Spectroscopic characterization of peroxynitrous acid in cis-perp configurations

This paper presents experimental evidence, supported by two-dimensional theoretical calculations, that HOONO can be observed in cis-perp (cp) configurations in a pulsed supersonic expansion. The spectral properties (transition frequency, rotational constants, and transition type) of OH overtone transitions originating from a state with predominately cp character are predicted theoretically and compared with those associated with a weak feature at 6996.2 cm(-1) observed experimentally using infrared action spectroscopy. This spectral feature is attributed to HOONO in cp configurations based on its vibrational frequency, rotational band contour, and resultant OH product state distribution.     

Directed biosynthesis of alkaloid analogs in the medicinal plant Catharanthus roseus

Terpene indole alkaloids are plant natural products with diverse structures and biological activities. A highly branched biosynthetic pathway is responsible for the production of approximately 130 different alkaloids in Madagascar periwinkle (C. roseus) from a common biosynthetic intermediate derived from tryptamine. Although numerous biosynthetic pathways can incorporate unnatural starting materials to yield novel natural products, it was not clear how efficiently the complex, eukaryotic TIA pathway could utilize unnatural substrates to make new alkaloids. This work demonstrates that the TIA biosynthetic machinery can be used to produce novel alkaloid structures and also highlights the potential of this pathway for future metabolic engineering efforts.     

Cluster kinetics of pressure-induced glass formation

A prior correlation model for glass formation based on cluster-size distribution kinetics is here extended to account for pressure effects as well as temperature effects. The model describes how rapidly cooling or compressing a liquid or colloid leads to structural arrest and a consequent sharp rise in viscosity or dielectric relaxation time. In addition to activation energies, we include activation volumes in the rate coefficients for monomer-cluster addition and dissociation and cluster aggregation and breakage. The approach leads to scaled pressure correlations and plots for viscosity that reveal strong and fragile glass behavior, and agree with experimental data. A simple relationship among viscosity, attractive interparticle energy, and particle volume fraction displays how hard spheres with attractive forces can vitrify at small particle densities.     

Cluster kinetics and dynamics during spinodal decomposition

Spinodal decomposition (barrierless phase transition) is a spontaneous phase separation caused by conditions that force the system to become thermodynamically unstable. We consider spinodal decomposition to occur under conditions of large supersaturation S and/or small ratio of interfacial to thermal energies omega, such that the computed number of monomers in a critical nucleus xi*=(omega/ln S)3 is less than unity. The small critical nucleus size is consistent with a negligible energy barrier for initiating condensation. Thus, in contrast to conventional opinion, it is suggested that the spinodal decomposition is related to the homogeneous nucleation of metastable fluids. Population balance equations show how clusters aggregate and rapidly lead to phase separation. Different mass dependences of aggregation rate coefficients are proposed to investigate the fundamental features of spinodal decomposition. When the mass dependency is an integer, the equations are solved by the moment technique to obtain analytical solutions. When the mass dependency is a noninteger, the general cases are solved numerically. All solutions predict the two time regimes observed experimentally: the average length scale of condensed-phase domains increases as a power law with an exponent of 1/3 at early times, followed by a linear increase at longer times.     

Optical and resonant X-ray diffraction studies confirm a SmC*FI2-SmC* liquid crystal phase sequence reversal

Employing both null transmission ellipsometry and resonant x-ray diffraction, we confirmed the SmC*FI2-SmC* phase sequence reversal in one liquid crystal compound and specially prepared binary mixtures. This phase sequence reversal was predicted by two recent theoretical advances. Moreover, the temperature range for the SmC*FI2 phase increases significantly in the mixture suggesting that such a phase sequence may exist in other compounds.     

Spaces of lower semicontinuous set-valued maps I

We introduce a lower semicontinuous analog, L ^?(X), of the well-studied space of upper semicontinuous set-valued maps with nonempty compact interval images. Because the elements of L ^?(X) contain continuous selections, the space C(X) of real-valued continuous functions on X can be used to establish properties of L ^?(X), such as the two interrelated main theorems. The first of these theorems, the Extension Theorem, is proved in this Part I. The Extension Theorem says that for binormal spaces X and Y, every bimonotone homeomorphism between C(X) and C(Y) can be extended to an ordered homeomorphism between L ^?(X) and L ^?(Y). The second main theorem, the Factorization Theorem, is proved in Part II. The Factorization Theorem says that for binormal spaces X and Y, every ordered homeomorphism between L ^?(X) and L ^?(Y) can be characterized by a unique factorization.     

Function spaces and product topologies on powers of spaces

A study is made of two classes of product topologies on powers of spaces: the general box product topologies, and the general uniform product topologies. Some examples are given and some results are shown about the properties of these general product spaces. This is applied to show that certain spaces of continuous functions with the fine topology are homeomorphic to box product spaces, and certain spaces of continuous functions with the uniform topology are homeomorphic to uniform product spaces.     

A theoretical and computational study of the anion, neutral, and cation Cu(H(2)O) complexes

An ab initio investigation of the potential energy surfaces and vibrational energies and wave functions of the anion, neutral, and cation Cu(H(2)O) complexes is presented. The equilibrium geometries and harmonic frequencies of the three charge states of Cu(H(2)O) are calculated at the MP2 level of theory. CCSD(T) calculations predict a vertical electron detachment energy for the anion complex of 1.65 eV and a vertical ionization potential for the neutral complex of 6.27 eV. Potential energy surfaces are calculated for the three charge states of the copper-water complexes. These potential energy surfaces are used in variational calculations of the vibrational wave functions and energies and from these, the dissociation energies D(0) of the anion, neutral, and cation charge states of Cu(H(2)O) are predicted to be 0.39, 0.16, and 1.74 eV, respectively. In addition, the vertical excitation energies, that correspond to the 4 (2)P<--4 (2)S transition of the copper atom, and ionization potentials of the neutral Cu(H(2)O) are calculated over a range of Cu(H(2)O) configurations. In hydrogen-bonded, Cu-HOH configurations, the vertical excitation and ionization energies are blueshifted with respect to the corresponding values for atomic copper, and in Cu-OH(2) configurations where the copper atom is located near the oxygen end of water, both quantities are redshifted.     

Reactive scattering dynamics in atom+polyatomic systems: F+C2H6-->HF(v,J)+C2H5

State-to-state scattering dynamics of F+C2H6-->HF(v,J)+C2H5 have been investigated at Ecom=3.2(6) kcalmol under single-collision conditions, via detection of nascent rovibrationally resolved HF(v,J) product states with high-resolution infrared laser absorption methods. State-resolved Doppler absorption profiles are recorded for multiple HF(v,J) transitions originating in the v=0,1,2,3 manifold, analyzed to yield absolute column-integrated densities via known HF transition moments, and converted into nascent probabilities via density-to-flux analysis. The spectral resolution of the probe laser also permits Doppler study of translational energy release into quantum-state-resolved HF fragments, which reveals a remarkable linear correlation between (i) HF(v,J) translational recoil and (ii) the remaining energy available, Eavail=Etot-E(HF(v,J)). The dynamics are interpreted in the context of a simple impulsive model based on conservation of linearangular momentum that yields predictions in good agreement with experiment. Deviations from the model indicate only minor excitation of ethyl vibrations, in contrast with a picture of extensive intramolecular vibrational energy flow but consistent with Franck-Condon excitation of the methylene CH2 bending mode. The results suggest a relatively simple dynamical picture for exothermic atom+polyatomic scattering, i.e., that of early barrier dynamics in atom+diatom systems but modified by impulsive recoil coupling at the transition state between translationalrotational degrees of freedom.