Carbohydrates in asymmetric synthesis: enantioselective allylation of aldehydes

An enantioselective metal-mediated addition of allylic bromides to carbonyl compounds was achieved in the presence of the inexpensive and easily accessible carbohydrates saccharose and beta-cyclodextrin. The desired products were obtained in moderate to excellent yields and with up to 93% enantiomeric excess. (C) 2008 Elsevier Ltd. All rights reserved.

Nucleophilic addition of potassium organotrifluoroborates to chiral cyclic N-acyliminium ions: stereoselective synthesis of functionalized N-heterocycles

The stereoselective nucleophilic addition of potassium aryl- and alkynyltrifluoroborates to cyclic N-acyliminium ion derivatives from N-benzyl-3,4,5-triacetoxy-2-pyrrolidinone, affording the respective 5-substituted 2-pyrrolidinone is described. The products were obtained in moderate to good yields and with preference for the syn diastereomer. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis of potassium and tetra n-butylammonium 2-substituted-1,3-dithianotrifluoroborate salts and addition to chiral cyclic N-acyliminium ions

The synthesis of potassium 2-substituted-1,3-dithianotrifluoroborate salts and tetra-n-butyl ammonium derivatives is described. The reaction proceeds under mild reaction conditions and the corresponding products were obtained in moderate to good yields. The reactivity of these compounds in rections with chiral cyclic N-acyliminium ions was evaluated.

Asymmetric dimethylarginine endogenous inhibition of nitric oxide synthase causes differential vasculature effects

Background: Asymmetric dimethylarginine (ADMA), produced during protein metabolism, is an endogenous inhibitor of nitric oxide synthase, but little is known about its direct vasoactive properties in different arterial beds. Material/Methods: Segments of canine coronary, renal, and femoral arteries were pretreated with increasing concentrations of ADMA, and endothelial function was evaluated in organ chambers. Results: In precontracted canine coronary arteries, the highest concentrations of ADMA inhibited endothelium-dependent relaxation mediated by acetylcholine (n=7), but no concentration of ADMA inhibited receptor-independent relaxation mediated by calcium ionophore (n=7) (P<.001). The effect of ADMA on acetylcholine-mediated relaxation was shown to be competitive inhibition of the nitric oxide synthase pathway, because the addition of L-arginine (10(-3) M), but not D-arginine (101 M), reversed the effect produced by 10(-5) M ADMA. Further, ADMA did not alter endothelium-independent relaxation mediated by sodium nitroprusside (10(-9) to 10(-6) M; n=7). Femoral arteries (n=7) and renal arteries (n=7) were more sensitive to ADMA than were coronary arteries, and they demonstrated significant ADMA inhibition to receptor dependent relaxation induced by acetylcholine (P=.03 and P=.01, respectively) and to receptor-independent relaxation induced by calcium ionophore (P=.02 and P=.01, respectively). Conclusions: Endothelium-dependent relaxation mediated by ADMA is more marked in femoral and renal arteries than in coronary arteries. The response in coronary arteries may be overall protective. Considering these different effects in various artery types, the role of ADMA as a confiable and specific cardiovascular risk factor is questioned.

Asymmetric cheating opportunities and partner control in a cleaner fish mutualism

How can cooperation persist if, for one partner, cheating is more profitable than cooperation in each round, while the other partner has no option to cheat? Our laboratory experiments suggest that such a situation exists between the cleaner fish Labroides dimidiatus and its nonpredatory client reef fish species, which actively seek cleaners to have their ectoparasites removed. Clients Ctenochaetus striatus regularly jolted in response to cleaner mouth contact, and these jolts were not linked to the removal of parasites. In addition, cleaners did not search for parasites but fed on mucus when exposed to anaesthetized clients, which could not control the cleaners' behaviour. Field data showed that clients often terminated an interaction immediately after a jolt. Client species with access to only one cleaning station, owing to their small territories or home ranges, terminated interactions mainly by chasing cleaners while clients with access to two or more cleaning stations mainly swam away. Thus, the chasing of cleaners appeared to be a form of punishment, imposing costs on the cleaner at the client's (momentary) expense. Chasing yields future benefits, as jolts were on average less frequent during interactions between cleaners and individuals that had terminated their previous interaction by aggressive chasing. 2002 The Association for the Study of Animal Behaviour.

