Synthesis and characterization of poly(higher‐α‐olefin)s with a nickel(α‐diimine)/methylaluminoxane catalyst system: Effect of chain running on the polymer properties

Homopolymerization of octadecene‐1 at different reaction conditions has been studied. Significant chain running can be seen at higher polymerization temperatures. Interestingly, insertion of octadecene‐1 into a sterically hindered nickel‐cation/carbon (secondary) bond is observed. The microstructure of the polymer was established using NMR spectroscopy. The effects of chain running on polymer melting, crystallization behavior, and dynamic mechanical thermal properties were studied using DSC and DMTA. The extent of chain running (i.e., 2,ω‐, 1,ω‐enchainments) decreases with an increase in the carbon number of α‐olefins. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 191–210, 2007     

Speeding up the FMMR perfect sampling algorithm: A case study revisited

In a previous paper by the second author, two Markov chain Monte Carlo perfect sampling algorithms—one called coupling from the past (CFTP) and the other (FMMR) based on rejection sampling—are compared using as a case study the move‐to‐front (MTF) self‐organizing list chain. Here we revisit that case study and, in particular, exploit the dependence of FMMR on the user‐chosen initial state. We give a stochastic monotonicity result for the running time of FMMR applied to MTF and thus identify the initial state that gives the stochastically smallest running time; by contrast, the initial state used in the previous study gives the stochastically largest running time. By changing from worst choice to best choice of initial state we achieve remarkable speedup of FMMR for MTF; for example, we reduce the running time (as measured in Markov chain steps) from exponential in the length n of the list nearly down to n when the items in the list are requested according to a geometric distribution. For this same example, the running time for CFTP grows exponentially in n. © 2003 Wiley Periodicals, Inc. Random Struct. Alg., 2003     

Production systems with interruptions, arbitrary topology and finite buffers

We consider a production system with finite buffers and arbitrary topology where service time is subject to interruptions in one of three ways, viz. machine breakdown, machine vacations or Npolicy. We develop a unified approximation (analytical) methodology to calculate the throughput of the system using queueing networks together with decomposition, isolation and expansion techniques. The methodology is rigorously tested covering a large experimental region. Orthogonal arrays are used to design the experiments in order to keep the number of experiments manageable. The results obtained using the approximation methodology are compared to the simulation results. The ttests carried out to investigate the differences between the two results show that they are statistically insignificant. Finally, we test the methodology by applying it to several arbitrary topology networks. The results show that the performance of the approximation methodology is consistent, robust and produces excellent results in a variety of experimental conditions.     

Off-diagonal long-range order of the wave function in terms of the alternate molecular bonding geminals

It is shown that in the quantum structural approach to high-Tc superconductivity, the wave function in terms of the alternate molecular bonding geminals possesses off-diagonal long-range order (ODLRO).     

Selection of suitable operating conditions to minimize the gradient equilibration time in the separation of drugs by Ultra-High-Pressure Liquid Chromatography with volatile (mass spectrometry-compatible) buffers

Reversed phase gradient elution is the method of choice for pharmaceuticals analysis since it allows reducing the analysis time while improving both the quality of the separation and the detection limits. The current trends are towards faster separations which can be achieved thanks to equipments withstanding ultra-high pressures and/or high temperatures. Under such conditions, gradient separations can be carried out within a few minutes or even a few tens of seconds. A long equilibration time in addition to the gradient time can be therefore very detrimental. In this work, we investigated the extent to which the gradient equilibration time can be reduced and which parameters mainly affect the retention variability of ionizable compounds when using volatile buffers. We first found out an excellent repeatability between run-to-run experiments whatever the equilibration time and the operating conditions. We then pointed out the key operating parameters which allow achieving reproducible runs when varying the equilibration time between runs. With a view of reducing the equilibration time, the effects of various conditions were examined. The latter include the type of additive for mobile phase pH adjustment, the initial eluent composition, the type of stationary phase, the temperature and the flow-rate. Although much remains to be understood about the equilibration process, our study allows making progress in the knowledge of this phenomenon. Based on the present results, a beneficial effect of both temperature and flow-rate was highlighted and operating conditions leading to faster column equilibration are suggested.     

化学跑合剂对跑合效果的影响

在ＢＪ５２Ａ胶合试验机、ＪＰ－ＢＤ１５００型接触疲劳试验机和ＣＬ－１００齿轮试验机上考察了化学跑合剂的作用，并就其机理进行了探讨。结果表明：采用化学跑合剂跑合后，表面粗糙度明显降低；表面接触面积增大，可以实现１次满载快速跑合；与采用含磨料的跑合方法比较，化学跑合剂可以明显提高表面接触精度，减少裂纹源的发生和发展，使表面承载能力明显提高。当齿轮加工精度较低或高速、重载齿轮的硬齿面精加工存在困难时，可     

Kinetic Buffers

This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH‐sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH–t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di‐copper(II) bistren complex in a single run, in a completely automatic experiment.     

Solvation consequences of polymer PVP with biological buffers MES,MOPS, and MOPSO in aqueous solutions

Densities and viscosities were measured for the aqueous buffer (MES, MOPS, or MOPSO) solutions containing different concentrations of polyvinylpyrrolidone (PVP) (5, 10, 15, 20 and 30) mass% at temperatures from (298.15 to 318.15) K under atmospheric pressure. The DFT calculations were also performed and the binding energies of the possible (PVP + buffer) complexes were obtained. The experimental and computational results reveal the interactions of the PVP with the constituent compounds in the aqueous buffer solutions. Additionally we have explored the solvation behavior of the buffers by measuring the densities and the viscosities data of the aqueous buffer solutions from (0.0 to 1.0) mol · kg⁻¹ at temperatures from (298.15 to 318.15) K. The viscosity results were correlated with the Jones–Dole equation. The correlated results confirmed that all the investigated buffers behave as Kosmotropes (structure makers).     

Alternate pacing of border-collision period-doubling bifurcations

Unlike classical bifurcations, border-collision bifurcations occur when, for example, a fixed point of a continuous, piecewise C ¹ map crosses a boundary in state space. Although classical bifurcations have been much studied, border-collision bifurcations are not well understood. This paper considers a particular class of border-collision bifurcations, i.e., border-collision period-doubling bifurcations. We apply a subharmonic perturbation to the bifurcation parameter, which is also known as alternate pacing, and we investigate the response under such pacing near the original bifurcation point. The resulting behavior is characterized quantitatively by a gain, which is the ratio of the response amplitude to the applied perturbation amplitude. The gain in a border-collision period-doubling bifurcation has a qualitatively different dependence on parameters from that of a classical period-doubling bifurcation. Perhaps surprisingly, the differences are more readily apparent if the gain is plotted versus the perturbation amplitude (with the bifurcation parameter fixed) than if plotted versus the bifurcation parameter (with the perturbation amplitude fixed). When this observation is exploited, the gain under alternate pacing provides a useful experimental tool to identify a border-collision period-doubling bifurcation.     

两款原子吸收光谱仪的塞曼背景校正装置

讨论了永久磁场塞曼背景校正原子吸收光谱仪的外光路和磁场的设计工艺,描述了可以同时获得交流磁场和直流磁场塞曼背景校正测定结果的新系统,以及可以克服洛伦兹力对测定产生影响的磁场和石墨炉的供电系统.