Vorticity transformation in high Karlovitz number premixed flames

To better understand the two-way coupling between turbulence and chemistry, the changes in turbulence characteristics through a premixed flame are investigated. Specifically, this study focuses on vorticity, ω, which is characteristic of the smallest length and time scales of turbulence, analyzing its behavior within and across high Karlovitz number (Ka) premixed flames. This is accomplished through a series of direct numerical simulations (DNS) of premixed n-heptane/air flames, modeled with a 35-species finite-rate chemical mechanism, whose conditions span a wide range of unburnt Karlovitz numbers and flame density ratios. The behavior of the terms in the enstrophy, ω^2 = ω ⋅ ω, transport equation is analyzed, and a scaling is proposed for each term. The resulting normalized enstrophy transport equation involves only a small set of parameters. Specifically, the theoretical analysis and DNS results support that, at high Karlovitz number, enstrophy transport obtains a balance of the viscous dissipation and production/vortex stretching terms. It is shown that, as a result, vorticity scales in the same manner as in homogeneous, isotropic turbulence within and across the flame, namely, scaling with the inverse of the Kolmogorov time scale, τ_η. As τ_η is a function only of the viscosity and dissipation rate, this work supports the validity of Kolmogorov’s first similarity hypothesis in premixed turbulentflames for sufficiently high Ka numbers. Results are unaffected by the transport model, chemical model, turbulent Reynolds number, and finally the physical configuration

Functionalized polyhydroquinolines from amino acids using a key one-pot cyclization cascade and application to the synthesis of (±)-Δ7-mesembrenone

Substituted polyhydroquinolines are ubiquitous skeletal cores found in drugs and bioactive natural products. As a new route to access this motif, we successfully developed a one-pot cyclization cascade with high chemocontrol and diastereoselectivi-ty. The sequence generates two cycles, three carbon-carbon bonds, and an all-carbon quaternary center in a highly conver-gent process. Functionalized polyhydroquinolines and congeners are accessible from commercially available amino acids. This versatile and robust strategy was applied to the synthesis of (±)-D7-mesembrenon

Radical azidation reactions and their application in the synthesis of alkaloids

Recent advances in radical azidation using sulfonyl azides are presented. For instance, radical carboazidation using α-iodoketones, desulfitative carboazidation, and anti-Markovnikov hydroazidation of alkenes are described. These novel methods tolerate a large number of functional groups and allow the synthesis of organic azides that would be difficult to synthesize otherwise. The transformation of the azides using reductive processes as well as a Schmidt reaction under nonacidic conditions were used to synthesize alkaloids including indolizidine 167B, monomorine I, cylindricine C, and lepadiformine

Production, purification, sequencing and activity spectra of mutacins D-123.1 and F-59.1

<p>Abstract</p> <p>Background</p> <p>The increase in bacterial resistance to antibiotics impels the development of new anti-bacterial substances. Mutacins (bacteriocins) are small antibacterial peptides produced by <it>Streptococcus mutans </it>showing activity against bacterial pathogens. The objective of the study was to produce and characterise additional mutacins in order to find new useful antibacterial substances.</p> <p>Results</p> <p>Mutacin F-59.1 was produced in liquid media by <it>S. mutans </it>59.1 while production of mutacin D-123.1 by <it>S. mutans </it>123.1 was obtained in semi-solid media. Mutacins were purified by hydrophobic chromatography. The amino acid sequences of the mutacins were obtained by Edman degradation and their molecular mass was determined by mass spectrometry. Mutacin F-59.1 consists of 25 amino acids, containing the YGNGV consensus sequence of pediocin-like bacteriocins with a molecular mass calculated at 2719 Da. Mutacin D-123.1 has an identical molecular mass (2364 Da) with the same first 9 amino acids as mutacin I. Mutacins D-123.1 and F-59.1 have wide activity spectra inhibiting human and food-borne pathogens. The lantibiotic mutacin D-123.1 possesses a broader activity spectrum than mutacin F-59.1 against the bacterial strains tested.</p> <p>Conclusion</p> <p>Mutacin F-59.1 is the first pediocin-like bacteriocin identified and characterised that is produced by <it>Streptococcus mutans</it>. Mutacin D-123.1 appears to be identical to mutacin I previously identified in different strains of <it>S. mutans</it>.</p

Mutacin H-29B is identical to mutacin II (J-T8)

