Chiral environments for asymmetric hydrogenation of model didehydro-amino acid residues

Dedicated to Professor John C. Sheehan on the occasion of his sixty-fifth birthday Nmr and glc analysis of diastereoisomeric mixtures of dipeptides has been used to study the asymmetric hydrogenation of model benzoyldidehydro- and trifluoroacetyldidehydro-dipeptide methyl esters. Chiral enhancement of one isomeric form appears to be independent of the N-terminal acyl group, but is significantly influenced by the choice of amino-acid in the C-terminal position. C-Terminal aromatic amino-acids and their derivatives give the best chiral enhancement during hydrogenation of a neighbouring dehydroamino-acid residue.     

A novel way to study the initial stages of soap-free emulsion polymerizations: The intercalation of polystyrene oligomers into hydrotalcite

The dominant species in the early stages of an emulsifier-free emulsion polymerization of styrene has been found to be an oligomer of two to three monomer units using a novel trapping technique. This involved the intercalation of charged primary oligomers between the layers of a hydrotalcite, [Mg₄Al₂(OH)₁₂]²⁺[A]^2- (where A = dianion). Hydrotalcites are an important class of lamellar, inorganic compounds whose interlayer spacing can be mod-ified by anion exchange. Our approach first involved preparing a hydrotalcite precursor in which the layers were propped apart by an organic dianion (terephthalate = TA). This material was then used to capture the negatively charged polystyrene oligomers from the emulsion polymerization reaction mixture. We found that TA was rapidly ion-exchanged for the charged oligomers. The resulting pillared hydrotalcite material was characterized using XRD and SEC. We found that the interlayer spacing between the hydroxide layers increased to 23.2 Å on exposure to the emulsion reaction mixture. This represents an interlayer expansion of 18.3 Å (after subtraction of the hydroxide layer contribution), which is cnsistent with intercalation of oligomers with two to three monomer units arranged in a bilayer. This size estimate was confirmed by the results of size exclusion chromatography. © 1995 John Wiley & Sons, Inc.     

Enantiospecific synthesis of the (9S,18R)-diastereomer of the leukocyte adhesion inhibitor cyclamenol A

Cyclamenol A is one of the very few non-carbohydrate and non-peptide natural products that inhibit leukocyte adhesion to endothelial cells. We report on the first enantioselective total synthesis of the (9S, 18R)-diastereomer of this macrocyclic polyene lactam. Key elements of the synthesis are i) the synthesis of the required chiral building blocks by employing readily accessible building blocks from the chiral pool, that is, (S)-malic acid and (R)-hydroxyisobutyric acid, ii) assembly of a linear polyene precursor by means of Wittig and Horner olefination reactions as key C-C bond-forming transformations, iii) ring closure by means of a vanadium-mediated pinacolisation reaction and iv) conversion of the generated cis-diol into a (Z)-olefin to complete the entire polyene system of the natural product. Attempts to close the macrocyclic ring by a macrolactamisation, a double Stille coupling or direct olefination in a McMurry reaction failed. Crucial to the successful completion of the synthesis was the correct orchestration of the final steps. It was necessary to first deprotect the intermediate formed after macrocycle formation and to generate the sensitive heptaene system in the last step by means of a Corey-Hopkins sequence.     

Energy distribution among reaction products. XIV. F + CH4, F + CH3X(X  Cl,Br, I), F + CHnCl4−n(n = 1−3)

The infrared chemiluminescence technique has been used to obtain relative rate constants k(ν′) for HF(ν′) formed in the following reaction:

For reaction (1) the detailed rate constants [k(ν′ = 1) = 0.30;k(ν′ = 2) = 1.00; k(ν′ = 3) = 0.15; mean fraction of the available energy entering vibration <?^′_ν> = 0.56] confirmed, at much lower reagent pressures, results obtained by previous workers. In series I there was a slight increase in fraction of the energy entering vibration as the molecular reagent altered from CH₃Cl to CH₃Br to CH₃I, viz <?^′_ν> = 0.50 (1a), <?^′_ν> = 0.58 (1b), <?^′_ν> = 0.60 (1c). In series 2, by contrast, there was a marked decrease in fractional conversion of the available energy into vibration with increasing chlorination of the molecular reagent; <?^′_ν> = 0.50 (1a), <?^′_ν> = 0.23 (2a), <?^′_ν> = 0.13 (2b). The rate constants into ν′ = 0, k(ν′ = 0), were obtained by extrapolation of surprisal plots; the trends for both series were, however, also evident from k(ν′ > 0). No separate initial rotational distribution was observed for any of these reactions, indicating that the peak of the initial distribution is not far removed from a 300 K thermal distribution. The decrease in <?^′_ν> for the HF products along series 2 was tentatively ascribed to increasing internal excitation in the ejected radicals CH₂Cl, CHCl₂, CCl₃, due to increase in the number of secondary encounters between HF and the departing radical.     

