Interference of homonuclear decoupling and exchange in the solid-state NMR of perfluorocyclohexane

We observe an interference between RF irradiation used for homonuclear decoupling of 19F and conformational exchange in the 13C spectrum of perfluorocyclohexane. We show that these effects can be readily reproduced in simulation, and characterise their dependence on the various NMR and experimental parameters. Their application to observing exchange rates on the kHz timescale is evaluated with respect to T(1rho) measurements and the connections between the two approaches established. The implications for experiments that use homonuclear decoupling of 1H to resolve 1J(CH)couplings in the solid-state are also evaluated in detail.     

Millimeter-wave atmospheric turbulence measurements: Instrumentation, selected results, and system effects

Increasing interest in and greater usage of the millimeter-wave frequency bands has resulted in a need for better characterization of atmospheric effects at these frequencies. While attenuation is recognized as the most significant effect, recent measurements of fluctuations in intensity and phase caused by atmospheric turbulence have shown that these phenomena will also degrade system performance at both millimeter-wave and microwave frequencies. This paper describes the millimeter-wave and meteorological instrumentation used to make these measurements and gives selected results. It is determined that phase fluctuations as great as 1.5 radians and intensity fluctuations as large as 2.8 dB are observed over a 1370 m path in hot, humid weather. The effects of these fluctuations on the performance of practical, existing microwave phased array and monopulse systems are assessed. It is determined that phase fluctuations in particular will degrade the performance of microwave adaptive nulling arrays and monopulse trackers. Intergovernmental Personnel Act appointee from the Georgia Institute of Technology supported by the University Resident Research Program of the Air Force Office of Scientific Research.     

Activation analysis with standards containing two or more active nuclides A computerized method of calculation involving decay and gamma spectral resolution

The resolution of the gamma spectra of activities induced in materials by fast neutron, charged particle and gamma photon activation is complicated by the fact that many elements produce more than one active nuclide in significant amounts. Direct resolution by least-squares fitting of the spectra of standards is only possible in these circumstances if the standard and sample spectra are obtained at the same time after irradiation, as the shapes of the standard spectra change with time. An alternative to the practical collection of spectra in this way is the correction of the standard spectra to the mid-time of counting of a sample spectrum. This may be achieved by recording spectra for a standard at different times and resolving the decay curves obtained for each channel on the basis of the half-lives of the component nuclides, which may be decay-independent or related or both. From the component nuclide count-rates in each channel at some arbitrary time, the standard spectrum at the time of counting of the sample can be generated and then used in a conventional least squares-fit of the sample spectrum. A FORTRAN IV program has been written to carry out this type of calculation on an IBM 360 65 computer. The feasibility of using this method is demonstrated by its application to activation analyses involving standards containing decay-related and independent nuclides.     

Discussion on a possible neutrino detector located in India

We have identified some important and worthwhile physics opportunities with a possible neutrino detector located in India. Particular emphasis is placed on the geographical advantage with a stress on the complimentary aspects with respect to other neutrino detectors already in operation.     

Fermentation performance characteristics of a prehydrolyzate-adapted xylose-fermenting recombinant Zymomonas in batch and continuous fermentations

Long-term (149 d) continuous fermentation was used to adapt a xylose-fermenting recombinant Zymomonas mobilis, strain 39676:pZB 4L, to conditioned (overlimed) dilute-acid yellow poplar hemicellulose hydrolyzate (“prehydrolyzate”). An “adapted” variant was isolated from a chemostat operating at a dilution rate of 0.03/h with a 50% (v/v) prehydrolyzate, corn steep liquor, and sugar-supplemented medium, at pH 5.75. The level of xylose and glucose in the medium was kept constant at 4% (w/v) and 0.8% (w/v), respectively. These sugar concentrations reflect the composition of the undiluted hardwood prehydrolyzate. The level of conditioned hardwood prehydrolyzate added to the medium was increased in 5% increments startingata level of 10%. At the upper level of 50% prehydrolyzate, the acetic-acid concentration was about 0.75% (w/v). The adapted variant exhibited improved xylose-fermentation performance in a pure-sugar, synthetic hardwood prehydrolyzate medium containing 4% xylose (w/v), 0.8% (w/v) glucose, and acetic acid in the range 0.4–1.0% (w/v). The ethanol yield was 0.48–0.50 g/g; equivalent to a sugar-to-ethanol conversion efficiency of 94–96% of theoretical maximum. The maximum growth yield and maintenance energy coefficients were 0.033 g dry cell mass (DCM)/g sugars and 0.41 g sugars/g DCM/h, respectively. The results confirm that long-term continuous adaptation is a useful technique for effecting strain improvement with respect to the fermentation of recalcitrant feedstocks.     

