A Collaboration-based Approach to CFD Model Validation and Uncertainty Quantification (VUQ) Using Data from a Laminar Helium Plume

An effective approach to the model VUQ process by means of direct collaboration between computationalist and experimental data analyst is proposed. An analysis of data from a laminar helium plume experiment provides a demonstration of the proposed collaboration process. Consistency analysis serves a central role in the collaboration. It takes the data and uncertainties from both analyst and computationalist and provides an objective and quantifiable measure of agreement between the two. Despite the simplicity of the laminar helium system and the computational model, certain phenomena brought to light in the collaboration process make it difficult to find quantitative agreement in the data. These phenomena include the unsteady behavior of air flow in an open room, and the presence of helium permeation to the region near the plume. Important sources of error in the simulation include uncertainty in the room temperature (295.15 to 305.15 K), uncertainty in the helium inlet velocity (0.1215 \(\frac {m}{s}\) to 0.1415 \(\frac {m}{s}\)), and uncertainty in local helium permeation (0 % to 3 % by mass.) The collaboration process allows for a better understanding of the phenomena affecting the plume and the relative sensitivies of the system to these phenomena.     

Exploitation of the Ornithine Effect Enhances Characterization of Stapled and Cyclic Peptides

A method to facilitate the characterization of stapled or cyclic peptides is reported via an arginine-selective derivatization strategy coupled with MS/MS analysis. Arginine residues are converted to ornithine residues through a deguanidination reaction that installs a highly selectively cleavable site in peptides. Upon activation by CID or UVPD, the ornithine residue cyclizes to promote cleavage of the adjacent amide bond. This Arg-specific process offers a unique strategy for site-selective ring opening of stapled and cyclic peptides. Upon activation of each derivatized peptide, site-specific backbone cleavage at the ornithine residue results in two complementary products: the lactam ring-containing portion of the peptide and the amine-containing portion. The deguanidination process not only provides a specific marker site that initiates fragmentation of the peptide but also offers a means to unlock the staple and differentiate isobaric stapled peptides.

Open image in new window

Graphical Abstract ?

     

Biotreatment of refinery spent-sulfidic caustic using an enrichment culture immobilized in a novel support matrix

Sodium hydroxide solutions are used in petroleum refining to remove hydrogen sulfide (H₂S) and mercaptans from various hydrocarbon streams. The resulting sulfide-laden waste stream is called spent-sulfidic caustic. An aerobic enrichment culture was previously developed using a gas mixture of H₂S and methylmercaptan (MeSH) as the soleenergy source. This culture has now been immobilized in a novel support matrix, DuP ont BIO-SEP^TM beads, and is used to biotreat a refinery spent-sulfidic caustic containing both inorganic sulfide and mercaptans in a continuous flow, fluidized-bed column bioreactor. Complete oxidation of both inorganic and organic sulfur to sulfate was observed with no breakthrough of H₂S and <2 ppmv of MeSH produced in the bioreactor outlet gas. Excessive buildup of sulfate (>12 g/L) in the bioreactor medium resulted in an upset condition evidenced by excessive MeSH breakthrough. Therefore, bioreactor performance was limited by the steady-state sulfate concentration. Further improvement in volumetric productivity of a bioreactor system based on this enrichment culture will be dependent on maintenance of sulfate concentrations below inhibitory levels.

     

Two Efficient and Practical Syntheses of Methyl 4-Mercaptobenzoate

Two efficient syntheses of methyl 4-mercaptobenzoate are described, one utilizing the dianion of 4-bromothiophenol, the other a S_NAr reaction starting with 4-fluorobenzonitrile.     

Semiconductor lasers and fiber lasers for fiber-optic telecommunications

Be performance characteristics of semiconductor lasers for fiber telecommunication systems will be reviewed. Modulation speed, intensity noise, singlefrequency line width, and tunability are addressed. In addition, recent results concerning the same characteristics in single-frequency, tunable, fiber lasers are reviewed and compared with the semiconductor laser.     

Reductive dechlorination of tetrachloroethylene (PCE) catalyzed by cyanocobalamin

A biomimetic system has been developed for the reductive dechlorination of tetrachloroethylene (PCE). PCE was dechlorinated to trichloroethylene (TCE) and 1,2-dichloroethylene (DCE) in the presence of dithiothreitol or Ti (III) citrate and catalytic amounts of cyanocobalamin in both homogeneous reaction mixtures and packed bed reactor systems. In packed bed reactors with Ti (III) citrate as the reductant, PCE (0.18 mM) conversion averaged 55% at residence times of 1.75 and 3.5 h. The product distribution was 94% TCE and 6% DCE at the lower residence time. DCE formation increased to 45% at the higher residence time. No reduction of PCE was observed in the absence of cyanocobalamin. This system may be useful as a means of pretreatment of halogenated aliphatic hydrocarbons in advance of biological treatment.     

Flexible Ultrathin PolyDVB/EVB Composite Membranes for the Optimization of a Lactate Sensor

An ultrathin composite membrane has been developed as the outer covering barrier in a model amperometric lactate oxidase enzyme electrode. The membrane was formed by cathodic electropolymerization of divinylbenzene/ethylvinylbenzene at the surface of a gold coated polyester support membrane. Permeability coefficients were determined for O₂ and lactate across membranes with a range of polymer thicknesses. Anionic interferents (such as ascorbate) were screened from the working electrode by the composite membrane. The composite enzyme electrode showed an increased working concentration range and extended linearity of responses in comparison to an uncoated enzyme electrode.     

epi-Aszonalenins A, B, and C from Aspergillus novofumigatus

Three new benzodiazepines have been isolated from an unusual chemotype of Aspergillus novofumigatus: epi-aszonalenins A, B, and C. The structures were elucidated by use of one- and two-dimensional NMR spectroscopic techniques and HR ESI MS. The relative configuration was established on the basis of a single crystal X-ray diffraction study of epi-aszonalenin A and the absolute configuration was determined by optical rotation comparison with the literature data. The absolute configurations of epi-aszonalenins B and C were determined by circular dichroism comparison to epi-aszonalenin A.     

A preliminary cost analysis of the biotreatment of refinery spent-sulfidic caustic

Caustics are used in petroleum refining to remove hydrogen sulfide from various hydrocarbon streams. Spent-sulfidic caustics from three refineries have been successfully biotreated on the bench and pilot scale, resulting in neutralization and removal of active Sulfides. Sulfides were completely oxidized to sulfate byThiobacillus denitrificans strain F. Microbial oxidation of sulfide produced acid, which at least partially neutralized the caustic. A commercial-scale treatment system has been designed that features a bioreactor with a suspended culture of flocculatedT. denitrificans, a settler and acid and nutrient storage and delivery systems. A cost analysis has been performed for nine cases representing a range of spent caustic sulfide and hydroxide concentrations at a base treatment rate of 10 gpm. This analysis shows that refinery spent-sulfidic caustic can be biotreated for 4-8.3￠/gal.