Coculture of Two Developmental Stages of a Marine-Derived Aspergillus alliaceus Results in the Production of the Cytotoxic Bianthrone Allianthrone A.

The genetically encoded, small-molecule chemical diversity of filamentous fungi is still largely unexplored and represents an attractive source for the discovery of new compounds. Here we report the production of new chlorinated bianthrones from coculture of two different developmental stages, or morphs, of a marine alga-derived Aspergillus alliaceus (teleomorph: Petromyces alliaceus) strain. The vegetative stage (asexual morph) can be separated from the morph that switched to sexual development (sclerotial morph); both produce distinct secondary metabolite patterns. Ochratoxin (1) was mainly found in the monoculture of the sclerotial morph, while the anthraquinone pigment nalgiovensin (2) was produced by the asexual morph. Surprisingly, combining cultures from both developmental stages in a coculture experiment changed the metabolite profile drastically. The chlorinated congener nalgiolaxin (3) was abundant, and newly produced bianthrones were found. Allianthrone A (4) and its two diastereomers [allianthrones B (5) and C (6)] were isolated, and the new structures were determined by extensive NMR spectroscopic analysis, supported by optical properties and X-ray crystallography. All metabolites were tested in antibiotic and cytotoxicity assays, and allianthrone A (4) showed weak cytotoxic activity against the HCT-116 colon cancer and SK-Mel-5 melanoma cell lines.

Synthesis and characterization of a highly strained donor-acceptor nanohoop.

A highly-strained, nitrogen-doped cycloparaphenylene (CPP), aza[6]CPP, was synthesized and then converted to a donor-acceptor nanohoop, N-methylaza[6]CPP, via alkylation of the nitrogen center. The energy levels of the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) for both molecules were then probed by cyclic voltammetry (CV), which revealed that the donor-acceptor nanohoop had a significantly lower LUMO energy relative to [6]CPP and aza[6]CPP. Density functional theory (DFT) revealed that the donor-acceptor nanohoop underwent a redistribution of the frontier molecular orbital (FMO) density such that a significant portion of the LUMO density resided upon the electron-deficient nitrogen-containing ring. This localization of LUMO density caused a large lowering in the LUMO energy of nearly a full electron volt, while the HOMO energy was less affected due to a large centralization of the FMO on the electron-rich phenylene backbone. This ultimately resulted in a net lowering of the HOMO-LUMO energy gap which was observed both experimentally and computationally. In addition, N-methylaza[6]CPP has a significantly lower energy LUMO than N-methylaza[8]CPP, illustrating that the FMO levels of donor-acceptor nanohoops can be tuned by adjusting the hoop size.

Bridging the opposite chemistries of tantalum and tungsten polyoxometalates.

The disparate solubility, redox activity, and pH stability of the group V and group VI polyoxometalates (POMs) confer very different functionality on these species, and tailoring cluster properties by varying the ratio of group V to group VI metals poses both an opportunity and a synthetic challenge. A classic series of studies reported over 40 years ago provided some insight into W/Nb POMs, from which researchers have built on to date. However, the analogous W/Ta series has never been addressed in a systematic manner. Three members of this W/Ta series are presented here, synthesized from simple oxo- and peroxocoltanate precursors. [Ta3W3O19](5-) displays the Lindqvist-type structure, while [TaW9O32](5-) and [Ta2W8O32](6-) are isostructural with decatungstate ([W10O32](4-)). Additionally, the use of peroxoniobate instead of hexaniobate as the starting material drives the formation of the decatungstate-type structure [NbW9O32](5-) instead of the Lindqvist ion that was established to be the foundational cluster geometry in prior work. The electronic structure of the Nb/Ta substituted decatungstates is directly related to the degree of substitution inasmuch as the HOMO-LUMO energy gap (Egap) slightly increases as more Nb/Ta atoms are incorporated into the structure. The poor mixing of the d-orbitals of Nb/Ta and W is responsible for the observed trends in the UV spectra and cyclic voltammetry. Moreover, the stability of the molecular frameworks in the gas phase is also related to the extent of substitution as revealed by electrospray mass-spectrometry (ESI-MS).

A flowing liquid lithium limiter for the Experimental Advanced Superconducting Tokamak.

