Ultraviolet photolysis of CH2I2 in methanol: O-H insertion and HI elimination reactions to form a dimethoxymethane product

Ultraviolet photolysis of low concentrations of CH2I2 in methanol solution found that CH2I2 is converted into dimethoxymethane and some H+ and I- products. Picosecond time-resolved resonance Raman (ps-TR3) experiments observed that the isodiiodomethane (CH2I-I) photoproduct decayed faster as the concentration of methanol increases, suggesting that isodiiodomethane is reacting with methanol. Ab initio calculations indicate isodiiodomethane is able to react with methanol via an O-H insertion/HI elimination to form an iodoether (ICH2-O-CH3) and HI products. The iodoether can then further react via another O-H insertion/HI elimination reaction to form the dimethoxymethane (CH3-O-CH2-O-CH3) observed in the photochemistry experiments. A reaction mechanism consistent with these experimental and theoretical observations is proposed.     

Comparison of the dehalogenation of dihalomethanes (CH2XI, where X = Cl, Br, I) following ultraviolet photolysis in aqueous and NaCl saltwater environments

The ultraviolet photolysis of low concentrations of CH(2)XI (X = Cl, Br, I) were investigated in water and saltwater solutions by photochemistry and picosecond time-resolved resonance Raman spectroscopy. Photolysis in both kinds of solutions formed mostly CH(2)(OH)(2) and HI and HX products. However, photolysis of the CH(2)XI molecules in saltwater resulted in production of some CH(2)XCl products not observed in aqueous solutions without salt present. The appearance of these new products in saltwater solutions is accompanied by a decrease in the amount of CH(2)(OH)(2), HI, and HX products compared to photolysis in aqueous solutions without salt present. The possible implications for photolysis of CH(2)XI and other polyhalomethanes in seawater and other salt aqueous environments compared to nonsaltwater solvated environments is briefly discussed.     

Recent developments in zinc oxide target chemistry

Zinc oxide targets irradiated with high energy protons at the Los Alamos Meson Physics Facility (LAMPF) contain a number of radioactive spallation products in quantities large enough to warrant recovery. This paper describes methods for recovering⁷Be,⁴⁶Sc, and⁴⁸V from such targets and offers suggestions on possible ways to recover additional isotopes. The proposed methods are based on traditional precipitation and ion exchange techniques, are readily adaptable to hot cell use, and produce no hazardous waste components. The products are obtained in moderate to high yields and have excellent radionuclidic purity.     

The vibrational spectra of some 1,3-dimethyl-1,3-diaza-2-boracyclopentanes

A detailed vibrational assignment is proposed for 1,3-dimethyl-1,3-diaza-2-boracyclopentanes:

where X = Cl, Br or NMe₂. The assignments are generally in accord with C_2v symmetry, but there is some evidence for a slight breakdown, as some A₂ modes appear in the IR. The BN₂ stretches are near 1500 cm^?1, (antisymmetric) and 1300 cm^?1 (symmetric), consistent with a large degree of π-bonding.     

Comparative Photophysical Study of Disulfonated Aluminum Phthalocyanine in Unilamellar Vesicles and Leukemic K562 Cells

Abstract— The photophysical properties of cis -disulfonated aluminum phthalocyanine (AlPcS₂) in unilamellar vesicles (liposomes) of DL-a-dipalmitoyl-phosphatidylcholine have been measured. Both the fluorescence and triplet quantum yields decreased with increasing sensitizer concentration. The time-resolved fluorescence decays, analyzed by both the sum of exponentials and decay time distribution analyses, are compared with those reported for AlPcS₂ in leukemic K562 cells. Information on the pho-todynamic transport and localization mechanism has been obtained by drawing correlations between the two systems, indicating active transport of the phthalocyanine into tumor cells involving lysosomal accumulation.     

A lower bound for the optimal crossing-free Hamiltonian cycle problem

Consider a drawing in the plane ofK _n , the complete graph onn vertices. If all edges are restricted to be straight line segments, the drawing is called rectilinear. Consider a Hamiltonian cycle in a drawing ofK _n . If no pair of the edges of the cycle cross, it is called a crossing-free Hamiltonian cycle (cfhc). Let (n) represent the maximum number of cfhc's of any drawing ofK _n , and (n) the maximum number of cfhc's of any rectilinear drawing ofK _n . The problem of determining (n) and (n), and determining which drawings have this many cfhc's, is known as the optimal cfhc problem. We present a brief survey of recent work on this problem, and then, employing a recursive counting argument based on computer enumeration, we establish a substantially improved lower bound for (n) and (n). In particular, it is shown that (n) is at leastk × 3.2684 ⁿ . We conjecture that both (n) and (n) are at mostc × 4.5 ⁿ .This research, part of which was conducted at Queen's University, was supported by an N.S.E.R.C. postgraduate scholarship.