Vibrational action spectroscopy of the C-H and C-D stretches in partially deuterated formic acid dimer

Vibrational action spectroscopy of jet-cooled formic acid dimer measures the frequency of the C-H(D) stretching vibration and its coupling to nearby states. The action spectrum of (DCOOH)2 reveals a specific Fermi resonance between the C-D stretch and two antisymmetric combination states formed from the C-O stretch and DCO bend. A three-state deperturbation analysis shows that there is a relatively strong coupling between the fundamental vibration and each of the combination vibrations (mid R:13 cm(-1)mid R:) as well as between the combination states themselves (mid R:7 cm(-1)mid R:). This situation contrasts with that for the action spectrum of (HCOOD)2, where the C-H oscillator is isolated and not strongly coupled to other states.     

Boundary Spanners as Bridges of Student and School Discourses in an Urban Science and Mathematics High School

A key to improving urban science and mathematics education is to facilitate the mutual understanding of the participants involved and then look for strategies to bridge differences. Educators need new theoretical tools to do so. In this paper the argument is made that the concept of “boundary spanner” is such a tool. Boundary spanners are individuals, objects, media, and other experiences that link an organization to its environment. They serve critical communicative roles, such as bridges for bringing distinct discourses together, cultural guides to make discourses of the “other” more explicit, and change agents for potentially reshaping participants' discourses. This ethnographic study provides three examples of boundary spanners found in the context of an urban public high school of science, mathematics, and technology: boundary media, boundary objects, and boundary experiences. The analysis brings to the foreground students' and teachers' distinct discourses about “good student identity,”“good student work,” and “good summer experience” and demonstrates how boundary spanners shaped, were shaped by, and sometimes brought together participants' distinct discourses. An argument is made for boundary spanners' practical and theoretical utility: practically, as a tool for enhancing meaning‐making between diverse groups, and theoretically, as a heuristic tool for understanding the reproductive and transformative aspects of urban science education.     

Rheology and gelation kinetics in laponite dispersions containing poly(ethylene oxide)

We report results on the rheology of a model polymer/clay system, laponite clay particles with added poly(ethylene oxide) (PEO), focusing on the kinetics of gel formation and on molecular weight effects. We examined solutions at both pH = 7, where interparticle attractions are present and a networked gel is formed; and at pH = 10, where repulsive forces dominate and laponite forms a colloidal glass. We found that PEO of low to moderate molecular weight significantly slows down gelation and decreases the complex viscosity and elastic modulus of the dispersion by several orders of magnitude for both pH = 7 and 10. In the former case, adsorbed PEO likely forms a steric barrier to the formation of an attractive gel. In the latter case, we propose that free PEO chains in solution induce a depletion attraction between particles, preventing or slowing the formation of a colloidal glass. At higher molecular weights, PEO chains are long enough to bridge between particles and form an associative network, enhancing the viscosity and elastic modulus for both pH = 7 and 10. Finally, we have shown the critical molecular weight for transitioning between these two types of behavior scales with the interparticle distance. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 233–240, 2005     

Identification, cloning and characterization of a novel 47 kDa murine PKA C subunit homologous to human and bovine Cβ2

Background  

SCF ubiquitin ligases target numerous proteins for ubiquitin dependent proteolysis, including p27 and cyclin E. SCF and other cullin-RING ligases (CRLs) are regulated by the ubiquitin-like protein Nedd8 that covalently modifies the cullin subunit. The removal of Nedd8 is catalyzed by the Jab1/MPN domain metalloenzyme (JAMM) motif within the Csn5 subunit of the Cop9 Signalosome.     

Identification of a NBD1-binding pharmacological chaperone that corrects the trafficking defect of F508del-CFTR

Most cases of cystic fibrosis (CF) are attributable to the F508del allele of CFTR, which causes the protein to be retained in the endoplasmic reticulum (ER) and subsequently degraded. One strategy for CF therapy is to identify corrector compounds that help traffic F508del-CFTR to the cell surface. Pharmacological chaperones, or correctors that bind specifically to F508del-CFTR and restore function, would be the most promising drug development candidates, but few pharmacological chaperones exist for F508del-CFTR. Using differential scanning fluorimetry (DSF), we have surveyed corrector compounds and identified one, RDR1, which binds directly to the first nucleotide binding domain (NBD1) of F508del-CFTR. We show that RDR1 treatment partially rescues F508del-CFTR function in both cells and in an F508del-CF mouse model. Thus, RDR1 is a pharmacological chaperone of F508del-CFTR and represents a novel scaffold for drug development.     