Asymmetric contribution of α and β subunits to the activation of αβ heteromeric glycine receptors

This study investigated the role of beta subunits in the activation of alphabeta heteromeric glycine receptor (GlyR) chloride channels recombinantly expressed in HEK293 cells. The approach involved incorporating mutations into corresponding positions in alpha and beta subunits and comparing their effects on receptor function. Although cysteine-substitution mutations to residues in the N-terminal half of the alpha subunit M2-M3 loop dramatically impaired the gating efficacy, the same mutations exerted little effect when incorporated into corresponding positions of the beta subunit. Furthermore, although the alpha subunit M2-M3 loop cysteines were modified by a cysteine-specific reagent, the corresponding beta subunit cysteines showed no evidence of reactivity. These observations suggest structural or functional differences between alpha and beta subunit M2-M3 loops. In addition, a threonine-->leucine mutation at the 9' position in the beta subunit M2 pore-lining domain dramatically increased the glycine sensitivity. By analogy with the effects of the same mutation in other ligand-gated ion channels, it was concluded that the mutation affected the GlyR activation mechanism. This supports the idea that the GlyR beta subunit is involved in receptor gating. In conclusion, this study demonstrates that beta subunits contribute to the activation of the GlyR, but that their involvement in this process is significantly different to that of the alpha subunit.

Tailoring of structures and permeation properties of asymmetric nanocomposite cellulose acetatesilver membranes

Cellulose acetate (CA)-silver (Ag) nanocomposite asymmetric membranes were prepared via the wet-phase inversion method by dispersing polyvinylpirrolydone-protected Ag nanoparticles in the membrane casting solutions of different compositions. Silver nanoparticles were synthesized ex situ and added to the casting solution as a concentrated aqueous colloidal dispersion. The effects of the dispersion addition on the structure and on the selective permeation properties of the membranes were studied by comparing the nanocomposites with the silver-free materials. The casting solution composition played an important role in the adequate dispersion of the silver nanoparticles in the membrane. Incorporation of nanoscale silver and the final silver content resulted in structural changes leading to an increase in the hydraulic permeability and molecular weight cut-off of the nanocomposite membranes. (c) 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41796.

Efficiency Comparison of DFT/IDFT Algorithms by Evaluating Diverse Hardware Implementations

In this paper we investigate various algorithms for performing Fast Fourier Transformation (FFT)/Inverse Fast Fourier Transformation (IFFT), and proper techniques for maximizing the FFT/IFFT execution speed, such as pipelining or parallel processing, and use of memory structures with pre-computed values (look up tables -LUT) or other dedicated hardware components (usually multipliers). Furthermore, we discuss the optimal hardware architectures that best apply to various FFT/IFFT algorithms, along with their abilities to exploit parallel processing with minimal data dependences of the FFT/IFFT calculations. An interesting approach that is also considered in this paper is the application of the integrated processing-in-memory Intelligent RAM (IRAM) chip to high speed FFT/IFFT computing. The results of the assessment study emphasize that the execution speed of the FFT/IFFT algorithms is tightly connected to the capabilities of the FFT/IFFT hardware to support the provided parallelism of the given algorithm. Therefore, we suggest that the basic Discrete Fourier Transform (DFT)/Inverse Discrete Fourier Transform (IDFT) can also provide high performances, by utilizing a specialized FFT/IFFT hardware architecture that can exploit the provided parallelism of the DFT/IDF operations. The proposed improvements include simplified multiplications over symbols given in polar coordinate system, using sinе and cosine look up tables, and an approach for performing parallel addition of N input symbols.

Efficiency Comparison of DFT/IDFT Algorithms by Evaluating Diverse Hardware : Implementations,Parallelization Prospectsand Possible Improvements

In this paper we investigate various algorithms for performing Fast Fourier Transformation (FFT)/Inverse Fast Fourier Transformation (IFFT), and proper techniquesfor maximizing the FFT/IFFT execution speed, such as pipelining or parallel processing, and use of memory structures with pre-computed values (look up tables -LUT) or other dedicated hardware components (usually multipliers). Furthermore, we discuss the optimal hardware architectures that best apply to various FFT/IFFT algorithms, along with their abilities to exploit parallel processing with minimal data dependences of the FFT/IFFT calculations. An interesting approach that is also considered in this paper is the application of the integrated processing-in-memory Intelligent RAM (IRAM) chip to high speed FFT/IFFT computing. The results of the assessment study emphasize that the execution speed of the FFT/IFFT algorithms is tightly connected to the capabilities of the FFT/IFFT hardware to support the provided parallelism of the given algorithm. Therefore, we suggest that the basic Discrete Fourier Transform (DFT)/Inverse Discrete Fourier Transform (IDFT) can also provide high performances, by utilizing a specialized FFT/IFFT hardware architecture that can exploit the provided parallelism of the DFT/IDF operations. The proposed improvements include simplified multiplications over symbols given in polar coordinate system, using sinе and cosine look up tables,and an approach for performing parallel addition of N input symbols.

Asymmetric and differential gene introgression at a contact zone between two highly divergent lineages of field voles (Microtus agrestis).

