Ab initio Studies on polymers

Ab initio crystal orbital calculations have been performed on the infinite all-trans polyene. A structure with r _c=c= 1.346 Å, r _c-c = 1.446 Å, r _c-h = 1.08 Å, and CCC = 125.3 ° was found to be most stable. The most important force constants, the band structure and the density of states were determined as well.     

Prospects of the search for neutrino bursts from supernovae with Baksan large volume scintillation detector

Observing a high-statistics neutrino signal from the supernova explosions in the Galaxy is a major goal of low-energy neutrino astronomy. The prospects for detecting all flavors of neutrinos and antineutrinos from the core-collapse supernova (ccSN) in operating and forthcoming large liquid scintillation detectors (LLSD) are widely discussed now. One of proposed LLSD is Baksan Large Volume Scintillation Detector (BLVSD). This detector will be installed at the Baksan Neutrino Observatory (BNO) of the Institute for Nuclear Research, Russian Academy of Sciences, at a depth of 4800 m.w.e. Low-energy neutrino astronomy is one of the main lines of research of the BLVSD.     

Vertex and Edge Orbits of Fibonacci and Lucas Cubes

The Fibonacci cube \({\Gamma_{n}}\) is obtained from the n-cube Q _n by removing all the vertices that contain two consecutive 1s. If, in addition, the vertices that start and end with 1 are removed, the Lucas cube \({\Lambda_{n}}\) is obtained. The number of vertex and edge orbits, the sets of the sizes of the orbits, and the number of orbits of each size, are determined for the Fibonacci cubes and the Lucas cubes under the action of the automorphism group. In particular, the set of vertex orbit sizes of \({\Lambda_{n}}\) is \({\{k \geq 1; k |n\} \cup \{k \geq 18; k |2n\}}\), the number of vertex orbits of \({\Lambda_{n}}\) of size k, where k is odd and divides n, is equal to \({\sum_{d | k} \mu (\frac{k}{d})F_{\lfloor{\frac{d}{2}}\rfloor+2}}\), and the number of edge orbits of \({\Lambda_{n}}\) is equal to the number of vertex orbits of \({\Gamma_{n-3}}\). Dihedral transformations of strings and primitive strings are essential tools to prove these results.     

Sol-gel materials doped with 3-(3-(4-(dimethylamino)phenyl)propenoyl)-2H-chromen-2-one: spectroscopic and structural elucidation

Conventional and linear-polarized IR-spectroscopic tools based on reducing-difference procedures for non-polarized and polarized IR-spectra interpretation as well as orientation technique of solids (colloidal suspension in nematic liquid crystal) and UV/vis spectroscopy are applied for investigation of new sol-gel materials with potential optical application of doped organic dye 3-(3-(4-(dimethylamino)phenyl)propenoyl)-2H-chromen-2-one (K2) and Sm3+ ions. The results show that during aging of the monoliths Sm3+ forms an unstable complex with K2, [Sm(K2)(2)(H2O2](NO3)(3), which transforms to [Sm(H2O)(6)](3+) one, typical for gel-Sm3+ system. Quantum chemical ab initio and DFT calculations are reported with a view to support experimental IR-characteristic bands of the system studied.     

Impact of model perfumes on surfactant and mixed surfactant self-assembly

The impact of some model perfumes on surfactant self-assembly has been investigated, using small-angle neutron scattering. A range of different model perfumes, with differing degrees of hydrophilicity/hydrophobicity, have been explored, and in order of increasing hydrophobicity include phenyl ethanol (PE), rose oxide (RO), limonene (LM), linalool (LL), and dihydrogen mercenol (DHM). The effect of their solubilization on the nonionic surfactant micelles of dodecaethylene monododecyl ether (C12EO12) and on the mixed surfactant aggregates of C12EO12 and the cationic dialkyl chain surfactant dihexadecyl dimethyl ammonium bromide (DHDAB) has been quantified. For PE and LL the effect of their solubilization on the micelle, mixed micelle/lamellar and lamellar regimes of the C12EO12/DHDAB mixtures, has also been determined. For the C12EO12 and mixed DHDAB/C12EO12 micelles PE is solubilized predominantly at the hydrophilic/hydrophobic interface, whereas the more hydrophobic perfumes, from RO to DHM, are solubilized predominantly in the hydrophobic core of the micelles. For the C12EO12 micelles, with increasing perfume concentration, the more hydrophobic perfumes (RO to DHM) promote micellar growth. Relatively modest growth is observed for RO and LM, whereas substantial growth is observed for LL and DHM. In contrast, for the addition of PE the C12EO12 micelles remain as relatively small globular micelles, with no significant growth. For the C12EO12/DHDAB mixed micelles, the pattern of behavior with the addition of perfume is broadly similar, except that the micellar growth with increasing perfume concentration for the more hydrophobic perfumes is less pronounced. In the Lbeta (Lv) region of the DHDAB-rich C12EO12/DHDAB phase diagram, the addition of PE results in a less structured (less rigid) lamellar phase, and ultimately a shift toward a structure more consistent with a sponge or bicontinuous phase. In the mixed L1/Lbeta region of the phase diagram PE induces a slight shift in the coexistence from Lbeta toward L1. The addition of LL to the Lbeta (Lv) region of the DHDAB-rich C12EO12/DHDAB phase diagram also results in a reduction in the lamellar structure (less rigid lamellae), and a shift toward a structure more consistent with a sponge or bicontinuous phase, or a coexisting phase of small vesicles. For the mixed L1/Lbeta region of the phase diagram LL induces a shift toward a greater L beta component.     