A program involving the extensive and systematic use of lithium (Li) as a "first," or plasma-facing, surface in Tokamak fusion research devices located at Institute of Plasma Physics, Chinese Academy of Sciences, was started in 2009. Many remarkable results have been obtained by the application of Li coatings in Experimental Advanced Superconducting Tokamak (EAST) and liquid Li limiters in the HT-7 Tokamak-both located at the institute. In furtherance of the lithium program, a flowing liquid lithium (FLiLi) limiter system has been designed and manufactured for EAST. The design of the FLiLi limiter is based on the concept of a thin flowing film which was previously tested in HT-7. Exploiting the capabilities of the existing material and plasma evaluation system on EAST, the limiter will be pre-wetted with Li and mechanically translated to the edge of EAST during plasma discharges. The limiter will employ a novel electro-magnetic pump which is designed to drive liquid Li flow from a collector at the bottom of limiter into a distributor at its top, and thus supply a continuously flowing liquid Li film to the wetted plasma-facing surface. This paper focuses on the major design elements of the FLiLi limiter. In addition, a simulation of incoming heat flux has shown that the distribution of heat flux on the limiter surface is acceptable for a future test of power extraction on EAST.

Methods and preliminary measurement results of liquid Li wettability.

A test of lithium wettability was performed in high vacuum (< 3 × 10(-4) Pa). High magnification images of Li droplets on stainless steel substrates were produced and processed using the MATLAB(®) program to obtain clear image edge points. In contrast to the more standard "θ/2" or polynomial fitting methods, ellipse fitting of the complete Li droplet shape resulted in reliable contact angle measurements over a wide range of contact angles. Using the ellipse fitting method, it was observed that the contact angle of a liquid Li droplet on a stainless steel substrate gradually decreased with increasing substrate temperature. The critical wetting temperature of liquid Li on stainless steel was observed to be about 290 °C.

Trapped electron mode turbulence driven intrinsic rotation in Tokamak plasmas.

Progress from global gyrokinetic simulations in understanding the origin of intrinsic rotation in toroidal plasmas is reported. The turbulence-driven intrinsic torque associated with nonlinear residual stress generation due to zonal flow shear induced asymmetry in the parallel wave number spectrum is shown to scale close to linearly with plasma gradients and the inverse of the plasma current, qualitatively reproducing experimental empirical scalings of intrinsic rotation. The origin of current scaling is found to be enhanced k(∥) symmetry breaking induced by the increased radial variation of the safety factor as the current decreases. The intrinsic torque is proportional to the pressure gradient because both turbulence intensity and zonal flow shear, which are two key ingredients for driving residual stress, increase with turbulence drive, which is R/L(T(e)) and R/L(n(e)) for the trapped electron mode.

Magnetic diagnostics for equilibrium reconstructions in the presence of nonaxisymmetric eddy current distributions in tokamaks (invited).

The lithium tokamak experiment (LTX) is a modest-sized spherical tokamak (R(0)=0.4 m and a=0.26 m) designed to investigate the low-recycling lithium wall operating regime for magnetically confined plasmas. LTX will reach this regime through a lithium-coated shell internal to the vacuum vessel, conformal to the plasma last-closed-flux surface, and heated to 300-400 °C. This structure is highly conductive and not axisymmetric. The three-dimensional nature of the shell causes the eddy currents and magnetic fields to be three-dimensional as well. In order to analyze the plasma equilibrium in the presence of three-dimensional eddy currents, an extensive array of unique magnetic diagnostics has been implemented. Sensors are designed to survive high temperatures and incidental contact with lithium and provide data on toroidal asymmetries as well as full coverage of the poloidal cross-section. The magnetic array has been utilized to determine the effects of nonaxisymmetric eddy currents and to model the start-up phase of LTX. Measurements from the magnetic array, coupled with two-dimensional field component modeling, have allowed a suitable field null and initial plasma current to be produced. For full magnetic reconstructions, a three-dimensional electromagnetic model of the vacuum vessel and shell is under development.

New A2/3-xRh2O4 compounds with the CaFe2O4 structure where A is a rare earth or Bi.

New compounds of the type R(2/3-x)Rh(2)O(4) with the CaFe(2)O(4) structure have been prepared, where R is a rare earth. For crystals grown in a Bi/V/O flux, the rare earth was partially replaced by Bi. No evidence of ordering of the A cation vacancies is found, but the A cations are displaced from the ideal A cation site by about 0.24 A. Electrical conductivity measurements on crystals suggest that the materials are degenerate semiconductors with Seebeck measurements showing p-type behavior. This is consistent with our observation that x in R(2/3-x)Rh(2)O(4) ranges up to about 0.09. The compounds were also characterized by magnetic susceptibility and diffuse reflectance measurements.

Fast soft x-ray images of magnetohydrodynamic phenomena in NSTX.

