Aptamer-based folding fluorescent sensor for cocaine.

We adapted in two steps a deoxyribonucleotide-based aptamer to signal the recognition of cocaine: an instability was engineered in one stem of a three-way junction that forms the cocaine-binding pocket and the resulting short stem was end labeled with a fluorophore and a quencher. In the absence of cocaine, two stems are open, but in its presence they close and the three-way junction forms. This major structural change brings fluorophore and quencher together thereby signaling the presence and concentration of ligand. The sensor is selective for cocaine over its metabolites, can operate in serum, and is useful for the screening of cocaine hydrolases.     

Influence of Numerical Cementation on Multiphase Displacement in Rough Fractures

We present an application of 3D X-ray computed microtomography for studying the influence of numerical cementation on flow in a cement-lined rough-walled fracture. The imaged fracture geometry serves as input for flow modeling using a combination of the level set and the lattice Boltzmann methods to characterize the capillary-dominated fluid displacement properties and the relative permeability of the naturally cemented fracture. We further numerically add cement to the naturally cement-lined fracture to quantify the effect of increasing cement thickness and diminishing aperture on flow properties. Pore space geometric tortuosity and capillary pressure as a function of water saturation both increase with the numerically increased fracture cement thickness. The creation of unevenly distributed apertures and cement contact points during numerical cement growth causes the wetting and non-wetting fluids to impede each other, with no consistent trends in relative permeability with increasing saturation. Tortuosity of wetting and non-wetting fluid phases exhibits none to poor correlation with relative permeability and thus cannot be used to predict it, contrary to previous findings in smoother fractures.     

Synthesis, structure, and reactivity of a new Ti-containing microporous/mesoporous material

A new class of porous, mixed phase titanosilicate materials containing a microporous TS-1 phase and a mesoporous Ti-MCM-48 phase has been successfully synthesized. A novel, one-pot synthesis method was used in which the organic templates for the mesoporous and microporous phases were added sequentially to the same reaction mixture, followed by crystallization at 150 degrees C. The gemini surfactant 18-12-18 was used to form the Ti-MCM-48 mesophase; subsequent addition of tetrapropylammonium cation (TPA+) led to the formation of TS-1. The relative amounts of the two phases within the final products were controlled by optimizing the crystallization time. Crystallization times between 12 and 50 h gave materials containing both phases, with an increasing amount of microphase formed at longer crystallization times. These materials, called "Ti-MMM-2" (microporous/mesoporous materials) were characterized using powder XRD, N2 physisorption, TEM, FTIR, DR-UV/Vis spectroscopy, and 29Si MAS NMR. In the epoxidation of cyclohexene with tert-butyl hydroperoxide (TBHP), Ti-MMM-2 samples exhibited higher catalytic activity (approximately 61%) than either TS-1 (16%) or Ti-MCM-48 (42%), with a very high selectivity (97%) for formation of cyclohexene oxide.     

Laser nitriding investigated with Mössbauer spectroscopy

The effect of the nitrogen take‐up upon irradiation of iron or steel with excimer laser pulses in air or in nitrogen atmosphere is well established. The resulting phase compositions and nitrogen depth profiles were measured by a combination of simultaneous Conversion Electron Mössbauer Spectroscopy (CEMS), Conversion X‐ray Mössbauer Spectroscopy (CXMS), and Resonant Nuclear Reaction Analysis (RNRA) as a function of the nitrogen gas pressure during irradiation. A maximum nitrogen content and a maximum fraction of the ?-nitride was found at 0.1 MPa. This result is in accordance with hardness measurements performed by the nanoindentation technique.     

Application de l'électrode sélective au plomb à la détermination de constantes d'équilibre

Chemical equilibria in lead-halide systems are studied by means of ion-selective electrodes. The stability constants of the complexes and ionic products have been determined.     

