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.     

Fluorometric sensing of alkaline Earth metal cations by new lariat ethers having plural pyrenylmethyl groups on the electron-donating sidearms

[structure: see text] New fluorescent compounds (1), lariat ethers having plural pyrenylmethyl groups on the sidearms, were prepared, and their complexation behavior with alkaline earth metal cations was examined by fluorescence spectrometry. The pyrene excimer emission decreased accompanied with an increase in the monomer emission upon complexation with the metal ion. This finding is ascribed to the cooperative participation of one of the two sidearms in the complexation of the crown ring with the metal ion.     

Interfacial and micellar properties of binary mixtures of surfactant and phospholipid in an aqueous medium

Mixed micelles formed by zwitterionic surfactant dimethyldodecylammniopropane sulfonate and short-chain phospholipid 1,2-diheptanoyl-sn-glycero-3-phosphocholine in different proportions in an aqueous medium have been studied physicochemically at an air/water interface and in the bulk by using interfacial tension and pyrene fluorescence intensity measurements, respectively. The critical micellar concentration and free energies of micellization and of interfacial adsorption have been determined. The interfacial study reveals that a mixed monolayer is formed at the air/water interface by the adsorption of surfactant and phospholipid monomers. This has been confirmed by evaluating the interfacial parameters; the maximum surface excess, the minimum area per molecule of a surface-active compound, and the Gibbs surface excess related to surface pressure. The nonideality of mixing, expressed in the terms of the regular solution interaction parameter, #, has negative values over the whole mole fraction range. The negative # values indicate the mutual synergism between the surfactant and phospholipid monomers. The equilibrium distribution of components between micelle and monomer phases was evaluated using a theoretical treatment based on excess thermodynamics quantities evaluated by Motomura's formulation.     

Rate constants of the O(D) reactions with N2, O2, N2O, and H2O at 295 K

Using a technique of laser flash photolysis coupled with vacuum ultraviolet laser-induced fluorescence spectroscopy, the rate coefficients of O(¹D) reactions with N₂, O₂, N₂O, and H₂O at 295 ± 2 K have been determined to be , k_O2=(4.06±0.24)×10^-11, k_N2O=(1.35±0.08)×10^-10 and . The quoted uncertainties include estimated errors and are the 95% confidence level. The k_N2 and k_N2O values obtained are larger than the current NASA/JPL recommendations by 26% and 16%, respectively, although they are still within the error limits associated with the recommendations.     

Influence of β‐Cyclodextrin on the Mixed Micellization Process of Sodium Dodecyl Sulfate and Sodium Lauroyl Sarcosine and Formation of Inclusion Complexes

In this work, we have studied the influence of different concentrations of β‐Cyclodextrin (β‐CD) on the mixed micellization of anionic surfactants sodium dodecyl sulfate (SDS) and sodium lauroyl sarcosine (SLAS) at different SDS mole fractions (α_SDS). From conductivity data, the critical micellar concentration (cmc), the equivalent ionic conductivities of the monomeric species (Λ_m), the associated species (Λ_assc) and the micelle (Λ_mic), the degree of counterion dissociation (α) in the presence of β‐CD were evaluated from the slope of the conductivity versus concentration plots for the pure and binary mixtures. The apparent cmc of the surfactants vary linearly with the β‐CD concentrations. From the dependence of cmc of the surfactants on β‐CD concentration, we have deduced the association constant (K) of surfactant‐β‐CD inclusion complexes assuming 1∶1 stoichiometry. Theories of Clint, Regular solution, and Motomura's have been used for the evaluation of ideality or nonideality of the mixed system. Mixed micelles were found to be rich in SDS content at the cmc in the presence and the absence of β‐CD. The cmc values have been used to evaluate the transfer of standard free energy of micelles (ΔG⁰ _M,tr) from the aqueous medium to additive medium.     

Interactions of γ-Cyclodextrin with the Mixed Micelles of Anionic Surfactants and Their Inclusion Complexes Formation

Interactions of γ-cyclodextrin (γ-CD) with the single and mixed micelles of sodium dodecyl sulfate (SDS) and sodium lauroyl sarcosine (SLAS) have been studied at different concentrations of γ-CD by using conductivity measurements. From conductivity data, the pure and mixed critical micellar concentration (cmc), the equivalent ionic conductivities of the monomeric species (Λ _m), the associated species (Λ _assc) and the micelle (Λ _mic), the degree of counterion dissociation (χ) in the presence of γ-CD have been evaluated from the slope of the conductivity versus concentration plots for the pure and binary mixture of surfactants. From the dependence of cmc of the surfactantson γ-CD concentration, we have deduced the association constant (K) of surfactant-γ-CD inclusion complexes assuming 2:1 stoichiometry. Theories of Clint, regular solution, and Motomura's have been used for the evaluation of ideality or nonideality of the mixed system. Mixed micelles were found to be rich in SDS content in the presence and the absence of γ-CD. The cmc values have been used to evaluate the transfer of standard free energy of micelles (ΔG⁰ _M,tr) from the aqueous medium to additive medium.     

Measurement of the total active 8B solar neutrino flux at the Sudbury Neutrino Observatory with enhanced neutral current sensitivity

The Sudbury Neutrino Observatory has precisely determined the total active (nu(x)) 8B solar neutrino flux without assumptions about the energy dependence of the nu(e) survival probability. The measurements were made with dissolved NaCl in heavy water to enhance the sensitivity and signature for neutral-current interactions. The flux is found to be 5.21 +/- 0.27(stat)+/-0.38(syst) x 10(6) cm(-2) s(-1), in agreement with previous measurements and standard solar models. A global analysis of these and other solar and reactor neutrino results yields Deltam(2)=7.1(+1.2)(-0.6) x 10(-5) eV(2) and theta=32.5(+2.4)(-2.3) degrees. Maximal mixing is rejected at the equivalent of 5.4 standard deviations.