Redox magnetohydrodynamic enhancement of stripping voltammetry: toward portable analysis using disposable electrodes, permanent magnets, and small volumes

The use of redox magnetohydrodynamics (MHD) to enhance the anodic stripping voltammetry (ASV) response of heavy metals has been investigated, with respect to achieving portability: disposable electrodes consisting of screen-printed carbon (SPC) on a low temperature co-fired ceramic (LTCC) substrate, small volumes, and permanent magnets. The analytes tested (Cd(2+), Cu(2+), and Pb(2+)) were codeposited on SPC with Hg(2+) to form a Hg thin film electrode. High concentrations of Fe(3+) were used to produce a high cathodic current which generates a significant Lorentz force in the presence of a magnetic field. This Lorentz force induces solution convection during the deposition step, enhancing the mass transport of analytes to the electrode and increasing their preconcentrated quantity in the mercury thin film. Therefore, larger ASV peaks and improved sensitivities are obtained, compared to analyses performed without a magnet. The effects on ASV signal of varying Hg(2+) concentration (0.10 and 1.0 mM), deposition time (10-600 s), and electrode surface roughness were investigated. In addition, analyses were performed using a real lake water matrix. By using the disposable LTCC-SPC working electrodes in small volumes (150 microL) and with small permanent magnets (0.78 T), peak areas were increased by 75% when compared to the signal obtained in the absence of a magnetic field. A limit of detection of 25 nM for Cd(2+) was observed with only a 1 min preconcentration time.     

Evaluation of two-beam fluorescence cross correlation spectroscopy for electrophoretic analysis of protein digests

In this report, we evaluate experimentally and through the use of simulations and calculations the possibility of using 2-beam fluorescence cross correlation spectroscopy (2BFCCS) for the multicomponent electrophoretic analysis of peptides. The concept described has potential as a high throughput, extraordinarily sensitive means of identifying proteins and accelerating proteome studies. We present Monte Carlo simulation methods and results using them that help in understanding the capabilities and limitations of 2BFCCS for protein identification. We have calculated the expected pH dependent mobility and resultant 2BFCCS fingerprint spectra for a randomly selected subset of the peptides present upon digestion of horse myoglobin by trypsin. We demonstrate experimentally the multicomponent analysis of a mixture containing a fluorescently labeled peptide and a free fluorophore. We also demonstrate experimentally the ability to measure migration rates of dilute, single-fluorophore species over more than 2 orders of magnitude in linear velocity (between 4.2 mm s(-1) and 640 mm s(-1)).     

A Collaboration-based Approach to CFD Model Validation and Uncertainty Quantification (VUQ) Using Data from a Laminar Helium Plume

An effective approach to the model VUQ process by means of direct collaboration between computationalist and experimental data analyst is proposed. An analysis of data from a laminar helium plume experiment provides a demonstration of the proposed collaboration process. Consistency analysis serves a central role in the collaboration. It takes the data and uncertainties from both analyst and computationalist and provides an objective and quantifiable measure of agreement between the two. Despite the simplicity of the laminar helium system and the computational model, certain phenomena brought to light in the collaboration process make it difficult to find quantitative agreement in the data. These phenomena include the unsteady behavior of air flow in an open room, and the presence of helium permeation to the region near the plume. Important sources of error in the simulation include uncertainty in the room temperature (295.15 to 305.15 K), uncertainty in the helium inlet velocity (0.1215 \(\frac {m}{s}\) to 0.1415 \(\frac {m}{s}\)), and uncertainty in local helium permeation (0 % to 3 % by mass.) The collaboration process allows for a better understanding of the phenomena affecting the plume and the relative sensitivies of the system to these phenomena.     

Travelling‐wave ion mobility mass spectrometry and negative ion fragmentation of hybrid and complex N‐glycans

