Simulation of the Processes of Irreversible Aggregation in the Systems of Molecular Chains with Different Distribution of Associating Groups

The processes of the irreversible aggregation of chain molecules with various numbers of associating groups are studied by the Monte Carlo method using the Eden model. Three-dimensional lattice systems are considered. The model developed qualitatively reproduces the main structural (morphological) characteristics that are observed experimentally for the aggregates composed of macromolecules of ionic polymers under the conditions of strong segregation. It is established that the chains with one associating terminal group form tree-like coral-shaped aggregates; associating groups form the skeleton with a large number of branches at the periphery. It is shown that the chains with the number n _s 2 of associating groups form aggregates whose structures correspond to a three-dimensional network. Integral characteristics of a system are scale-invariant; molecular parameters, such as the chain length N and the number of associating groups n _s, enter into corresponding scaling dependences in the form of scaling multipliers N and n _s . Critical indices and , as well as main index determining the dependence of the mean aggregate sizes on the number n of constituting molecules, are estimated. It is established that an increase in the number of associating groups in a chain results in the formation of more compact aggregates with smaller characteristic size of a network cell. For the model considered, such an effective compression is explained by the intensification of branching, i.e., by the dispersal of growth points, rather than by the folding of chains (on the contrary, their substantial fraction is attached to the cluster in greatly extended conformations). The important role of intra- and interchain screening effects arising during the formation of local morphology of aggregates is demonstrated. As a result of such screening, the sizes of lattice nodes composed of associating groups seem to be the nonmonotonic function of the number of these groups in the chain.     

Electronic absorption spectra or carbonium and dicarbonium ions containing heterocyclic rings with a biphenylene base

An analysis has been made of -^* -electronic excitations of carbonium and dicarbonium ions obtained by the interaction of concentrated sulfuric or fluoboric acid with alcohols or glycols containing a heterocyclic bridge structure, i.e., nuclei of dibenzofuran, dibenzothiophene, carbazole, and N-methylcarbazole; this analysis has been aimed at establishing a correlation of their structure and spectral characteristics. From an analysis of experimental data, calculated results, and indexes quantitatively characterizing the structure of the -^* -electronic excitations, it has been established that there are four electronic transitions in the visible region of the electronic absorption spectrum of the carbonium ions. The long-wave, intense band of the spectrum is due to superposition of intense (p-type) and weak (-type) transitions proceeding from corresponding excitations of the heterocyclic fragment. In the electronic spectra of the dicarbonium ions, a doublet of p-transitions is clearly manifested. It has been shown that the interaction of chromophores through the bridge structure increases by a factor of approximately 1.8 when the change is made from dibenzofuran to dibenzothiophene, carbazole, and Nmethylcarbazole; in comparison with the corresponding dihydroxycarbonium ions, the degree of interaction of the chromophores is greater by a factor of approximately 1.5.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 3, pp. 284–291, May–June, 1990.     

Mechanism of photoluminescence excitation of Mn<Superscript>2+</Superscript> ions in ZnS crystals

The mechanisms of photoluminescence excitation of Mn²⁺ ions in ZnS crystals have been investigated on the basis of complex analysis of the temperature dependences of the photoluminescence and photoluminescence-excitation spectra of ZnS:Mn crystals. The activation energy of a manganese luminescence center was estimated at E_a = 0.17 ± 0.05 eV. It is shown that E_a represents an energy band with a width ΔE_a = 0.1 eV, within which a manganese luminescence center can experience radiationless recombination. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 788–793, November–December, 2005.     

The effect of rate of stimulation on perception of spectral shape by cochlear implantees

The effect of rate of stimulation on spectral shape perception was measured in six users of the Nucleus CI24 cochlear implant. Three spectral shapes were created by using three profiles of current across seven electrode positions. Each current profile was replicated in three stimuli that interleaved stimulus pulses across the seven electrodes with cycle rates (rate per electrode) of 450, 900, and 1800 Hz. The stimulus space resulting from a multidimensional scaling experiment showed a clear dimension related to the rate of stimulation that was orthogonal to the dimension related to the spectral shapes. A second experiment was performed with the same subjects to investigate whether the perceptual dimension related to rate in Experiment 1 could be attributed to different perceptual flatness of the profiles at different rates. In Experiment 2, the rate of stimulation was fixed at 900 Hz and three profiles were created for each spectral shape that differed in flatness. This experiment did not, however, result in an independent perceptual dimension related to the flatness of the profile. In conclusion, rate of stimulation provided an independent perceptual dimension in the multiple-electrode stimuli, in spite of the rates being not discriminable or barely discriminable in single-electrode stimulation.