Preparation and characterization of a suite of ephedra-containing standard reference materials

The National Institute of Standards and Technology, the U.S. Food and Drug Administration, Center for Drug Evaluation and Research and Center for Food Safety and Applied Nutrition, and the National Institutes of Health, Office of Dietary Supplements, are collaborating to produce a series of Standard Reference Materials (SRMs) for dietary supplements. A suite of ephedra materials is the first in the series, and this paper describes the acquisition, preparation, and value assignment of these materials: SRMs 3240 Ephedra sinica Stapf Aerial Parts, 3241 E. sinica Stapf Native Extract, 3242 E. sinica Stapf Commercial Extract, 3243 Ephedra-Containing Solid Oral Dosage Form, and 3244 Ephedra-Containing Protein Powder. Values are assigned for ephedrine alkaloids and toxic elements in all 5 materials. Values are assigned for other analytes (e.g., caffeine, nutrient elements, proximates, etc.) in some of the materials, as appropriate. Materials in this suite of SRMs are intended for use as primary control materials when values are assigned to in-house (secondary) control materials and for validation of analytical methods for the measurement of alkaloids, toxic elements, and, in the case of SRM 3244, nutrients in similar materials.     

High-level ab initio studies of hydrogen abstraction from prototype hydrocarbon systems

Symmetric and nonsymmetric hydrogen abstraction reactions are studied using state-of-the-art ab initio electronic structure methods. Second-order M?ller-Plesset perturbation theory (MP2) and the coupled-cluster singles, doubles, and perturbative triples [CCSD(T)] methods with large correlation consistent basis sets (cc-pVXZ, where X = D,T,Q) are used in determining the transition-state geometries, activation barriers, and thermodynamic properties of several representative hydrogen abstraction reactions. The importance of basis set, electron correlation, and choice of zeroth-order reference wave function in the accurate prediction of activation barriers and reaction enthalpies are also investigated. The ethynyl radical (*CCH), which has a very high affinity for hydrogen atoms, is studied as a prototype hydrogen abstraction agent. Our high-level quantum mechanical computations indicate that hydrogen abstraction using the ethynyl radical has an activation energy of less than 3 kcal mol(-1) for hydrogens bonded to an sp(2) or sp(3) carbon. These low activation barriers further corroborate previous studies suggesting that ethynyl-type radicals would make good tooltips for abstracting hydrogens from diamondoid surfaces during mechanosynthesis. Modeling the diamond C(111) surface with isobutane and treating the ethynyl radical as a tooltip, hydrogen abstraction in this reaction is predicted to be barrierless.     

Global Stringy Orbifold Cohomology,K-Theory and de Rham Theory

There are two approaches to constructing stringy multiplications for global quotients. The first one is given by first pulling back and then pushing forward. The second one is given by first pushing forward and then pulling back. The first approach has been used to define a global stringy extension of the functors K ₀ and K ^top by Jarvis–Kaufmann–Kimura, A* by Abramovich–Graber–Vistoli, and H* by Chen–Ruan and Fantechi–Göttsche. The second approach has been applied by the author in the case of cyclic twisted sector and in particular for singularities with symmetries and for symmetric products. The second type of construction has also been discussed in the de Rham setting for Abelian quotients by Chen–Hu. We give a rigorous formulation of de Rham theory for any global quotient from both points of view. We also show that the pull–push formalism has a solution by the push–pull equations in the setting case of cyclic twisted sectors. In the general, not necessarily cyclic case, we introduce ring extensions and treat all the stringy extension of the functors mentioned above also from the second point of view. A first extension provides formal sections and a second extension fractional Euler classes. The formal sections allow us to give a pull–push solution while fractional Euler classes give a trivialization of the co-cycles of the pull–push formalism. The main tool is the formula for the obstruction bundle of Jarvis–Kaufmann–Kimura. This trivialization can be interpreted as defining the physics notion of twist fields. We end with an outlook on applications to singularities with symmetries aka. orbifold Landau–Ginzburg models.     

Efficient photoconductive terahertz source using line excitation

We report significant improvement in terahertz (THz) power and efficiency using photoconductive sources by use of a spatially extended line source excitation and the trap enhanced field effect that occurs in sources made on semi-insulating GaAs. The combination of high electric fields and reduced screening effects allows 10 microW of THz power to be generated with 14 mW of absorbed optical power, demonstrating nearly 0.1% optical-to-THz conversion efficiency.     

