Comparison of photophysical and colloidal properties of biocompatible semiconductor nanocrystals using fluorescence correlation spectroscopy

A number of different surface chemistries have been developed in recent years to render semiconductor nanocrystals (NCs) stable in water and biocompatible. However, most of these surface modifications affect NCs' photophysical properties, calling for a method to simultaneously monitor colloidal and fluorescence properties. Fluorescence correlation spectroscopy (FCS) combined with ensemble spectroscopic methods and Monte Carlo simulations were used to interpret and derive photophysical as well as colloidal properties of four different NC surface treatments. Using a novel FCS scheme with alternating laser excitation at two different intensities, we first ruled out influences from optical gradient forces (optical trapping). We then compared concentration of emitting particles, brightness per particle, saturation intensity, blinking (intermittency), hydrodynamic radius, and propensity for aggregation of the different bioconjugated NCs. This approach was successfully applied during the development and optimization of peptide-coated NCs.     

Analysis of Amadori compounds by high-performance cation exchange chromatography coupled to tandem mass spectrometry

High-performance cation exchange chromatography coupled to tandem mass spectrometry or electrochemical detection was found to be an efficient tool for analyzing Amadori compounds derived from hexose and pentose sugars. The method allows rapid separation and identification of Amadori compounds, while benefiting from the well-known advantages of mass spectrometry, such as specificity and sensitivity. Glucose- and xylose-derived Amadori compounds of several amino acids, such as glycine, alanine, valine, leucine/isoleucine, methionine, proline, phenylalanine, and glutamic acid, were separated or discriminated using this new method. The method is suitable for the analysis of both model reaction mixtures and food products. Fructosylglutamate was found to be the major Amadori compound in dried tomatoes (approximately 1.5 g/100 g) and fructosylproline in dried apricots (approximately 0.2 g/100 g). Reaction of xylose and glycine at 90 degrees C (pH 6) for 2 h showed rapid formation of xylulosylglycine (approximately 12 mol %, 15 min) followed by slow decrease over time. Analysis of pentose-derived Amadori compounds is shown for the first time, which represents a major breakthrough in studying occurrence, formation, and decomposition of these labile Maillard intermediates.     

Least-squares support vector machines modelization for time-resolved spectroscopy

By use of time-resolved spectroscopy it is possible to separate light scattering effects from chemical absorption effects in samples. In the study of propagation of short light pulses in turbid samples the reduced scattering coefficient and the absorption coefficient are usually obtained by fitting diffusion or Monte Carlo models to the measured data by use of numerical optimization techniques. In this study we propose a prediction model obtained with a semiparametric modeling technique: the least-squares support vector machines. The main advantage of this technique is that it uses theoretical time dispersion curves during the calibration step. Predictions can then be performed by use of data measured on different kinds of sample, such as apples.     

Analysis of liquid-phase chemical detection using guided shear horizontal-surface acoustic wave sensors

Direct chemical sensing in liquid environments using polymer-guided shear horizontal surface acoustic wave sensor platforms on 36 degrees rotated Y-cut LiTaO3 is investigated. Design considerations for optimizing these devices for liquid-phase detection are systematically explored. Two different sensor geometries are experimentally and theoretically analyzed. Dual delay line devices are used with a reference line coated with poly (methyl methacrylate) (PMMA) and a sensing line coated with a chemically sensitive polymer, which acts as both a guiding layer and a sensing layer or with a PMMA waveguide and a chemically sensitive polymer. Results show the three-layer model provides higher sensitivity than the four-layer model. Contributions from mass loading and coating viscoelasticity changes to the sensor response are evaluated, taking into account the added mass, swelling, and plasticization. Chemically sensitive polymers are investigated in the detection of low concentrations (1-60 ppm) of toluene, ethylbenzene, and xylenes in water. A low-ppb level detection limit is estimated from the present experimental measurements. Sensor properties are investigated by varying the sensor geometries, coating thickness combinations, coating properties, and curing temperature for operation in liquid environments. Partition coefficients for polymer-aqueous analyte pairs are used to explain the observed trend in sensitivity for the polymers PMMA, poly(isobutylene), poly(epichlorohydrin), and poly(ethyl acrylate) used in this work.     