Bis- and tris(2-seleno-1-methylimidazolyl)hydroborato complexes, {[BseMe]ZnX}2(X=Cl, I), [BseMe]2Zn and [TseMe]Re(CO)3: structural evidence that the [BseMe] ligand is not merely a "heavier" version of the sulfur counterpart, [BmMe

New bidentate and tridentate ligands that feature selenium donors, namely the bis- and tris(2-seleno-1-methylimidazolyl)hydroborato ligands [BseMe] and [TseMe], have been constructed via the reaction of MBH4(M=Na, K) with 1-methylimidazole-2-selone. Comparison of the structure of {[BseMe]ZnI}2 with its sulfur counterpart, [BmMe]ZnI, demonstrates that the seleno ligand exhibits a greater tendency than the mercapto ligand to bridge two metal centers, while comparison of [TseMe]Re(CO)3 and [TseMes]Re(CO)3 indicates that the [TseMe] ligand is more electron donating and less sterically demanding than the [TseMes] ligand.     

Porcine dentin sialoprotein glycosylation and glycosaminoglycan attachments

Background  

Dentin sialophosphoprotein (Dspp) is a multidomain, secreted protein that is critical for the formation of tooth dentin. Mutations in DSPP cause inherited dentin defects categorized as dentin dysplasia type II and dentinogenesis imperfecta type II and type III. Dentin sialoprotein (Dsp), the N-terminal domain of dentin sialophosphoprotein (Dspp), is a highly glycosylated proteoglycan, but little is known about the number, character, and attachment sites of its carbohydrate moieties.     

Effect of fluorescently labeling protein probes on kinetics of protein-ligand reactions

We studied the effect of fluorescently labeling proteins on protein-ligand reactions. Unlabeled ligands (streptavidin-binding peptides and rabbit immunoglobulin G (IgG) as antigen targets) are immobilized on epoxy-functionalized glass slides. Unlabeled and Cy3-labeled protein probes from the same batch (streptavidin and goat antibodies) subsequently react with the surface-immobilized targets. By monitoring in situ the surface mass density change using an oblique-incidence reflectivity difference scanning microscope (a label-free detector), we measured k(on) and k(off) for streptavidin-peptide reactions and antibody-antigen reaction. We found that (1) equilibrium dissociation constants, defined as K(D) = k(off)/k(on), for streptavidin-peptide reactions increases by a factor of 3-4 when the solution-phase streptavidin is labeled with Cy3 dye and (2) K(D) for reactions of solution-phase goat anti-rabbit antibodies with rabbit IgG targets also change significantly when the goat antibodies are labeled with Cy3 dye.     

3D ultrasound analysis of carotid plaque volume and surface morphology

Morphological characterization of carotid plaques has been used for risk stratification and evaluation of response to therapy, evaluation of new risk factors, genetic research, and for quantifying effects of new anti-atherosclerotic therapies. We developed a 3D US system that allows detailed studies of carotid plaques in 3D. Our software includes 3D reconstruction, viewing, manual and semi-automated segmentation of carotid plaques, and surface morphology analysis to be used for quantitative tracking of plaque changes. We evaluated our plaque quantification software by examining plaque volume measurement accuracy, variability, and plaque surface morphology. We used vascular test phantoms to study segmentation accuracy, and used 48 3D US carotid plaques of patients ranging in size from 13.2 mm(3) to 544.0 mm(3) to study plaque volume measurement variability. We compared results from the semi-automated plaque measurements to the results obtained from manual measurements, which were used as the "gold" standard. We developed a surface plaque morphology quantification technique based on the segmented plaque surface curvature and used it to analyze plaques. Accuracy of plaque volume measurements for the simulated plaques ranged from 4.2% to 1.5% for volumes ranging from 68.5 mm(3) to 286 mm(3). The variability study showed that coefficients of variation in the measurement of plaque volume decreased with increasing plaque size for both inter- (90.8-3.9%) and intra-observer (70.2-3.1%) measurements over the plaque sizes measured. Surface morphology analysis showed that 1 mm ulceration could be quantified and monitored for changes over time. The automated plaque quantification approach showed a little higher intra-observer variability than the manual technique, and its performance was better for segmenting the wall than the lumen. Our results indicate that our approach is sensitive tool and can be used in studies of plaque progression and regression as it relates to atherosclerosis treatment effects and can be used effectively in longitudinal studies for direct measurement carotid plaque volume.