Feasibility of low-voltage cathodic electroluminescence at oxide-covered aluminum electrodes for trace metal determinations in aqueous solutions

Metal-catalyzed electroluminescence is generated at an oxide-covered aluminum electrode during the reduction of oxygen, potassium peroxodisulfate, and especially hydrogen peroxide in aqueous solutions. The feasibility of this electroluminescence for the determination of copper (5 × 10^?9 M) and thallium (> 10^?10 M) is demonstrated.     

Electrokinetic characterization of poly(dimethylsiloxane) microchannels

This paper characterizes the basic electrokinetic phenomena occurring within native poly(dimethylsiloxane) (PDMS) microchannels. Using simple buffers and current measurements, current density and electroosmosis data were determined in trapezoidal, reversibly sealed PDMS/PDMS and hybrid PDMS/glass channels with a cross-sectional area of 1035.5 microm(2) and about 6 cm length. This data was then compared to that obtained in an air-thermostated 50 microm inner diameter (1963.5 microm(2) cross-sectional area) fused-silica (FS) capillary of 70 cm length. Having a pH 7.8 buffer with an ionic strength (I) of 90 mM, Ohms's law was observed in the microchannels with electric field strengths of up to about 420 V/cm, which is about twice as high as for the FS capillary. The electroosmotic mobility (micro(EO)) in PDMS and FS is shown to exhibit the same general dependences on I and pH. For all configurations tested, the experimentally determined micro(EO) values were found to correlate well with the relationship micro(EO) = a + b log(I), where a and b are coefficients that are determined via nonlinear regression analysis. Electroosmotic fluid pumping in native PDMS also follows a pH dependence that can be estimated with a model based upon the ionization of silanol. Compared to FS, however, the magnitude of the electroosmotic flow in native PDMS is 50-70% smaller over the entire pH range and is difficult to maintain at acidic pH values. Thus, the origin of the negative charge at the inner wall of PDMS, glass, and FS appears to be similar but the density is lower for PDMS than for glass and FS.     

Heterogeneous and homogeneous electrochemiluminoimmunoassays of hTSH at disposable oxide-covered aluminum electrodes

Heterogeneous and homogeneous immunoassays of human thyroid stimulating hormone (hTSH) were developed on immunometric basis using aromatic Tb(III) chelates as electrochemiluminescent labels and varied types of disposable oxide-covered aluminum electrodes as the solid phase of the immunoassays. The long luminescence lifetime of the present labels allows the use of time-resolved electrochemiluminescence detection and provide the low detection limits of these labels and, thus, sensitive immunoassays. The primary antibody of immunometric immunoassays was coated upon aluminum oxide surface by physical absorption. In homogeneous immunoassays using 66 μl cell and 15 min incubation time, a linear calibration range of 0.25-324 μU/ml was obtained by applying only a single cathodic excitation pulse in the detection step of the assay.     

Rapid Autoxidation Forms Highly Oxidized RO2 Radicals in the Atmosphere

Gas‐phase oxidation routes of biogenic emissions, mainly isoprene and monoterpenes, in the atmosphere are still the subject of intensive research with special attention being paid to the formation of aerosol constituents. This laboratory study shows that the most abundant monoterpenes (limonene and α‐pinene) form highly oxidized RO₂ radicals with up to 12 O atoms, along with related closed‐shell products, within a few seconds after the initial attack of ozone or OH radicals. The overall process, an intramolecular ROO→QOOH reaction and subsequent O₂ addition generating a next R′OO radical, is similar to the well‐known autoxidation processes in the liquid phase (QOOH stands for a hydroperoxyalkyl radical). Field measurements show the relevance of this process to atmospheric chemistry. Thus, the well‐known reaction principle of autoxidation is also applicable to the atmospheric gas‐phase oxidation of hydrocarbons leading to extremely low‐volatility products which contribute to organic aerosol mass and hence influence the aerosol–cloud–climate system.     

