Extension of the chain‐end,free‐volume theory for predicting glass temperature as a function of conversion in hyperbranched polymers obtained through one‐pot approaches

Compared with linear polymers, more factors may affect the glass‐transition temperature (T_g) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. T_g's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of T_g to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. T_g's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. T_g values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. T_g values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of T_g versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that T_g increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004     

A sequential injection system for the spectrophotometric determination of calcium, magnesium and alkalinity in water samples.

A sequential injection methodology for the spectrophotometric determination of calcium, magnesium and alkalinity in water samples is proposed. A single manifold is used for the determination of the three analytes, and the same protocol sequence allows the sequential determination of calcium and magnesium (the sum corresponds to the water hardness). The determination of both metals is based on their reaction with cresolphtalein complexone; mutual interference is minimized by using 8-hydroxyquinoline for the determination of calcium and ethylene glycol-bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA) for the determination of magnesium. Alkalinity determination is based on a reaction with acetic acid, and corresponding color change of Bromcresol Green. Working ranges of 0.5 - 5 mg dm(-3) for Ca, 0.5 - 10 mg dm(-3) for Mg, and 10 - 100 mg HCO3- dm(-3), for alkalinity have been achieved. The results for water samples were comparable to those of the reference methods and to a certified reference water sample. RSDs lower than 5% were obtained, a low reagent consumption and a reduced volume of effluent have been accomplished. The determination rate for calcium and magnesium is 80 h(-1), corresponding to 40 h(-1) per element, while 65 determinations of alkalinity per hour could be carried out.     

Book Review

Structural Chemistry -     

On a Definitizable Analog of the Trigonometric Moment Problem Generating an Indefinite Toeplitz Form

We prove the existence of an integro-polynomial representation for a sequence of numbers such that there exists a difference operator mapping this sequence to a sequence that generates the solvable trigonometric moment problem. A similar result related to the power moment problem was given in [12].     

Synthesis of paramagnetic BODIPY dyes as new double (spin and fluorescence) sensors

Paramagnetic pyrroline and 1,2,3,6-tetrahydropyridine derivatives of BODIPY and their diamagnetic analogs have been synthesized and characterized as novel redox double sensor and cation sensitive reagents.     

Stable nonequilibrium probability densities and phase transitions for meanfield models in the thermodynamic limit

A nonlinear Fokker-Planck equation is derived to describe the cooperative behavior of general stochastic systems interacting via mean-field couplings, in the limit of an infinite number of such systems. Disordered systems are also considered. In the weak-noise limit; a general result yields the possibility of having bifurcations from stationary solutions of the nonlinear Fokker-Planck equation into stable time-dependent solutions. The latter are interpreted as non-equilibrium probability distributions (states), and the bifurcations to them as nonequilibrium phase transitions. In the thermodynamic limit, results for three models are given for illustrative purposes. A model of self-synchronization of nonlinear oscillators presents a Hopf bifurcation to a time-periodic probability density, which can be analyzed for any value of the noise. The effects of disorder are illustrated by a simplified version of the Sompolinsky-Zippelius model of spin-glasses. Finally, results for the Fukuyama-Lee-Fisher model of charge-density waves are given. A singular perturbation analysis shows that the depinning transition is a bifurcation problem modified by the disorder noise due to impurities. Far from the bifurcation point, the CDW is either pinned or free, obeying (to leading order) the Grüner-Zawadowki-Chaikin equation. Near the bifurcation, the disorder noise drastically modifies the pattern, giving a quenched average of the CDW current which is constant. Critical exponents are found to depend on the noise, and they are larger than Fisher's values for the two probability distributions considered.     

Luttinger liquid with asymmetric dispersion

We present an extension of the Tomonaga-Luttinger model in which left and right-moving particles have different Fermi velocities. We derive expressions for one-particle Green's functions, momentum-distributions, density of states, charge compressibility and conductivity as functions of both the velocity difference ε and the strength of the interaction β. This allows us to identify a novel restricted region in the parameter space in which the system keeps the main features of a Luttinger liquid but with an unusual behavior of the density of states and the static charge compressibility κ. In particular κ diverges on the boundary of the restricted region, indicating the occurrence of a phase transition. Received 20 May 2002 / Received in final form 23 August 2002 Published online 19 November 2002     

Singular terms of helicity amplitudes at one loop in QCD and the soft limit of the cross sections of multi-parton processes

We describe a general method that enables us to obtain all the singular terms of helicity amplitudes of n-parton processes at one loop. The algorithm uses helicity amplitudes at tree level and simple color algebra. We illustrate the method by calculating the singular part of the one-loop helicity amplitudes of all 2 → 3 parton subprocesses. The results are used to derive the soft gluon limit of the cross sections of all 2 → 4 parton scattering subprocesses which provide a useful initial condition for the angular ordering approximation to coherent multiple soft gluon emission, incorporated in existing Monte Carlo simulation programs.     

Erratum: Synthesis and characterization of diorganotin(IV) complexes of Schiff bases with ONO‐type donors and crystal structure of [N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐ethoxysalicylideneiminato]diphenyltin(IV)

The article referenced above was first published online on 30 August 2007 with incorrect pagination; the pagination has now been corrected online and in print. Copyright © 2007 John Wiley & Sons, Ltd.