Nitrogen collisional cross sections (CCSs) of hybrid and complex glycans released from the glycoproteins IgG, gp120 (from human immunodeficiency virus), ovalbumin, α1‐acid glycoprotein and thyroglobulin were measured with a travelling‐wave ion mobility mass spectrometer using dextran as the calibrant. The utility of this instrument for isomer separation was also investigated. Some isomers, such as Man₃GlcNAc₃ from chicken ovalbumin and Man₃GlcNAc₃Fuc₁ from thyroglobulin could be partially resolved and identified by their negative ion fragmentation spectra obtained by collision‐induced decomposition (CID). Several other larger glycans, however, although existing as isomers, produced only asymmetric rather than separated arrival time distributions (ATDs). Nevertheless, in these cases, isomers could often be detected by plotting extracted fragment ATDs of diagnostic fragment ions from the negative ion CID spectra obtained in the transfer cell of the Waters Synapt mass spectrometer. Coincidence in the drift times of all fragment ions with an asymmetric ATD profile in this work, and in the related earlier paper on high‐mannose glycans, usually suggested that separations were because of conformers or anomers, whereas symmetrical ATDs of fragments showing differences in drift times indicated isomer separation. Although some significant differences in CCSs were found for the smaller isomeric glycans, the differences found for the larger compounds were usually too small to be analytically useful. Possible correlations between CCSs and structural types were also investigated, and it was found that complex glycans tended to have slightly smaller CCSs than high‐mannose glycans of comparable molecular weight. In addition, biantennary glycans containing a core fucose and/or a bisecting GlcNAc residue fell on different mobility‐m/z trend lines to those glycans not so substituted with both of these substituents contributing to larger CCSs. Copyright © 2016 John Wiley & Sons, Ltd.     

Charged behaviour from neutral ligands: synthesis and properties of N-heterocyclic pseudo-amides

Deprotonation of the 1-isopropyl-3-(phenylamino)pyridin-1-ium iodide gives the corresponding neutral betaine, which is formalised as a pyridinium-amido ligand when coordinated to a metal. Spectroscopic, structural and theoretical methods have been used to investigate the metal-ligand bonding, ligand dynamics and electron distribution. Collectively, the data show that the ligand can be characterised as a pseudo-amide and is a strong donor akin to alkyl phosphines and N-heterocyclic carbenes. Furthermore, rotation about both N substituent C-N bonds occurs, which is in contrast to the two alternative pyridinium positional isomers that exhibit neutral resonance structures. For comparison, compounds and complexes derived from norharman were prepared, which contain an additional C-C bond supporting conjugation and the accessibility of a neutral resonance structure. Notwithstanding the formal neutral structure, norharman-derived ligands are comparably strong donors, and have the additional advantage of exhibiting stability to dioxygen and water.     

Selective photochemistry at stereogenic metal and ligand centers of cis-[Ru(diphosphine)2(H)2]: preparative, NMR, solid state, and laser flash studies

Three ruthenium complexes Λ-[cis-Ru((R,R)-Me-BPE)(2)(H)(2)] Λ-R,R-Ru1H(2), Δ-[cis-Ru((S,S)-Me-DuPHOS)(2)(H)(2)] Δ-S,S-Ru2H(2), and Λ-[cis-Ru((R,R)-Me-DuPHOS)(2)(H)(2)] Λ-R,R-Ru2H(2) (1 = (Me-BPE)(2), 2 = (Me-DuPHOS)(2)) were characterized by multinuclear NMR and CD spectroscopy in solution and by X-ray crystallography. The chiral ligands allow the full control of stereochemistry and enable mechanistic studies not otherwise available. Oxidative addition of E-H bonds (E = H, B, Si, C) was studied by steady state and laser flash photolysis in the presence of substrates. Steady state photolysis shows formation of single products with one stereoisomer. Solid state structures and circular dichroism spectra reveal a change in configuration at ruthenium for some Δ-S,S-Ru2H(2)/Λ-R,R-Ru2H(2) photoproducts from Λ to Δ (or vice versa) while the configuration for Λ-R,R-Ru1H(2) products remains unchanged as Λ. The X-ray structure of silyl hydride photoproducts suggests a residual H(1)···Si(1) interaction for Δ-[cis-Ru((R,R)-Me-DuPHOS)(2)(Et(2)SiH)(H)] and Δ-[cis-Ru((R,R)-Me-DuPHOS)(2)(PhSiH(2))(H)] but not for their Ru(R,R-BPE)(2) analogues. Molecular structures were also determined for Λ-[cis-Ru((R,R)-Me-BPE)(2)(Bpin)(H)], Λ-[Ru((S,S)-Me-DuPHOS)(2)(η(2)-C(2)H(4))], Δ-[Ru((R,R)-Me-DuPHOS)(2)(η(2)-C(2)H(4))], and trans-[Ru((R,R)-Me-DuPHOS)(2)(C(6)F(5))(H)]. In situ laser photolysis in the presence of p-H(2) generates hyperpolarized NMR spectra because of magnetically inequivalent hydrides; these experiments and low temperature photolysis with D(2) reveal that the loss of hydride ligands is concerted. The reaction intermediates [Ru(DuPHOS)(2)] and [Ru(BPE)(2)] were detected by laser flash photolysis and have spectra consistent with approximate square-planar Ru(0) structures. The rates of their reactions with H(2), D(2), HBpin, and PhSiH(3) were measured by transient kinetics. Rate constants are significantly faster for [Ru(BPE)(2)] than for [Ru(DuPHOS)(2)] and follow the substrate order H(2) > D(2) > PhSiH(3) > HBpin.     

