Analysis of CL-20 in environmental matrices: water and soil

Analytical techniques for the detection of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo(5.5.0.05,9.03,11)dodecane (CL-20) in water and soil are developed by adapting methods traditionally used for the analysis of nitroaromatics. CL-20 (a new explosives compound) is thermally labile, exhibits high polarity, and has low solubility in water. These constraints make the use of specialized sample handling, preparation, extraction, and analysis necessary. The ability to determine the concentrations of this new explosive compound in environmental matrices is helpful in understanding the environmental fate and effects of CL-20; understanding the physical, chemical, and biological fate of CL-20; and can be used in developing remediation technologies and determining their efficiency. The toxicity and mobility of new explosives in soil and groundwater are also of interest, and analytical techniques for quantitating CL-20 and its degradation products in soil and natural waters make these investigations possible.     

Characterizing the transmission properties of an ion funnel

The characteristic features of ion transmission properties in a radio-frequency (RF) electric-field driven ion funnel using the SIMION ion trajectory simulation package is presented. A user program applying the Douglas ion-neutral collisional drag coefficient model is incorporated to properly account for the ion focusing and transport effect of the background gas under the effect of the driving RF and a superimposed DC field. The simulated m/z transmission window compares favorably with the experimental results reported by Smith et al. RF amplitude and pressure dependence of experimentally observed m/z transmission windows are also examined, and an approximated effective potential model based on Gerlich's equation is proposed to interpret the low-m/z cutoff behavior. A modified ion funnel configuration is described.     

51V magic angle spinning NMR spectroscopy of Keggin anions [PVnW12-nO40](3+n)-: effect of countercation and vanadium substitution on fine structure constants

Vanadium environments in Keggin oxopolytungstates were characterized by (51)V solid-state MAS NMR spectroscopy. (C(4)H(9))(4)N(+)-, K(+)-, Cs(+)-, as well as mixed Na(+)/Cs(+)- salts of the mono-, di-, and trivanadium substituted oxotungstates, [VW(11)O(40)](4-), [V(2)W(10)O(40)](5-), and [V(3)W(9)O(40)](6-), have been prepared as microcrystalline and crystalline solids. Solid-state NMR spectra report on the local environment of the vanadium site in these Keggin ions via their anisotropic quadrupolar and chemical-shielding interactions. These (51)V fine structure constants in the solid state are determined by the number of vanadium atoms present in the oxoanion core. Surprisingly, the quadrupolar anisotropy tensors do not depend to any significant extent on the nature of the countercations. On the other hand, the chemical-shielding anisotropy tensors, as well as the isotropic chemical shifts, display large variations as a function of the cationic environment. This information can be used as a probe of the local cationic environment in the vanadium-substituted Keggin solids.     

Self-assembly of phosphate fluorosurfactants in carbon dioxide

Anionic phosphodiester surfactants, possessing either two fluorinated chains (F/F) or one hydrocarbon chain and one fluorinated chain (H/F), were synthesized and evaluated for solubility and self-assembly in liquid and supercritical carbon dioxide. Several surfactants, of both F/F and H/F types and having varied counterions, were found to be capable of solubilizing water-in-CO2 (W/C), via the formation of microemulsions, expanding upon the family of phosphate fluorosurfactants already found to stabilize W/C microemulsions. Small-angle neutron scatteringwas used to directly characterize the microemulsion particles at varied temperatures, pressures, and water loadings, revealing behavior consistent with previous results on W/C microemulsions.     

The preparation and properties of BAB block copolymers based on polyethylene sulphide and polyisoprene

Block copolymers of ethylene sulphide (B) and isoprene (A) have been prepared by anionic synthesis using alkali metal complexes of naphthalene as initiator. Two series of block copolymers have been synthesized, one (based on sodium naphthalenide as initiator) having high molecular weights and the other (based on lithium naphthalenide) having low molecular weights.Physical properties of the block copolymers as a function of composition, molecular weight and polyisoprene microstructure have been studied. Polymers containing high molecular weight polyethylene sulphide sequences were difficult to process without degradation. By lowering the molecular weight of the polyethylene sulphide segment, block copolymers of improved processibility were obtained.The centre block polyisoprene microstructure has been varied from 100% 1,2/3,4 configuration to 80% 1,4 configuration by preparing a “seed” polymer in tetrahydrofuran followed by solvent removal and replacement by hexane. Changes in microstructure affect low temperature flexibility, resilience and tensile strength of the block copolymer.The BAB block copolymers are biphasic and exhibit elastomeric properties with improved network stability compared with polystyrene-polybutadiene-polystyrene ABA block copolymers.     

Bis[bis­(3‐phenyl­pyrazol‐1‐yl)­(pyrazol‐1‐yl)­methane]­copper(II) bis­(per­chlor­ate) acetonitrile disolvate

The title copper(II) complex, [Cu(C₂₂H₁₈N₆)₂](ClO₄)₂·2C₂H₃N, comprises two neutral substituted tris­(pyrazol‐1‐yl)­methane ligands bonded to a central Cu^II ion, which is positioned on a crystallographic inversion center. Six Cu—N bonds are arranged in a distorted octa­hedral fashion. The unsubstituted pyrazole rings on each ligand are oriented trans with respect to each other, inter­digitated with the two 3‐phenyl­pyrazole rings of the other ligand.     

