Isocyanide addition to MN2(CO)5(Ph2PCH2PPh2)2 and the formation of a four-electron doubly-bridging isocyanide

The reactions of Fe(CO)₅, Fe(CO)₄P(C₆H₅)₃, M(CO)₆ (M  W, Mo, Cr), and (CH₃C₅H₄Mn(CO)₃ with KH and several boron and aluminium hydrides were investigated. Iron pentacarbonyl was converted quantitatively to K⁺Fe(CO)₄-(CHO) by hydride transfer from KBH(OCH₃)₃ allowing isolation of [P(C₆H₅)₃]₂-Nⁿ⁺Fe(CO)₄(CHO)^? in 50% yield. Lower yields were obtained with LiBH(C₂H₅)₃, and other hydride sources gave little or no formyl product. The stability of Fe(CO)₄(CHO)^? in THP was found to depend on the cation, decreasing in the order [P(C₆H₅)₃]₂N⁺ > K⁺ > Na⁺ > Li⁺. No formyl complexes were isolated and no spectroscopic evidence for formyl formation was observed in the reactions of the other transition metal carbonyls with several hydride sources. Fe(CO)₄-P(C₆H₅)₃ gave K₂Fe(CO)₄ when treated with KHB(OCH₃)₃. When treated with LiBH(C₂H₅)₃, W(CO)₆ gave a mixture of HW₂(CO)₁₀^?and (OC)₅W(COC₂H₅)^?; the latter was methylated to give the carbene complex (OC)₅WC(OCH₃)C₂H₅.     

Flash photolysis and antioxidant activity

The photo-chemical behaviour of a number of mono- and polyfunctional commercial phenolic antioxidants has been examined using kinetic micro-second flash photolysis. The technique provides useful information on the relationship between antioxidant structure and the efficiency of phenoxy radical production. The kinetics of decay of the phenoxy radicals are also found to be dependent on structure. Mono-functional antioxidants give phenoxy radicals which decay by a second-order process whereas polyfunctional antioxidants give phenoxy radicals that decay by a first-order process. In the former case dimerisation to give bisphenolic coupling products is observed whereas, with the latter, this process is sterically inhibited. The value of flash photolysis as a probe for studying antioxidant activity is discussed.     

Overtone spectroscopy of H2O clusters in the V(OH) = 2 manifold: infrared-ultraviolet vibrationally mediated dissociation studies

Spectroscopy and predissociation dynamics of (H2O)2 and Ar-H2O are investigated with vibrationally mediated dissociation (VMD) techniques, wherein upsilon(OH) = 2 overtones of the complexes are selectively prepared with direct infrared pumping, followed by 193 nm photolysis of the excited H2O molecules. As a function of relative laser timing, the photolysis breaks H2O into OH and H fragments either (i) directly inside the complex or (ii) after the complex undergoes vibrational predissociation, with the nascent quantum state distribution of the OH photofragment probed via laser-induced fluorescence. This capability provides the first rotationally resolved spectroscopic analysis of (H2O)2 in the first overtone region and vibrational predissociation dynamics of water dimer and Ar-water clusters. The sensitivity of the VMD approach permits several upsilon(OH) = 2 overtone bands to be observed, the spectroscopic assignment of which is discussed in the context of recent anharmonic theoretical calculations.     

The Synthesis and Reactions of Yomogi Alcohol. Conversion of the artemisyl skeleton to the santolinyl skeleton by a 1,2-shift of a vinyl group. Synthesis of santolinatriene

