Nitroxide‐mediated radical polymerization in miniemulsion: Bimolecular termination in monomer‐free model systems

Bimolecular termination in nitroxide‐mediated radical polymerization in miniemulsion has been investigated through the heating of a polystyrene–2,2,6,6‐tetramethylpiperidinyl‐1‐oxy macroinitiator and its 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyl‐1‐oxy analogue in an aqueous toluene dispersion with sodium dodecyl benzenesulfonate as a surfactant at 125 °C. The level of bimolecular termination by combination, evaluated from the high‐molecular‐weight shoulder, was higher in miniemulsion than in solution and increased with decreasing particle size. Quantitative analysis revealed that these results cannot be rationalized solely by nitroxide partitioning to the aqueous phase. The results are explained by an interface effect, by which nitroxide is adsorbed or located at the aqueous–organic interface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4995–5004, 2007     

带利息力和干扰的批量索赔一般到达风险模型

本文在经典风险模型的基础上,将索赔到达过程推广为更新过程,索赔可以批量到达,且带有常数利息力和Brown运动干扰项,得到一个新的风险模型,运用Markov骨架过程的方法,得出盈余过程的瞬时分布和生存概率.     

Local polynomial fitting under association

We consider the estimation of multivariate regression functions r(x₁,…,x_d) and their partial derivatives up to a total order p1 using high-order local polynomial fitting. The processes {Y_i,X_i} are assumed to be (jointly) associated. Joint asymptotic normality is established for the estimates of the regression function r and all its partial derivatives up to the total order p. Expressions for the bias and variance/covariance matrix (of the asymptotic distribution) are given.     

Model-dependent nature of blowtorch effect on the escape and equilibration rates

We analyze the relaxation behavior of a bistable system when the background temperature profile is inhomogeneous due to the presence of a localized hot region (blowtorch) on one side of the potential barrier. Since the diffusion equation for inhomogeneous medium is model-dependent, we consider two physical models to study the kinetics of such system. Using a conventional stochastic method, we obtain the escape and equilibration rates of the system for the two physical models. For both models, we find that the hot region enhances the escape rate from the well where it is placed while it retards the escape rate from the other well. However, the value of the escape rate from the well where the hot region is placed differs for the two models while that of the escape rate from the other well is identical for both. This work, for the first time, gives a detailed report of the similarities and differences of the escape rates and, hence, exposes the common and distinct features of the two known physical models in determining the way the bistable system relaxes. Received 25 September 2001     

Some time change representations of stable integrals, via predictable transformations of local martingales

From the predictable reduction of a marked point process to Poisson, we derive a similar reduction theorem for purely discontinuous martingales to processes with independent increments. Both results are then used to examine the existence of stochastic integrals with respect to stable Lévy processes, and to prove a variety of time change representations for such integrals. The Knight phenomenon, where possibly dependent but orthogonal processes become independent after individual time changes, emerges as a general principle.     

A simple formula for mean multiplexing delay for independent regenerative sources

Simple expressions are given for the mean delay, mean waiting time, and mean busy period length in a multiplexer. Data streams with active periods having a general distribution are permitted, and the data rate during the active periods can be random. Data can also arrive in batches. The key restrictions of the model are that the sources are independent, idle periods are exponentially distributed, and a source generates at least enough data during an active period to keep the server busy throughout the period. The exact formulas allow evaluation of the error in approximations such as a heavy traffic diffusion approximation.Both continuous and discrete time models are considered. The discrete-time model includes that studied by Viterbi and subsequently generalized by Neuts. The Pollaczek-Khinchine formula for the mean amount of work in anM/GI/1 queue is retrieved as a limiting case.Preliminary version presented at IEEE INFOCOM, San Francisco, April 1993.     

On distributionally regenerative processes

The paper is concerned with characterization results for distributional regeneration. It is shown that distributional regeneration is equivalent to renewal representation of the associated (shift) Markov operator. A sufficient condition for the distributional regeneration of the transfer operator in terms of variation is also formulated. Finally, a minorization condition is formulated and proved to be sufficient for recurrent co-Feller operators.     

Effective-field theory and the nuclear many-body problem

We review many-body calculations of the equation of state of dilute neutron matter in the context of effective-field theories of the nucleon-nucleon interaction.     

A new formula for the saddle-to-scission time

We propose a new formula for the saddle-to-scission time that is more general that the one based on Kramers' approach. Its validity and applicability is then studied in detail. Such a formula is useful for the evaluation of the fission time of very heavy nuclei.     

2‐Cyanoprop‐2‐yl dithiobenzoate mediated reversible addition–fragmentation chain transfer polymerization of acrylonitrile targeting a polymer with a higher molecular weight

The reversible addition–fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2‐cyanoprop‐2‐yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANs were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. ¹H NMR analysis confirmed the high chain‐end functionality of the resultant polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1272–1281, 2007