Phytoremediation of effluents from aluminum smelters: a study of Al retention in mesocosms containing aquatic plants

Four mesocosms were exposed to circumneutral and aluminum (Al)-rich wastewater during two successive summers (2000, 2001). The goals of the study were to measure the bioaccumulation of dissolved Al by the aquatic plants Typha latifolia, Lemna minor, Nuphar variegatum and Potamogeton epihydrus, and to evaluate their importance in the retention of Al by the mesocosms. In 2000, inlet concentrations of total monomeric Al were reduced by 56% and 29% at the Arvida and Laterrière mesocosms, respectively, whereas in 2001 inlet dissolved Al concentrations in the inlet decreased by 40% and 33%. L. minor had the highest Al uptake rate (0.8--17 mg Al g(-1)d(-1)). However, because T. latifolia (cattails) yielded the highest biomass, it was responsible for 99% of the Al uptake, largely in its root tissue. In 2001, Al uptake by macrophytes accounted for 2--4% and 15--54% of the total Al retained by the Laterrière and Arvida mesocosms, respectively. In the Laterrière mesocosms, Al uptake by cattails could account for 12% and 18% of the dissolved Al retained by both mesocosms. In contrast, dissolved Al was not significantly reduced in the Arvida enclosures, yet cattails did accumulate Al in their roots. Further research is needed to identify the species community composition that would optimize dissolved Al retention.     

Secondary organic aerosol formation by irradiation of 1,3,5-trimethylbenzene-NOx-H2O in a new reaction chamber for atmospheric chemistry and physics

A new environmental reaction smog chamber was built to simulate particle formation and growth similar to that expected in the atmosphere. The organic material is formed from nucleation of photooxidized organic compounds. The chamber is a 27 m3 fluorinated ethylene propylene (FEP) bag suspended in a temperature-controlled enclosure. Four xenon arc lamps (16 kW total) are used to irradiate primary gas components for experiments lasting up to 24 h. Experiments using irradiations of 1,3,5-trimethylbenzene-NOx-H2O at similar input concentrations without seed particles were used to determine particle number and volume concentration wall loss rates of 0.209+/-0.018 and 0.139+/-0.070 h(-1), respectively. The particle formation was compared with and without propene.     

Reactions of hypochlorous acid with biological substrates are activated catalytically by tertiary amines

MinE is an oligomeric protein that, in conjunction with other Min proteins, is required for the proper placement of the cell division site of Escherichia coli. We have examined the self-association properties of MinE by analytical ultracentrifugation and by studies of hetero-oligomer formation in non-denaturing polyacrylamide gels. The self-association properties of purified MinE predict that cytoplasmic MinE is likely to exist as a mixture of monomers and dimers. Consistent with this prediction, the C-terminal MinE22-88 fragment forms hetero-oligomers with MinE+ when the proteins are co-expressed. In contrast, the MinE36-88 fragment does not form MinE+/MinE36-88 hetero-oligomers, although MinE36-88 affects the topological specificity of septum placement as shown by its ability to induce minicell formation when co-expressed with MinE+ in wild-type cells. Therefore, hetero-oligomer formation is not necessary for the induction of minicelling by expression of MinE36-88 in wild-type cells. The interference with normal septal placement is ascribed to competition between MinE36-88 and the corresponding domain in the complete MinE protein for a component required for the topological specificity of septal placement.     

Toxicity of Phenolic Compounds Extracted from Bark Residues of Different Ages

In Quebec, Canada, industrial bark wastelands cover several hundred hectares of land. Bark residue that has piled up for decades tends to remain free of vegetation for years. To assess the revegetation potential of such sites, we sought to determine those factors responsible for poor plant growth. Phenolic compounds from fresh to 20-year-old bark residues were extracted with four solvents and quantified by high-performance liquid chromatography (HPLC). We simulated solutions (mixtures of standard phenolic compounds) to evaluate the potential toxic effects of phenolic compounds on the rhizobial growth, germination index, plant growth, nodule number, and nitrogen fixation activity of two legume species under laboratory conditions. The concentration of individual phenolic compounds varied from none detected to 350 μg/g bark residue. The extracted phenolic compounds differed among solvents and bark residues. The highest concentration of total phenolic compounds was from fresh bark; most of these were soluble in water or 0.1 M NaOH. For older bark residues, the total phenolic content depended on solvent strength, generally in the order of 2.0 M NaOH > 0.1 M NaOH = hot water > cold water. The biological activity of the simulated bark extracts was not established with the rhizobial growth inhibition test but with the germination index and rhizobium–legume symbiosis tests. With these, the toxicity of the simulated phenolic extracts decreased from fresh to the older bark residues. Plant dry weight, nodule number, and nitrogen fixation activity of vetch (Vicia sativa L.) were less negatively affected by high concentrations of phenolics than birdsfoot trefoil (Lotus corniculatus L.), although birdsfoot trefoil grew at lower concentrations. The rhizobium–legume symbiosis has potential for revegetating bark wastelands with less than 1 year old and older bark residues.