Investigation of copper oxide impregnants prepared from various precursors for respirator carbons

Copper oxide impregnated activated carbon was prepared by three methods and studied as a respirator carbon. Using techniques such as dynamic flow testing, X-ray diffraction (XRD), thermal analysis, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX), copper oxide impregnants, derived from different sources such as basic copper carbonate (Cu₂CO₃(OH)₂), copper nitrate (Cu(NO₃)₂) and copper chloride (CuCl₂) reacted with sodium hydroxide (NaOH), have been studied. Dynamic flow tests performed using sulfur dioxide (SO₂), ammonia (NH₃) and hydrogen cyanide (HCN) challenge gases allow the determination of the stoichiometric ratio of reaction (SRR) between challenge gas and impregnant. Thermal gravimetric analysis experiments showed that an inert heating environment was required when thermally decomposing the Cu(NO₃)₂ impregnant to CuO to avoid damaging the activated carbon substrate. SEM has been used to investigate dispersal and particle size of the impregnant on the activated carbon. XRD permits the identification of crystalline and amorphous phases as well as the grain size of the impregnant. XRD analysis of samples before and after exposure to SO₂ has allowed the active impregnant in SO₂ adsorption to be identified. The relationship between SRR, impregnant loading and grain size is discussed. Methods to improve impregnant distribution are presented and their impact discussed.     

Spanwise variations in nominally two-dimensional rough-wall boundary layers

Laboratory experiments have been conducted in two separate boundary layer facilities to investigate steady spanwise variations in mean velocity discovered during studies of developing flows over regular arrays of large roughness elements. Regular spanwise variation was found with a steady wavelength, moderated by the growing boundary layer, which was an integer multiple of the repeating unit of roughness. Amplitude variations greater than ±5% in the mean were found over the roughness and greater than ±10% in turbulence quantities. Due to the dominating nature of this phenomena throughout the layer, care should be taken in undertaking local measurements aimed at identifying flow variations caused by roughness heterogeneity.     

Determination of MDL 201,012 at femtomole/millilitre levels in human plasma by liquid chromatography with electrochemical detection.

A sensitive and selective liquid chromatographic method to quantitate MDL 201,012 in human plasma was developed and validated. MDL 201,012 (I), diethyl-MDL 201,012 (internal standard, II) and desmethyldiol-MDL 201,012 (masking agent, III) were isolated from basified plasma (2 mL) by solid phase extraction using Bond-Elut C-18 cartridges. Endogenous components were selectively removed prior to eluting the analytes from the sorbent. Components were separated using on-line LC column switching with a cyanopropyl precolumn and a phenyl analytical column. The analytical column effluent was monitored electrochemically at a glassy carbon electrode at a potential of +1025 mV vs. Ag/AgCl. Peak-height ratios were proportional to the amount of MDL 201,012 added to plasma over the range 125-7500 pg/mL MDL 201,012. Absolute recovery of MDL 201,012 from human plasma was > 94% across the calibration range. The minimum quantitation limit was 125 pg/mL. Assay precision (%RSD) ranged from 5.2 to 13% based on the analysis of quality control standards containing 125, 250, 500, 1000, 2500, 5000 and 7500 pg/mL MDL 201,012. Corresponding assay accuracy (% relative error) was +/- 8.5%. The method has been successfully used to quantitate MDL 201,012 in samples from acute dose tolerance studies in human volunteers.     

Clustering Rules: A Comparison of Partitioning and Hierarchical Clustering Algorithms

Previous research has resulted in a number of different algorithms for rule discovery. Two approaches discussed here, the ‘all-rules’ algorithm and multi-objective metaheuristics, both result in the production of a large number of partial classification rules, or ‘nuggets’, for describing different subsets of the records in the class of interest. This paper describes the application of a number of different clustering algorithms to these rules, in order to identify similar rules and to better understand the data.     

Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5 ng to 5 μg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2 ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer.     

Energy transfer between conjugated polyelectrolytes in layer-by-layer assembled films

We present a study of Fo?rster resonance energy transfer (FRET) between two emissive conjugated polyelectrolytes (CPEs) in layer-by-layer (LbL) self-assembled films as a means of examining their organization and architecture. The two CPEs are a carboxylic acid functionalized polyfluorene (PFl-CO(2)) and thienylene linked poly(phenylene ethynylene) (PPE-Th-CO(2)). The PFl-CO(2) presents a maximum emission at 418 nm, while the PPE-Th-CO(2) has an absorption λ(max) centered at 431 nm, in sufficient proximity for effective FRET. Several LbL films have been constructed using varied concentrations of the deposition solutions and identity of the buffer layers separating the two emissive layers, using a system of either weak polyelectrolytes, poly(allylamine hydrochloride) (PAH)/poly(sodium methacrylate) (PMA), or strong polyelectrolytes, poly(diallylammonium chloride) (PDDA)/poly(styrene sulfonate) sodium (PSS). The efficiency of FRET has been monitored using fluorescence spectroscopy. Initially, the fluorescence of the PFl-CO(2) (E(g) ～ 3.0 eV), which emits at 420 nm, is quenched by the lower band gap PPE-Th-CO(2) (E(g) ～ 2.5 eV). For films using the PAH/PMA system as buffer bilayers and deposited from 1 mM solutions, the PFl-CO(2) fluorescence is progressively recovered as the number of intervening buffer bilayers is increased. Ellipsometry measurements indicate that energy transfer between the two emissive layers is efficient to a distance of ca. 7 nm.     

Use of engineered unique cysteine residues to facilitate oriented coupling of proteins directly to a gold substrate

A prerequisite for any "lab on a chip" device that utilizes an electrical signal from the sensor protein is the ability to attach the protein in a specific orientation onto a conducting substrate. Here, we demonstrate the covalent attachment to a gold surface of light-harvesting membrane proteins, from Rhodobacter sphaeroides, via cysteine (Cys) residues engineered on either the cytoplasmic or periplasmic face. This simple directed attachment is superior in its ability to retain light-harvesting complex (LHC) function, when compared to a similar attachment procedure utilizing a self-assembled monolayer on gold. LH 1 has previously been observed to have superior photostability over LH 2 (Magis et al. [2010] Biochim. Biophys. Acta, 1798, 637-645); this characteristic is maintained even with the introduction of Cys residues.