Comparative tests to improve the gas chromatographic analysis of chlorobornanes in fish samples

A comparison was made between electron capture negative ionization quadrupole mass spectrometry (ECNI-MS) and electron capture detection (ECD) with regard to repeatability and reproducibility for the gas chromatographic (GC) analysis of toxaphene congeners [chlorobornanes (CHBs)]. The tests, including standard solutions and several cleaned fish extracts, showed larger relative standard deviations (RSDs) for the repeatability of ECNI-MS but no differences in the reproducibility of the 2 techniques. The sensitivity of the GC-ECNI-MS was considerably better than that of GC/ECD. Four stepwise-designed comparative tests were also conducted on GC analysis, cleanup, and the complete method. The results showed that, according to the current state-of-the-art, coefficients of variation for the between-laboratory performance were not < 20% and were usually between 20 and 30%. In spite of separation problems, e.g., for CHB 26, which cannot be separated into a single-component peak, a 95% methyl 5% phenyl polysiloxane (CP Sil 8) column was preferred to more polar columns for the analysis of CHBs 26, 40, 41, 44, 50, and 62. CHB 62 was more difficult to determine than CHB 26 and 50. Addition of the CHBs 40, 41, and 44 to the standard set of 3 chlorobornanes (26, 50, and 62) resulted in more separation problems. A 3-step cleanup method was recommended.     

XAFS studies of anti-inflammatory dinuclear and mononuclear Zn(II) complexes of indomethacin

Zinc K-edge X-ray absorption fine structure (XAFS) experiments were performed in the solid and solution states at low temperature (10 K), on dimeric and monomeric anti-inflammatory Zn(II) complexes of indomethacin [1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-acetic acid=IndoH] of the formula [Zn2(Indo)4L2] [L=pyridine (Py), N,N-dimethylacetamide (DMA)], [Zn(Indo)2L2] [L=ethanol (EtOH), methanol (MeOH)], and Zn(II) acetate dihydrate [Zn(OAc)2(OH2)2]. The bond distances and angles obtained from multiple-scattering fits to the XAFS data of the Zn(II) dimeric complexes in the solid and solution states exhibit excellent correspondence with those obtained from single crystal diffraction studies. The Zn...Zn separations of 2.97 and 2.96 A and carboxylate group O-C-O angles of 125 degrees for powdered [Zn2(Indo)4(Py)2] and [Zn2(Indo)4(DMA)2] agree well with the XRD values of 2.969(1) and 2.9686(6) A and 125.8(4) degrees and 126.1(2) degrees, respectively. The calculated Zn-O(RCOO) and Zn-L bond distances of 2.03 and 2.04 A, or 2.02 and 1.98 A for Py or DMA complexes, respectively, also agree well with crystallographic data. The X-ray powder diffraction data on samples of the monomers exhibited additional reflections apart from those due to the crystallographically characterized cis-[Zn(eta2-O,O'-Indo)2L2], but microanalyses were consistent with this formulation. Therefore, mixed models that contained the cis complex and a second component consisting of a trans-six-coordinate complex, a five-coordinate complex, or a four-coordinate complex were used to model the XAFS. The best fits to the XAFS data were obtained with a mixture of the cis-six-coordinate complex and a four-coordinate complex containing two monodentate Indo ligands. The bond lengths for the six-coordinate structure were consistent with those determined on a single crystal, and those for the four-coordinate complexes were consistent with related four-coordinate structures with two monodentate carboxylate ligands. Dissolution of the dimer (DMA adduct) in DMF resulted in a mixture of dimer and monomer species as shown by MS XAFS fitting. This is the first time that solution structures have been determined for anti-inflammatory Zn(II) complexes, and this is an important first step in understanding the pharmacology of the complexes.     

