Nitroxide‐mediated radical polymerization of 2‐(dimethylamino)ethyl acrylate and its sequential block copolymerization with styrene and N‐butyl acrylate

Nitroxide‐mediated radical polymerization (NMRP) of 2‐(dimethylamino)ethyl acrylate (DMAEA) was carried out at 100–120 °C, initiated by MONAMS, an alkoxyamine based on N‐tert‐butyl‐N‐(1‐diethyl phosphono‐2,2‐dimethylpropyl)nitroxide, SG1. Controlled polymerization can be achieved by the addition of free SG1 (the initial molar ratio of SG1 to MONAMS ranged from 0.06 to 0.12), giving a linear first‐order kinetic plot up to 55–70% conversion depending on the reaction conditions. The molecular weights show a near linear increase with conversion; however, they deviate to some extent with theoretical values. SG1‐mediated polymerization of DMAEA at 112 °C is also controlled in organic solvents (N,N‐dimethylformide, anisole, xylene). Polymerization rate increases with increasing solvent polarity. Chain transfer to polymer produces ～1 mol % branches in bulk and 1.2–1.9 mol % in organic solvents, typical of those for acrylates. From poly(styrene) (pS) and poly(n‐butyl acrylate) (pBA) macroinitiators, amphiphilic di‐ and triblock copolymers p(S‐b‐DMAEA), p(DMAEA‐b‐S‐b‐DMAEA), p(BA‐b‐DMAEA), and p(DMAEA‐b‐BA‐b‐DMAEA) were synthesized via NMRP at 110 °C. Polymers were characterized by GPC, NMR, surface tension measurements, and DSC. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 414–426, 2006     

Sulfonated poly(aryl ether ether ketone ketone)s containing fluorinated moieties as proton exchange membrane materials

A series of sulfonated poly(aryl ether ether ketone ketone)s statistical copolymers with high molecular weights were synthesized via an aromatic nucleophilic substitution polymerization. The sulfonation content (SC), defined as the number of sulfonic acid groups contained in an average repeat unit, could be controlled by the feed ratios of monomers. Flexible and strong membranes in sodium sulfonate form could be prepared by the solution casting method, and readily transformed to their proton forms by treating them in 2 N sulfuric acid. The polymers showed high T_gs, which increased with an increase in SC. Membranes prepared from the present sulfonated poly(ether ether ketone ketone) copolymers containing the hexafluoroisopropylidene moiety (SPEEKK‐6F) and copolymers containing the pendant 3,5‐ditrifluoromethylphenyl moiety (SPEEKK‐6FP) had lower water uptakes and lower swelling ratios in comparison with previously prepared copolymers containing 6F units. All of the polymers possessed proton conductivities higher than 1 × 10^?2 S/cm at room temperature, and proton conductivity values of several polymers were comparable to that of Nafion at high relative humidity. Their thermal stability, oxidative stability, and mechanical properties were also evaluated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2299–2310, 2006     

Quantum relativistic action at a distance

A well-known relativistic action at a distance interaction of two unequal masses is altered so as to yield purely Newtonian radial forces with fixed particle rest masses in the system center-of-momentum inertial frame. Although particle masses experience no kinematic mass increase in this frame, speeds are naturally restricted to less than the speed of light. We derive a relation between the center-of-momentum frame total Newtonian energy and the composite rest mass. In a new proper time quantum formalism, we obtain an L²(R⁴ R⁴, C) Hilbert space by varying individual particle rest masses. We propose the use of density operators, recognizing that the auxiliary proper time parameter is not an observable. The quantum formalism is applied to our altered version of the relativistic harmonic oscillator. Our generalized coherent states yield four-dimensional wave packets which follow the correct classical world lines. Appendices contain reviews of classical Hamiltonian reparametrization (incorporating our notion of manifest covariance), and a comparison of this work with the literature.     

Zur Katalysierten Verflüchtigung von rotem Phosphor und von Claudetit

The Catalysed Volatilization of Red Phosphorus and of Claudetite The catalysis of the volatilization of P_red (as P₄) by AlCl_3,g, and of the volatilization of claudetite (as As₄O₆) by I_2,g is observed by mass spectrometry.     

Controlled vesicle self-assembly in microfluidic channels with hydrodynamic focusing

Traditional liposome preparation methods are based on mixing of bulk phases, leading to inhomogeneous chemical and/or mechanical conditions during formation; hence liposomes are often polydisperse in size and lamellarity. Here we show the formation of liposomes that encapsulate reagents in a continuous two-phase flow microfluidic network with precision control of size from 100 to 300 nm by manipulation of liquid flow rates. We demonstrate that by creating a solvent-aqueous interfacial region in a microfluidic format that is homogeneous and controllable on the length scale of a liposome, we can facilitate the fine control of liposome size and polydispersity.     

Microchemical techniques as applied to radiochemistry

Microchimica Acta - The techniques for investigating the chemistry of radioactive elements usingμg quantities of material are described. These include methods of transfer and carrying out...     

A novel sensitized chemiluminescence: Infrared emissions from thiazine dyes sensitized by singlet oxygen

An unusual infrared chemiluminescence emission (8130Å) of methylene blue, and other thiazine dyes, sensitized by singlet molecular oxygen is reported. This chemiluminescence does not correspond to the ordinary fluorescence of the dye and cannot be explained by previously proposed mechanisms for singlet oxygen sensitized emissions of dyes. From energetic considerations singlet molecular oxygen in its ¹Σ_g⁺ state is postulated as the sensitizing agent for the thiazine dye chemiluminescences. Schemes in which ¹Σ_g⁺ oxygen transfers electronic excitation energy (a) to the lowest triplet state of the dye, (b) to a combined multiplicity state of the lowest triplet state of the dye, and triplet molecular oxygen, or (c) to a charge-transfer state between the dye and oxygen, are compared. The chemiluminescence of methylene blue in aqueous solution may be used as a luminescent probe for ¹Σ_g⁺ oxygen.