Synthesis of highly enantioenriched hydroxy- and dihydroxy-fatty esters: substrate precursors for cytochrome P450BioI

A series of highly enantioenriched hydroxy- and dihydroxy-fatty esters were required as part of our ongoing investigation into cytochrome P450_BioI. This mediates the biosynthesis of pimelic acid via C–C bond cleavage of long chain fatty acids within Bacillus subtilis. Herein we report the synthesis of various stereoisomers of methyl 7-hydroxytetradecanoate, methyl 8-hydroxytetradecanoate, and methyl 7,8-dihydroxytetradecanoate in highly enantioenriched form, using a combination of asymmetric synthesis and a preparative enantioselective HPLC is reported.     

Blast noise propagation above a snow cover.

A porous medium model of a snow cover, rather than a viscoelastic treatment, has been used to simulate measured, horizontally traveling acoustic waveform propagation above a dry snow cover 11-20 cm thick. The waveforms were produced by explosions of 1-kg charges at propagation distances of 100 to 1400 m. These waveforms, with a peak frequency around 30 Hz, show pulse broadening effects similar to those previously seen for higher-frequency waves over shorter propagation distances. A rigid-ice-frame porous medium ("rigid-porous") impedance model, which includes the effect of the pores within the snow but ignores any induced motion of the ice particles, is shown to produce much better agreement with the measured waveforms compared with a viscoelastic solid treatment of the snow cover. From the acoustic waveform modeling, the predicted average snow cover depth of 18 cm and effective flow resistivities of 16-31 kPa s m(-2) agree with snow pit observations and with previous acoustic measurements over snow. For propagation in the upwind direction, the pulse broadening caused by the snow cover interaction is lessened, but the overall amplitude decay is greater because of refraction of the blast waves.     

Eulerian graphs and automorphisms of a maximal graph

Let R be a commutative ring with identity. Let Γ(R) denote the maximal graph corresponding to the non-unit elements of R, i.e., Γ(R) is a graph with vertices the non-unit elements of R, where two distinct vertices a and b are adjacent if and only if there is a maximal ideal of R containing both. In this paper, we have shown that, for any finite ring R which is not a field, Γ(R) is a Euler graph if and only if R has odd cardinality. Moreover, for any finite ring R ? R ₁×R ₂× · · · ×R _n, where the R _i is a local ring of cardinality p _i ^αi for all i, and the p _i’s are distinct primes, it is shown that Aut(Γ(R)) is isomorphic to a finite direct product of symmetric groups. We have also proved that clique(G(R)’) = χ(G(R)’) for any semi-local ring R, where G(R)’ denote the comaximal graph associated to R.     

Optimal portfolio execution under cointegrated vector autoregressive systems

Abstract

In this paper, an optimal portfolio execution problem under price model which exhibits cointegration behaviour is proposed. The proposed problem is formulated as a quadratic programming problem. With different statistical procedures and parameter estimation methods, employed on real market financial data, the four portfolios are constructed with which, computational study is performed. It is shown that the trading strategies constructed out of portfolios with cointegrated price dynamics show significant reduction in execution cost.     

Intramolecularly coordinated organotin(IV) sulphides and their reactivity to iodine

Organotin(IV) sulphides (LSnPhS)₂ (3) and (LSnPh₂)₂S (4) containing O,C,O chelating ligand (L = 2,6-(t BuOCH₂)₂C₆H₃⁻) were prepared by the reaction of parent organotin chlorides LSnPhCl₂ (1) and LSnPh₂Cl (2) with Na₂S · 9H₂O in toluene/water. Both sulphides were characterized by the help of elemental analysis, ESI-mass spectrometry, ¹H, ¹³C ¹¹⁹Sn NMR spectroscopy and the molecular structure of 3 was determined by X-ray diffraction techniques. Compounds 3 and 4 react with I₂ to organotin iodides LSnPhI₂ (5) and LSnPh₂I (6), instead of intended iodolysis of phenyl groups. Triorganotin iodide 6 reacts with the additional molecule of I₂ forming an ionic organotin compound [ LSnPh₂]⁺ I₃⁻ (7), which is unstable in solution and decomposes to Ph₂SnI₂ and 2,6-(tBuOCH₂)₂C₆H₃I (8).     

