Formation of free radicals in water under high-power laser uv irradiation

It has been shown that under high-power laser UV irradiation (I = 10⁸–10¹⁰ W/cm², λ = 266 nm, τ_p = 30 ps) water becomes ionized by a two-photon mechanism to form some free radicals including the hydrated electron e^?_aq.     

An Efficient Straightforward Synthesis of Benz[a]azulene

Benz[a]azulene ( 1 ) is synthesized in five steps (cf. Scheme 2) starting from commercially available 2-iodobenzyl alcohol ( 4 ) and tropylium tetrafluoroborate in an overall yield of 44%. The key step (cf. also Scheme 1) is the intramolecular Heck reaction of the 8-phenylsulfonyl-substituted heptafulvene 7 , which leads in nearly quantitative yield directly to 10-(phenylsulfonyl)benz[a]azulene ( 8 ). The desulfonylation of 8 can be accomplished by Julia's method with Na₂S₂O₄/NaHCO₃ in DMF/H₂O at 85–90°, thus leading to pure 1 in 78% yield. The phenylation of 8 with PhLi or PhCul at ?78° in THF occurs regioselectively at C(9). Dehydrogenation of the formed dihydroazulenes with o-chloroanil in toluene at room temperature gives 9-phenyl-10-(phenylsulfonyl)-benz[a]azulene ( 9 ) in 70% yield (cf. Scheme 3), which, again, can be desulfonylated with Na₂S₂O₄/NaHCO₃ in DMF/H₂O in good yields. The addition of PhLi to 1 in THF occurs at temperatures ? ?25°. Ionic dehydrogenation (1. Ph₃C⁺BF/MeCN; 2. Et₃N) of the dihydro forms leads to 3 , as the main product, and its positional isomers.     

Studies on polymers and composites from lignin and fiber derived from sugar cane

Sugarcane fiber (i.e. bagasse) lignin has a larger fraction of aromatics unsubstitution in the ortho position than hardwood or softwood lignin and hence has the greater ability to be derivatized. Furthermore, organosolv lignin has a higher purity than sulfonated and kraft lignins. This work examines the purification of organosolv lignin derived from bagasse and the physico‐chemical properties of the lignin and lignin‐phenol formaldehyde (PF) resin coatings, and composites. The wetability tests have shown that lignin and lignin‐PF resin films are effective water barrier coatings, though the contact angles of lignin‐PF resin films were considerably less than the wax films. The overall mechanical properties (i.e. peak stress, peak strain and modulus) of the bagasse fiber composites were lower than the values obtained with the composites without the inclusion of bagasse fiber. Copyright © 2007 John Wiley & Sons, Ltd.     

Reactivity ratios in conventional and nickel-mediated radical copolymerization of methyl methacrylate and functionalized methacrylate monomers

Copolymerization of an excess of methyl methacrylate (MMA) relative to 2-hydroxyethyl methacrylate (HEMA) was carried out in toluene at 80 °C according to both conventional and controlled Ni-mediated radical polymerizations. Reactivity ratios were derived from the copolymerization kinetics using the Jaacks method for MMA and integrated conversion equation for HEMA (r_MMA = 0.62 ± 0.04; r_HEMA = 2.03 ± 0.74). Poly(ethylene glycol) α-methyl ether, ω-methacrylate (PEGMA, M_n = 475 g mol⁻¹) was substituted for HEMA in the copolymerization experiments and reactivity ratios were also determined (r_MMA = 0.75 ± 0.07; r_PEGMA ∼ 1.33). Both the functionalized comonomers were consumed more rapidly than MMA indicating the preferred formation of heterogeneous bottle-brush copolymer structures with bristles constituted by the hydrophilic (macro)monomers. Reactivity ratios for nickel-mediated living radical polymerization were comparable with those obtained by conventional free radical copolymerization. Interactions between functional monomers and the catalyst (NiBr₂(PPh₃)₂) were observed by ¹H NMR spectroscopy.     

Electrophilic lactonization as a tool in acyclic stereocontrol. Synthesis of serricornin

Several electrophilic lactonization procedures have been explored as a means of functionalizing olefinic carboxylic acids with relative asymmetric induction, Iodolactonization of δ,? -unsaturated acids under conditions of thermodynamic control exhibits good 1,2- and 1,3-, but not 1,4-induction in the formation of δ-lactones. Mercurilactonization proceeds with good stereocontrol in the formation of both γ- and δ-lactones (1,2-induction), but suffers from the difficulty of elimination during reductive demercuration; phenylselenolactonization with N-(phenylseleno)phthalimide is apparently kinetically controlled, affording high induction with 10, a strongly sterically biased substrate leading to a δ-lactone, but not with 16, which leads to a γ-lactone. In contrast, hydroxymethyllactonization proceeds with good stereocontrol in the case of 26, the ester of 10, but not with the analogous ester of 16. The lactones resulting from cyclization of 10 and 13 were converted in stereospecific fashion into each of the stereoisomers of(±)-serricornin.     