Capabilities of HPLC with APEX-Q nebulisation ICP-MS and ESI MS/MS to compare selenium uptake and speciation of non-malignant with different B cell lymphoma lines

The formation of intracellular dimethylselenide (DMSe) as a product of exposure of non-malignant (PBMCs) and lymphoma (RL and DHL-4) cell lines to methylseleninic acid (MSA) at clinical levels is suggested here for the first time. This was achieved by analysis of cell lysates by HPLC coupled to ICP-MS via APEX-Q nebulisation, enabling limits of detection for target methyl-Se species which are up to 12-fold lower than those obtained with conventional nebulisation. Methyl-Se-glutathione (CH₃Se-SG), although detected in lysates of cells exposed to MSA, was found to be a reaction product of MSA with glutathione. This was confirmed by HPLC-ESI MS (MS) analysis of lysates of control cells (unexposed to Se) spiked with MSA. The MS/MS data obtained by collision-induced dissociation fragmentation of the ion m/z 402 (for [M+H]^{+ 80}Se) were consistent with the presence of CH₃Se-SG. Formation of DMSe was not detected by HPLC-ICP-MS in these spiked lysates, and it was found to require live cells in cell media containing MSA. Interestingly, the ratio of DMSe to CH₃Se-SG was significantly higher in lymphoma cells exposed to MSA in comparison to non-malignant cells. Moreover, maximum Se uptake levels in lymphoma cell lines seemed to be reached much earlier (after 10 min of MSA exposure) than in non-malignant cells. Finally, the GC-TOF-MS speciation data obtained for cell headspace suggested that the major Se species (dimethyldiselenide) appeared to be present in lymphoma cell headspace at significantly higher concentrations than in non-malignant cell headspace after only 10 min of exposure to MSA. Evidence for the presence of dimethylselenidesulfide in lymphoma cell headspace is also provided for the first time.     

Identification of superfluous roads in terms of sustainable military land carrying capacity and environment

A great challenge the US military land managers are often faced with is how to optimize road networks in order to maintain roads (including all roads, trails, and paths) for the purpose of military training and reducing negative impacts on environment. In this study, a methodology was developed to identify superfluous roads for being closed in terms of both sustainable military land carrying capacity and environment for Fort Riley. In this method, Geographic Information Systems (GIS), remote sensing, and landscape analysis technologies were combined to derive various spatial data layers of factors that had significant impacts on both military training and environment. The factors included maintenance cost of roads, road access area, military training intensity, soil erosion, water quality, landscape fragmentation, and noise production. The factors were quantified and normalized. A spatial multicriteria decision was then developed to obtain the weights of the factors, combine the data layers, and derive a priority map of all the roads for being closed. This map summarized the negative and positive impacts of the factors on environment and military land carrying capacity and can provide the US military land managers with useful guidelines and tools for determining superfluous roads in terms of both sustainable military training and environment. It is expected this effort can provide a method to quickly ascertain which roads are most cost-effective for being closed without hindering the mission and at the same time with benefits for environmental protection and thus provide the land managers with a comprehensive analysis and assessment of alternatives at their disposal.     

Onset of Thermal Convection in a Vertical Porous Cylinder with a Partly Conducting and Partly Penetrative Cylinder Wall

The onset of thermal convection in a vertical porous cylinder in three dimensions is investigated analytically. Top and bottom of the cylinder are set to be perfectly heat conducting and impermeable, and is uniformly heated from below. The convection problem is solved for a cylinder wall that is partly conducting and partly penetrative. The expressions for semi-conduction and semi-penetration are based on a porous medium separated from its surroundings by a thin wall. The eigenvalue problem is split into two Helmholtz equations, and the results are expressed by Bessel functions in the radial direction. Comparisons are made with existing solutions for the limit cases of a closed cylinder wall that is either conducting or insulating. Two different models are compared for the kinematic limit condition of an open boundary.     

An allelic ladder based upon reference alleles for mtDNA SNP analysis using the SNaPshot technique

The analysis of mitochondrial DNA (mtDNA) single-nucleotide polymorphisms (SNPs) using the SNaPshot technique (Applied Biosystems) is a fast and sensitive method for the reliable identification of disease-associated mtDNA SNPs, genetic ancestry mtDNA SNPs and forensically important mtDNA SNPs. The detection of many SNPs in one multiplex PCR and one subsequent multiplex minisequencing reaction is challenging for laboratories who want to establish this technique, due to the problem that there is no allelic ladder available for mtDNA SNP analysis via SNaPshot technique. Normally, the laboratory has to invent long-term testing and studies. The interpretation of false and correct alleles is up to some specialists knowing the expected and the estimated size of each allele SNP. We here present a protocol to assemble up to 84 alleles of 42 different mtDNA SNPs in an allelic ladder that is based upon reference alleles. We recommend using allelic ladders/reference alleles for SNP analysis to maintain high-quality analysis standards.     

Optimization of multiple-layer microperforated panels by simulated annealing

Sound absorption by microperforated panels (MPP) has received increasing attention the past years as an alternative to conventional porous absorbers in applications with special cleanliness and health requirements. The absorption curve of an MPP depends on four parameters: the holes diameter, the panel thickness, the perforation ratio, and the thickness of the air cavity between the panel and an impervious wall. It is possible to find a proper combination of these parameters that provides an MPP absorbing in one octave band or two, within the frequency range of interest for noise control applications. However, when a wider absorption frequency band is required, it is necessary to design multiple-layer MPP (ML-MPP). The design of an N-layers MPP depends on 4N parameters. Consequently, the tuning of an optimal ML-MPP by exhaustive search within a prescribed frequency band becomes impractical. Therefore, simulated annealing is proposed in this paper as a tool to solve the optimization problem of finding the best combination of the constitutive parameters of an ML-MPP providing the maximum average absorption within a prescribed frequency band.