The Development of the Asymptotic Viscous Dissipation Profile in a Vertical Free Convective Boundary Layer Flow in a Porous Medium

The effect of viscous dissipation on the development of the boundary layer flow from a cold vertical surface embedded in a Darcian porous medium is investigated. It is found that the flow evolves gradually from the classical Cheng–Minkowycz form to the recently discovered asymptotic dissipation profile which is a parallel flow.     

Structure of enantiopure and racemic alanine adlayers on Cu(1 1 0)

Plane wave density functional theory has been employed to analyze the structure of alanine adlayers on the Cu(1 1 0) surface. Alanine forms (3 × 2) adlayers on Cu(1 1 0) that are closely related to the structures of glycine on the same surface. There is essentially no energy difference between the most stable racemic and enantiopure alanine adlayers. This observation implies that adsorption of racemic alanine on Cu(1 1 0) will result in a pseudoracemate adlayer.     

A Network Simulation of High-congestion Road-traffic Flows in Cities with Marine Container Terminals

Port cities where marine cargo terminals are located are generally near urban areas characterized by high-congestion road traffic. Changes in cargo traffic volumes into a marine terminal, or in the surrounding traffic arteries, which carry this traffic, can significantly affect the terminal's operations. Conversely, activity at the terminal can have an impact on the traffic levels and congestion for a considerable distance from the terminal. This paper demonstrates a methodology useful for studying the impact of road traffic flows on marine container terminals located in highly congested areas. This model was developed at the request of the Virginia Center for World Trade and was used to answer three planning questions in the port of Hampton Roads, Virginia, USA-what would be the impact of: opening a new section of interstate highway, a projected doubling of container traffic at one terminal, and a daily unit train in the vicinity of another terminal. The problem was made more challenging by limited data-collection funds. None the less, the model was deemed valid by a panel of traffic experts and officials from several major state and private agencies involved in marine traffic management. The model results were subsequently a factor in two major decisions related to terminal management.     

Synthesis of an asymmetric fullerene dimer via sequential cycloadditions

A single isomer of a monofunctionalised C₇₀ fullerene is isolated and characterised using variable temperature NMR spectroscopy. Pendant methylene bromide groups allow for further cycloaddition reactions and a C₆₀-C₇₀ asymmetric fullerene dimer is thus prepared.     

Combinatorial Characterizations of Authentication Codes II

For any authentication code for k source states and v messages having minimum possible deception probabilities (namely, % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9qq-f0-yqaqVeLsFr0-vr% 0-vr0db8meaabaqaciGacaGaaeqabaWaaeaaeaaakeaacaWGqbWaaS% baaSqaaiaadsgaaeqaaOWaaSbaaSqaaiaaicdaaeqaaOGaeyypa0Za% aSGbaeaacaWGRbaabaGaamODaaaaaaa!3F28!\[P_d _0 = {k \mathord{\left/ {\vphantom {k v}} \right. \kern-\nulldelimiterspace} v}\] and % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9qq-f0-yqaqVeLsFr0-vr% 0-vr0db8meaabaqaciGacaGaaeqabaWaaeaaeaaakeaacaWGqbWaaS% baaSqaaiaadsgaaeqaaOWaaSbaaSqaaiaaigdaaeqaaOGaeyypa0Ze% xLMBb50ujbqeguuDJXwAKbacfaGae8hkaGIaam4AaiabgkHiTiaaig% dacqWFPaqkcqWFVaWlcqWFOaakcqWF2bGDcqGHsislcaaIXaGae8xk% aKIae8xkaKcaaa!4CD1!\[P_d _1 = (k - 1)/(v - 1))\], we show that there must be at least v encoding rules. (This can be thought of as an authentication-code analogue of Fisher's Inequality.) We derive several properties that an extremal code must satisfy, and we characterize the extremal codes for equiprobable source states as arising from symmetric balanced incomplete block designs. We also present an infinite class of extremal codes, in which the source states are not equiprobable, derived from affine planes.Dedicated to Gus Simmons     

Simultaneous determination of clebopride and a major metabolite N-desbenzylclebopride in plasma by capillary gas chromatography-negative-ion chemical ionization mass spectrometry

