Synthesis, antimicrobial properties and in silico evaluation of coumarin derivatives mediated by 1,4-dibromobutane.

In this study, monobrominated coumarins (5-6) and bis-coumarins (7-9) were synthesized from 3-carboxylic coumarin and 7-hydroxy-4-methyl coumarin using 1,4-dibromobutane as a binding agent, according to the synthesis procedures described in the literature. Amongst these coumarins, three are new compounds: monobrominated coumarin 5 and bis-coumarins 7 and 9. The structures of the synthesized coumarins were confirmed by FTIR, NMR and HRMS-ESI. In vitro antimicrobial evaluation of these coumarins against strains of twelve bacteria and four fungi revealed their bactericidal and fungicidal properties, with increased antibacterial activity for monocoumarins and improved antifungal activity for bis-coumarins. It was also found that the antibacterial activity was enhanced by the etheric bond, Br atom and alkyl chain and reduced by the ester bonds at position 3 of the pyrone ring or an additional coumarin unit, while the antifungal activity was reinforced by ester bonds and deactivated by the Br atom. For the first time, the in silico investigations of such coumarins were carried out and it was observed that they are less toxic, suitable for oral administration with good permeability through cell membrane, are able to circulate freely in the bloodstream and cross Blood-Brain-Barriers. Moreover, their molecular docking in DNA indicated stable coumarin-DNA complexes with good scores. The results of molecular dynamics simulations performed for 200 ns revealed the rigidity and stability of bis-coumarins (7-9) in the DNA binding pocket and predict that they are potent binders.Communicated by Ramaswamy H. Sarma.

In vitro and in silico studies of antibacterial activities of secofriedelane derivatives from Senna alata (L) Roxb.

In this study, six compounds were obtained from a methanolic extract of air-dried leaves of Senna alata and one of them, a triterpenoid (secofriedelane) named as 7-(2-carboxyethyl)-3, 4b, 6a, 8, 10a, 12a-hexamethyl-8-vinyloctadecahydrochrysene-3-carboxylic acid (5) was isolated for the first time from this plant. Then, its chemical structure was detailed and characterised by FT-IR, 1H and 13C- NMR and ESI-MS. Besides, two chemical-modified derivatives of secofriedelane (5a, 5b) were synthesised by methylation and allylation reactions, respectively, and their in vitro antibacterial activities were also evaluated. The results revealed that all the triterpenes showed, against gram-positive and -negative bacterial strains, good and moderate antibacterial activities with bactericidal effects that were enhanced by the methyl groups and altered with the allyl ones. Moreover, the molecular docking results of 5, 5a and 5b in the DNA gyrase (2XCT) active site showed that triterpene 5 has a good score very close to reference (ciprofloxacin).

Pushing the Lewis Acidity Boundaries of Boron Compounds With Non-Planar Triarylboranes Derived from Triptycenes.

Bending the planar trigonal boron center of triphenylborane by connecting its aryl rings with carbon or phosphorus linkers gave access to a series of 9-boratriptycene derivatives with unprecedented structures and reactivities. NMR spectroscopy and X-ray diffraction of the Lewis adducts of these non-planar boron Lewis acids with weak Lewis base revealed particularly strong covalent bond formation. The first Lewis adduct of a trivalent boron compounds with the Tf2 N- anion illustrates the unrivaled Lewis acidity of these species. Increasing the pyramidalization of the boron center and using a cationic phosphonium linker resulted in an exceptional enhancement of Lewis acidity. Introduction of a phosphorus and a boron atom at each edge of a triptycene framework, allowed access to new bifunctional Lewis acid-base 9-phospha-10-boratriptycenes featuring promising reactivity for the activation of carbon-halogen bonds.

Characterization of rabies post-exposure prophylaxis in a region of the eastern Amazon, state of Pará, Brazil, between 2000 and 2014.