THE SPECTROSCOPY AND PHOTOCHEMISTRY OF ENAMINONITRILES INCLUDING THE SYNTHESIS AND IDENTIFICATION OF CIS-β-AMINOACRYLONITRILE

Abstract— The absorption spectral and photochemical properties of β-aminoacrylonitrile (AAN), β-aminocrotonitrile (ACN) and three other enaminonitriles have been studied. The synthesis and identification of cis -β-aminoacrylonitrile are also included. Each enaminonitrile has one intense absorption band (1–2 × 10⁴M^-1cm^-1) in the 254–273 nm region. Photoisomerization and photocyclization to imidazoles are observed. Imidazole formation is quite strongly inhibited by oxygen and the presence of oxygen can cause wavelength dependent photochemistry, other reactions and destruction of the reactant. The quantum yield of formation of imidazoles is low (<10^-4) for β-aminoacrylonitrile and β-aminocrotonitrile and photoisomerization dominates in those four cases where it can occur. Imidazole formation from a dimethylamino compound proves that the presence of H atoms on the amino group is not a prerequisite for photocyclization.     

Convergence of a Penalty Method for Mathematical Programming with Complementarity Constraints

We adapt the convergence analysis of the smoothing (Ref. 1) and regularization (Ref. 2) methods to a penalty framework for mathematical programs with complementarity constraints (MPCC); we show that the penalty framework shares convergence properties similar to those of these methods. Moreover, we give sufficient conditions for a sequence generated by the penalty framework to be attracted to a B-stationary point of the MPCC.     

Heterocyclic quinones with bridgehead nitrogen atoms. Part I. Pyrrolo[1,2-a]quinoxaline-6,9-dione and pyrrolo[2,1-c][1,2,4]benzotriazine-6,9-dione

The synthesis and some reactions of pyrrolo[1,2-a]quinoxaline-6,9-dione and pyrrolo[2,1-c][1,2,4]benzotriazine-6,9-dione are described.     

Ab initio calculations on large molecules using molecular fragments. Initial studies on open shell systems

An ab initio procedure, designed for investigation of large molecules and based upon studies of molecular fragments, is extended to open shell systems using the unrestricted Hartree-Fock method. Investigated initially are the ethyl and vinyl radicals, and the ethylene triplet state.     

Unprecedented catalytic asymmetric reduction of N-H imines

[Reaction: see text] Addition of lithium bis(trimethylsilyl)amide to perfluorinated ketones 1a-j affords (E)-N-TMS-ketimines 2a-j that are reduced in situ to afford racemic perfluoromethylated amine hydrochloride salts 3a-j in 54-97% yields. Solvolysis of the N-Si bond in MeOH leads to formation of bench-stable, isolable N-H imine Z/E isomer mixtures along with a methanol adduct. Enantioselective reduction of these three-component mixtures provides the first catalytic asymmetric synthesis of trifluoromethylated amines in 72-95% yields and 75-98% ee.     

An investigation of the scales in transitional boundary layers under high free-stream turbulence conditions

The scales in a transitional boundary layer subject to high (initially 8%) free-stream turbulence and strong acceleration (K as high as 9×10^–6) were investigated using wavelet spectral analysis and conditional sampling of experimental data. The boundary layer shows considerable evolution through transition, with a general shift from the lower frequencies induced by the free-stream unsteadiness to higher frequencies associated with near-wall-generated turbulence. Within the non-turbulent zone of the intermittent flow, there is considerable self-similarity in the spectra from the beginning of transition to the end, with the dominant frequencies in the boundary layer remaining constant at about the dominant frequency of the free-stream. The frequencies of the energy-containing scales in the turbulent zone change with streamwise location and are significantly higher than in the non-turbulent zone. When normalized on the local viscous length scale and velocity, however, the turbulent zone spectra also show good self-similarity throughout transition. Turbulence dissipation occurs almost exclusively in the turbulent zone. The velocity fluctuations associated with dissipation are isotropic, and their normalized spectra at upstream and downstream stations are nearly identical. The distinct differences between the turbulent and non-turbulent zones suggest the potential utility of intermittency based transition models in which these zones are treated separately. The self-similarity noted in both energy containing and dissipation scales in both zones suggests possibilities for simplifying the modeling for each zone.

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