Asymmetric Total Syntheses,Stereostructures, and Cytotoxicities of Marine Bromotriterpenoids Aplysiol B (Laurenmariannol) and Saiyacenol A

There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis.     

Multi-Interactions in Ionic Liquids for Natural Product Extraction

Natural products with a variety of pharmacological effects are important sources for commercial drugs, and it is very crucial to develop effective techniques to selectively extract and isolate bioactive natural components from the plants against the background of sustainable development. Ionic liquids (ILs) are a kind of designable material with unique physicochemical properties, including good thermal stability, negligible vapor pressure, good solvation ability, etc. ILs have already been used in pharmaceuticals for extraction, purification, drug delivery, etc. It has been reported that multi-interactions, like hydrogen bonding, hydrophobic interactions, play important roles in the extraction of bioactive components from the plants. In this review, recent progress in the understanding of scientific essence of hydrogen bonding, the special interaction, in ILs was summarized. The extraction of various natural products, one important area in pharmaceutical, by conventional and functional ILs as well as the specific roles of multi-interactions in this process were also reviewed. Moreover, problems existing in bioactive compound extraction by ILs and the future developing trends of this area are given, which might be helpful for scientists, especially beginners, in this field.     

Physico-chemical aspects of polyethylene processing in an open mixer. Part 26: Formal kinetics of aldehyde and carboxylic acid formation at a constant rate

Formation of carboxylic acids at a constant rate can be easily explained. It seems to result from the formation and decomposition of α,γ-keto-hydroperoxides. Formal kinetics based on formation and decomposition of these structural units is in agreement with the experimental findings. The activation energy deduced from the calculations is negligible, in agreement with the experimental data showing the constant rate to be practically temperature independent. Comparison of the acids with the hydroperoxides and ketones formed initially shows that the rate of oxygen addition to alkyl radicals is significantly smaller than in low molecular mass liquids. The same conclusion is reached on comparing directly the acids formed on decomposition of α,γ-keto-hydroperoxides in polyethylene melt and in hexadecane. The rate of oxygen addition in polyethylene melt is closer to 2 × 10⁵ than to 6 × 10⁵ (s⁻¹) that is valid in hexadecane.It is possible to attribute the relatively small amount of aldehydes that might be formed at a constant rate to different reactions of alkoxy radicals that are not in a cage with other radicals. These alkoxy radicals result from the addition of peroxy radicals to unsaturated bonds. This addition is followed mainly by epoxide formation and simultaneous release of an alkoxy radical.     

Localization effects and measure source terms in numerical schemes for balance laws

This paper investigates the behavior of numerical schemes for nonlinear conservation laws with source terms. We concentrate on two significant examples: relaxation approximations and genuinely nonhomogeneous scalar laws. The main tool in our analysis is the extensive use of weak limits and nonconservative products which allow us to describe accurately the operations achieved in practice when using Riemann-based numerical schemes. Some illustrative and relevant computational results are provided.

     

A MODEL OF TROPICAL MARINE RESERVE‐FISHERY LINKAGES

ABSTRACT. The excessive and unsustainable exploitation of our marine resources has led to the promotion of marine reserves as a fisheries management tool. Marine reserves, areas in which fishing is restricted or prohibited, can offer opportunities for the recovery of exploited stock and fishery enhancement. In this paper we examine the contribution of fully protected tropical marine reserves to fishery enhancement by modeling marine reserve‐fishery linkages. The consequences of reserve establishment on the long‐run equilibrium fish biomass and fishery catch levels are evaluated. In contrast to earlier models this study highlights the roles of both adult (and juvenile) fish migration and larval dispersal between the reserve and fishing grounds by employing a spawner‐recruit model. Uniform larval dispersal, uniform larval retention and complete larval retention combined with zero, moderate and high fish migration scenarios are analyzed in turn. The numerical simulations are based on Mombasa Marine National Park, Kenya, a fully protected coral reef marine reserve comprising approximately 30% of former fishing grounds. Simulation results suggest that the establishment of a fully protected marine reserve will always lead to an increase in total fish biomass. If the fishery is moderately to heavily exploited, total fishery catch will be greater with the reserve in all scenarios of fish and larval movement. If the fishery faces low levels of exploitation, catches can be optimized without a reserve but with controlled fishing effort. With high fish migration from the reserve, catches are optimized with the reserve. The optimal area of the marine reserve depends on the exploitation rate in the neighboring fishing grounds. For example, if exploitation is maintained at 40%, the ‘optimal’ reserve size would be 10%. If the rate increases to 50%, then the reserve needs to be 30% of the management area in order to maximize catches. However, even in lower exploitation fisheries (below 40%), a small reserve (up to 20%) provides significantly higher gains in fish biomass than losses in catch. Marine reserves are a valuable fisheries management tool. To achieve maximum fishery benefits they should be complemented by fishing effort controls.     

Equilibrium in Queueing Systems with Complementary Products

We study a model of a queueing system with two complementary products/services. In our model, there is one M/M/1 system and another facility that provides instantaneous service. The two services are complementary and the customer has no benefit from obtaining just one of them. We investigate the model under various price structures and ownership assumptions.AMS subject classification: 90B22, 91A10The authors are equal in their contribution to this paper. This paper is submitted by the first author to the Tokyo Institute of Technology as partial fulfillment of the requirements for the Ph.D. program in the Department of Value and Decision Sciences, and the order of names was chosen in compliance with program conditions. This research was supported by the Israel Science Foundation (grant No. 237/02).     

The first total syntheses of (±)-Preussomerins K and L using 2-arylacetal anion technology

The first syntheses of newly isolated members of the Preussomerin family, Preussomerins K and L, are reported. Key steps include the functionalisation of a 2-arylacetal anion, one-pot Friedel-Crafts cyclisation-deprotection and reductive opening of epoxides.     

Stemmosides C and D, two novel unusual pregnane glycosides from Solenostemma argel: structural elucidation and configurational study by a combined NMR-quantum mechanical strategy

Stemmosides C and D, two novel pregnane glycosides characterized by an unusual C-17 side chain were isolated from the pericarps of Solenostemma argel. In addition, stemmoside D displays an uncommon 14β proton configuration, apparently being the first pregnane isolated from plants known to have a 15 keto, cis CD ring junction. Their structures have been established by ESIMS and NMR experiments. The relative configuration of the molecules was determined using a strategy based on the simulation of ¹H, ¹³C, and J coupling NMR parameters. DFT calculations of ¹H and ¹³C chemical shifts, and of the ¹H homonuclear spin–spin coupling constants were performed with the mPW1PW91 functional using the 6-31G(d,p) basis set on the fully optimized geometries of all the possible stereoisomers.     

Polynomial Quantization on Rank One Para-Hermitian Symmetric Spaces

We construct the polynomial quantization on the space G/H where G=SL(n,R),H=GL(n–1,R). It is a variant of quantization in the spirit of Berezin. In our case covariant and contravariant symbols are polynomials on G/H. We introduce a multiplication of covariant symbols, establish the correspondence principle, study transformations of symbols (the Berezin transform) and of operators. We write a full asymptotic decomposition of the Berezin transform.