A variety of magnetohydrodynamic (MHD) phenomena have been observed on NSTX. Many of these affect fast particle losses, which are of major concern for future burning plasma experiments. Usual diagnostics for studying these phenomena are arrays of Mirnov coils for magnetic oscillations and p-i-n diode arrays for soft x-ray emission from the plasma core. Data reported here are from a unique fast soft x-ray imaging camera (FSXIC) with a wide-angle (pinhole) tangential view of the entire plasma minor cross section. The camera provides a 64x64 pixel image, on a charge coupled device chip, of light resulting from conversion of soft x rays incident on a phosphor to the visible. We have acquired plasma images at frame rates of 1-500 kHz (300 frames/shot) and have observed a variety of MHD phenomena: disruptions, sawteeth, fishbones, tearing modes, and edge localized modes (ELMs). New data including modes with frequency >90 kHz are also presented. Data analysis and modeling techniques used to interpret the FSXIC data are described and compared, and FSXIC results are compared to Mirnov and p-i-n diode array results.

Magnetic diagnostics for the lithium tokamak experiment.

The lithium tokamak experiment (LTX) is a spherical tokamak with R(0)=0.4 m, a=0.26 m, B(TF) approximately 3.4 kG, I(P) approximately 400 kA, and pulse length approximately 0.25 s. The focus of LTX is to investigate the novel low-recycling lithium wall operating regime for magnetically confined plasmas. This regime is reached by placing an in-vessel shell conformal to the plasma last closed flux surface. The shell is heated and then coated with liquid lithium. An extensive array of magnetic diagnostics is available to characterize the experiment, including 80 Mirnov coils (single and double axis, internal and external to the shell), 34 flux loops, 3 Rogowskii coils, and a diamagnetic loop. Diagnostics are specifically located to account for the presence of a secondary conducting surface and engineered to withstand both high temperatures and incidental contact with liquid lithium. The diagnostic set is therefore fabricated from robust materials with heat and lithium resistance and is designed for electrical isolation from the shell and to provide the data required for highly constrained equilibrium reconstructions.

The motional Stark effect diagnostic for ITER using a line-shift approach.

The United States has been tasked with the development and implementation of a motional Stark effect (MSE) system on ITER. In the harsh ITER environment, MSE is particularly susceptible to degradation, as it depends on polarimetry, and the polarization reflection properties of surfaces are highly sensitive to thin film effects due to plasma deposition and erosion of a first mirror. Here we present the results of a comprehensive study considering a new MSE-based approach to internal plasma magnetic field measurements for ITER. The proposed method uses the line shifts in the MSE spectrum (MSE-LS) to provide a radial profile of the magnetic field magnitude. To determine the utility of MSE-LS for equilibrium reconstruction, studies were performed using the ESC-ERV code system. A near-term opportunity to test the use of MSE-LS for equilibrium reconstruction is being pursued in the implementation of MSE with laser-induced fluorescence on NSTX. Though the field values and beam energies are very different from ITER, the use of a laser allows precision spectroscopy with a similar ratio of linewidth to line spacing on NSTX as would be achievable with a passive system on ITER. Simulation results for ITER and NSTX are presented, and the relative merits of the traditional line polarization approach and the new line-shift approach are discussed.

Enhanced energy confinement and performance in a low-recycling tokamak.

Extensive lithium wall coatings and liquid lithium plasma-limiting surfaces reduce recycling, with dramatic improvements in Ohmic plasma discharges in the Current Drive Experiment-Upgrade. Global energy confinement times increase by up to 6 times. These results exceed confinement scalings such as ITER98P(y,1) by 2-3 times, and represent the largest increase in energy confinement ever observed for an Ohmic tokamak plasma. Measurements of Dalpha emission indicate that global recycling coefficients decrease to approximately 0.3, the lowest documented for a magnetically confined hydrogen plasma.

Bis(mu-3,5-di-tert-butylcatecholato-O1:O1,O2)bis[tris(pyridine-N)cadmium(II)] dipyridine solvate.

X-ray diffraction shows that the title cadmium(II) complex, [Cd(2)(C(14)H(20)O(2))(2)(C(5)H(5)N)(6)].2C(5)H(5)N, has a dimeric structure in which two (py)(3)Cd(3,5-di-tert-butylcatecholate) units (py is pyridine) are connected by two bridging O atoms, the coordination of the Cd atoms being distorted octahedral. There are two symmetrically independent dimers in the crystal structure; one is in a general position and the other lies about an inversion centre. In both cases, the bridging Cd-O distances between the Cd-catecholate units [2.224 (2)-2.237 (2) A] are shorter than the bridging Cd-O distances within the catecholate cycle [2.273 (2)-2.281 (2) A]. The Cd-N(py) distances are 2.354 (2)-2.471 (2) A. Besides the main molecules, the crystal also contains pyridine solvate molecules.