1H NMR spectroscopic study of complexation of citalopram with beta-cyclodextrin in aqueous solution

(1)H NMR spectroscopic study of citalopram (CT) in the absence as well as in the presence of beta-cyclodextrin (beta-CD) in aqueous solution revealed the formation of four 1:1 beta-CD-CT inclusion complexes. The stoichiometry of the complexes was determined by the continuous variation (Job) method, which was further confirmed by Scott's method. The binding constants (K(R) and K(R, S)) were calculated using Scott's method. The structures of all the complexes have been proposed as shown in the diagrams. All the CT proton resonances showed splitting in the presence of beta-CD, owing to chiral discrimination by the beta-CD, between the two enantiomers. The chiral discrimination appears to be due to different modes of binding of the R- and S-CT in the complexes involving a CN-containing aromatic ring.     

Field dependence of liquid-crystalline phase in liquid-crystal and carbon nanotubes composite

Due to their exceptional properties, liquid crystals are useful for a wide range of applications. As reported in the literature, a slight dispersion of liquid crystals with carbon nanotubes has a detectable effect on the liquid-crystal properties making them appropriate for various applications. The present work reports a new application of these composites disclosing a process of transformation of commercially available high-temperature liquid crystals into low-temperature liquid crystals. This is accomplished by using high concentration of carbon nanotubes in liquid-crystal materials wherein the carbon nanotubes form cluster inside the liquid-crystal cells. The application of bias on these heavily doped samples resulted in the appearance of liquid-crystal phases at room temperature which, in the case of pure liquid crystals, were observable only at high temperature. The process is reversible and hence phase change can be controlled by external field.     

Radiation products at 77 K in trehalose single crystals: EMR and DFT analysis

The radicals obtained in trehalose dihydrate single crystals after 77 K X-irradiation have been investigated at the same temperature using X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and ENDOR-induced EPR (EIE) techniques. Five proton hyperfine coupling tensors were unambiguously determined from the ENDOR measurements and assigned to three carbon-centered radical species (T1, T1*, and T2) based on the EIE spectra. EPR angular variations revealed the presence of four additional alkoxy radical species (T3 to T6) and allowed determination of their g tensors. Using periodic density functional theory (DFT) calculations, T1/T1*, T2, and T3 were identified as H-loss species centered at C4, C1', and O2', respectively. The T4 radical is proposed to have the unpaired electron at O4, but considerable discrepancies between experimental and calculated HFC values indicate it is not simply the (net) H-loss species. No suitable models were found for T5 and T6. These exhibit a markedly larger g anisotropy than T3 and T4, which were not reproduced by any of our DFT calculations.     

Single-molecule enzyme kinetics in the presence of inhibitors

Recent studies in single-molecule enzyme kinetics reveal that the turnover statistics of a single enzyme is governed by the waiting time distribution that decays as mono-exponential at low substrate concentration and multi-exponential at high substrate concentration. The multi-exponentiality arises due to protein conformational fluctuations, which act on the time scale longer than or comparable to the catalytic reaction step, thereby inducing temporal fluctuations in the catalytic rate resulting in dynamic disorder. In this work, we study the turnover statistics of a single enzyme in the presence of inhibitors to show that the multi-exponentiality in the waiting time distribution can arise even when protein conformational fluctuations do not influence the catalytic rate. From the Michaelis-Menten mechanism of inhibited enzymes, we derive exact expressions for the waiting time distribution for competitive, uncompetitive, and mixed inhibitions to quantitatively show that the presence of inhibitors can induce dynamic disorder in all three modes of inhibitions resulting in temporal fluctuations in the reaction rate. In the presence of inhibitors, dynamic disorder arises due to transitions between active and inhibited states of enzymes, which occur on time scale longer than or comparable to the catalytic step. In this limit, the randomness parameter (dimensionless variance) is greater than unity indicating the presence of dynamic disorder in all three modes of inhibitions. In the opposite limit, when the time scale of the catalytic step is longer than the time scale of transitions between active and inhibited enzymatic states, the randomness parameter is unity, implying no dynamic disorder in the reaction pathway.