Chirale 2,2′-Polyoxaalkano-9,9′-spirobifluorene

Chiral 2,2′-polyoxaalkano-9,9′-spirobifluorenes From 2,2′-diacetyl-9,9′-spirobifluorene (2) , twelve chiral polyethers have been prepared as potential ion- and enantiomer-selective ionophores. The absolute configuration of the polyethers 15 – 17 , 19 – 22 , and 25 has been determined by chemical correlation with vespirenes [11] [29], by circular dichroism, and by X-ray analysis. The circular dichroism of 15 – 17 , 19 and 21 depends on the size of the macrocycle and indicates that the fluorene chromophores of 19 and 21 with 13- and 16-membered rings respectively deviate considerably from orthogonality.     

Magnetic switch of permeability for polyelectrolyte microcapsules embedded with Co@Au nanoparticles

We explored using a magnetic field to modulate the permeability of polyelectrolyte microcapsules prepared by layer-by-layer self-assembly. Ferromagnetic gold-coated cobalt (Co@Au) nanoparticles (3 nm diameter) were embedded inside the capsule walls. The final 5 mum diameter microcapsules had wall structures consisting of 4 bilayers of poly(sodium styrene sulfonate)/poly(allylamine hydrochloride) (PSS/PAH), 1 layer of Co@Au, and 5 bilayers of PSS/PAH. External alternating magnetic fields of 100-300 Hz and 1200 Oe were applied to rotate the embedded Co@Au nanoparticles, which subsequently disturbed and distorted the capsule wall and drastically increased its permeability to macromolecules like FITC-labeled dextran. The capsule permeability change was estimated by taking the capsule interior and exterior fluorescent intensity ratio using confocal laser scanning microscopy. Capsules with 1 layer of Co@Au nanoparticles and 10 polyelectrolyte bilayers are optimal for magnetically controlling permeability. A theoretical explanation was proposed for the permeability control mechanisms. "Switching on" of these microcapsules using a magnetic field makes this method a good candidate for controlled drug delivery in biomedical applications.     

Selective hydrogenation of butadiene-styrene copolymers using a Ziegler-Natta type catalyst 2. Thermal properties

Three types of butadiene-styrene copolymers, diblock, triblock and random, were partially hydrogenated in their elastomeric units in order to determine the influence of hydrogenation extent on their thermal properties. The hydrogenation reactions were carried out using a Ziegler-Natta type catalyst and the extent of hydrogenation was evaluated by FTIR spectroscopic technique. The percentage of crystallinity was determined by differential scanning calorimetry (DSC), considering the low density polyethylene (LDPE) as reference since the saturation of elastomeric units with low content of 1,2-vinyl bonds gives a structure which resembles to LDPE, thus semi-crystalline polymers were obtained. On the other hand, the glass transition temperature (T_g) for the hydrogenated and non-hydrogenated copolymers as well as their heat of fusion, were also determined by DSC. An equation to evaluate the T_g of partially hydrogenated random copolymers is proposed considering both the saturated and unsaturated fractions. The thermo-oxidative behaviour of certain hydrogenated and non-hydrogenated copolymers was evaluated by thermogravimetric analyses (TGA). The results obtained by TGA suggest that a minimum saturation level is necessary in order to improve the thermo-oxidative resistance of the polymers.     

IR spectra simulation as auxiliary tool for gas chromatography/Fourier transform IR spectroscopy/mass spectrometry identification of unknown compounds. 2. PM3, AM1, MNDO and MINDO3 simulations for simple nitriles

A set of the semi-empirical methods (PM3, AM1, MNDO and MINDO3) supplied by the HyperChem™ package has been tested to find the best auxiliary tool for the gas chromatography/Fourier transform IR spectroscopy/mass spectrometry identification of nitriles, taking 23 relatively simple nitriles as test compounds. Of the four methods, MNDO can be considered as the most advantageous since: (1) for 17 compounds of 23 tested, the IR spectra simulated by this method best match the experimental spectra (and in additional 3 cases, the results are as good as those obtained by AM1 method); (2) within the range of experimental wavenumbers of 900–3100 cm⁻¹, MNDO provides the best linearity between the calculated and experimental values (with a correlation coefficient of 0.989). A scaling factor of 0.85 can be used to afford better correspondence between the calculated and experimental wavenumbers. A disadvantage of the MINDO simulations is underestimation of ν_CN (and sometimes ν_CH) band intensities.     

