A novel fully implicit finite volume method applied to the lid‐driven cavity problem—Part I: High Reynolds number flow calculations

A novel implicit cell‐vertex finite volume method is described for the solution of the Navier–Stokes equations at high Reynolds numbers. The key idea is the elimination of the pressure term from the momentum equation by multiplying the momentum equation with the unit normal vector to a control volume boundary and integrating thereafter around this boundary. The resulting equations are expressed solely in terms of the velocity components. Thus any difficulties with pressure or vorticity boundary conditions are circumvented and the number of primary variables that need to be determined equals the number of space dimensions. The method is applied to both the steady and unsteady two‐dimensional lid‐driven cavity problem at Reynolds numbers up to 10000. Results are compared with those in the literature and show excellent agreement. Copyright © 2003 John Wiley & Sons, Ltd.     

First measurement of the polarisation transfer on the proton in the reactionsH(\vec e,e'\vec p) andD(\vec e,e'\vec p)

The measurement of the polarisation transfer to the proton in the reactions $H(\vec e,e'\vec p)$ and $D(\vec e,e'\vec p)$ performed with longitudinally polarised electrons in quasi-free kinematics is presented. The coincidence measurement was executed atQ ²≈8fm ^?2 using the 855 MeV, c.w. beam of the Mainz Microtron MAMI. The recoil polarisation was determined by means of a carbon analyser. The experiment shows that the binding of the nucleon does not modify the polarisationP _x of the recoil proton within an error ofΔ P _x/P_x≈10%. The measured polarisation agrees with recent theoretical predictions. Implications for the measurement of the electric form factor of the neutron using the $D(\vec e,e'\vec n)$ reaction are discussed.     

Molecular Clefts Derived from 9,9′-spirobi[9H-fluorene] for enantioselective complexation of pyranosides and dicarboxylic acids

The molecular clefts (R)- and (S)- 3 , incorporating 9,9′-spirobi[9H-fluorene] as a spacer and two N-(5,7-dimethyl-1,8-naphthyridin-2-yl)carboxamide (CONH(naphthy)) units as H-bonding sites were prepared via the bis(succinimid-N-yl esters) of (R)-and (S)-9,9′-spirobi[9H-fluorene]-2,2′-dicarboxylic acid ( 5 ). Derivative 6 , with one CONH(naphthy) unit and one succinimid-N-yl ester residue allowed easy access to spirobifluorene clefts with two different H-bonding sites, as exemplified by the synthesis of 4 . Binding studies with (R)- and (S)- 3 and optically active dicarboxylic acids in CDCl₃ exhibited differences in free energy of the formed diastereoisomeric complexes (Δ(ΔGº)) between 0.5 and 1.6 kcal mol^?1 (T 300 K). Similar enantioselectivities were observed with the spirobifluorene clefts (R)- and (S)- 1 , bearing two N-(6-methylpyridin-2-yl)carboxamide (CONH(py)) H-bonding sites. The thermodynamic quantities ΔHº and ΔSº for the recognition processes with (R)- and (S)- 1 were determined by variable-temperature ¹H-NMR titrations and compared to those with (R)- and (S)- 2 , which have two CONH(py) moieties attached to the 6,6′-positions of a conformationally more flexible 1,1′-binaphthyl cleft. All association processes showed high enthalpic driving forces which are partially compensated by unfavorable changes in entropy. Pyranosides bind to the optically active clefts 1 and 3 in CDCl₃ with ?ΔGº = 3.0–4.3 kcal mol^?1. Diastereoisomeric selectivities up to 1.2 kcal mol^?1 and enantioselectivities up to 0.4 kcal mol^?1 were observed. Cleft 4 and N-(5,7-dimethyl-1,8-naphthyridin-2-yl)acetamide ( 25 ) complexed pyranosides 22–24 as effectively as 3 indicating that only one CONH(naphthy) site in 3 associates strongly with the sugar derivatives. Based on the X-ray crystal structure of 3 , a computer model for the complex between (S)- 3 and pyranoside 22 was constructed. Molecular-dynamics (MD) simulations showed that differential geometrical constraints are at the origin of the high enantioselectivity in the complexation of dicarboxylic acid (S)- 7 by (R)- and (S)- 1 and (R)- and (S)- 3 .     

