Growth dynamics and intracluster reactions in Ni+(CO2)n complexes via infrared spectroscopy

Ni(+)(CO(2))(n), Ni(+)(CO(2))(n)Ar, Ni(+)(CO(2))(n)Ne, and Ni(+)(O(2))(CO(2))(n) complexes are generated by laser vaporization in a pulsed supersonic expansion. The complexes are mass-selected in a reflectron time-of-flight mass spectrometer and studied by infrared resonance-enhanced photodissociation (IR-REPD) spectroscopy. Photofragmentation proceeds exclusively through the loss of intact CO(2) molecules from Ni(+)(CO(2))(n) and Ni(+)(O(2))(CO(2))(n) complexes, and by elimination of the noble gas atom from Ni(+)(CO(2))(n)Ar and Ni(+)(CO(2))(n)Ne. Vibrational resonances are identified and assigned in the region of the asymmetric stretch of CO(2). Small complexes have resonances that are blueshifted from the asymmetric stretch of free CO(2), consistent with structures having linear Ni(+)-O=C=O configurations. Fragmentation of larger Ni(+)(CO(2))(n) clusters terminates at the size of n=4, and new vibrational bands assigned to external ligands are observed for n> or =5. These combined observations indicate that the coordination number for CO(2) molecules around Ni(+) is exactly four. Trends in the loss channels and spectra of Ni(+)(O(2))(CO(2))(n) clusters suggest that each oxygen atom occupies a different coordination site around a four-coordinate metal ion in these complexes. The spectra of larger Ni(+)(CO(2))(n) clusters provide evidence for an intracluster insertion reaction assisted by solvation, producing a metal oxide-carbonyl species as the reaction product.     

Titanium alkoxide complexes: condensed phase and gas phase comparisons

The complex [Ti(2,4-dimethyl-2,4-pentanediolate)2]2 (1) has been synthesized from [Ti(OiPr)4] by transesterification with a stoichiometric amount of 2,4-dimethyl-2,4-pentanediol. We have characterized complex 1 in the solid state by single-crystal X-ray diffraction and in the gas phase by desorption chemical ionization mass spectrometry (DCI-MS). The structural and mass spectrometric data show complex 1 to be stable as a dimer in both the solid and gas phases. The retention of dimeric nuclearity in the gas phase sets complex 1 apart from other simple titanium alkoxide complexes [Ti(OiPr)4] and [Ti(OMe)4]4 that give rise to respective families of molecular ions in the DCI-MS experiment. The highest mass molecular ions for Ti alkoxide complexes in the gas phase may reveal the highest nuclearity that these complexes achieve in condensed phases. According to this interpretation the complex [Ti(OiPr)4] is principally dimeric in the gas phase and probably also in the pure liquid phase and should be represented by the formula [Ti(OiPr)4]2.     

Unambiguous identification of three beta-decaying isomers in 70Cu

Using resonant laser ionization, beta-decay studies, and for the first time mass measurements, three beta-decaying states have been unambiguously identified in 70Cu. A mass excess of -62 976.1(1.6) keV and a half-life of 44.5(2) s for the (6-) ground state have been determined. The level energies of the (3-) isomer at 101.1(3) keV with T(1/2)=33(2) s and the 1+ isomer at 242.4(3) keV with T(1/2)=6.6(2) s are confirmed by high-precision mass measurements. The low-lying levels of 70Cu populated in the decay of 70Ni and in transfer reactions compare well with large-scale shell-model calculations, and the wave functions appear to be dominated by one proton-one neutron configurations outside the closed Z=28 shell and N=40 subshell. This does not apply to the 1+ state at 1980 keV which exhibits a particular feeding and deexcitation pattern not reproduced by the shell-model calculations.     

Nuclear magnetic resonance studies of the microscopic protonation of L-cysteine

The protonation scheme of L-cysteine has been investigated by nuclear magnetic resonance. Chemical shift data as a function of pH are given for L-cysteine, L-cysteine methyl ester and S-methyl-L-cysteine. Use of derivatives of L-cysteine permits determination of the effect of protonation of the amino, sulfhydryl and carboxylic sites on the chemical shift of the -CH and -CH₂ protons. On the basis of these results, a set of simultaneous equations was written whose solution yielded the fraction of protonation of each site upon the addition of n equivalents of acid to the initially completely deprotonated molecule.     