Parameterization and evaluation of a flexible water model

The thermodynamic, dielectric, and dynamic properties of a newly parameterized flexible water model are studied using molecular dynamics simulations. The potential function developed is based on the popular simple point charge (SPC) rigid model with the addition of appropriate harmonic and anharmonic energy terms for stretching and bending. Care was taken to account for the self-polarization and gas-phase monomer energy corrections during the parameterization, which have typically been ignored in past studies. The results indicate that an increased Lennard-Jones repulsive coefficient and slightly scaled partial charges are required when adding flexibility to the rigid model potential to reliably reproduce the experimental density, energy, and O ? O radial distribution function of water at 298 K and 1 atm. Analysis of the power spectrum derived from the H-velocity autocorrelation function allowed the water potential to be evaluated further and refined by adjusting the valence forces to fit the vibrational frequencies of the gas and liquid. Once a consistent set of parameters was determined, the static dielectric properties of the water model were calculated at two temperatures using the reaction field method to treat long-range forces and correlations. The dielectric constant of 75 ± 7 calculated at 300 K is in good agreement with the experimental value of 78.5. The Kirkwood g factor was also examined for temperature dependence and showed the correct increasing behavior with decreasing T. As a final check of the water potential, the free energies of solvation of a flexible water molecule and neon were predicted using thermodynamic perturbation methods. The calculated solvation energies of ?7.0 ± 0.8 for water and 2.7 ± 0.7 for neon are both consistent with the experimental values of ?6.3 and 2.7 kcal/mol. Comparisons are made throughout the study with the results of previous rigid and flexible model simulations. © 1995 by John Wiley & Sons, Inc.     

Sulfite-sensitive solvent/polymeric-membrane electrode based on bis(diethyldithiocarbamato)mercury(II)

A new solvent/polymeric-membrane electrode which exhibits significant potentiometric response toward sulfite ion in the 1 × 10_?6?1 × 10^?3 M range is described. The membrane is prepared by incorporation of neutral bis(diethyldithiocarbamato)mercury (II) in a thin film of plasticized poly (vinyl chloride). In sharp contrast to classical Hofmeister behavior, the resulting membrane displays little or no response to a wide range of anions (log K^pot_i,j ? ?4, i being sulfite) including sulfate, nitrate, nitrite, chloride, perchlorate, salicylate, and alkylsulfonates. Bromide and thiocyanate are moderate interferents, while significant response to iodide, thiosulfate, and sulfide is observed. These selectivity data, along with other response characteristics of the membrane, are used to postulate the mechanism by which the electrode responds to sulfite. Preliminary studies demonstrate that the electrode can be used in conjunction with an outer gas-permeable membrane for highly selective detection of total sulfite species in the form of sulfur dioxide.     

Stable and efficient algorithms for Xα multiple scattering calculations

Solutions to some practical problems that arise in multiple scattering calculations on large molecules are discussed. (1) Numerical instabilities near the zero of energy can be removed by rescaling the secular matrix. (2) The calculation of structure factors can be made much more efficient by the application of symmetry projection operators. (3) An energy search procedure is described that ensures that no states are inadvertently neglected. Test calculations incorporating these changes illustrate the improved numerical stability, and show decreases in computation time of 30–60%, when compared to previous codes. The procedures suggested here are applicable to both relativistic and nonrelatitistic calculations.     

Uniform semiclassical self-consistent-field calculations of vibrational resonance energies and widths

Using the Breit—Wigner definition of a resonance, we calculate both resonance positions and widths for a model non-separable hamiltonian, using a uniform semiclassical self-consistent-field (SCF) method. Excellent agreement with recent complex-coordinate quantum SCF calculations is obtained.     

Transition metalcarbon bonds XXXVII. platinum acetylide complexes formed from ethynyl alcohols or ethers

Several new platinum(II) acetylide complexes, trans-{Pt[CCCR₁R₂(OR₃)]₂-L₂} (R₁, R₂  H, Me, Et; CR₁R₂  cyclohexylidene; R₃  H, Me or Ph), trans-[Pt(CCCH₂CH₂OH)₂L₂], trans-[Pt(p-tolylacetylide)₂L₂] and trans-[PtX(p-tolylacetylide)L₂] (L  PMe₂Ph or in one case, AsMe₂Ph) have been prepared. Platinum(II) acetylide complexes with tertiary hydroxyl groups are easily dehydrated by acetic anhydride/pyridine to give platinum-enyne complexes. Analogous compounds with primary hydroxyl groups do not dehydrate but give acetates. ¹H and ¹³C NMR data are given and the shift reagent Eu(fod)₃ was used to analyse the ¹H NMR spectrum of trans-[Pt(CCCH₂CH₂OH)₂(PMe₂Ph)₂].