Stability of (C60)2 and epoxide dimers, (C60)2ON, and their anions

The PM3, AM1, and MINDO3 semiemperical methods are used to calculate the the energy difference between C60ON and C60ON- and the bond dissociation energy necessary to cleave neutral and negatively charged (C60)2 dimers and epoxide dimers, (C60)2ON, to their respective monomers C60, and C60ON/2. The results show that the anions of the dimers are significantly more stable than neutral dimers. This result may explain the higher thermal stability of the observed ferromagnetic phase in photolyzed C60. which has been attributed to epoxide dimers and oligomers. It also provides an explanation for the origin of unpaired electron spin necessary for ferromagnetism.     

MULTIPLE EFFECTS OF UV RADIATION (265–330 NM) ON FUNGAL SPORE EMERGENCE

We have investigated the influence of narrow-band UV radiation, 265–330 nm. on germination of spores of the fungus Cladosporium cucumerinum Ellis and Arth., using a Xe arc lamp and filters. Reciprocity of time and dose rate was demonstrated when fungal spores were subjected to UV radiation at 325 nm but failed to hold at 265 nm. Based on these findings, data on fluence response, and partial action spectra, we propose that there are two biologically active sites in this organism that are affected by radiation between 265 and 330 nm and that might be influenced by changes in the stratospheric ozone layer: a short-wave-sensitive site (265–295 nm) and a long-wave-sensitive site (300–330 nm). Data obtained with narrow-band interference filters confirmed previous reports of damage to nucleic acid from UV at 265–295 nm and in addition demonstrated significant inhibition by UV at 300–320 nm. Further studies of the 300 330 nm portion of the spectrum, using combinations of plastic and glass filters, showed that the influence of UV radiation in this region was primarily to produce a non-photoreactivable delay in germ-tube emergence.     

2'-O-[2-(amino)-2-oxoethyl] oligonucleotides

[structure: see text] Oligonucleotides with novel modifications, 2'-O-[2-(amino)-2-oxoethyl] (2'-O-NAc), 2'-O-[2-(methylamino)-2-oxoethyl] (2'-O-NMAc), 2'-O-[2-(dimethylamino)-2-oxoethyl] (2'-O-DMAc), and 2'-O-[2-[[2-(dimethylamino)ethyl]amino]-2-oxoethyl] (2'-O-DMAEAc), have been synthesized. These modified oligonucleotides exhibit high binding affinity to complementary RNA (and not to DNA) and considerably enhance the nuclease stability of oligonucleotides with t(1/2) > 24 h.     

Continuous beds with vancomycin as chiral stationary phase for capillary electrochromatography

Enantiomeric separations in capillary electrochromatography (CEC) carried out using a continuous-bed chiral stationary phase (CSP) based on the macrocyclic antibiotic, vancomycin, is presented. The continuous beds were prepared from methacryloxypropyl modified fused silica capillaries (100 microm ID) by in situ copolymerization of N-(hydroxymethyl)acrylamide and piperazine diacrylamide with vinyl sulfonic acid comonomer used to introduce ionic functionality and thus a strong electroosmotic flow (EOF). The CSP was subsequently prepared by immobilizing the vancomycin stationary phase by reductive amination. Preliminary results have indicated that an extremely strong EOF is obtained in both the nonaqueous polar organic (15.2 x 10(-5) cm2 V(-1) s(-1) and the aqueous reversed-phase modes of operation (8.5 x 10(-5) cm2 V(-1) s(-1)). Enantioselectivity was obtained for four racemic compounds, the best of which was in the case of thalidomide which was separated in 10 minutes with high resolution (Rs = 2.5) and efficiency (120,000 plates meter(-1)) values.