Animal bites are a serious public health issue, and prevention strategies have been consistently documented worldwide. The aim of this study was to characterize human anti-rabies treatment in 11 counties of the Salgado microregion, Pará state, Brazil, which borders the Bragantina microregion, where exposures of human rabies were reported in 2004 and 2005. A descriptive retrospective study was conducted using anti-rabies treatment notifications registered in the Information System for Notifiable Diseases (SINAN) database of the State Department of Public Health of Pará (SESPA) from January 2000 to December 2014. In this period, 13,403 exposures were reported, with a growing annual trend (Y = 68.571x + 344.96). The years 2012 and 2013 presented the highest exposure incidence. Salinópolis was the county with the highest average annual incidence per 10,000 persons (62.83), followed by São João de Pirabas (43.28) and São Caetano de Odivelas (41.27). Most patients were males (59.6%) and were 1-19 years old (48.7%). The main species involved in aggressions were dogs (74.1%), followed by bats (13.1%) and cats (7.4%). Biting was the most common kind of exposure, mostly on the lower limbs (39.6%). This study shows that aggression by bats was the second most common cause of demand for the service in the region for the past 14 years. The low quality of records may increase the difficulty of rabies surveillance in Pará.

Computational fluid dynamics in abdominal aorta bifurcation: non-Newtonian versus Newtonian blood flow in a real case study.

Hemodynamic in abdominal aorta bifurcation was investigated in a real case using computational fluid dynamics. A Newtonian and non-Newtonian (Walburn-Schneck) viscosity models were compared. The geometrical model was obtained by 3D reconstruction from CT-scan and hemodynamic parameters obtained by laser-Doppler. Blood was assumed incompressible fluid, laminar flow in transient regime and rigid vessel wall. Finite volume-based was used to study the velocity, pressure, wall shear stress (WSS) and viscosity throughout cardiac cycle. Results obtained with Walburn-Schneck's model, during systole, present lower viscosity due to shear thinning behavior. Furthermore, there is a significant difference between the results obtained by the two models for a specific patient. During the systole, differences are more pronounced and are preferably located in the tortuous regions of the artery. Throughout the cardiac cycle, the WSS amplitude between the systole and diastole is greater for the Walburn-Schneck's model than for the Newtonian model. However, the average viscosity along the artery is always greater for the non-Newtonian model, except in the systolic peak. The hemodynamic model is crucial to validate results obtained with CFD and to explore clinical potential.

Hydrodynamic analysis of different finger positions in swimming: a computational fluid dynamics approach.

The aim of this research was to numerically clarify the effect of finger spreading and thumb abduction on the hydrodynamic force generated by the hand and forearm during swimming. A computational fluid dynamics (CFD) analysis of a realistic hand and forearm model obtained using a computer tomography scanner was conducted. A mean flow speed of 2 m · s(-1) was used to analyze the possible combinations of three finger positions (grouped, partially spread, totally spread), three thumb positions (adducted, partially abducted, totally abducted), three angles of attack (a = 0°, 45°, 90°), and four sweepback angles (y = 0°, 90°, 180°, 270°) to yield a total of 108 simulated situations. The values of the drag coefficient were observed to increase with the angle of attack for all sweepback angles and finger and thumb positions. For y = 0° and 180°, the model with the thumb adducted and with the little finger spread presented higher drag coefficient values for a = 45° and 90°. Lift coefficient values were observed to be very low at a = 0° and 90° for all of the sweepback angles and finger and thumb positions studied, although very similar values are obtained at a = 45°. For y = 0° and 180°, the effect of finger and thumb positions appears to be much most distinct, indicating that having the thumb slightly abducted and the fingers grouped is a preferable position at y = 180°, whereas at y = 0°, having the thumb adducted and fingers slightly spread yielded higher lift values. Results show that finger and thumb positioning in swimming is a determinant of the propulsive force produced during swimming; indeed, this force is dependent on the direction of the flow over the hand and forearm, which changes across the arm's stroke.

Multiscale gyrokinetics for rotating tokamak plasmas: fluctuations, transport and energy flows.

