A sensitive method for the quantification of acrolein and other volatile carbonyls in ambient air

Acrolein, an unsaturated aldehyde found in both indoor and outdoor air, is considered one of the greatest noncancer health risks of all organic air pollutants. Current methods for determining acrolein often employ sorbent-filled cartridges containing a carbonyl derivatizing agent (e.g., dinitrophenylhydrazine). These methods are of limited use for unsaturated compounds due to the formation of unstable derivatives, coelution of similar compounds, long sample collection times, and ozone interferences that result in poor sensitivity, selectivity, and reproducibility. The goal of this research was to develop an analytical method for determining ppt concentrations of acrolein and other carbonyls in air with short sampling times (10 min). The method uses a mist chamber to collect carbonyls by forming water-soluble carbonyl-bisulfite adducts. The carbonyls are then liberated from the bisulfite, derivatized, and quantified by gas chromatography/electron capture negative ionization mass spectrometry. The method was applied to determine atmospheric acrolein concentrations at three sites in northern California reflecting hemispheric background concentrations, biogenic-dominated regions, and urban environments. The resulting acrolein concentrations were 0.056, 0.089, and 0.29 microg/m3, respectively, which are all above the EPA Reference Concentration of 0.02 microg/m3. The minimum detection limit of 0.012 microg/m3 is below that of other published methods. Methacrolein, methyl vinyl ketone, crotonaldehyde, glyoxal, methyl glyoxal, and benzaldehyde were also quantified.     

Mixed monolayer-protected gold nanoclusters as selective peptide extraction agents for MALDI-MS analysis

Cationic and anionic nanoparticles selectively target peptides with low and high isoelectric points, respectively. Additionally, their high surface area-to-volume ratios make these nanoparticles (approximately 2-nm core diameter) very efficient extraction and concentration agents. Upon extraction, the peptide-bound nanoparticles can be analyzed by MALDI-MS to provide highly sensitive detection of the targeted peptides. We demonstrate that MALDI-MS can detect peptide concentrations as low as 500 pM from 250-microL solutions using these nanoparticle scaffolds as extraction and concentration agents.     

Phase-stepped gauge block interferometry using a frequency-tunable visible laser diode

Frequency changes induced by bias or temperature modulation of injection diode lasers can provide an economical and effective method of applying phase-stepping interferometry to optical metrology. However, the intrinsic frequency instability of these devices limits their use in gauge block interferometry where precise and repeatable phase steps must be maintained simultaneously on two discontinuous surfaces and over relatively long path lengths. We demonstrate a method using a visible injection diode laser, the frequency of which is locked by using a Fabry-Perot interferometer. Small changes to the length of the Fabry-Perot interferometer shift the frequency of the laser producing proportional and repeatable phase steps to the gauge block interferogram. This method has been successfully implemented with a Fizeau-type gauge block interferometer with a phase measurement resolution of 0.005 lambda. The phase data are then processed to map the surface form of gauge blocks up to 100 mm in length and to objectively assess surface shape parameters.     

Effect of spurious diffraction orders in arbitrary multifoci patterns produced via phase-only holograms

We analyze the effect of spurious diffraction orders when generating functional multifoci patterns produced by illuminating a phase-only hologram with a single Gaussian beam. Using a practical device for encoding a hologram generates an undesirable zero order and high-diffraction orders at the Fourier plane. This translates to the fact that a significant fraction of the incident light does not necessarily convert to functional multifoci patterns. In most applications, the zero order can be avoided by generating foci patterns shifted off the optical axis, which further increases the amount of light distributed to spurious high-diffraction orders owing to the reduction of light directed to the desired foci pattern. We analyze the amount of light dispersed to spurious orders and show that these unwanted orders can be a major limiting factor for most applications based on arbitrary multifoci patterns.     

Organization and mobility of water in amorphous and crystalline trehalose

The disaccharide trehalose is accumulated by microorganisms, such as yeasts, and multicellular organisms, such as tardigrades, when conditions of extreme drought occur. In this way these organisms can withstand dehydration through the formation of an intracellular carbohydrate glass, which, with its high viscosity and hydrogen-bonding interactions, stabilizes and protects the integrity of complex biological structures and molecules. This property of trehalose can also be harnessed in the stabilization of liposomes, proteins and in the preservation of red blood cells, but the underlying mechanism of bioprotection is not yet fully understood. Here we use positron annihilation lifetime spectroscopy to probe the free volume of trehalose matrices; specifically, we develop a molecular picture of the organization and mobility of water in both amorphous and crystalline states. Whereas in amorphous matrices, water increases the average intermolecular hole size, in the crystalline dihydrate it is organized as a confined one-dimensional fluid in channels of fixed diameter that allow activated diffusion of water in and out of the crystallites. We present direct real-time evidence of water molecules unloading reversibly from these channels, thereby acting as both a sink and a source of water in low-moisture systems. We postulate that this behaviour may provide the overall stability required to keep organisms viable through dehydration conditions.     