Secondary contact zones have the potential to shed light on the mode and rate at which reproductive isolation accumulates during allopatric speciation. We investigated the population genetics of a contact zone between two highly divergent lineages of field voles (Microtus agrestis) in the Swiss Jura mountains. To shed light on the processes underlying introgression, we used maternally, paternally, and bi-parentally inherited markers. Though the two lineages maintained a strong genetic structure, we found some hybrids and evidence of gene flow. The extent of introgression varied with the mode of inheritance, being highest for mtDNA and absent for the Y chromosome. In addition, introgression was asymmetric, occurring only from the Northern to the Southern lineage. Both patterns seem parsimoniously explained by neutral processes linked to differences in effective sizes and sex-biased dispersal rates. The lineage with lower effective population size was also the more introgressed, and the mode-of-inheritance effect correlated with the male-biased dispersal rate of microtine rodents. We cannot exclude, however, that Haldane's effect contributed to the latter, as we found a marginally significant deficit in males (the heterogametic sex) among hybrids. We propose a possible demographic scenario to account for the patterns documented, and empirical extensions to further investigate this contact zone.

Complex patterns of global spread in invasive insects: eco-evolutionary and management consequences

The advent of simple and affordable tools for molecular identification of novel insect invaders and assessment of population diversity has changed the face of invasion biology in recent years. The widespread application of these tools has brought with it an emerging understanding that patterns in biogeography, introduction history and subsequent movement and spread of many invasive alien insects are far more complex than previously thought. We reviewed the literature and found that for a number of invasive insects, there is strong and growing evidence that multiple introductions, complex global movement, and population admixture in the invaded range are commonplace. Additionally, historical paradigms related to species and strain identities and origins of common invaders are in many cases being challenged. This has major consequences for our understanding of basic biology and ecology of invasive insects and impacts quarantine, management and biocontrol programs. In addition, we found that founder effects rarely limit fitness in invasive insects and may benefit populations (by purging harmful alleles or increasing additive genetic variance). Also, while phenotypic plasticity appears important post-establishment, genetic diversity in invasive insects is often higher than expected and increases over time via multiple introductions. Further, connectivity among disjunct regions of global invasive ranges is generally far higher than expected and is often asymmetric, with some populations contributing disproportionately to global spread. We argue that the role of connectivity in driving the ecology and evolution of introduced species with multiple invasive ranges has been historically underestimated and that such species are often best understood in a global context.

Unsaturated Oxazolopiperidone Lactams: an Unexpected Domino-type Double Conjugate Additioncyclization Process

Reactions of 2-acetylindole enolate with unsaturated oxazolopiperidones 3, 4 and 10 unexpectedly gives pentacyclic dilactams 6, 7 and 11, respectively, resulting from a domino-type process involving two successive conjugate additions and a final cyclization.

Stereoselective syntheses of (+)- isoretronecanol and (+)-5-epi-tashiromine via addition of chiral titanium (iv) enolates to cyclic n-acyliminium ions

The stereoselective addition of the titanium (IV) enolates derived from (S)-4-isopropyl-N-4-chlorobutyryl-1,3-thiazolidine-2-thione (8) and from (S)-4-isopropyl-N-4-chloropentanoyl-1,3-thiazolidine-2-thione (9) to N-Boc-2-methoxypyrrolidine (5b) afforded the addition products (+)-10 and (+)-11 in 84% yield in both cases, as 8.6:1 and 10:1 diastereoisomeric mixtures, respectively. A three-step sequence allowed to convert these adducts to (+)-isoretronecanol (1) and (+)-5-epi-tashiromine (2) in 43% and 49% overall yield, respectively.

ASYMMETRIC SULFOXIDATION OF ALBENDAZOLE TO RICOBENDAZOLE BY FUNGI: EFFECT OF pH

Albendazole (ABZ) is an anthelmintic drug used for the treatment of infectious diseases in veterinary and human medicine. This drug is a prochiral drug that after administration, is rapidly oxidized in the pharmacologically active sulfoxide metabolite, which is also known as ricobendazole (ABZSOX). ABZSOX has a stereogenic center and possibly two enantiomers, (+)-ABZSOX and (-)-ABZSOX. In the present work, we investigate the pH effect on the asymmetric stereoselective sulfoxidation of ABZ into ABZSOX by employing the fungi Nigrospora sphaerica, Papulaspora immera Hotson, and Mucor rouxii. The results show a possibility of obtaining the pure enantiomers of the ricobendazole drug using fungi as biocatalytic agents. The three fungi showed a high degree of enantioselectivity expressed by enantiomeric excess. In addition, M. rouxii can be used as an alternative to obtain the (+)-ABZSOX enantiomer (ee 89.8%).