A new efficient route for multigram asymmetric synthesis of alkannin and shikonin

A short and convergent approach for the synthesis of alkannin, shikonin and shikalkin is presented. A Hauser-type annulation of cyanophthalide 26 with enone 7 affords the complete aromatic system in just one step with concomitant attachment of the entire side chain. Subsequent Corey's oxazaborolidine mediated asymmetric reduction of the above advanced intermediate, leads to the required isomer in high enantiomeric excess. Finally, a selective and high yielding deprotection protocol furnishes the title compounds as pure crystalline precipitates. Thus, a multigram synthesis of shikonin, alkannin and shikalkin is achieved in high yield and enantioselectivity.     

Novel synthesis of (−)-trans-Δ9,11-tetrahydrocannabinol

Addition of hydrogen chloride gas to a solution of Δ⁸-tetrahydrocannabinol in dry dichloromethane at -60° in the presence of zinc chloride results in the formation of a higher concentration of 9-α-chlorohexa-hydrocannabinol (75%) than the thermodynamically more stable 9-β-chlorohexahydrocannabinol (25%). The two isomers can be separated by reverse-phase hplc. Elimination of hydrogen chloride from 9-α-chlorohexa-hydrocannabinol using potassium t-amylate under anhydrous conditions gives exclusively Δ^9,11-tetrahydrocannabinol in overall yield of 65%.     

Complementary liposomes based on phosphatidylcholine: interaction effectiveness vs protective coating

A prospective targeted drug delivery system was prepared by the introduction of complementary and protective moieties at the external surfaces of liposomes. Thus recognition between hydrogenated phosphatidylcholine-cholesterol-based liposomes was achieved by the interaction of the complementary phosphate and guanidinium groups incorporated in separate liposomes while polyethylene glycol chains (PEG) protected both liposomes from environmental factors. In general, protective coating of liposomes in the range of 5% molar incorporation exerted an inhibitory effect on their recognition but it also permitted effective interaction between complementary liposomes.     

A concise methodology for the synthesis of (−)-Δ-tetrahydrocannabinol and (−)-Δ-tetrahydrocannabivarin metabolites and their regiospecifically deuterated analogs

The availability of tetrahydrocannabinols (Δ⁹-THC), tetrahydrocannabivarins (Δ⁹-THCV), and their metabolites in both their undeuterated and deuterated forms is critical for the analysis of biological and toxicological samples. We report here a concise methodology for the syntheses of (−)-Δ⁹-THC and (−)-Δ⁹-THCV metabolites in significantly improved overall yields using commercially available starting materials. Our approach allowed us to obtain the key intermediates (6aR,10aR)-9-nor-9-oxo-hexahydrocannabinols in four steps from (+)-(1R)-nopinone. This was followed by an optimized Shapiro reaction to give the (−)-11-nor-9-carboxy-metabolites, which were converted to their respective (−)-11-hydroxy analogs. The synthetic sequence involves a minimum number of steps, avoids undesirable oxidative conditions, and incorporates the costly deuterated resorcinols near the end of the synthetic sequence. This methodology enabled us to synthesize eight regiospecifically deuterated (−)-Δ⁹-THC and (−)-Δ⁹-THCV metabolites in a preparative scale and high optical purity without deuterium scrambling or loss.     

Interactions between C.I. Basic Blue 41 and aluminosilicate sorbents

Four aluminosilicate sorbents (montmorillonite, bentonite, raw perlite, and expanded perlite) were employed for retention of the cationic dye C.I. Basic Blue 41. Interactions between the clay and the dyestuff were investigated at several temperatures and clay:dye ratios. The mechanism behind the adsorption involves the formation of H-aggregates of the dye on both clays, followed by dye migration into the interlayer in the case of montmorillonite. Time-dependent absorbance spectra revealed the presence of various dye species in montmorillonite. Introduction of the dye molecules into the interlamellar space occurs more rapidly in bentonite than in montmorillonite. The dye molecules inserted between the clay leaves adopt different orientations and, eventually, stack in layers at increased dye loadings for both montmorillonite and bentonite. Higher dye aggregates are then present as suggested by diffuse reflectance spectroscopy. Dye sorption on both raw and expanded perlite proceeds via H-aggregate formation as well.     

