Characterization of cross-linking structures in UV-cured acrylic ester resin by MALDI-MS combined with supercritical methanolysis.

The cross-linking structure of the ultra violet (UV)-cured resin prepared from dipentaerithritol hexacrylate (DPHA) was characterized by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) combined with supercritical methanolysis. The MALDI-mass spectrum of the decomposition products obtained by supercritical methanolysis contained a series of peaks of sodium-cationized methyl acrylate (MA) oligomers up to around m/z = 4000 formed through selective cleavage and methylation occurred at ester linkages in UV-cured DPHA. Furthermore, in order to observe widely distributed sequence lengths in the cross-linking junctions, the decomposed products of the cured resin were then fractionated using size exclusion chromatography followed by the MALDI-MS measurements of the individual fractions. The MALDI-mass spectra of the lower molar mass fractions mainly consisted of a series of peaks of MA oligomers around m/z values of several thousands, whereas those of higher molecular weight showed a broad peak up to m/z ca. 180000. The observed distributions of the supercritical methanolysis products suggested that the network junctions in the given UV-cured resin were composed of up to around 2000 acrylate units.     

Molecular probe for a fluorous medium: long-lived phosphorescence of alpha-diketones in perfluoromethylcyclohexane at room temperature.

We found that alpha-diketones (2,3-butanedione (BD) and 1-phenyl-1,2-propanedione (PPD)) were very suitable luminescence probes for studying the properties of a perfluorinated solvent (i.e., fluorous solvent; perfluoromethylcyclohexane (PFMC)), since these compounds were soluble in PFMC and showed long-lived phosphorescence even at room temperature. The phosphorescence lifetime (tau(p)) of BD in PFMC (650 micros) was much longer than that in cyclohexane (CH, 270 micros). The longer tau(p) value of BD in PFMC was ascribed to the variation of the intersystem crossing rate constant (k(isc)) from the excited triplet state (T1) to the ground state (S0) with the solvent. Some possible reasons for the change in k(isc) were discussed in terms of solute-solvent interactions. Furthermore, by utilizing phosphorescence quenching of BD by pyrene, we, determined a rate constant of the diffusion-controlled reaction in PFMC. Characteristic behaviors of mixing/separation processes between PFMC and a common organic solvent observed by Schlieren photographs were also reported.     

Polymerization of vinyl compounds in the presence of perfluoroisopropenyl ester

To report a new polymerization reaction phenomenon, this article examines the polymerization of butyl vinyl ether and N‐vinylcarbazole in the presence of 2‐benzoxypentafluoropropene [CF₂?C(CF₃)OCOC₆H₅ or BPFP]. The homopolymer of butyl vinyl ether was produced in the presence of a catalytic amount of BPFP in high yields. N‐Vinylcarbazole, which is a monomer well‐known for producing its homopolymer under cationic polymerization conditions, also yielded its homopolymer in the presence of BPFP. It was concluded that some cationic species would be yielded by the addition of BPFP. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 908–910, 2007.     

Separation of zirconium from fission products in silica gel—nitric acid systems

A method for the separation of zirconium from fission products based on the system 100–200 mesh silica gel—2.0 M nitric acid is described. Decontamination factors are over 500 for ⁹⁵Nb, ¹⁰⁶Ru, ¹²⁴Sb, ¹³⁷Cs, molybdate and uranium(VI), and the yield of zirconium is 98 %.     

The chemistry of O-silylated ketene acetals; diastereoselective Aldol reaction of 2,3-O-isopropylidene-D (and L)-glyceraldehydes leading to 2-deoxy-D (and L)-riboses

Diastereoselective carbon-carbon bond forming reaction of 2,3-O-isopropylidene-D (and L)-glyceraldehydes (D and L-2) with ketene silyl acetals (1a,b) occurred in acetonitrile under mild conditions to give the corresponding $\text{anti}$-β-siloxyesters (D and L-3a) as major products, which could be converted through a few additional steps to 2-deoxy-D(and L)-riboses.     

Open-shell SCF calculations with a model potential method

A model potential proposed by Huzinaga and his coworkers has been incorporated into the generalized coupling operator for open-shell SCF. With this modified operator, valence-only calculations have been performed on the ground and Rydberg excited states of the water molecule and compared with the ab initio SCF results previously reported.     

Ruthenium-complex-catalyzed regio- and stereoselective linear codimerization of 2-norbornenes with acrylic compounds

A linear codimerization of 2-norbornenes with acrylic compounds such as acrylates and an acrylamide proceeded efficiently by ruthenium catalyst systems, RuCl3(tpy)/Zn (tpy = 2,2':6',2' '-terpyridine) or [RuCl2(C6H6)]2/Zn in a primary or secondary alcoholic solvent, to afford the corresponding exo-trans-2-norbornylacrylates as major products regio- and stereoselectively along with a small amount of cis isomers. The reaction of 2,5-norbornadiene with methyl acrylate also gave the linear exo-trans codimer, which was effectively catalyzed by the addition of triarylphosphines to the RuCl3(tpy)/Zn catalyst system.