BACKGROUND: Streptococcus mutans produces bacteriocins named mutacins. Studies of mutacins have always been hampered by the difficulties in obtaining active liquid preparations of these substances. Some of them were found to be lantibiotics, defined as bacterial ribosomally synthesised lanthionine-containing peptides with antimicrobial activity. The goal of this study was to produce and characterize a new mutacin from S. mutans strain 29B, as it shows a promising activity spectrum against current human pathogens. RESULTS: Mutacin H-29B, produced by S. mutans strain 29B, was purified by successive hydrophobic chromatography from a liquid preparation consisting of cheese whey permeate (6% w/v) supplemented with yeast extract (2%) and CaCO(3 )(1%). Edman degradation revealed 24 amino acids identical to those of mutacin II (also known as J-T8). The molecular mass of the purified peptide was evaluated at 3246.08 ± 0.1 Da by MALDI-TOF MS. CONCLUSION: A simple procedure for production and purification of mutacins along with its characterization is presented. Our results show that the amino acid sequence of mutacin H-29B is identical to the already known mutacin II (J-T8) over the first 24 residues. S. mutans strains of widely different origins may thus produce very similar bacteriocins

Fuel and chemistry effects in high Karlovitz premixed turbulent flames

Direct numerical simulations of turbulent premixed flames at high Karlovitz numbers are performed using detailed chemistry. Different fuels, chemical mechanisms, and equivalence ratios are considered and their effects on turbulent flame speed, geometry of the reaction zone, and fuel burning rate are analyzed. Differential diffusion effects are systematically isolated by performing simulations with both non-unity and unity Lewis numbers. Heavy fuels with above unity Lewis numbers are considered. In the unity Lewis number limit, the n-heptane, iso-octane, toluene, and methane flames at a given reaction zone Karlovitz number present similar normalized turbulent flame speeds and fuel burning rates close to their respective laminar values. When differential diffusion effects are included, the turbulent flame speeds are lower than their unity Lewis number counterparts due to a reduction in the fuel burning rate. The turbulent reaction zone surface areas increase with the turbulence intensity but are not strongly affected by fuel, equivalence ratio, chemical mechanism, or differential diffusion. The geometry of the reaction zone is studied through the probability density functions of strain rate and curvature which are very similar when normalized by Kolmogorov scales at the reaction zone. The dependence of the chemical source terms on the scalar dissipation rate in the unity Lewis number case is shown and the distributions of scalar dissipation rate on the reaction surface are similar to those of passive scalars in homogeneous isotropic turbulence. The reduced burning rates in the presence of differential diffusion are discussed. The present results indicate that mean turbulent flame properties such as burning velocity and fuel consumption can be predicted with the knowledge of only a few global laminar flame properties. Once normalized by the corresponding laminar flame quantities, fuel and chemistry effects in high Karlovitz number premixed turbulent flames are mostly limited to differential diffusion

Synthesis of Aryl Ketoamides via Aryne Insertion into Imides

An insertion of arenes into both imides and anhydrides via reactive aryne intermediates is presented. The reaction is performed under exceptionally mild conditions, and the corresponding ketoamide products are amenable to derivatization to deliver a variety of synthetically useful motifs such as quinolones, indoles, and ketoanilines

Optimization of temporal versus spatial replication in the development of habitat use models to explain among-reach variations of fish density estimates in rivers

Abstract: We evaluated the effects of temporal variation of fish density estimates on the explanatory power of habitat use models. Fish density estimates were obtained using visual surveys (10 visits) in eighteen 100 m reaches over a 7-week period. Physical attributes of reaches were estimated. Field data were used to develop a simulation domain (10 000 reaches) that reflected the spatio-temporal variability of fish density estimates and physical attributes. Simulations indicated that for a sampling effort of approximately 200 surveys, the number of reaches surveyed (25 to 200) and the number of surveys per reach (1 to 8) affected the adjusted R 2 of models by 5% to 42%. The established practice of sampling a maximized number of reaches once did not appear necessarily optimal for developing habitat use models. Analysis of temporal coefficients of variation suggests that species within the same family may require a similar survey design. Hence, for salmonids, it may be more appropriate to sample more reaches once, and for cyprinids, it may be more optimal to repeatedly sample fewer reaches

Concise total syntheses of (–)-jorunnamycin A and (–)-jorumycin enabled by asymmetric catalysis

The bis-tetrahydroisoquinoline (bis-THIQ) natural products have been studied intensively over the past four decades for their exceptionally potent anticancer activity, in addition to strong gram-positive and -negative antibiotic character. Synthetic strategies toward these complex polycyclic compounds have relied heavily on electrophilic aromatic chemistry, such as the Pictet-Spengler reaction, that mimics their biosynthetic pathways. Herein we report an approach to two bis-THIQ natural products, jorunnamycin A and jorumycin, that instead harnesses the power of modern transition-metal catalysis for the three major bond-forming events and proceeds with high efficiency (15 and 16 steps, respectively). By breaking from biomimicry, this strategy allows for the preparation of a more diverse set of non-natural analogs