Interlayer stacking disorder in zeolite beta family: a Raman spectroscopic study

Raman spectroscopy has been applied to series of BEA- and BEC-type samples differing from each other in size, Si/Al ratio and polymorph percentage in order to analyse the effect of interlayer stacking arrangements on the vibrational modes of zeolite beta. The Raman peaks observed in the spectral range 250-550 cm-1 were assigned to the rings building the basic (001)-layer and to those linking the adjacent layers in zeolite beta. It is shown that the intensity ratio rho between the Raman signals at 314 and 343 cm-1 is most sensitive to the degree of periodicity faults along the c direction. A larger value of rho indicates a larger size of polymorph stacking sequence, i.e. improvement of the stacking faultlessness. The interlayer stacking disorder and the degree of connectivity point defects are higher in nanosized zeolite beta than in micron-sized crystals. The Al content influences the concentration of defected SiOH groups, but is less important for the interlayer stacking sequences in colloidal zeolite beta.     

Ethylene polymerization with a catalyst system titanium tetrachloride—diethylaluminium chloride—diphenylmagnesium in the presence of hydrogen

A study was made of ethylene polymerization with the catalyst system titanium tetrachloride-diethylaluminium chloride—diphenylmagnesium in the presence of hydrogen. The system is highly active even at high content of hydrogen in the system and at high reaction temperatures (90–130°). In the presence of hydrogen, polyethylene was obtained with high density and a full commercial melt index range (0–50 g/10 min), i.e. a wide range of molecular weights. At higher reaction temperatures, some activation of the catalyst system was observed.     

The crystallization of polypropylene/halloysite fibers

Journal of Thermal Analysis and Calorimetry - The halloysite (HNT) in the form of nanotubes was used as an agent for the improved mechanical, thermo-mechanical as well as surface properties of...     

The luminescence response of Eu(III)-thenoyltrifluoroacetonate complexes upon preresonant excitation with femtosecond laser pulses

The luminescence of thenoyltrifluoroacetonate (TTA) coordination complexes of trivalent europium ion (Eu(III)) in aqueous solutions and in solid-state polymeric films is probed upon single- and two-photon preresonant excitation with Ti:sapphire femtosecond laser. Particularly, diamine-liganded Eu(III)(TTA)₃ and poly(oxyethylene phosphate)tris(β-diketonate)Eu(III) complexes are examined aiming their possible applications as luminescent labels for sensing and imaging of biological molecules. Even at a pre-resonance, the excitation of these compounds with high-intensity, broadband light of frequency-doubled Ti:sapphire femtosecond laser centered around 400 nm results in a luminescence response suitable for fluorometric applications.     

Ab initio HF, density functional and experimental studies on the IR spectra and structure of 1,2-benzisothiazol-3-(2H)-thione-1,1-dioxide (thiosacchanin) and its nitranion

The spectral and structural changes taking place in the course of the conversion of 1,2-benzisothiazol-3-(2H)-thione-1,1-dioxide (thiosaccharin) into a nitranion have been studied on the basis of both IR spectra and ab initio HF 6-31G(d) and BLYP 6-31G(d,p) force field calculations. The conversion causes nu(as)SO2 and nu(s)SO2 frequency decreases of 47 and 13 cm(-1), respectively, and other spectral changes. The nuC=S coordinate is strongly delocalized. The ab initio geometries of the isolated molecule and nitranion agree well with the single-crystal X-ray ones, determined for thiosaccharin and its sodium (potassium) monohydrate salts, respectively. The nitranionic charge is delocalized almost uniformly within the thiocarbonyl (0.29 e-), sulfonyl (0.24 e-), and phenylene (0.24 e-) groups, and the nitranionic center (0.23 e-).