Michael additions to trifluoromethylvinyl sulfone

Michael addition reactions of trifluoromethyl vinyl sulfone with organic compounds with labile hydrogen atoms are studied. Such additions can be successfully accomplished using potassium fluoride and 18-crown-6-ether or benzyltrimethylammonium hydroxide (Triton B) as catalysts.     

Medium-size polarized basis sets for high-level-correlated calculations of molecular electric properties

Summary The first-order polarized basis sets for the use in high-level-correlated investigations of molecular electric properties have been generated for Pb, Bi, Po, and At. The performance of the standard [10.17.14.5/13.11.8.2] and extended [20.17.14.9/13.11.8.4] basis sets has been examined in nonrelativistic and quasirelativistic calculations for atoms and simple closed-shell hydrides. The relativistic contributions to electric dipole properties of those systems have been evaluated by using the recently developed quasirelativistic scheme. The predicted dipole polarizability of At is in good agreement with the results of other relativistic calculations. The calculated quasirelativistic dipole moments of BiH₃ (–0.499 a.u.), PoH₂ (–0.207 a.u.), and AtH (+0.036 a.u.) involve a significant relativistic contribution which amounts to —0.230 a.u., –0.177 a.u., and –0.097 a.u., respectively. The basis set details append this paper. They are also available as a part of the basis set library of the MOLCAS system.     

Artificial neural network modification of simulation-based fitting: application to a protein-lipid system

Simulation-based fitting has been applied to data analysis and parameter determination of complex experimental systems in many areas of chemistry and biophysics. However, this method is limited because of the time costs of the calculations. In this paper it is proposed to approximate and substitute a simulation model by an artificial neural network during the fitting procedure. Such a substitution significantly speeds up the parameter determination. This approach is tested on a model of fluorescence resonance energy transfer (FRET) within a system of site-directed fluorescence labeled M13 major coat protein mutants incorporated into a lipid bilayer. It is demonstrated that in our case the application of a trained artificial neural network for the substitution of the simulation model results in a significant gain in computing time by a factor of 5 x 10(4). Moreover, an artificial neural network produces a smooth approximation of the noisy results of a stochastic simulation.     

Solubility Behavior in Ternary Water-Salt Systems under Sub- and Supercritical Conditions

Summary.  Two main types of binary systems with distinctive solubility behavior under sub- and supercritical conditions were used to subdivide ternary water-salt systems into three classes. Characteristic features of solubility behavior and phase equilibria in ternary water-salt systems of each class at temperatures above 200°C are discussed on the basis of available experimental data and some conclusions obtained as a result of theoretical derivation of fluid and complete phase diagrams. Corresponding author. E-mail: Valyashko@IGIC.RAS.RU Received September 25, 2002; accepted (revised) November 28, 2002 Published online April 24, 2003 RID="a" ID="a" Dedicated to Prof. Dr. H. Gamsjaeger on the occasion of his 70^th birthday anniversary     

Principal part of resolvent and factorization of an increasing nonanalytic operator-function

Let a selfadjoint operator-valued functionL() be given on the interval [a,b] such thatL(a)0,L(b)0,L()0 (ab), andL() has a certain smoothness (for instance, it satisfies Hölder's condition). It turns out that the spectral theory of the operator-valued functionL() can be reduced to the spectral theory of one operatorZ, the spectrum of which lies on (a, b) and which is similar to a selfadjoint operator. In particular, the factorization takes place:L()=M()(I–Z), where the operator-valued functionM() is invertible on [a, b]. Earlier similar results were known only for analytic operator-valued functions. The authors had to use new methods for the proof of the described theorem. The key moment is the decomposition ofL ^–1() into the sume of its principal and regular parts.     

Photon-deuteron diffractive scattering

One expects a similarity of the energy dependence of the difference _tot(*p)– _tot(*n) for virtual (deep inelastic scatteringQ ²m ²) and real (Q ²=0) photons. Previous analysis of D structure functions with allowence for nuclear shadowing (NS) in the deuteron has led to conclusion that _tot(*p)– _tot(*n)<0>x<0.015. the=" early=" evidence=" from=" the=" real=" photoproduction=" data="> _tot(p)– _tot(n)<0. we=" critically=" reexamine=" determinations=" of=" the="> _tot(p)– _tot(n), using more accurate calculations of NS correction to _tot(D), and discuss a possibility of _tot(n) _tot(p) at moderately high energies.