This paper presents a complete theoretical framework for studying turbulence and transport in rapidly rotating tokamak plasmas. The fundamental scale separations present in plasma turbulence are codified as an asymptotic expansion in the ratio ε = ρi/α of the gyroradius to the equilibrium scale length. Proceeding order by order in this expansion, a set of coupled multiscale equations is developed. They describe an instantaneous equilibrium, the fluctuations driven by gradients in the equilibrium quantities, and the transport-timescale evolution of mean profiles of these quantities driven by the interplay between the equilibrium and the fluctuations. The equilibrium distribution functions are local Maxwellians with each flux surface rotating toroidally as a rigid body. The magnetic equilibrium is obtained from the generalized Grad-Shafranov equation for a rotating plasma, determining the magnetic flux function from the mean pressure and velocity profiles of the plasma. The slow (resistive-timescale) evolution of the magnetic field is given by an evolution equation for the safety factor q. Large-scale deviations of the distribution function from a Maxwellian are given by neoclassical theory. The fluctuations are determined by the 'high-flow' gyrokinetic equation, from which we derive the governing principle for gyrokinetic turbulence in tokamaks: the conservation and local (in space) cascade of the free energy of the fluctuations (i.e. there is no turbulence spreading). Transport equations for the evolution of the mean density, temperature and flow velocity profiles are derived. These transport equations show how the neoclassical and fluctuating corrections to the equilibrium Maxwellian act back upon the mean profiles through fluxes and heating. The energy and entropy conservation laws for the mean profiles are derived from the transport equations. Total energy, thermal, kinetic and magnetic, is conserved and there is no net turbulent heating. Entropy is produced by the action of fluxes flattening gradients, Ohmic heating and the equilibration of interspecies temperature differences. This equilibration is found to include both turbulent and collisional contributions. Finally, this framework is condensed, in the low-Mach-number limit, to a more concise set of equations suitable for numerical implementation.

Numerical simulation of two-phase flow around flatwater competition kayak design-evolution models.

The aim of the current study was to analyze the hydrodynamics of three kayaks: 97-kg-class, single-rower, flatwater sports competition, full-scale design evolution models (Nelo K1 Vanquish LI, LII, and LIII) of M.A.R. Kayaks Lda., Portugal, which are among the fastest frontline kayaks. The effect of kayak design transformation on kayak hydrodynamics performance was studied by the application of computational fluid dynamics (CFD). The steady-state CFD simulations where performed by application of the k-omega turbulent model and the volume-of-fluid method to obtain two-phase flow around the kayaks. The numerical result of viscous, pressure drag, and coefficients along with wave drag at individual average race velocities was obtained. At an average velocity of 4.5 m/s, the reduction in drag was 29.4% for the design change from LI to LII and 15.4% for the change from LII to LIII, thus demonstrating and reaffirming a progressive evolution in design. In addition, the knowledge of drag hydrodynamics presented in the current study facilitates the estimation of the paddling effort required from the athlete during progression at different race velocities. This study finds an application during selection and training, where a coach can select the kayak with better hydrodynamics.

Analysis of wind velocity and release angle effects on discus throw using computational fluid dynamics.

The aim of this paper is to study the aerodynamics of discus throw. A comparison of numerical and experimental performance of discus throw with and without rotation was carried out using the analysis of lift and drag coefficients. Initial velocity corresponding to variation angle of around 35.5° was simulated. Boundary condition, on the top and bottom boundary edges of computational domain, was imposed in order to eliminate external influences on the discus; a wind resistance was calculated for the velocity values of 25 and 27 m/s. The results indicate that the flight distance (D) was strongly affected by the drag coefficient, the initial velocity, the release angle and the direction of wind velocity. It was observed that these variables change as a function of discus rotation. In this study, results indicate a good agreement of D between experimental values and numerical results.

The computational fluid dynamics study of orientation effects of oar-blade.

The distribution of pressure coefficient formed when the fluid contacts with the kayak oar blade is not been studied extensively. The CFD technique was employed to calculate pressure coefficient distribution on the front and rear faces of oar blade resulting from the numerical resolution equations of the flow around the oar blade in the steady flow conditions (4 m/s) for three angular orientations of the oar (45°, 90°, 135°) with main flow. A three-dimensional (3D) geometric model of oar blade was modeled and the k-ε turbulent model was applied to compute the flow around the oar. The main results reported that, under steady state flow conditions, the drag coefficient (Cd = 2.01 for 4 m/s) at 90° orientation has the similar evolution for the different oar blade orientation to the direction of the flow. This is valid when the orientation of the blade is perpendicular to the direction of the flow. Results indicated that the angle of oar strongly influenced the Cd with maximum values for 90° angle of the oar. Moreover, the distribution of the pressure is different for the internal and external edges depending upon oar angle. Finally, the difference of negative pressure coefficient Cp in the rear side and the positive Cp in the front side, contributes toward propulsive force. The results indicate that CFD can be considered an interesting new approach for pressure coefficient calculation on kayak oar blade. The CFD approach could be a useful tool to evaluate the effects of different blade designs on the oar forces and consequently on the boat propulsion contributing toward the design improvement in future oar models. The dependence of variation of pressure coefficient on the angular position of oar with respect to flow direction gives valuable dynamic information, which can be used during training for kayak competition.

