Computer Study of Stimuli-Responsive Polyelectrolyte Micelles in Aqueous Media. Comparison of Monte Carlo and Self-Consistent Field Approaches

The behavior of polyelectrolyte micelles with kinetically frozen hydrophobic cores in aqueous solutions was studied by Monte Carlo (MC) simulations and self-consistent field (SCF) calculations. Some results have already been published. The structure of water-soluble shells formed by weak polyelectrolytes, both pure and containing a low fraction of strongly hydrophobic units arranged either in a short sequence or distributed uniformly in the shell-forming chains was studied in detail. In the case of sequenced system, the analysis of concentration profiles of individual species reveals strong segregation and important self-organization of hydrophobic units in the shell. A comparison and critical analysis of results of MC and SCF methods is presented.     

pH-Dependent Behavior of Hydrophobically Modified Polyelectrolyte Shells of Polymeric Nanoparticles

Summary: The self-assembled core-shell nanoparticles based on fluorescently double-tagged high-molar-mass polystyrene-block-poly(methacrylic acid), PS-PMA, were prepared in aqueous buffers by dialysis from 1,4-dioxane – water mixtures. The conformations of shell-forming PMA chains were studied using nonradiative excitation energy transfer measurements. The study shows that two populations of distinctly different conformations (collapsed and stretched) coexist in the shell and their ratio depends on pH.     

Monitoring on-chip Pictet-Spengler reactions by integrated analytical separation and label-free time-resolved fluorescence

High-throughput screening for optimal reaction conditions and the search for efficient catalysts is of eminent importance in the development of chemical processes and for expanding the spectrum of synthetic methodologies in chemistry. In this context we report a novel approach for a microfluidic chemical laboratory integrating organic synthesis, separation and time-resolved fluorescence detection on a single microchip. The feasibility of our integrated laboratory is demonstrated by monitoring the formation of tetrahydroisoquinoline derivatives by Pictet-Spengler condensation. After on-chip reaction the products and residual starting material were separated enantioselectively on the same chip. On-chip deep UV laser-induced fluorescence detection with time-correlated single photon counting was applied for compound assignment. The system was utilized to screen reaction conditions and various substrates for Pictet-Spengler reactions on-chip. Finally, the microlab was successfully applied to investigate enantioselective reactions using BINOL-based phosphoric acids as organocatalysts.     

Fluorescence Depolarization Due to Excitation Energy Migration in Polymeric Micelles: A Monte Carlo Study

Cores of block copolymer micelles have been studied by Monte Carlo simulation. Core-forming chains have been modeled as self-avoiding chains enclosed in a spherical cavity and tethered to its surface. A fraction of the untethered end segments of chains (18–53%) has been treated as fluorescent probes. The time-dependent solution of the Pauli master equation that describes excitation energy migration among probes has been averaged in an ensemble of 10⁴ simulated cores. We have studied the dependence of the depolarization function G ^S(t), i.e., the probability that the originally excited probe is still excited at time t, on the chain length and on the energy migration critical radius of the probe. Cores with randomly solubilized probes and with clusters of probes have been also studied for comparison.     

The energy-momentum spectrum in local field theories with broken Lorentz-symmetry

Assuming locality of the observables and positivity of the energy it is shown that the joint spectrum of the energy-momentum operators has a Lorentz-invariant lower boundary in all superselection sectors. This result is of interest if the Lorentz-symmetry is (spontaneously) broken, such as in the charged sectors of quantum electrodynamics.     

Nuclear orientation study of the decay of204BiFe

The decay of²⁰⁴Bi nuclei (I =6⁺, T_1/2=11·22 h) oriented in an iron host was investigated on the JINR low-temperature nuclear orientation facility SPIN. The orientation parameterB ₂=1·17 (6) was obtained from the analysis of six prominent E1 gamma-transitions. From the measured normalized intensities of the gamma-rays observed some 70 values of multipole mixing ratios for the gamma-transitions in²⁰⁴Pb nucleus were determined for the first time. The spins 6, 6, 5 and 4 could be uniquely assigned to the²⁰⁴Pb negative parity levels at 3891·5 keV, 3768·4 keV, 3301·5 keV and 2338·2 keV, respectively. The spin-parity assignments of the levels at 4183·8 keV, 4094·2 keV, 3782·0 keV, 2506·9 keV and 2065·1 keV were confirmed as 6^–, 6^–, 5^–, 5^– and 5⁺, respectively. For the level at 3105·1 keV spin-parity 5^– was suggested and spinparity 7^– of the level at 2696·4 keV was called in question. The possible placements of the gammatransitions 3 1351·7 keV and 1353·4 keV in the decay scheme is discussed. The reorientation parameters for the long-living levels at 2264·2 keV (T _1/2=0·45 s) and 1273·9 keV (T _1/2= =265 ns) were determined asG ₂=0·41 (14) andG ₂=0·60 (17), respectively. For the isomeric level at 2185·7 keV (T _1/2=67·2 min) the value ofG ₂=0·88 (49) was proposed.The authors would like to express their thanks to T. I. Kracíková and M. Trhlík for the valuable discussions in the course of the evaluation of the experimental data.     

Special issue on: Ultrashort Pulse Ti: Sapphire lasers and amplifiers

Announcement

Special issue on: Ultrashort Pulse Ti: Sapphire lasers and amplifiers