Continuous fermentation studies with xylose-utilizing recombinant Zymomonas mobilis

This study examined the continuous cofermentation performance characteristics of a dilute-acid “prehydrolysate-adapted” recombinant Zymomonas 39676:pZB4L and builds on the pH-stat batch fermentations with this recombinant that we reported on last year. Substitution of yeast extract by 1% (w/v) corn steep liquor (CSL) (50% solids) and Mg (2 mM) did not alter the coferm entation performance. Using declared assumptions, the cost of using CSL and Mg was estimated to be 12.5c/gal of ethanol with a possibility of 50% cost reduction using fourfold less CSL with 0.1% diammonium phosphate. Because of competition for a common sugar transporter that exhibits a higher affinity for glucose, utilization of glucose was complete whereas xylose was always present in the chemostat effluent. The ethanol yield, based on sugar used, was 94% of theoretical maximum. Altering the sugar ratio of the synthetic dilute acid hardwood prehydrolysate did not appear to significantly change the pattern of xylose utilization. Using a criterion of 80% sugar utilization for determining the maximum dilution rate (D _max), changing the composition of the feed from 4% xylose to 3%, and simultaneously increasing the glucose from 0.8 to 1.8% shifted D _max from 0.07 to 0.08/h. With equal amounts of both sugars (2.5%), D _max was 0.07/h. By comparison to a similar investigation with rec Zm CP4:pZB5 with a 4% equal mixture of xylose and glucose, we observed that at pH 5.0, the D _max was 0.064/h and shifted to 0.084/h at pH 5.75. At a level of 0.4% (w/v) acetic acid in the CSL-based medium with 3% xylose and 1.8% glucose at pH 5.75, the D _max for the adapted recombinant shifted from 0.08 to 0.048/h, and the corresponding maximum volumetric ethanol productivity decreased 45%, from 1.52 to 0.84 g/(L·h). Under these conditions of continuous culture, linear regression of a Pirt plot of the specific rate of sugar utilization vs D showed that 4 g/L of acetic acid did not affect the maximum growth yield (0.030 g dry cell mass/g sugar), but did increase the maintenance coefficient twofold, from 0.46 to 1.0 g of sugar/(g of cell·h).     

Equivalent Conditions for the Solvability of Nonstandard and Singular LQ-Problems with Application to Parabolic Equations

We consider an optimal control problem with indefinite cost for an abstract model, which covers, in particular, parabolic systems in a general bounded domain. Necessary and sufficient conditions are given for the synthesis of the optimal control, which is given in terms of the Riccati operator arising from a nonstandard Riccati equation. The theory extends also a finite-dimensional frequency theorem to the infinite-dimensional setting. Applications include the heat equation with Dirichlet and Neumann controls, as well as the strongly damped Euler–Bernoulli and Kirchhoff equations with the control in various boundary conditions.     

Effect of successive sprays on liquid distribution in fluidized beds

In processes such as Fluid Coking^?,agglomerate formation should be minimized since it reduces the yield of valuable products,and degrades operability because of the fouling of internals.An experimental model,consisting of an aqueous solution of gum arabic with a dye,has been successfully developed to simulate the formation of agglomerates in the Fluid Coking^?process,where bitumen is sprayed into a fluidized bed of coke particles The particles wetted by a spray could be predicted by assuming that all the particles in the wake of bubbles formed from the tip of the spray jet have been wetted by the injected liquid.The transfer of liquid from particles wetted with the spray to dry bed particles was relatively ineffective,as the number of wet particles increased by only 50%.With successive liquid injections,the proportion of the liquid trapped in agglomerates increases in latter injections:large agglomerates from earlier injections accumulate above the grid and are carried by gas bubbles into the spray jet cavity,where they seed fresh agglomerates.     

Condensed matter chemistry under ‘extreme’ high pressure–high temperature conditions

Improved techniques for high-pressure experiments have led to new studies of the structure and physical properties of materials compressed to extremely high densities. Now we must fully enable the field of condensed matter chemistry under extreme high-pressure conditions. This will require development of strategies for the analysis and control of the chemical composition during reactions between solid, liquid and fluid phases. Such approaches already exist within the fields of experimental geochemistry and petrology, and they can be readily adapted to the wider area of chemistry. The first consideration is the manipulation and determination of stable and metastable pressure–temperature phase diagrams, illustrated here for the one-component system Si. Next, relationships between P, T and the chemical composition, X, expressed in terms of the chemical potential (μ) or the activity–composition relations, can be used to constrain and determine components within the system. This is illustrated by examples drawn from our recent work on high-pressure syntheses of boron suboxides (B₆O_1???δ) and (Si, Ge)₃N₄ nitride spinels.     

Supramolecular assembly facilitating adsorbate-induced chiral electronic states in a metal surface

Through the application of optically active second-harmonic generation measurements (OA-SHG) we have demonstrated that the adsorption of amino acids cysteine (HSCH(2)CHNH(2)COOH) and penicillamine (HSC(CH3)(2)CHNH(2)COOH) from solution can induce chiral electronic states in an initially achiral polycrystalline Au film. The chiral induction is strongly dependent upon the pH of the deposition solution; adsorption of penicillamine and cysteine under acidic conditions (pH = 3) induces the same level of optical activity, whereas at pH = 11, the optical activity induced by cysteine is reduced by ca. 50% and penicillamine does not induce optical activity at all. The pH dependence indicates that the presence of interadsorbate hydrogen bonds, and consequently the supramolecular assembly of the adsorbates, facilitates the induction of chiral electronic states in the Au surface. This observation demonstrates that the symmetry properties of the extended structure of the self-assembled layer, and not the local adsorption geometry of the isolated adsorbed moiety, play the lead role in the induction of chiral metallic electronic states. The dependence of the chiral induction on COOH groups is identical to that observed in studies of optical activity in chiral thiol-protected nanoparticles, suggesting a common mechanism for the chiral perturbation in extended films and nanoparticles.