The energy of the spin-glass state of a binary mixture at T = 0 and its variational properties

In the random-bond model of Ising spins, the concept of a multiple-bond distribution of effective field was introduced in the pair approximation. The integral equation for a single-bond distribution was derived intuitively. The variational energy at T = 0 is expressed in terms of two parameters μ and η where μ is the probability of zero effective field in the single-bond distribution and η is the magnetization per spin. For η = 0, the energy of the spin-glass state corresponds to a local minimum as a function of μ, for an even z (number of the nearest neighbours) and to an inflection point for an odd z. It was shown that the spin-glass state corresponds to a local minimum with respect to μ and η for z = 4, to an inflection point with respect to μ and a local minimum with respect to η for z = 3. It is conjectured that the maximum of the energy of the spin-glass state of Sherrington and Kirkpatrick is attributed not to the replica method, but to the mean field approximation. Stationary properties of the energy as a function of both μ and η were examined in detail.     

The contribution of high frequencies to human brain activity underlying horizontal localization of natural spatial sounds

Background  

In the field of auditory neuroscience, much research has focused on the neural processes underlying human sound localization. A recent magnetoencephalography (MEG) study investigated localization-related brain activity by measuring the N1m event-related response originating in the auditory cortex. It was found that the dynamic range of the right-hemispheric N1m response, defined as the mean difference in response magnitude between contralateral and ipsilateral stimulation, reflects cortical activity related to the discrimination of horizontal sound direction. Interestingly, the results also suggested that the presence of realistic spectral information within horizontally located spatial sounds resulted in a larger right-hemispheric N1m dynamic range. Spectral cues being predominant at high frequencies, the present study further investigated the issue by removing frequencies from the spatial stimuli with low-pass filtering. This resulted in a stepwise elimination of direction-specific spectral information. Interaural time and level differences were kept constant. The original, unfiltered stimuli were broadband noise signals presented from five frontal horizontal directions and binaurally recorded for eight human subjects with miniature microphones placed in each subject's ear canals. Stimuli were presented to the subjects during MEG registration and in a behavioral listening experiment.     

Determination of organic compounds from wood combustion aerosol nanoparticles by different gas chromatographic systems and by aerosol mass spectrometry

Organic compounds in atmospheric nanoparticles have an effect on human health and the climate. The determination of these particles is challenged by the difficulty of sampling, the complexity of sample composition, and the trace-level concentrations of the compounds. Meeting the challenge requires the development of sophisticated sampling systems for size-resolved particles and the optimization of sensitive, accurate and simple analytical techniques and methods. A new sampling system is proposed where particles are charged with a bipolar charger and size-segregated with a differential mobility analyzer. This system was successfully used to sample particles from wood pyrolysis with particle sizes 30–100 nm. Particles were analyzed by four techniques: comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry, gas chromatography–time-of-flight mass spectrometry, gas chromatography–quadrupole mass spectrometry, and aerosol mass spectrometry (aerosol MS). In the chromatographic techniques, particles were collected on a filter and analyzed off-line after sample preparation, whereas in the aerosol MS, particle analysis was performed directly from the particle source. Target compounds of the samples were polyaromatic hydrocarbons and n-alkanes. The analytical techniques were compared and their advantages and disadvantages were evaluated. The sampling system operated well and target compounds were identified in low concentrations.     

Comparison of quartz and Teflon filters for simultaneous collection of size-separated ultrafine aerosol particles and gas-phase zero samples

In this research, the two most common filter media, quartz and Teflon, were tested to obtain information about the possible adsorption of gas-phase compounds onto filters during long sample collection of atmospheric aerosols. Particles of nanometer-size for off-line chemical characterization were collected using a recently introduced differential mobility analyzer for size separation. Samples were collected at an urban site (Helsinki, SMEARIII station) during spring 2010. Sampling time was 4 to 10 days for particles 50, 40, or 30 nm in diameter. Sample air flow was 4 L/min. The sampling setup was arranged so that two samples were obtained for each sampling period almost simultaneously: one containing particles and adsorbed gas-phase compounds and one containing adsorbed gas-phase compounds only. Filters were extracted and analyzed for the presence of selected carboxylic acids, polyols, nitrogen-containing compounds, and aldehydes. The results showed that, in quartz filter samples, gas-phase adsorption may be responsible for as much as 100% of some compound masses. Whether quartz or Teflon, simultaneous collection of gas-phase zero samples is essential during the whole sampling period. The dependence of the adsorption of gas-phase compounds on vapor pressure and the effect of adsorption on the deposited aerosol layer are discussed.