Macromolecules at surfaces: Research challenges and opportunities from tribology to biology

A comprehensive review of ongoing and recommended research directions concerning the structure, dynamics, and interfacial activity of synthetic and naturally occurring macromolecules at the solid–liquid interface is presented. Many new developments stem from the ability to target new size regimes of 1–100 nm. These rapid developments are reviewed critically with respect to chemical synthesis, processing, structural characterization, dynamic processes, and theoretical and computational analysis. The common problems shared by flat and particulate surfaces are emphasized. A broad spectrum of material properties are discussed, from the control of interfacial friction between surfaces in moving contact, to the mechanical strength and durability of the interfaces in hybrid materials, to optical and electronic properties. Future research opportunities are identified that involve (1) the emergence of nanoscale material properties, (2) polymer‐assisted nanostructures, and (3) the crossroads between interfacial science and biological and bioinspired applications. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2755–2793, 2003     

ICP-AES analysis of impurities in PuO2 after separation of Pu by TOPO impregnated XAD-4

Nuclear fuels should meet some specified characteristics to achieve their better performance in the reactor. Hence controlling and monitoring of trace level elements in the fuel materials are essential. Atomic emission spectroscopic methods are most popular for the trace level analysis. An ICP-AES procedure is described here for the trace level impurity analysis of PuO₂ produced through PUREX process. To avoid the Pu interference in the impurity analysis, initially the Pu was separated by extraction chromatography using TOPO impregnated XAD-4 resin. Magnitude of Pu interference in the impurities spectra lines was investigated. Moreover the recovery of impurity elements using the resin was established.     

A note on random coin tossing

Harris and Keane [Probab. Theory Related Fields 109 (1997) 27-37] studied absolute continuity/singularity of two probabilities on the coin-tossing space, one representing independent tosses of a fair coin, while in the other a biased coin is tossed at renewal times of an independent renewal process and a fair coin is tossed at all other times. We extend their results by allowing possibly different biases at the different renewal times. We also investigate the contiguity and asymptotic separation properties in this kind of set-up and obtain some sufficient conditions.Keywords:renewal process, absolute continuity, singularity, contiguity, asymptotic separation, martingale convergence theorem     

Compensation for temperature dependence of Stokes signal and dynamic self-calibration of a Raman distributed temperature sensor

This article discusses a powerful calibration technique that compensates for the temperature dependence of the Stokes signal in a Raman distributed temperature sensor. The Stokes signal is conventionally used for normalization since its scattering cross-section is a weaker function of temperature than that of the anti-Stokes signal. The potential of this temperature dependence of the Stokes signal to introduce errors in measurements has received only cursory mention in the literature. We show that this effect degrades the temperature accuracy by as much as 90%. Additionally the heavy fiber attenuation at the operating wavelength also makes calibration non-trivial. The technique described implements a corrective mechanism for this temperature dependence, offers the additional benefit of self-referencing of a heated curve rather than referencing to the fiber at room temperature, and demonstrates the viability of such a system despite the heavy fiber attenuation at the operating wavelength. This obviates the impractical and erroneous approach of storing an initial room temperature profile for subsequent temperature calculation. This dynamic self-referencing adds substantial immunity to the tolerances in the actual numerical values of the Raman wavelengths thereby making the system robust.     

Coupling of spontaneous emission from GaN-AlN quantum dots into silver surface plasmons

We have demonstrated the decay of spontaneous emission (SE) from AlN-GaN quantum dots (QDs) into silver surface plasmon (SP) modes in the ultraviolet at approximately 375-380 nm. Using time-resolved photoluminescence (PL), we show that the electron-hole recombination rate in AlN-GaN QDs is enhanced when SE is resonantly coupled to a metal SP mode, corresponding to the dip in the continuous-wave PL spectrum. Exciton recombination by means of silver SP modes is as much as 3-7 times faster than in normal QD SE and depends strongly on emission wavelength and thickness of the silver.     

Accuracy of the bootstrap approximation

Summary The sampling distribution of several commonly occurring statistics are known to be closer to the corresponding bootstrap distribution than the normal distribution, under some conditions on the moments and the smoothness of the population distribution. These conditional approximations are suggestive of the unconditional ones considered in this paper, though one cannot be derived from the other by elementary methods. In this paper, probabilistic bounds are provided for the deviation of the sampling distribution from the bootstrap distribution. The rate of convergence to one, of the probability that the bootstrap approximation outperforms the normal approximation, is obtained. These rates can be applied to obtain theL ^p bounds of Bhattacharya and Qumsiyeh (1989) under weaker conditions. The results apply to studentized versions of functions of multivariate means and thus cover a wide class of common statistics. As a consequence we also obtain approximations to percentiles of studentized means and their appropriate modifications. The results indicate the accuracy of the bootstrap confidence intervals both in terms of the actual coverage probability achieved and also the limits of the confidence interval.Research supported in part by NSA Grant MDA 904-90-H-1001     

Extended Conjugation in Polyaniline Like Structure Prepared by Plasma Polymerization Suitable for Optoelectronic Applications

Plasma polymerization of aniline is carried out in a radiofrequency plasma reactor and the effect of polymerization time is examined in the structural, optical and optoelectronic properties of deposited films. Conjugated structures of polyaniline like films are obtained with unique and broad optical absorption band in the ultraviolet and entire visible region. The width of the absorption band increases and hence the optical band gap decreases with polymerization time. The optical constants are extracted by Swanepoel method and the optical dispersion parameters are determined by employing the Wemple-DiDomenico single oscillator model. The films exhibit similar thermal stability in air and argon atmosphere in the region of interest for optoelectronic applications. The photoluminescence study suggests, like the chemically synthesized polyaniline, the benzenoid units to be responsible for fluorescence. The fluorescence peaks due to defect states confirm the formation of spectroscopic units in the plasma polyaniline films.     

Conductance and bulk vertical detachment energy of hydrated sulphate and oxalate dianions: a theoretical study

Analytical expressions have been derived for the vertical detachment energy (VDE) for hydrated sulphate (SO^{2 ?}₄) and oxalate (C₂O^{2 ?}₄) dianions that can be used to calculate the same over a wide range of cluster sizes including the bulk from the knowledge of VDE for a finite number of stable clusters. The calculated bulk detachment energies are found to be very good in agreement (within 5%) with the available experimental results for both the systems. It is observed that two or more water molecules will be essential for the stability of sulphate and oxalate dianions against spontaneous electron loss and this is consistent with the experiment. We have, for the first time, provided a scheme to calculate the radius of the solvent berg for sulphate and oxalate dianions. The calculated conductivity values for the sulphate and oxalate dianions using Stokes–Einstein relation and the radius of solvent berg are found to be very good in agreement (within 4%) with the available experimental results.