On the Energy of Distributions, with Application to the Quaternionic Hopf Fibrations

 The energy of an oriented q-distribution ? in a compact oriented manifold M is defined to be the energy of the section of the Grassmannian manifold of oriented q-planes in M induced by ?. In the Grassmannian, the Sasaki metric is considered. We show here a condition for a distribution to be a critical point of the energy functional. In the spheres, we see that Hopf fibrations are critical points. Later, we prove the instability for these fibrations.     

On the Energy of Distributions, with Application to the Quaternionic Hopf Fibrations

 The energy of an oriented q-distribution ? in a compact oriented manifold M is defined to be the energy of the section of the Grassmannian manifold of oriented q-planes in M induced by ?. In the Grassmannian, the Sasaki metric is considered. We show here a condition for a distribution to be a critical point of the energy functional. In the spheres, we see that Hopf fibrations are critical points. Later, we prove the instability for these fibrations. (Received 30 December 2000; in revised form 11 April 2001)     

B3LYP calculations on bishomoaromaticity in substituted semibullvalenes*

B3LYP/6‐31G* calculations on the degenerate rearrangements of substituted semibullvalenes spuriously predict the relative enthalpies of the bishomoaromatic TSs to be lower than the experimental values. However, the calculations do make the useful and experimentally testable prediction that the two cyano and two phenyl substituents in 2,6‐dicyano‐4,8‐diphenylsemibullvalene ( 9d ) are more likely than four cyano substituents in 2,4,6,8‐tetracyanosemibullvalene ( 9f ) or the four phenyl substituents in 2,4,6,8‐tetraphenylsemibullvalene ( 9g ) to produce a semibullvalene that has a bishomoaromatic equilibrium geometry in the gas phase. The major reason for the surprising finding that 9d is more likely to be bishomoaromatic than 9g is shown to be steric interactions between the phenyl groups at C‐2 and C‐8 and at C‐4 and C‐6 in bishomoaromatic structure 10g . These interactions inhibit the conjugative stabilization of 10g ; but they are absent in bishomoaromatic structure 10d , where cyano groups replace the phenyl groups at C‐2 and C‐6 in 10g . © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1565–1573, 2001     

High-field MRS studies in brain slices

We are applying multi-nuclear high-field (500 MHz) MR spectroscopy of metabolising whole tissue preparations of the mammalian brain to studies on individual components of convulsions, which include prolonged depolarization, metabolic deprivation, and the effects of excitotoxins. The responses of glial cells and neurones can be partially distinguished by following labelling patterns of metabolic intermediates from ¹³C-labelled glucose or acetate (which enters only glial cells). This approach clearly confirmed our earlier indications that the metabolic response to depolarization (40 mM extracellular K⁺) occurs essentially in glial cells. Some evidence for metabolic shuttling between glia and neurones was obtained from the changes in C3/C4 ratios of glutamate and glutamine, and the C2/C3 of GABA. Mechanisms for metabolic support of neurones by glia may be of importance in neuronal protection under such metabolic stress as occurs in epilepsy. Changes in free intracellular divalent cations ([Ca²⁺]_i and [Zn²⁺]_i) were monitored using the ¹⁹F-MRS indicator, 5FBAPTA. Large increases in [Ca²⁺]_i and decreases in PCr were produced by excitotoxins (glutamate and NMDA), depolarization or ischaemia, but intracellular Zn²⁺ appeared only after exposure to the excitotoxins. The NMDA receptor blocker, MK801, removed all of the responses to NMDA, but only prevented the appearance of Zn²⁺ observed with glutamate. These results indicate that the damage caused to neurones by such insults as convulsions is not due simply to the presence of excessive excitotoxic glutamate.