Asymmetric Synthesis of a Fused Tricyclic Hydronaphthofuran Scaffold by Desymmetric [2+2+2] Cycloaddition

A rhodium(I)‐BINAP‐catalyzed highly enantioselective [2+2+2] cycloaddition of enynes with alkynes has been developed. Diverse fused tricyclic hydronaphthofuran scaffolds with three consecutive stereogenic centers were constructed in one step from easily available materials with excellent chemo‐, regio‐, diastereo‐, and enantioselectivity. Notable features of these reactions include 100 % atom economy, very broad scope, and mild reaction conditions.     

A facile route for creating "reverse" vesicles: insights into "reverse" self-assembly in organic liquids

Reverse vesicles are spherical containers in organic liquids (oils) consisting of an oily core surrounded by a reverse bilayer. They are the organic counterparts to vesicles in aqueous solution and could potentially find analogous uses in encapsulation and controlled release. However, few examples of robust reverse vesicles have been reported, and general guidelines for their formation do not exist. We present a new route for forming stable unilamellar reverse vesicles in nonpolar organic liquids, such as cyclohexane and n-hexane. The recipe involves mixing short- and long-chain lipids (lecithins) with a trace of a salt such as sodium chloride. The ratio of short- to long-chain lecithin controls the type and size of self-assembled structure. As this ratio is increased, a spontaneous transition from reverse micelles to reverse vesicles occurs. Small-angle neutron scattering (SANS) and transmission electron microscopy (TEM) confirm the presence of unilamellar vesicles in the corresponding solutions. Average vesicle diameters can be tuned from 60 to 250 nm depending on the sample composition.     

Synthesis and molecular structure of substituted 2-hydroxyperhydro-[1,3,2]dioxaborinino[5,4-<Emphasis Type="Italic">c</Emphasis>]pyridines,perhydro[1,3]dioxano[5,4-<Emphasis Type="Italic">c</Emphasis>]pyridine,and their precursor-4-hydroxy-3-(α-hydroxybenzyl)-1-methyl-4-phenylpiperidine

4,8a-Diphenyl-substituted 2-(2-propoxy)perhydro[1,3,2]dioxaborinino[5.4-c]pyridine was obtained by the condensation of 4-hydroxy-3-(α-hydroxybenzyl)-1-methyl-4-phenylpiperidine with triisopropyl borate, and its 2-hydroxysubstituted analog in the presence of water. 1-Methyl-4,8a-diphenyl-perhidro[1,3]dioxano[5,4-c]pyridine was synthesized by the reaction of the same piperidol with formaldehyde. A comparative study of the molecular structures of the three products was carried out by X-ray crystallography. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, 1726–1735, November, 2008.     

A first eigenvalue estimate for embedded hypersurfaces

Suppose that M is a compact orientable hypersurface embedded in a compact n-dimensional orientable Riemannian manifold N. Suppose that the Ricci curvature of N is bounded below by a positive constant k. We show that 2λ₁>k−(n−1)maxM|H| where λ₁ is the first eigenvalue of the Laplacian of M and H is the mean curvature of M.     

Saccharomyces cerevisiae oxidosqualene‐lanosterol cyclase: A chemistry–biology interdisciplinary study of the protein's structure–function–reaction mechanism relationships

The oxidosqualene cyclases (EC 5.4.99‐) constitute a family of enzymes that catalyze diverse cyclization/rearrangement reactions of (3S)‐2,3‐oxidosqualene into a distinct array of sterols and triterpenes. The relationship between the cyclization mechanism and the enzymatic structure is extremely complex and compelling. This review covers the historical achievements of biomimetic studies and current progress in structural biology, molecular genetics, and bioinformatics studies to elucidate the mechanistic and structure–function relationships of the Saccharomyces cerevisiae oxidosqualene‐lanosterol cyclase‐catalyzed cyclization/rearrangement reaction. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 302–325; 2008: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20157     

Static Charge Susceptibility in the <Emphasis Type=Italic>t-J-V</Emphasis> Model

We describe the static charge susceptibility and correlation function of the charge density in the twodimensional t-J-V model based on the method of equations of motion for the relaxation functions of the Hubbard operators. We obtain the dependence of the susceptibility and correlation function on the hole concentration and temperature. Charge density waves can develop if the intersite Coulomb interaction is sufficiently strong.     

Transmission properties of electromagnetic metamaterials: From split-ring resonator to fishnet structure

We experimentally presented the electromagnetic behavior of transformative magnetic metamaterials: from the early invented split-ring resonator to its improvement, the cut-wire pair, for providing a negative magnetic permeability. By adding the continuous wire to cut-wire pair structure, the left-handed (LH) transmission made by doubly negative permittivity and permeability was demonstrated in combined structure. Interestingly, until the width of cut-wire pair increases to be physically merged with the adjacent continuous wire, in other words, to form the so-called fishnet structure, the LH behavior is still observed. This result indicates that in a broad sense, the essence of the electromagnetic response in the fishnet structure is similar to that in a combined structure. Our experimental results show a good agreement with previous theoretical study.     

Thermocapillary convection in an absorbing-scattering medium subjected to irradiation

The criteria for the onset of thermocapillary convection in a horizontal radiating fluid layer heated by an incident thermal radiative energy source are determined. The fluid layer is an absorbing and isotropically scattering medium confined between a free upper surface and an insulated rigid lower surface. Linear analysis is performed on the continuity, momentum, energy, and approximate radiative equations. The resulting disturbance equations are solved using a numerical optimization technique to obtain the eigenvalues governing the onset of convective motion. The influence of thermal radiation on the critical Marangoni number is examined. Attention is drawn to the physical significance of the heat transfer mode, gravitational force, the scattering effect, and the surface radiative properties. The conditions leading to the onset of convection are presented as functions of the optical thickness, scattering albedo, Planck number, surface emissivities, and transmissivities.     

Energy transfer of ionic dyes in mixed surfactant vesicle

Stable vesicles composed of cationic and anionic single-tailed-surfactant were prepared, and their image obtained by electron microscopy with negative staining technique. Significant fluorescence enhancement for acridine orange in vesicle with regards to water has been observed. In heterogeneous vesicle solution composed of mixed cationic and anionic surfactants for the energy transfer between acridine orange (D) and pyronine (A), the Förster dipole-dipole model was valid, and it is interesting to note that the energy transfer rate constant (k_ET) was smaller than that in homogeneous aqueous solution. On the inside and outside of the stable vesicle, immiscible water solution of acridine orange and pyronine could be obtained, and the distance calculated from the energy transfer between D and A separated by the bilayer membrane implied that the location of ionic dye molecules was in the Gouy-Chapman layers of the vesicles. Furthermore, due to the electrostatic absorption of the dye molecules to charged headgroups of surfactants, acridine orange and pyronine accumulated and aggregated to the vesicle bilayer membrane.