Publications by authors named "Michael Barclay"

Hydroxyl radicals (∙OH) are powerful oxidizing species formed naturally in the environment or artificially produced to destroy contaminants in water treatment facilities. Their short lifetime and high reactivity, however, present a significant challenge to quantifying their concentration in solution. Herein, we developed a novel method to accurately measure the steady-state ∙OH concentration and total ∙OH dose produced during the UV photolysis of hydrogen peroxide (HO) by monitoring the loss of salicylic acid (SA).

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Building energy consumption accounts for 30%-45% of the global energy demand. With an ever-increasing world population, it has now become essential to minimize the energy consumption for the future of the environment. One of the most crucial aspects in this regard is the utilization of sensing and environmental monitoring technologies in buildings as these technologies provide stakeholders, such as owners, designers, managers, and occupants, with important information regarding the energy performance, safety and cost-effectiveness of the building.

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We present a combined theoretical and experimental study on the ionization and primary fragmentation channels of the mono-halogenated biphenyls; 2-chlorobiphenyl, 2-bromobiphenyl and 2-iodobiphenyl. The ionization energies (IEs) of the 2-halobiphenyls and the appearance energies (AEs) of the principal fragments are determined through electron impact ionization, while quantum mechanical calculations at the coupled cluster level of theory are used to elucidate the observed processes and the associated dynamics. The primary fragmentation channels are the direct loss of the halogen upon ionization, the loss of the respective hydrogen halides (HX) as well as loss of the hydrogen halide and an additional hydrogen.

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The determination of the negative ion yield of 2'-chloro-1,1'-biphenyl (2-Cl-BP), 2'-bromo-1,1'-biphenyl (2-Br-BP) and 2'-iodo-1,1'-biphenyl (2-I-BP) upon dissociative electron attachment (DEA) at an electron energy of 0 eV revealed cross section values that were more than ten times higher for iodide loss from 2-I-BP than for the other halogenides from the respective biphenyls (BPs). Comparison with dissociative ionization mass spectra shows that the ratio of the efficiency of electron impact ionization induced fragmentation of 2-I-BP, 2-Br-BP, and 2-Cl-BP amounts to approximately 1:0.7:0.

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The ability of electrons and atomic hydrogen (AH) to remove residual chlorine from PtCl deposits created from -Pt(CO)Cl by focused electron beam induced deposition (FEBID) is evaluated. Auger electron spectroscopy (AES) and energy-dispersive X-ray spectroscopy (EDS) measurements as well as thermodynamics calculations support the idea that electrons can remove chlorine from PtCl structures via an electron-stimulated desorption (ESD) process. It was found that the effectiveness of electrons to purify deposits greater than a few nanometers in height is compromised by the limited escape depth of the chloride ions generated in the purification step.

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We determine p53 protein abundances and cell to cell variation in two human cancer cell lines with single cell resolution, and show that the fractional width of the distributions is the same in both cases despite a large difference in average protein copy number. We developed a computational framework to identify dominant mechanisms controlling the variation of protein abundance in a simple model of gene expression from the summary statistics of single cell steady state protein expression distributions. Our results, based on single cell data analysed in a Bayesian framework, lends strong support to a model in which variation in the basal p53 protein abundance may be best explained by variations in the rate of p53 protein degradation.

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A lack of synthetic control and reproducibility during vertically aligned carbon nanotube (CNT) synthesis has stifled many promising applications of organic nanomaterials. Oxygen-containing species are particularly precarious in that they have both beneficial and deleterious effects and are notoriously difficult to control. Here, we demonstrated diatomic oxygen's ability, independent of water, to tune oxide-supported catalyst thin film dewetting and influence nanoscale (diameter and wall number) and macro-scale (alignment and density) properties for as-grown vertically aligned CNTs.

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The elementary processes associated with electron beam-induced deposition (EBID) and post-deposition treatment of structures created from three metal(II)(hfac)2 organometallic precursors (metal = Pt, Pd, Cu; hfac = CF3C(O)CHC(O)CF3) have been studied using surface analytical techniques. Electron induced reactions of adsorbed metal(II)(hfac)2 molecules proceeds in two stages. For comparatively low electron doses (doses <1 × 10(17) e(-)/cm(2)) decomposition of the parent molecules leads to loss of carbon and oxygen, principally through the formation of carbon monoxide.

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Article Synopsis
  • * The EGFP protein assay can detect fewer than 30 EGFP proteins, with a dynamic range over five orders of magnitude, while the antibody sandwich assay identifies around 21 p53 proteins, achieving a range greater than three orders of magnitude.
  • * Our methods effectively allow for retrospective data calibration, enabling determination of absolute protein copy numbers at the single cell level in two types of human cancer cells.
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Measuring protein expression in single cells is the basis of single cell proteomics. The sensitivity and dynamic range of a single cell immunoassay should ideally be such that proteins that are expressed between 1-10(6) copies per cell can be detected and counted. We have investigated the effect of miniaturizing antibody microarrays by reducing capture spot sizes from 100 μm to 15 μm using dip-pen nanolithography.

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Tungsten hexacarbonyl (W(CO)(6)) is frequently used as an organometallic precursor to create metal-containing nanostructures in electron beam induced deposition (EBID). However, the fundamental electron stimulated reactions responsible for both tungsten deposition and the incorporation of carbon and oxygen atom impurities remain unclear. To address this issue we have studied the effect of 500 eV incident electrons on nanometer thick films of W(CO)(6) under Ultra-High Vacuum (UHV) conditions.

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A detailed experimental and theoretical study has been undertaken of the UV photofragmentation spectroscopy of the alkaline earth metal dications Mg(2+), Ca(2+), and Sr(2+) complexed with pyridine and 4-methyl pyridine (4-picoline). The ion complexes have been prepared using the pick-up technique and held in an ion trap where their internal temperature has been reduced to <150 K. Exposure of the trapped ions to tunable UV laser radiation leads to the appearance of photofragments with intensities that show significant variation as a function of wavelength.

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