The synthesis of yomogi alcohol (2, 5, 5-trimethylhepta-3,6-dien-2-ol, 2 ) is described, and experiments directed towards its allylic rearrangement to artemisia alcohol detervatives have been carried out. Acidic reagents open the ring of yomogi alcohol epoxide ( 16 ) at with participation of the 6,7-double-bond, a shift of the vinyl group results to yield a compound with the santolinyl skeleton. The same reagents are without effect when this double bond reduced. Action of butyllithium of the benzaldehyde acetal ( 41 ) of 2, 5-dimethyl-4-vinyl-2, dihydroxy-hex-5-ene ( 28 ), obtained by acid-catalyzed ring opening of yomogi alcohol epoxide in the presence of benzaldehyde, leads to santolinatriene ( 42 ). This vinyl shift is not observed in the case of O-acetyl yomogi alcohol epoxide ( 46 ), from white a compound believed to be an oxetan 48 (R ? COCH₃) is formed with concomitent shift of the acetate group. Further unusual reactions of the oxetan are described, and some observation about the epoxidation of sterically hindered allyl alcohols and their acetates are made.     

Quantum chemical studies on electrophilic addition

The geometries of the 2-aminoethyl cation and the isomeric protonated aziridine have been optimized using ab initio molecular orbital calculations employing the split-valence shell 4-31G basis set. The protonated aziridine is computed to be the more stable ion by 46.5 kcal/mole (4-31G level) and 44.9 kcal/mole (double-zeta basis set). The profile to interconversion is found to have a barrier of less than 15 kcal/mole (relative to the 2-aminoethyl cation) and this profile is compared with those computed for the similar ions XCH₂CH ₂ ⁺ where X=OH, F, SH and Cl.     

Calculation of the transport properties of carbon dioxide. III. Volume viscosity, depolarized Rayleigh scattering, and nuclear spin relaxation

Transport properties of pure carbon dioxide have been calculated from the intermolecular potential using the classical trajectory method. Results are reported in the dilute-gas limit for volume viscosity, depolarized Rayleigh scattering, and nuclear spin relaxation for temperatures ranging from 200 to 1000 K. Three recent carbon dioxide potential energy hypersurfaces have been investigated. Calculated values for the rotational collision number for all three intermolecular surfaces are consistent with the measurements and indicate that the temperature dependence of the Brau-Jonkman correlation is not applicable for carbon dioxide. The results for the depolarized Rayleigh scattering cross section and the nuclear spin relaxation cross section show that calculated values for the generally more successful potentials differ from the observations by 9% at about 290 K, although agreement is obtained for nuclear spin relaxation at about 400 K.     

Ab initio study of (13)C(alpha) chemical shift anisotropy tensors in peptides

This study reports magnitudes and the orientation of the (13)C(alpha) chemical shift anisotropy (CSA) tensors of peptides obtained using quantum chemical calculations. The dependency of the CSA tensor parameters on the energy optimization of hydrogen atom positions and hydrogen bonding effects and the use of zwitterionic peptides in the calculations are examined. Our results indicate that the energy optimization of the hydrogen atom positions in crystal structures is necessary to obtain accurate CSA tensors. The inclusion of intermolecular effects such as hydrogen bonding in the calculations provided better agreement between the calculated and experimental values; however, the use of zwitterionic peptides in calculations, with or without the inclusion of hydrogen bonding, did not improve the results. In addition, our calculated values are in good agreement with tensor values obtained from solid-state NMR experiments on glycine-containing tripeptides. In the case of peptides containing an aromatic residue, calculations on an isolated peptide yielded more accurate isotropic shift values than the calculations on extended structures of the peptide. The calculations also suggested that the presence of an aromatic ring in the extended crystal peptide structure influences the magnitude of the delta(22) which the present level of ab initio calculations are unable to reproduce.     

Field evaluations of the VDmax approach for substantiation of a 25 kGy sterilization dose and its application to other preselected doses

The International and European standards for radiation sterilization require evidence of the effectiveness of a minimum sterilization dose of 25 kGy but do not provide detailed guidance on how this evidence can be generated. An approach, designated VD_max, has recently been described and computer evaluated to provide safe and unambiguous substantiation of a 25 kGy sterilization dose. The approach has been further developed into a practical method, which has been subjected to field evaluations at three manufacturing facilities which produce different types of medical devices. The three facilities each used a different overall evaluation strategy: Facility A used VD_max for quarterly dose audits; Facility B compared VD_max and Method 1 in side-by-side parallel experiments; and Facility C, a new facility at start-up, used VD_max for initial substantiation of 25 kGy and subsequent quarterly dose audits. A common element at all three facilities was the use of 10 product units for irradiation in the verification dose experiment.