Quantum dot encapsulation in viral capsids

Incorporation of CdSe/ZnS semiconductor quantum dots (QDs) into viral particles provides a new paradigm for the design of intracellular microscopic probes and vectors. Several strategies for the incorporation of QDs into viral capsids were explored; those functionalized with poly(ethylene glycol) (PEG) can be self-assembled into viral particles with minimal release of photoreaction products and enhanced stability against prolonged irradiation.     

On the shoulders of students? The contribution of PhD students to the advancement of knowledge

Using the participation in peer reviewed publications of all doctoral students in Quebec over the 2000–2007 period, this paper provides the first large scale analysis of their research effort. It shows that PhD students contribute to about a third of the publication output of the province, with doctoral students in the natural and medical sciences being present in a higher proportion of papers published than their colleagues of the social sciences and humanities. Collaboration is an important component of this socialization: disciplines in which student collaboration is higher are also those in which doctoral students are the most involved in peer-reviewed publications. In terms of scientific impact, papers co-signed by doctorate students obtain significantly lower citation rates than other Quebec papers, except in natural sciences and engineering. Finally, this paper shows that involving doctoral students in publications is positively linked with degree completion and ulterior career in research.     

Tailoring in-plane crystallographic orientation of epitaxial YBa2Cu3O7 − x thin films having perpendicular c-axis texture

Control of the in-plane crystallographic orientation of YBa₂Cu₃O_7 − x (YBCO) films on (100) MgO substrates is of significant application value due to the selective enhancement of superconducting properties. In the present work, the preparation, crystallographic and superconducting properties of YBCO films deposited on MgO substrates are reported. Crystallographic in-plane orientation was realized by means of tailoring the pulsed laser deposition conditions and the use of interfacial buffering structures. Superconductiong properties were measured for films having different in-plane orienations. The results indicate that the 0^° in-plane oriented films showed the highest current density of 1.62 MA/cm² that was attributed to the elimination of high-angle grain boudaries. Additionally, the growth mechanism of YBCO films was discussed in terms of crystallographic and thermodynamic theory.     

Ultra acidic strong cation exchange enabling the efficient enrichment of basic phosphopeptides

We present a straightforward method to enrich phosphopeptides with multiple basic residues, an under-represented class in common enrichment strategies. Our method is based on a two-dimensional strong cation exchange (SCX) strategy, operating at two different acidic pHs, enabling both separation and enrichment of different classes of phosphopeptides. The principle of enrichment is based on the change of net charge of phosphorylated peptides under strong acidic conditions in the second SCX, whereas the net charge of regular peptides remains unchanged, thus enabling separation based on net charge. Application of our tandem SCX approach to a modest amount of human cells allowed the identification of over 10,000 unique "basic" phosphopeptides of which many represent putative targets of basophilic kinases.     

Growth of high Ge content SiGe on (110) oriented Si wafers

Growth of high (above 40%) Ge content SiGe by applying silane and dichlorosilane as Si precursors on (110) Si is investigated. In the case of silane based processes Ge concentration is ~ 20% higher, whereas for dichlorosilane based processes it is ~ 30% lower on (110) Si compared to (100) Si. The morphology of the grown layers is found to be dependent on Ge concentration, layer thickness and process temperature. Use of optimized deposition parameters and adequate thickness results in high quality strained SiGe layers. Integration of high Ge content SiGe layers in multiple gate filed-effect transistor structures shows the expected differences in Ge content on the different Si planes forming Si fin. These differences can be avoided by adjusting the fin orientation on the Si wafer resulting in equal planes on the fin's top and sidewalls. When the investigated SiGe layers are incorporated in the buried channel field effect transistor structures on (110) Si wafers a significant thickening at the active windows edge is observed. It is speculated that this effect is connected with elastic SiGe relaxation caused by a non optimized process temperature.