A procedure for the simultaneous assay of clebopride and its major metabolite N-desbenzylclebopride in plasma has been developed. The method utilizes capillary gas chromatography-negative-ion chemical ionization mass spectrometry with selected-ion monitoring of characteristic ions. Employing 2-ethoxy analogues as internal standards, the benzamides were extracted from basified plasma using dichloromethane. Subsequent reaction with heptafluorobutyric anhydride produced volatile mono- and diheptafluorobutyryl derivatives of clebopride and N-desbenzylclebopride, respectively. The methane negative-ion mass spectra of these derivatives exhibited intense high-mass ions ideal for specific quantitation of low levels in biological fluids. Using this procedure the recovery of the drug and metabolite from human plasma was found to be 84.4 +/- 1.5% (n = 3) and 77.4 +/- 4.7% (n = 3), respectively, at 0.5 ng/ml. Measurement of both compounds down to 0.10 ng/ml with a coefficient of variation of less than 10.5% is described. Plasma levels are reported in four volunteers up to 24 h following oral administration of 1 mg of clebopride malate salt.     

Abnormally mild synthesis of bis(dithiolo)pyrroles from 2,5-dimethylpyrroles

[chemical reaction: see text]. Treatment of N-substituted 2,5-dimethylpyrroles 2 with an equilibrated mixture of disulfur dichloride and DABCO in chloroform at 0 degrees C gives pentathiepinopyrroles 3 in moderate yields; further reaction of 3 with the same mixture at room temperature leads, in an extensive reaction cascade, to bis(dithiolo)pyrroles 4 in high yield; 2 can be converted into 4 in a one-pot operation under unusually mild conditions.     

Pyridine N-alkylation by lithium, magnesium, and zinc alkyl reagents: synthetic, structural, and mechanistic studies on the bis(imino)pyridine system

The 2,6-bis(alpha-iminoalkyl)pyridines 2,6-[ArNC(CR(3))](2)C(5)H(3)N [R = H, D; Ar = 2,6-i-Pr(2)C(6)H(3) (DIPP), 2,6-Me(2)C(6)H(3) (DMP)] react with MeLi in Et(2)O to give a binary mixture of products: the pyridine N-methylated species 2,6-[ArNC(CR(3))](2)C(5)H(3)N(Me)Li(OEt(2)) and the deprotonated/dedeuterated species 2-[ArNC(CR(3))],6-[ArNC(=CR(2))]C(5)H(3)NLi(OEt(2)). For R = D, the product ratio is 2:1 in favor of the N-methylated product, while, for R = H, the deprotonated product is favored by 5:1, increasing to 8:1 in toluene solvent. Warming solutions of the N-methylated species leads to clean conversion to the thermodynamically preferred deprotonated species. Crossover experiments show that MeLi is re-formed and dissociates from the terdentate ligand before deprotonating the ketimine methyl unit. For MgR(2) (R = Et, i-Pr) and ZnR(2) (R = Et) reagents, N-alkylation products are formed exclusively, but derivatives containing bulky aryl substituents are found to undergo further rearrangement to 2-alkylated species, arising by migration of the alkyl group of the N-alkyl moiety to the adjacent ring carbon atom. The reversibility of the N-alkylation process has been probed using deuterio-labeled Mg alkyl reagents and mixed alkyl zinc species. A cationic zinc derivative is shown to undergo "reverse" alkyl migration, from the heterocycle nitrogen atom to the zinc center. EPR spectroscopy reveals a paramagnetic intermediate in which the unpaired electron is delocalized over the heterocycle and di-imine moieties of the ligand, indicating that the N-alkylation reactions proceed via single electron-transfer processes.     

Fluorescence correlation spectroscopy of water-in-oil microemulsions: an application in specific characterisation of droplets containing biomolecules

Fluorescence correlation spectroscopy (FCS) has been successfully used to characterise water-in-oil (w/o) microemulsions. The investigated systems were stabilised by sodium bis-2-ethylhexyl sulphosuccinate (AOT) and the measured diffusion times have been related to the radii of the aggregated species, which for some systems, were separately determined by small-angle neutron scattering (SANS). We demonstrate that FCS is capable of measuring hydrodynamic radii of microemulsions rapidly and at surfactant concentrations lower than previously reported for other techniques. FCS was also used to specifically interrogate microemulsion droplets containing a fluorescently-labelled biomolecule, specifically phalloidin, a peptide fungal toxin from Amanita phalloides, and the enzyme -chymotrypsin (-CT). The microemulsion droplets are only marginally increased in size if a small peptide (phalloidin) is included in the water phase, whereas the droplet size is significantly increased when a larger protein (-CT) is included.