Development of Molecular Mechanics Torsion Parameters for alpha,beta-Cyclopropyl Ketones and Conformational Analysis of Bicyclo[m.1.0]alkan-2-ones

Conformations of cyclopropyl methyl ketone have been studied using ab initio methods in an effort to quantify the effects of conjugative overlap between the cyclopropane ring and an adjacent ketone carbonyl. Results were comparable with previous experimental and theoretical studies. Cyclopropyl methyl ketone exhibits a global energy minimum in the s-cis conformer and a local energy minimum near the s-trans conformer. The potential energy curve obtained was used to derive torsion parameters which were employed in molecular mechanics studies of the conformations of the set of bicyclo[m.1.0]alkan-2-ones having larger ring sizes from five- to 16-membered. Similar conformations for the cyclopropyl ketone substructure are observed for all the medium and large ring systems examined. Possible synthetic ramifications of local conformational anchoring by this functional group array are discussed.     

Crosslinked polydiacetylene and its two- and three-component interpenetrating polymer networks (IPNs)

The synthesis of crosslinked polydiacetylene [poly4ECMU (a polydiacetylene with ethoxy carbonyl methylene urethane substitution): where R = ? (CH₂)₄OCONHCH₂COOCH₂CH₃] was carried out utilizing its polar and flexible substituent groups. Polydiacetylene was crosslinked by the formation of allophanate linkages utilizing urethane groups in the substituent groups of the polydiacetylene. Two-component IPNs of polydiacetylene [poly4BCMU (a polydiacetylene with butoxy carbonyl methylene urethane substitution): where R = ? (CH₂)₄OCONHCH₂COO(CH₂)₃CH₃] and an epoxy resin (diglycidyl ether of Bisphenol A) were synthesized. Two-component IPNs of poly4ECMU with the above epoxy resin were also synthesized. For the first time, two-component stiff-backbone IPNs of two different kinds of polydiacetylene (poly4BCMU and polyECMU) and a three-component IPN of poly4BCMU, poly4ECMU, and the epoxy resin were synthesized. IPNs with fewer allophanate linkages were also made in order to examine morphological differences between them. The glass transition behavior of these networks was studied using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) by means of a Rheovibron.     

The relationship between the linear (oscillatory) and nonlinear (steady-state) flow properties of a series of polymer and colloidal systems

The Cox-Merz empirical relationship between the linear (oscillatory) and nonlinear (steady-state) viscosities has been shown to be valid for many polymeric systems. Here, we present an equivalent expression to relate the linear (G) and nonlinear (N ₁) elastic properties of viscoelastic systems. Like the Cox-Merz relationship, it uses a combination of elastic and viscous parameters. The modified form of the storage modulus is then equivalent to the Cox-Merz complex viscosity. It can be used to correlate with (half) the normal force at numerically equal circular frequency and shear rate, respectively.This new expression and the Cox-Merz rule are tested for a range of polymeric and colloidal systems. It is found that both expression work for the polymeric systems considered, but fail for the colloidal systems. In the latter, the steady state values of viscosity and elasticity are consistently low, and replacing them by the complex viscosity and our new elastic expression only makes matters worse.For polymer systems, we suggest this is a general but not universal observation, since we are aware of exceptions to the rule that polymeric systems obey the Cox-Merz rule for viscosity and our rule for elasticity. For colloidal systems we find that neither rule is obeyed for any of our systems.     

Optimization of an electrolytic conductivity detector for determination of toxic nitrogen-containing food contaminants separated by open tubular column gas chromatography

The combination of open tubular column gas chromatography with electrolytic conductivity detection has been evaluated for the determination of nitrogen-containing pesticide residues in food extracts. Optimization of the column position at the column-detector interface was crucial to the successful operation of the detector. The signal-to-noise ratio and response stability of the detector are greatly influenced by the composition of the electrolyte solvent. Large volume splitless injections using retention gaps and optimized detector operating conditions enabled pesticide residues in food extracts to be determined at sub parts-per-million levels. Although the electrolytic conductivity detector is less sensitive than the thermionic ionization detector, its greater nitrogen selectivity can he crucial to the determination of nitrogen-containing contaminants in food extracts, particularly in complex mixtures where phosphorus-containing contaminants or matrix compounds are also present.