polymerizations of some vinyl monomers containing ester and nitrile groups, photochemically initiated by azobissobutyronitrile (AIBN). Zinc chloride did not affect the rate of decomposition of AIBN. Therefore, it might be assumed that the acceleration effect of ZnCl2 influenced the propagation rate as result of a complex formation of the monomers with ZnCl2. It was proved from X-ray or infrared analyses that the polymers thus obtained did not show any crystallinity.



Eine Untersuchung uber den Einflus von ZnCl2 auf die radikalische Polymerisation verschiedener Vinylmonomerer wurde durchgefuhrt. Man beobachtete, das ZnCl2 die Polymerisationen einiger Vinylmonomerer mit Ester-und Nitrilgruppen beschleunigte. Die Initiierung erfolgte photochemisch mit Azoisobuttersaurenitril (AIBN); ZnCl2 beeinfluste die Zerfallsgeschwindigkeit des AIBN nicht. Man kann daher annehmen, das der Beschleunigungseffekt des ZnCl2 die Wachstumsgeschwindigkeit beeinfluste, und zwar als Folge einer Komplexbildung der Monomeren mit ZnCl2 Rontgen-und IR-Analysen ergaben keine Kristallinitat der erhaltenen Polymeren.

Minoru Imoto

Papers

Vinyl polymerization. 217. Vinyl compounds of nucleic acid basis. I. Synthesis of N-vinylthymine, and N-vinyladenine†

Vinyl polymerization. 93. Polar effects in radical polymerization of p‐substituted styrenes

The Syntheses and the Reactions of 9-Anthryldiazomethane and α-Naphthyldiazomethane

Vinyl polymerization. LXVIII. The polymerization of methyl methacrylate in the presence of zinc chloride

Vinyl polymerization. LXVI.. The effect of zinc chloride on the radical polymerization of vinyl monomers