A computational fluid dynamics study of propulsion due to the orientation effects of swimmer's hand.

The aim of the article is to determine the hydrodynamic characteristics of a swimmer's scanned hand model for various possible combinations of both the angle of attack and the sweepback angle, simulating separate underwater arm stroke phases of front crawl swimming. An actual swimmer's hand with thumb adducted was scanned using an Artec L 3D scanner. ANSYS Fluent code was applied for carrying out steady-state computational fluid dynamics (CFD) analysis. The hand model was positioned in nine different positions corresponding to the swimmer's hand orientations (angle of attack and sweepback angle) and velocities observed during the underwater hand stroke of front crawl. Hydrodynamic forces and coefficients were calculated. Results showed significantly higher drag coefficient values in the pull phase, when compared with previous studies under a steady-state flow condition. The mean value of the ratio of drag and lift coefficients was 2.67 ± 2.3 in underwater phases. The mean value of the ratio of drag and lift forces was 2.73 ± 2.4 in underwater phases. Moreover, hydrodynamic coefficients were not almost constant throughout different flow velocities, and variation was observed for different hand positions corresponding to different stroke phases. The current study suggests that the realistic variation of both the orientation angles influenced higher values of drag, lift and resultant coefficients and forces.

Experimental signatures of critically balanced turbulence in MAST.

Beam emission spectroscopy (BES) measurements of ion-scale density fluctuations in the MAST tokamak are used to show that the turbulence correlation time, the drift time associated with ion temperature or density gradients, the particle (ion) streaming time along the magnetic field, and the magnetic drift time are consistently comparable, suggesting a "critically balanced" turbulence determined by the local equilibrium. The resulting scalings of the poloidal and radial correlation lengths are derived and tested. The nonlinear time inferred from the density fluctuations is longer than the other times; its ratio to the correlation time scales as ν(*i)(-0.8 ± 0.1), where ν(*i) = ion collision rate/streaming rate. This is consistent with turbulent decorrelation being controlled by a zonal component, invisible to the BES, with an amplitude exceeding those of the drift waves by ∼ ν(*i)(-0.8).

The Effect of Depth on Drag During the Streamlined Glide: A Three-Dimensional CFD Analysis.

The aim of this study was to analyze the effects of depth on drag during the streamlined glide in swimming using Computational Fluid Dynamics. The Computation Fluid Dynamic analysis consisted of using a three-dimensional mesh of cells that simulates the flow around the considered domain. We used the K-epsilon turbulent model implemented in the commercial code Fluent(®) and applied it to the flow around a three-dimensional model of an Olympic swimmer. The swimmer was modeled as if he were gliding underwater in a streamlined prone position, with hands overlapping, head between the extended arms, feet together and plantar flexed. Steady-state computational fluid dynamics analyses were performed using the Fluent(®) code and the drag coefficient and the drag force was calculated for velocities ranging from 1.5 to 2.5 m/s, in increments of 0.50m/s, which represents the velocity range used by club to elite level swimmers during the push-off and glide following a turn. The swimmer model middle line was placed at different water depths between 0 and 1.0 m underwater, in 0.25m increments. Hydrodynamic drag decreased with depth, although after 0.75m values remained almost constant. Water depth seems to have a positive effect on reducing hydrodynamic drag during the gliding. Although increasing depth position could contribute to decrease hydrodynamic drag, this reduction seems to be lower with depth, especially after 0.75 m depth, thus suggesting that possibly performing the underwater gliding more than 0.75 m depth could not be to the benefit of the swimmer.

Three-dimensional CFD analysis of the hand and forearm in swimming.