Bubble particle heterocoagulation under turbulent conditions

An analytical model that enables the calculation of the flotation rate constant of particles as a function of particle size with, as input parameters, measurable particle, bubble, and hydrodynamic quantities has been derived. This model includes the frequency of collisions between particles and bubbles as well as their efficiencies of collision, attachment, and stability. The generalized Sutherland equation collision model and the modified Dobby-Finch attachment model developed previously for potential flow conditions were used to calculate the efficiencies of particle-bubble collision and attachment, respectively. The bubble-particle stability efficiency model includes the various forces acting between the bubble and the attached particle, and we demonstrate that it depends mainly on the relative magnitude of particle contact angle and turbulent dissipation energy. The flotation rate constants calculated with these models produced the characteristic shape of the flotation rate constant versus particle size curve, with a maximum appearing at intermediate particle size. The low flotation rate constants of fine and coarse particles result from their low efficiency of collision and low efficiencies of attachment and stability with gas bubbles, respectively. The flotation rate constants calculated with these models were compared with the experimental flotation rate constants of methylated quartz particles with diameters between 8 and 80 micro m interacting with gas bubbles under turbulent conditions in a Rushton flotation cell. Agreement between theory and experiment is satisfactory.     

Algorithms for Greechie Diagrams

We give a new algorithm for generating Greechie diagrams with arbitrary chosennumber of atoms or blocks (with 2, 3, 4, . . . atoms) and provide a computerprogram for generating the diagrams. The results show that the previous algorithmdoes not produce every diagram and that it is atleast 10⁵ times slower. We alsoprovide an algorithm and programs for checking Greechie diagram passage byequations defining varieties of orthomodular lattices and give examples fromHilbert lattices. We also discuss some additional characteristics of Greechiediagrams.     

Side-hole to anti-hole conversion in time-resolved spectral hole burning of ruby: Long-lived spectral holes due to ground state level population storage

We report time-resolved transient spectral hole burning of Verneuil-grown 20 ppm and ca. 0.6 ppm ruby (Al₂O₃:Cr³⁺) in zero field and low magnetic fields B∥c at 4 K. The hole-burning spectroscopy of the 20 ppm sample implies relatively rapid cross relaxation in the ⁴A₂ ground state on the ∼1 ms timescale both in zero field and in low magnetic fields, B∥c, up to 0.2 T. In the 0.6 ppm sample, side-hole to anti-hole conversion is observed both in zero field and in low magnetic fields. This conversion is caused by population storage in ⁴A₂ ground state levels. Spin-lattice relaxation, on the 200 ms timescale, is directly observed from the time dependence of the resonant hole and anti holes in B∥c, consistent with a very low cross-relaxation rate. However, in zero field cross relaxation in the ⁴A₂ ground state is still a significant relaxation mechanism for the 0.6 ppm sample resulting in hole decay in ∼50 ms.     

Modeling texture evolution in equal channel angular extrusion using crystal plasticity finite element models

A new approach to modeling crystallographic texture evolution in Equal Channel Angular Extrusion (ECAE) is presented in this paper. The proposed approach utilizes an elastic–viscoplastic single crystal constitutive model implemented in a finite element framework. A representative volume element of the polycrystal is subjected to boundary conditions that simulate the approximate deformation history experienced by different regions of the sample (at different through-thickness depths) in both Route A and Route C processing. The proposed approach aims to capture the influence of the complex interactions that ensue among the constituent individual crystals of a polycrystal in controlling the texture evolution in the sample, while capturing the boundary conditions inherent to ECAE deformation. The predictions from the proposed approach are compared against previously reported experimental measurements in ECAE of copper. It is observed that the proposed approach provides significantly better agreement with the measurements when compared against previously reported model predictions.     

The dynamics of gallamine: A potent neuromuscular blocker. A determination by quantum mechanics and molecular dynamics (i) in vacuo studies

The potent neuromuscular blocker, gallamine, possesses three chemically equivalent, flexible side chains, the motion of which has been proposed as important in its mode of action on the acetylcholine receptor in vivo. The flexibility of the side chains has been investigated in the present initial study by a combination of quantum mechanics and molecular dynamics on the isolated, unsolvated molecule. Net atomic charges for the gallamine molecule have been calculated using the semiempirical program MOPAC for use in the molecular dynamics simulation. The flexibility of the side chains has been shown to correlate with the range of fluctuations in torsion angles observed in the crystal structure of gallamine.