The field evaluations of the VD_max method were successful at all three facilities; they included many different types of medical devices/product families with a wide range of average bioburden and sample item portion values used in the verification dose experiments. Overall, around 500 verification dose experiments were performed and no failures were observed. In the side-by-side parallel experiments, the outcomes of the VD_max experiments were consistent with the outcomes observed with Method 1.

The VD_max approach has been extended to sterilization doses >25 and <25 kGy; verification doses have been derived for sterilization doses of 15, 20, 30, and 35 kGy. Widespread application of the VD_max method for doses other than 25 kGy must await controlled field evaluations and the development of appropriate specifications/standards.     

The synthesis and characterisation of 4,1,2-MC2B10 metallacarboranes

Reduction of the tethered carborane 1,2-(CH2)3-1,2-closo-C2B10H10 followed by treatment with CoCl2/NaCp, [(p-cymene)RuCl2]2(p-cymene=C6H4MeiPr-1,4), (PMe2Ph)2PtCl2 or (dppe)NiCl2(dppe=Ph2PCH2CH2PPh2) affords reasonable yields of the new 13-vertex metallacarboranes 1,2-(CH2)3-4-Cp-4,1,2-closo-CoC2B10H10 (1), 1,2-(CH2)3-4-(p-cymene)-4,1,2-closo-RuC2B10H10 (2), 1,2-(CH2)3-4,4-(PMe2Ph)2-4,1,2-closo-PtC2B10H10 (3) and 1,2-(CH2)3-4,4-(dppe)-4,1,2-closo-NiC2B10H10 (4), respectively. All compounds were characterised spectroscopically and crystallographically. The cobalt and ruthenium species 1 and 2 have Cs symmetry in both solution and the solid state, having henicosahedral cage structures featuring a trapezoidal C1C2B9B5 face. The platinum and nickel compounds 3 and 4 have asymmetric docosahedral cage structures in the crystal (the more so for 4 than for 3) although both appear, by 11B and 31P NMR spectroscopy, to have Cs symmetry in solution. Low-temperature experiments on the more soluble platinacarborane could not freeze out the diamond-trapezium-diamond fluctional process that we assume is operating in solution, and we therefore conclude that this process has a relatively low activation barrier, probably <35 kJ mol-1.     

Folding and unfolding kinetics of DNA hairpins in flowing solution by multiparameter fluorescence correlation spectroscopy

Dynamic equilibrium between the folded and unfolded conformations of single stranded DNA hairpin molecules containing polythymine hairpin loops was investigated using simultaneous two-beam fluorescence cross-correlation spectroscopy and single beam autocorrelation spectroscopy. The hairpins were end-labeled with a fluorescent dye and a quencher, such that folding and unfolding of the DNA hairpin primary structure caused the dye fluorescence to fluctuate on the same characteristic time scale as the folding and unfolding reaction. These fluctuations were observed as the molecules flowed sequentially between two spatially offset, microscopic detection volumes. Cross-correlation analysis of fluorescence from the two detection volumes revealed the translational diffusion and flow properties of the hairpins, as well as the average molecular occupancy of the two volumes. Autocorrelation analysis of the fluorescence from the individual detection volumes revealed the kinetics of hairpin folding and unfolding, with the parameters relating to diffusion, flow, and molecular occupancy constrained to the values determined from the cross-correlation analysis. This allowed unambiguous characterization of the folding and unfolding kinetics, without the need to determine the hydrodynamic properties by analyzing a separate control sample. The analysis revealed nonexponential relaxation kinetics and DNA size-dependent folding times characteristic of dynamic heterogeneity in the DNA hairpin-forming mechanism.