The purpose of this study was to analyze the hydrodynamic characteristics of a realistic model of an elite swimmer hand/forearm using three-dimensional computational fluid dynamics techniques. A three-dimensional domain was designed to simulate the fluid flow around a swimmer hand and forearm model in different orientations (0°, 45°, and 90° for the three axes Ox, Oy and Oz). The hand/forearm model was obtained through computerized tomography scans. Steady-state analyses were performed using the commercial code Fluent. The drag coefficient presented higher values than the lift coefficient for all model orientations. The drag coefficient of the hand/forearm model increased with the angle of attack, with the maximum value of the force coefficient corresponding to an angle of attack of 90°. The drag coefficient obtained the highest value at an orientation of the hand plane in which the model was directly perpendicular to the direction of the flow. An important contribution of the lift coefficient was observed at an angle of attack of 45°, which could have an important role in the overall propulsive force production of the hand and forearm in swimming phases, when the angle of attack is near 45°.

The Hydrodynamic Study of the Swimming Gliding: a Two-Dimensional Computational Fluid Dynamics (CFD) Analysis.

Nowadays the underwater gliding after the starts and the turns plays a major role in the overall swimming performance. Hence, minimizing hydrodynamic drag during the underwater phases should be a main aim during swimming. Indeed, there are several postures that swimmers can assume during the underwater gliding, although experimental results were not conclusive concerning the best body position to accomplish this aim. Therefore, the purpose of this study was to analyse the effect in hydrodynamic drag forces of using different body positions during gliding through computational fluid dynamics (CFD) methodology. For this purpose, two-dimensional models of the human body in steady flow conditions were studied. Two-dimensional virtual models had been created: (i) a prone position with the arms extended at the front of the body; (ii) a prone position with the arms placed alongside the trunk; (iii) a lateral position with the arms extended at the front and; (iv) a dorsal position with the arms extended at the front. The drag forces were computed between speeds of 1.6 m/s and 2 m/s in a two-dimensional Fluent(®) analysis. The positions with the arms extended at the front presented lower drag values than the position with the arms aside the trunk. The lateral position was the one in which the drag was lower and seems to be the one that should be adopted during the gliding after starts and turns.

Swimming propulsion forces are enhanced by a small finger spread.

The main aim of this study was to investigate the effect of finger spread on the propulsive force production in swimming using computational fluid dynamics. Computer tomography scans of an Olympic swimmer hand were conducted. This procedure involved three models of the hand with differing finger spreads: fingers closed together (no spread), fingers with a small (0.32 cm) spread, and fingers with large (0.64 cm) spread. Steady-state computational fluid dynamics analyses were performed using the Fluent code. The measured forces on the hand models were decomposed into drag and lift coefficients. For hand models, angles of attack of 0 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, 75 degrees, and 90 degrees, with a sweep back angle of 0 degrees, were used for the calculations. The results showed that the model with a small spread between fingers presented higher values of drag coefficient than did the models with fingers closed and fingers with a large spread. One can note that the drag coefficient presented the highest values for an attack angle of 90 degrees in the three hand models. The lift coefficient resembled a sinusoidal curve across the attack angle. The values for the lift coefficient presented few differences among the three models, for a given attack angle. These results suggested that fingers slightly spread could allow the hand to create more propulsive force during swimming.

Hydrodynamic drag during gliding in swimming.

This study used a computational fluid dynamics methodology to analyze the effect of body position on the drag coefficient during submerged gliding in swimming. The k-epsilon turbulent model implemented in the commercial code Fluent and applied to the flow around a three-dimensional model of a male adult swimmer was used. Two common gliding positions were investigated: a ventral position with the arms extended at the front, and a ventral position with the arms placed along side the trunk. The simulations were applied to flow velocities of between 1.6 and 2.0 m x s(-1), which are typical of elite swimmers when gliding underwater at the start and in the turns. The gliding position with the arms extended at the front produced lower drag coefficients than with the arms placed along the trunk. We therefore recommend that swimmers adopt the arms in front position rather than the arms beside the trunk position during the underwater gliding.

Hydrodynamic analysis of different thumb positions in swimming.

