Amine‐blocked polyisocyanates. I. Synthesis of novel N‐methylaniline‐blocked polyisocyanates and deblocking studies using hot‐stage fourier transform infrared spectroscopy

A series of substituted N‐methylaniline‐blocked polyisocyanates based on 4,4′‐methylenebis(phenyl isocyanate) and poly(tetrahydrofuran) were prepared and characterized thoroughly with FTIR, ¹H NMR, and ¹³C NMR spectroscopy methods. Compared with unsubstituted N‐methylaniline, a blocking agent with an electron‐releasing substituent at the para position took a shorter time, whereas those with an electron‐releasing substituent at the ortho position or an electron‐withdrawing substituent at the ortho and para positions took longer times for the blocking reaction. The thermal dissociation reactions of blocked polyisocyanates were carried out with an FTIR spectrophotometer attached to hot‐stage accessories under dynamic and isothermal conditions. The dynamic method was used to determine the deblocking temperature, and the isothermal method was used to calculate the deblocking kinetics and activation parameters. The cure times of blocked polyisocyanates with hydroxyl‐terminated polybutadiene were also determined. The deblocking temperatures, the results of cure‐time studies, and the kinetic parameters revealed that the thermal dissociation of the N‐methylaniline‐blocked polyisocyanates was retarded by electron‐donating substituents and facilitated by electron‐withdrawing substituents. The action of N‐methylanilines as blocking agents for isocyanate was explained by the formation of a four‐center, intramolecularly hydrogen‐bonded ring structure during the thermal dissociation of the blocked polyisocyanates. The formation of such a hydrogen‐bonded ring structure was confirmed and supported by variable‐temperature ¹H NMR studies and entropy parameters, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1557–1570, 2007     

Isosteres of peptides: boron analogs as dipolar forms of α‐amino acids – a theoretical study

Modification of peptides to produce peptidomimetics is of great interest, with the aim of designing potent, selective, and metabolically stable analogs having certain conformational properties. Organoboranes have been reported in the literature with a wide range of therapeutic applications. One of the therapeutically important class of molecules is amine‐carboxyboranes derived from amino acids by replacement of the Cα atom of an amino acid/peptide by boron. The conformational preferences of these peptides, with respect to backbone ω, ?, and ψ torsion angles, have been investigated by theoretical calculations. The amide bond in these molecules has the same geometry in the ground and transition states as the natural peptides. However, the boron isosteres of glycine and alanine peptides are less structured than their natural derivatives, but are distinguished by structures with a positive value for the ? angle, which is normally disfavored for natural peptides. This property could be used to build peptides with a geometry not usually seen in natural peptides. Copyright © 2007 John Wiley & Sons, Ltd.     

Speed of adaptation in structured populations

Adaptation of populations takes place with the occurrence and subsequent fixation of mutations that confer some selective advantage to the individuals which acquire it. For this reason, the study of the process of fixation of advantageous mutations has a long history in the population genetics literature. Particularly, the previous investigations aimed to find out the main evolutionary forces affecting the strength of natural selection in the populations. In the current work, we investigate the dynamics of fixation of beneficial mutations in a subdivided population. The subpopulations (demes) can exchange migrants among their neighbors, in a migration network which is assumed to have either a random graph or a scale-free topology. We have observed that the migration rate drastically affects the dynamics of mutation fixation, despite of the fact that the probability of fixation is invariant on the migration rate, accordingly to Maruyama's conjecture. In addition, we have noticed a topological dependence of the adaptive evolution of the population when clonal interference becomes effective.     

C++QED: an object-oriented framework for wave-function simulations of cavity QED systems

We present a framework for efficiently performing Monte Carlo wave-function simulations in cavity QED with moving particles. It relies heavily on the object-oriented programming paradigm as realised in C++, and is extensible and applicable for simulating open interacting qua ntum dynamics in general. The user is provided with a number of “elements”, e.g. pumped moving particles, pumped lossy cavity modes, and various interactions to compose complex interacting systems, which contain several particles moving in electromagnetic fields of various configurations, and perform wave-function simulations on such systems. A number of tools are provided to facilitate the implementation of new elements.     

Global and exploding solutions in a model of self-gravitating systems

We study asymptotic properties of solutions to an extension to arbitrary dimensions of the astrophysical model proposed by Chavanis et al. to explain phenomena of gravitational collapse in clouds of self-gravitating particles. In particular, we show that in the two-dimensional case the solutions can be continued to global ones, while in three space dimensions large data of negative energy blow up in a finite time. Relations between isothermal, Streater's energy-transport and the present models are also studied.     

A simple model for high fluence ultra-short pulsed laser metal ablation

The ultra-short laser metal ablation is a very complex process, the complete simulation of which requires applications of complicated hydrodynamics or molecular dynamics models, which, however, are often time-consuming and difficult to apply. For many practical applications, where the laser ablation depth is the main concern, a simplified model that is easy to apply but at the same time can also provide reasonably accurate predictions of ablation depth is very desirable. Such a model has been developed and presented in this paper, which has been found to be applicable for laser pulse duration up to 10 ps based on comparisons of model predictions with experimental measurements.     

On the Stability of Bifurcation Diagrams of Vanishing Flattening Points

On a smooth surface in Euclidean 3-space, we consider vanishing curves whose projections on a given plane are small circles centered at the origin. The bifurcations diagram of a parameter-dependent surface is the set of parameters and radii of the circles corresponding to curves with degenerate flattening points. Solving a problem due to Arnold, we find a normal form of the first nontrivial example of a flattening bifurcation diagram, which contains one continuous invariant.     

Focusing-defocusing phenomena of radio echo signal after passage of the morning solar terminator

Summary Campaign results of high-repetition ionospheric soundings, performed at the ionospheric station of Rome using a Digisonde 128P, are presented. We introduce an index derived from run rapid ionograms that can be used to detect oscillations of isodensity surfaces ofF ionospheric region started by morning solar terminator.     

高等师范学校物理专业课程结构改革研究

为解决高等师范院校物理专业学生的知识结构和实际能力与社会需要明显不相适应的矛盾，我们对四年制物理专业的课程结构进行了全面改革。改革后，毕业生不仅能胜任普通中学或职业中学（职业中专）的教学，而且有能力参与厂矿企业的技术工作，具有更广泛的适应性和更强的竞争力。