Salt‐Induced Depression of Lower Critical Solution Temperature in a Surface‐Grafted Neutral Thermoresponsive Polymer

Summary: Quartz crystal microbalance with dissipation monitoring (QCM‐D) is employed to determine the effect of salt on the volume phase transition of thermoresponsive polymer brushes. Changes in mass and viscoelasticity of poly(N‐isopropylacrylamide) (PNIPAM) layers grafted from a QCM‐D crystal are measured as a function of temperature, upon contact with aqueous solutions of varying salt concentrations. The phase‐transition temperature of PNIPAM brushes, T_C,graft, quantified from the QCM‐D measurements is found to decrease as the concentration of salt is increased. This phenomenon is explained by the tendency of salt ions to affect the structure of water molecules (Hofmeister effect). However, in contrast to the linear decrease in phase‐transition temperature upon increasing salt concentration observed for free PNIPAM, the trend in T_C,graft for PNIPAM brushes is distinctively non‐linear.

Schematic representation of the effect of salt concentration on the phase transition behavior of thermoresponsive polymer brushes.     

Dynamic mechanism of photochemical induction of turing superlattices in the chlorine dioxide-iodine-malonic acid reaction-diffusion system

We study the mechanism of development of superlattice Turing structures from photochemically generated hexagonal patterns of spots with wavelengths several times larger than the characteristic wavelength of the Turing patterns that spontaneously develop in the nonilluminated system. Comparison of the experiment with numerical simulations shows that interaction of the photochemical periodic forcing with the Turing instability results in generation of multiple resonant triplets of wave vectors, which are harmonics of the external forcing. Some of these harmonics are situated within the Turing instability band and are therefore able to maintain their amplitude as the system evolves and after illumination ceases, while photochemically generated harmonics outside the Turing band tend to decay.     

Anomalies in supercooled NaCl aqueous solutions: a microscopic perspective

In this work we studied the effect of NaCl on the thermodynamic and dynamic properties of supercooled water, for salt concentrations between 0.19 and 1.33 mol?kg(-1), using molecular dynamic simulations for TIP5P∕E water model and ion parameters specially designed to be used in combination with this potential. We studied the isobaric heat capacity (C(p)) temperature dependence and observed a maximum in C(p), occurring at T(m), that moves to lower temperature values with increasing salt concentration. Many characteristic changes were observed at scaled temperature T∕T(m) ～ 0.96, namely a minimum in the density of the system, a reduction of the slope of the number of hydrogen bonds vs. temperature, and a crossover from Vogel-Tamman-Fulcher to Arrhenius dynamics. Finally, at low temperatures we observed that water dynamics become heterogeneous with an apparently common relationship between the fraction of immobile molecules and T/T(m) for all studied systems.     

Shell model description of interacting bosons

The interacting boson model, describing collective states of even-even nuclei, is introduced as a drastic truncation of large scale shell model calculations. The shell model hamiltonian can be diagonalized by using a correspondence, or mapping, of the nucleon states in the truncated space into states obtained by coupling proton and neutron s- and d-bosons. The equivalent boson hamiltonian in a simple case is obtained and diagonalized. Eigenstates with definite proton-neutron symmetry (good F-spin) emerge for certain values of proton and neutron numbers. In general the situation is more complex but the results obtained follow closely the experimental data.     

Laser-microprobe elemental determinations with an optical multichannel detection system

The results obtained when a laser microprobe is adapted to imaging detectors for multiwavelength detection are described. Detectors evaluated are a silicon-intensified target vidicon and a second-generation photodiode array. Data are presented to illustrate how the combined system can be used to monitor both surface and depth profiles of elemental content of a variety of sample types including a ruby rod and ceramic material with blemishes, electrical capacitors, integrated circuits, and surface-coated electrical conductors. It is also shown how the gating capability of the intensified vidicon can be used to monitor time-dependent changes in the several nanosecond range during the laser microprobe excitation process. Detection limits obtained with both detectors are in the range 2–500 ppm depending on the element, the wavelength used, the matrix, and other variables. The uncertainty associated with the measurement step can be improved by a factor of 2–3 by using ratios of spectral lines. Principal limitations of the laser microprobe method are the nonlinear response of intensity vs. concentration and the resulting need for reference materials with matrices similar to samples for calibration purposes.     

Monte Carlo simulation and molecular theory of tethered polyelectrolytes

We investigate the structure of end-tethered polyelectrolytes using Monte Carlo simulations and molecular theory. In the Monte Carlo calculations we explicitly take into account counterions and polymer configurations and calculate electrostatic interaction using Ewald summation. Rosenbluth biasing, distance biasing, and the use of a lattice are all used to speed up Monte Carlo calculation, enabling the efficient simulation of the polyelectrolyte layer. The molecular theory explicitly incorporates the chain conformations and the possibility of counterion condensation. Using both Monte Carlo simulation and theory, we examine the effect of grafting density, surface charge density, charge strength, and polymer chain length on the distribution of the polyelectrolyte monomers and counterions. For all grafting densities examined, a sharp decrease in brush height is observed in the strongly charged regime using both Monte Carlo simulation and theory. The decrease in layer thickness is due to counterion condensation within the layer. The height of the polymer layer increases slightly upon charging the grafting surface. The molecular theory describes the structure of the polyelectrolyte layer well in all the different regimes that we have studied.     

A Time of Flight Model for Cloud’s Radiative Transfer

A model for fast calculation of path radiance of finite clouds is presented. The calculations are simplified by using the reciprocity principle and the homogenousness property of the incident light. Comparisons with reasonably accurate calculations for spherical cloud and two-dimensional infinite layer were made.Presented at the 7th International Workshop on Multiple Scattering Lidar/Light Experiments (MUSCLE7), July 21–23 1994, Chiba, Japan.     

Phase transfer catalysis in N-alkylation of the pharmaceutical intermediates phenothiazine and 2-chlorophenothiazine

The N-alkylation of the two title compounds was studied, utilizing phase transfer catalysis (PTC) methods. Very mild reaction conditions were developed, especially for three-carbon N-alkylation. Of special interest is the high-yield synthesis of N-(3-chloropropyl)-2-chlorophenothiazine. The results are discussed in terms of the classical PTC/OH⁻ mechanisms.     

Nanoscale memory provided by thermoreversible stochastically structured polymer aggregates on mica

Stimuli-responsive polymers are used in a large variety of applications due to the controlled manner in which their physical properties can be reversibly altered. In this study, we demonstrate the thermoreversible structuring of poly(N-isopropylacrylamide)-based polymer. By temperature-controlled atomic force microscopy, we demonstrate that polymer aggregates form on mica above the polymer lower critical solution temperature and disperse below it, and in so doing, display positional "memory" in that the nanodomains are retained in the same positions and with the same shapes during repeated cooling/heating cycles. Such positional "memory" may be useful for multiple applications in nano-microscale devices.     

How and why nanoparticle's curvature regulates the apparent pKa of the coating ligands

Dissociation of ionizable ligands immobilized on nanopaticles (NPs) depends on and can be regulated by the curvature of these particles as well as the size and the concentration of counterions. The apparent acid dissociation constant (pK(a)) of the NP-immobilized ligands lies between that of free ligands and ligands self-assembled on a flat surface. This phenomenon is explicitly rationalized by a theoretical model that accounts fully for the molecular details (size, shape, conformation, and charge distribution) of both the NPs and the counterions.