The aim of the present study was to analyze the hydrodynamic characteristics of a true model of a swimmer hand with the thumb in different positions using numerical simulation techniques. A three-dimensional domain was created to simulate the fluid flow around three models of a swimmer hand, with the thumb in different positions: thumb fully abducted, partially abducted, and adducted. These three hand models were obtained through computerized tomography scans of an Olympic swimmer hand. Steady-state computational fluid dynamics analyses were performed using the Fluent(®) code. The forces estimated in each of the three hand models were decomposed into drag and lift coefficients. Angles of attack of hand models of 0°, 45° and 90°, with a sweep back angle of 0° were used for the calculations. The results showed that the position with the thumb adducted presented slightly higher values of drag coefficient compared with thumb abducted positions. Moreover, the position with the thumb fully abducted allowed increasing the lift coefficient of the hand at angles of attack of 0° and 45°. These results suggested that, for hand models in which the lift force can play an important role, the abduction of the thumb may be better, whereas at higher angles of attack, in which the drag force is dominant, the adduction of the thumb may be preferable. Key pointsNumerical simulation techniques can provide answers to problems which have been unobtainable using experimental methods.The computer tomography scans allowed the creation of a complete and true digital anatomic model of a swimmer hand.The position with the thumb adducted presented slightly higher values of drag coefficient than the positions with the thumb abducted.The position with the thumb fully abducted allowed increasing the lift coefficient of the hand at angles of attack of 0 and 45 degrees.For hand positions in which the lift force can play an important role the abduction of the thumb may be better whereas at higher angles of attack, in which the drag force is dominant, the adduction of the thumb may be preferable for swimmers.

Two-channel dissociation of chemically and thermally activated n-butylbenzene cations (C10H14+).

The charge-transfer reaction O(2)(+) + n-butylbenzene (C(10)H(14)) --> O(2) + C(10)H(14)(+) was studied in a turbulent ion flow tube at temperatures between 423 and 548 K and pressures between 15 and 250 Torr in the buffer gases He and N(2). Under chemical activation conditions stabilization vs dissociation ratios S/D of vibrationally highly excited C(10)H(14)(+)* as well as branching ratios of the fragments C(7)H(7)(+) (m/z = 91) vs C(7)H(8)(+) (m/z = 92) of the dissociation of C(10)H(14)(+)* were measured. Under thermal activation conditions, the rate constant of the dominating dissociation channel 92 was measured at 498 and 523 K. Employing information on the specific rate constants k(E) of the two channels 91 and 92 and on collisional energy transfer rates from the literature, the measured S/D curves and branching ratios 91/92 could be modeled well. It is demonstrated that the charge transfer occurs approximately equally through resonant transfer and complex-forming transfer. The thermal dissociation experiments provide a high precision value of the energy barrier for the channel 92, being 1.14 (+/-0.02) eV.

Ion-molecule kinetics at 15-700 Torr.

Studies of ion-molecule chemistry are usually made at pressures of a few Torr and below. By contrast, there are numerous plasmas that occur at higher pressures. For that reason we have constructed a turbulent ion flow tube (TIFT) for studying ion-molecule kinetics from 15 to 700 Torr. Currently, the TIFT operates from room temperature to 700 K. Here we present a summary of the measurements we have made to date. The first measurements involved SF6- reactions with SO2, H2O, CH3OH and C2H5OH at room temperature. The SO2 reaction showed the same kinetics as low pressure measurements indicating that the reaction occurs rapidly. The other reactions were all found to be cluster-mediated with branching fractions that depend on pressure. More recently, charge transfer reactions of O2+ to alkylbenzenes have been studied at elevated temperatures, from 400 to 700 K. Both dissociative and non-dissociative charge transfer occurs with the latter being favored at high pressures indicating that excited states live long enough to be stabilized by the buffer gas. Combining the TIFT measurements with detailed statistical adiabatic channel model/classical trajectory (SACM/CT) calculations of the unimolecular decay constant allows energy transfer parameters to be derived. Extending the temperature range upwards to 750 K has allowed thermal decomposition rate constants to be measured. The thermal decomposition has been successfully modeled using the same parameters as for the collision quenching modeling. This allows bond strengths for the dissociation to be derived with high accuracy. Both the measurements and models show that the conditions correspond to the high pressure kinetics regime.