Ab initio modelling of crosslinking in polymers. A case of chains with furan rings

A quantum chemical model (Abinitio HF-MO and DFT-B3LYP) of polyfurfuryl alcohol crosslinking is shown. Two pathways were considered: (a) a Diels–Alder (D–A) reaction between a dihydrofuran moiety and a furan ring; (b) the addition reaction of electrophilic specimens on conjugated double bonds. The ability for the formation of D–A adducts (dienes and dienophiles) was investigated by the frontier molecular orbital (FMO) theory. Energy gaps between the FMO's of diene and dienophile structures suggest that the occurrence of the D–A reaction is possible. The results suggest that the carbons of the exo double bonds attached to dihydrofuran rings are the sites most likely to be attacked by electrophilic species, while the C₃ and C₄ atoms display the opposite tendency due to their low HOMO electron densities. Results of a thermochemical approach to these reactions at the MP2 level was in agreement with reactivity modelled by MO predictions.     

Periodic and partially periodic representations ofSU(N) q

The Gelfand-Zetlin basis is adapted toSU(N) _q forq a root of unit. Extra parameters are incorporated in the matrix elements of the generators to obtain all the invariants corresponding to the augmented center. A crucial identity is derived and proved, which guarantees the periodicity of the action of the generators. Full periodicity is relaxed by stages, some raising and lowering operators remaining injective while others become nilpotent with corresponding changes in the dimension of the representation. In the extreme case of highest weight representations. all the raising and lowering operators are nilpotent. As an alternative approach an auxiliary algebra giving all the periodic representations is presented. An explicit solution of this system forN=3, while fully equivalent to the G.-Z. basis, turns out to be much simpler.     

Investigation of radical decay mechanisms in a glow-discharge plasma in carbon tetrafluoride

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 54, No. 6, pp. 1004–1010, June, 1991.     

Electronic spectra of cationic forms of meso-tetrapropylporphin in a nanoporous silicate gel matrix

We have studied the fluorescence and fluorescence excitation spectra at 300 K, 77 K, and 4.2 K for silicate gel matrices colored with meso-tetrapropylporphin by impregnation of the matrix with a solution of the pigment. Comparison of the data obtained with the absorption spectra in acidified solutions and analysis of the low-temperature fine-structure vibronic spectra, and also taking into account data obtained earlier for octaethylporphin in a xerogel showed formation of two cationic forms of meso-tetrapropylporphin in the gel matrix: the short-wavelength form has a dicationic structure, while the long-wavelength form has a monocationic structure. We have traced out the correlations of the vibrational structure in the spectra of the dicationic form with data for the porphin dication, and we have drawn a number of conclusions concerning the normal vibrational modes that are active in the vibronic fluorescence and absorption spectra of the studied cationic forms. Using the AM1 semiempirical quantum chemical method, we optimized the geometry of the mesotetrapropylporphin dication: the most stable of the possible conformers is the dication structure with saddleshaped macrocycle nonplanarity. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 453–461, July–August, 2006.     

Ion synthesis and laser annealing of Cu nanoparticles in Al2O3

Al₂O₃ samples with Cu nanoparticles, synthesised by ion implantation at 40 keV with a dose of 1×10¹⁷ ion/cm² and a current density from 2.5 to 12.5 μA/cm², were annealed using ten pulses from a KrF excimer laser with a single pulse fluence of 0.3 J/cm². The copper depth distribution, formation and modification of metal nanoparticles under the ion implantation and laser treatment were studied by Rutherford backscattering (RBS), energy dispersive X-ray (EDX) analysis, atomic force microscopy (AFM) and optical spectroscopy. It was found that laser annealing leads to a reduction in the nanoparticle size without diffusion of metal atoms into the bulk. The change in particle size and the possibility for oxidation of the copper particles are examined in the framework of Mie theory. Calculations presented show that under excimer laser treatment, Cu nanoparticles are more likely to be reduced in size than to undergo oxidation. Received: 19 April 2001 / Accepted: 7 November 2001 / Published online: 23 January 2002     

Combined confocal and magnetic resonance microscopy

Confocal fluorescence optical microscopy and magnetic resonance microscopy are each used to study live cells in a minimally invasive way. Both techniques provide complementary information. Therefore, by examining cells simultaneously with both methodologies, more detailed information is obtained than is possible with each microscope individually. In this paper two configurations of a combined confocal and magnetic resonance microscope are described. The first configuration is capable of studying large single cells or three-dimensional cell agglomerates, whereas the second configuration is designed for the investigation of monolayers of mammalian cells. In both cases the sample compartment is part of a temperature regulated perfusion system. Images obtained with the combined system are shown forXenopus laevis oocytes, model JB6 tumor spheroids, and a single layer of Chinese hamster ovary cells. Finally, potential applications of the combined microscope are discussed.