Advanced MCMC methods for sampling on diffusion pathspace

The need to calibrate increasingly complex statistical models requires a persistent effort for further advances on available, computationally intensive Monte-Carlo methods. We study here an advanced version of familiar Markov-chain Monte-Carlo (MCMC) algorithms that sample from target distributions defined as change of measures from Gaussian laws on general Hilbert spaces. Such a model structure arises in several contexts: we focus here at the important class of statistical models driven by diffusion paths whence the Wiener process constitutes the reference Gaussian law. Particular emphasis is given on advanced Hybrid Monte-Carlo (HMC) which makes large, derivative-driven steps in the state space (in contrast with local-move Random-walk-type algorithms) with analytical and experimental results. We illustrate its computational advantages in various diffusion processes and observation regimes; examples include stochastic volatility and latent survival models. In contrast with their standard MCMC counterparts, the advanced versions have mesh-free mixing times, as these will not deteriorate upon refinement of the approximation of the inherently infinite-dimensional diffusion paths by finite-dimensional ones used in practice when applying the algorithms on a computer.     

Geographic characterization of Greek wine by inductively coupled plasma–mass spectrometry macroelemental analysis

Abstract

Studying wine mineral profile has been proven as a valuable tool in geographical origin discrimination and authenticity for both producers and consumers. Adulteration of wines, in terms of geographical origin or variety, is considered a major topic of extensive research. Traceability and authenticity of wines have been previously studied on the basis of typical mineral element patterns by means of chemometric methods. In this context, analytical methods were developed for the determination of mineral elements in wines by inductively coupled plasma–mass spectrometry. This study aimed at classifying selected varietal Greek wines from various regions by employing instrumental analysis. Preliminary data of wine mineral content enabled for the classification of samples according to geographical origin and variety. However, further work is required in order to draw more valid conclusions and to obtain a detailed map of the mineral element content of Greek wines according to their geographical origin and/or variety.     

Superconducting coatings of MgB2 prepared by electrophoretic deposition

The electrophoretic deposition technique was applied for the production of MgB₂ superconducting coatings on various substrates, by using a suspension of MgB₂ superconducting powder in an organic solvent. The main parameters that affect the deposition rate of the process and the quality of the coatings produced, such as the initial concentration of the suspension, the applied voltage and the distance between the electrodes, were investigated and optimized. The coatings produced were characterized and investigated for possible interaction between the substrate and the deposited superconductor by X-ray diffraction. The superconducting properties were measured by magnetic susceptibility (superconducting quantum interference device).     

A new series of sodium cobalt oxyhydrates

We report a new series of sodium cobalt oxyhydrates that contains the same two dimensional building blocks as superconducting NaxCoO2.yH2O. The absence of superconductivity emphasises the importance of the CoO2 stacking arrangement on the resultant electronic properties.     

Total asymmetric synthesis of (–)-Phenylhistine, (–)-Aurantiamine and related compounds. Part I

A new general, short, and efficient strategy for the construction of dehydro-diketopiperazines was developed. Horner–Emmons type coupling between a phosphinyl glycine ester and a formyl heterocycle is the key coupling reaction, which proceeds in good-to-excellent yields on several sterically-hindered substrates. Moreover, racemization of the parent L-amino acids is avoided as a result of the mild basic conditions used. The selection of the NH protective group of the formyl heterocycle was crucial. N-tosylated heterocycles proved ideal for this reaction sequence. Thus, the title compounds, (–)-Phenylhistine and (–)-Aurantiamine, were prepared in high yield (four steps, 47% overall) and optical purity. Furthermore, the synthesis of unnatural derivatives including an indole analogue was successfully completed.