Photoinduced Ru-Yb energy transfer and sensitised near-IR luminescence in a coordination polymer containing co-crystallised [Ru(bipy)(CN)4]2- and Yb(III) units

Co-crystallisation of the anionic cyanometallate chromophore [Ru(bipy)(CN)4]2- with Yb(III) provides coordination polymers or oligomers containing Ru-CN-Yb bridges; in [K(H2O)4][Yb(H2O)6][Ru(bipy)(CN)4]2.5H2O Ru-->Yb energy-transfer (k > 5 x 10(6) s(-1)) results in partial quenching of the Ru-based luminescence and sensitised near-IR luminescence from the Yb(III) unit.     

Direct drag measurements in a turbulent flat-plate boundary layer with turbulence manipulators

The effect of turbulence manipulators on the turbulent boundary layer above a flat plate has been investigated. These turbulence manipulators are often referred to as Large Eddy Break Up (LEBU) devices. The basic idea is that thin blades or airfoils are inserted into the turbulent flow in order to reduce the fluctuating vertical velocity component v above the flat plate. In this way, the turbulent momentum transfer and with it the wall shear stress downstream of the manipulator should be decreased. In our experiments, for comparison, a merely drag-producing wire also was inserted into the boundary layer.In particular, the trade-off between the drag of the turbulence manipulator and the drag reduction due to the shear-stress reduction on the flat plate downstream of the manipulator has been considered. The measurements were carried out with very accurate force balances for both the manipulator drag and the shear stress on the flat plate. As it turns out, no net drag reduction is found for a fairly large set of configurations. A single thin blade as a manipulator performed best, i.e., it was closest to break-even. However, a further improvement is unlikely, because the device drag of the thin blade elements used here has already been reduced to only that due to laminar skin friction, and is thus the minimum possible drag. Airfoils performed slightly worse, because their device drag was higher. A purely drag-producing wire device performed disastrously. The wire device, which consisted of a wire with another thin wire wound around it to suppress coherent vortex shedding and vibration, was designed to have (and did have) the same drag as the airfoil manipulator with which it was compared. The comparison showed that airfoil and blade manipulators recovered 75–90% of their device drag through a shear-stress reduction downstream, whereas the wire device recovered only about 25–30% of its device drag.Conventional LEBU manipulators with airfoils or thin blades produce between 0.25% and 1% net drag increase, whereas the wire device (with equal device drag) produces as much as 4% net drag increase. These data are valid for the specific plate length of our experiments, which was long enough in downstream extent to realize the full effect of the LEBU manipulators. Turbulence manipulators do indeed decrease the turbulent momentum exchange in the boundary layer by rectifying the turbulent fluctuations. This generates a significant shear-stress reduction downstream, which is much more than just the effect of the wake of the manipulator. However, the device drag of the manipulator cannot be reduced without simultaneously reducing the skin friction reduction. Thus, the manipulator's device drag exceeds, or at best cancels, the drag reduction achieved by the shear-stress reduction downstream. A critical survey of previous investigations shows that the suggestion that turbulence manipulators may produce net drag reduction is also not supported by the available previous drag force measurements. The issue had been stirred up by less conclusive measurements based on local velocity data, i.e., data collected using the so-called momentum balance technique.List of symbols b lateral breadth of test plate - c chord length of turbulence manipulator - d diameter of wire manipulator - e distance of the elastic center from the leading edge of the manipulator airfoil - h height of manipulator above test plate - q dynamic pressure of the potential flow above the test plate - s spacing of turbulence manipulator elements - t thickness of turbulence manipulator elements - u,v,w fluctuating velocities in downstream, platenormal, and lateral directions - x distance from the leading edge of the test plate in the downstream direction - x ₀ location of the trailing edge of the first manipulator - z distance from test plate center in the lateral direction - C _D drag coefficient - C _L lift coefficient - D _m drag of manipulated plate including device drag and shear stress, calculated from manipulator location to downstream location - D ₀ drag of unmanipulated plate boundary layer, consisting of the shear stress calculated from manipulator location to downstream location - F drag force - F ₀ total skin friction force, measured over a distance from 0.4 m upstream of manipulator to 6.35 m downstream of manipulator, measured without turbulence manipulator - F _LEBU device drag force of the LEBU, i.e., the turbulence manipulator - F _m total drag force of manipulated plate, consisting of - F _LEBU and skin friction force, measured over a distance from 0.4 m upstream of manipulator to 6.35 m downstream - F _cf skin friction force as measured by the floating element balance, manipulated case - F _cfo skin friction force, as measured by the floating element balance, unmanipulated case - F _cf skin friction saving, defined as F _cf = F _cf – F _cfo - F _cf cumulative skin friction savings, i.e., the sum of the skin friction savings F _cf , added up from the location of the manipulator to the downstream location , as shown in Fig. 11. In Fig. 13 the cumulative skin friction savings are summarized up to their asymptotic value, reached at 200 - Re _c Reynolds number of the manipulator elements, calculated with the chord length c and the local velocity in the boundary layer - Re ₀ Reynolds number at the location x ₀ of the manipulator, calculated with the momentum thickness of the boundary layer and the mean flow velocity U - U mean flow velocity in the potential regime of the wind tunnel test section - angle of attack of the manipulator airfoils - ₀ boundary layer thickness at the location x ₀ of the manipulator - dimensionless distance from the manipulator in the downstream direction, defined as - density of the air - ₀ local skin friction shear stress, unmanipulated case - _{0 Average} skin friction shear stress, average value over the lateral span (b = 2 m) of the test plate, unmanipulated case - _m local skin friction shear stress, manipulated case - momentum thickness of the undisturbed turbulent boundary layer at the location x ₀ The authors would like to thank Prof. H. H. Fernholz for his scientific and administrative support. The hardware for the experiments was designed and built by C. Daase, W. Hage and R. Makris. Funding for the project was provided by the Deutsche Forschungsgemeinschaft and is gratefully acknowledged.