Unsteady shrinking sheet with mass transfer in a rotating fluid

In this paper, the problem of unsteady flow induced by a shrinking sheet with mass transfer in a rotating fluid is studied. The transformed boundary layer equations are solved numerically by an implicit finite‐difference scheme known as the Keller‐box method. The influence of rotation, unsteadiness and mass suction parameters on the reduced skin friction coefficients f″(0) and g′(0), as well as the lateral velocity and velocity profiles are presented and discussed in detail. Copyright © 2010 John Wiley & Sons, Ltd.     

Structure and ion exchange properties of a new cobalt borate with a tunnel structure "templated" by Na+

The new anhydrous borate Na2Co2B12O21 has been synthesized by flux methods and studied by single-crystal X-ray diffraction (space group I2/a with a = 17.1447(15) A, b = 4.5530(5) A, c = 19.4408(15) A, beta = 103.212(5) degrees , V = 1477.4(2) A3, Z = 4). Refinement of its structure reveals it is the first metaborate exhibiting a tunnel network, with internal dimensions of 4.5 x 8.8 A2. Further single-crystal diffraction studies show that the Na+ ions within the tunnels are exchangeable with Li+ along with the absorption of water molecules to form Li2(H2O)2Co2B12O21, making this compound a unique non-siliceous zeotype.     

Injection locked multi-section gain-coupled dual mode DFB laser for terahertz generation

A dual mode multi-section gain-coupled distributed feedback laser with tunable mode spacing is subharmonically injection locked at 0.315 THz. The injected signal consists of an optical comb with harmonics 35 GHz apart and a bandwidth of approximately 1.9 THz. The optical comb is a result of strong four-wave mixing in a highly-nonlinear dispersion-shifted fiber. In order to observe locking of the multi-section laser, the output is optically downconverted to RF frequencies using the same optical comb. The locked multi-section DFB laser is a coherent and tunable optical source suitable for continuous-wave terahertz generation systems.     

Encapsulation and characterization of flurbiprofen loaded poly(є-caprolactone)–poly(vinylpyrrolidone) blend micropheres by solvent evaporation method

Flurbiprofen loaded PCL/PVP blend microspheres were prepared by o/w solvent evaporation method using various concentrations of gelatin as emulsifying agent. Microsphere recovery decreased with a decrease in the concentration of the emulsifier in the dispersion. Encapsulation efficiency and drug loading of microspheres increased with decrease in concentration of emulsifying agent. Hydration rate, encapsulation efficiency and drug loading of microspheres increased with increase in concentration of PVP. Rheological properties showed free flowing nature of microspheres. SEM (Scanning electron microscope) revealed microspheres were discrete, spherical and became porous with decrease in concentration of emulsifying agent but smooth with higher concentration of emulsifying agent. FTIR (Fourier transform infrared spectroscopy) spectra of pure and encapsulated flurbiprofen in all formulation showed no significant difference in characteristic peaks, suggesting stability of flurbiprofen during encapsulation process. X-RD (X-ray powder diffractometry) of pure flurbiprofen shows sharp peaks, which decreases on encapsulation, indicating dispersion at molecular level and hence decrease in the crystallinity of drug in microspheres. Microspheres showed an enteric nature at pH 1.2 and a sustained release pattern at pH 6.8. Rapid drug release was observed in microspheres with higher concentration of PVP (polyvinylpyrrolidone), PVP acts as channeling agent. Formulation with low concentration of emulsifying agent also showed a fast release due to porous structure. Drug release kinetics followed zero order at pH 1.2 while at pH 6.8 Higuchi model was best fitted and was found non fickian.