Progress toward the total synthesis of ciguatoxins: a convergent synthesis of the FGHIJKLM ring fragment

[structure: see text] A highly convergent synthetic route to the FGHIJKLM ring fragment of ciguatoxins has been developed, which relied on extensive use of the B-alkyl Suzuki-Miyaura coupling reaction.     

Convergent synthesis of the ABCDE ring fragment of ciguatoxins

Synthesis of the ABCDE ring fragment of ciguatoxins has been achieved in a highly stereocontrolled and convergent manner via the B-alkyl Suzuki-Miyaura coupling-based approach.     

Reversed-phase liquid chromatographic retention and membrane activity relationships of local anesthetics

The chromatographic retention and membrane activity relationships of local anesthetics were studied to address the possible mechanisms for structure specificity and inflammation-associated decrease of their effects. Five representative drugs (3 mM for each) were reacted with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine liposomes in 25 mM potassium phosphate buffer (pH 5.9-7.9, containing 100 mM NaCl and 0.1 mM EDTA) for 10 min at 37 degrees C and the membrane fluidity changes were analyzed by measuring fluorescence polarization with 1,6-diphenyl-1,3,5-hexatriene. Their capacity factors were determined on octadecyl-, octyl- and phenyl-bonded silica columns with a mobile phase consisting of 25 mM potassium phosphate buffer (pH 5.9-7.9, containing 100 mM NaCl and 0.1 mM EDTA)-methanol (30:70, v/v) at a flow rate of 1.0 ml/min and at a column temperature of 37 degrees C and diode-array detection. Mepivacaine, prilocaine, lidocaine, ropivacaine and bupivacaine fluidized membranes in increasing order of intensity, which agreed with their clinical potency. The relative degree of membrane fluidization correlated with that of retention on an octadecyl stationary phase more significantly than the other phases. Both membrane-fluidizing effects and capacity factors decreased by lowering the reaction and mobile phase pH, being consistent with the hypothesis that anesthetic potency is reduced in inflammation because of tissue acidity. Reversed-phase liquid chromatography appears to be useful for estimating the structure-specific and pH-dependent membrane-fluidizing effects of local anesthetics.     

Super‐Resolution Imaging of the Golgi in Live Cells with a Bioorthogonal Ceramide Probe

We report a lipid‐based strategy to visualize Golgi structure and dynamics at super‐resolution in live cells. The method is based on two novel reagents: a trans‐cyclooctene‐containing ceramide lipid (Cer‐TCO) and a highly reactive, tetrazine‐tagged near‐IR dye (SiR‐Tz). These reagents assemble via an extremely rapid “tetrazine‐click” reaction into Cer‐SiR, a highly photostable “vital dye” that enables prolonged live‐cell imaging of the Golgi apparatus by 3D confocal and STED microscopy. Cer‐SiR is nontoxic at concentrations as high as 2 μM and does not perturb the mobility of Golgi‐resident enzymes or the traffic of cargo from the endoplasmic reticulum through the Golgi and to the plasma membrane.     

Properties of a three-dimensional photonic jet

By focusing light with a sphere several wavelengths in diameter, we can obtain a photonic nanojet [Opt. Express 13, 526 (2005)]: if light is focused on the surface of the sphere, the width of the beam stays smaller than the wavelength along a distance of propagation of approximately two wavelengths and reaches a high intensity. We use the rigorous Mie theory to analyze the basic properties of the photonic jet in the general three-dimensional polarized case. This fast algorithm allows us to determine the influence of the radius and the refractive index of the sphere on the photonic jet. The polarization response is also studied. We observe that high-intensity concentrations and subwavelength focusing are two different effects. Their basic properties are analyzed, and explanations are proposed.     

An electronmicroscopic study of hexagonal phases related to quasicrystals in Zn-Mg-RE alloys

A number of hexagonal phases with inflated/deflated a lattice parameters but equal c parameters are found to exist with compositions close to that of the icosahedral phase. Surprisingly, no cubic or orthorhombic approximants are found. The closeness of the hexagonal phases to the icosahedral phase is shown through the electron diffraction features. Through stereographic analysis of the hexagonal phases it is shown that they consist of three icosahedral units rotated by 120 degrees about a common twofold axis, forming the sixfold axis. It is suggested that this phase falls into a class of crystals closely related to both the icosahedral and decagonal quasicrystals, but are not approximants to them. These phases can instead be considered to be approximant to the hexagonal quasicrystal.     

Breakup modes of a laminar hollow water jet

Graphical Abstract  

     

Radiation damage in Si photodiodes by high-temperature irradiation

Results are presented of a detailed study of the effects of high-temperature 4-MeV neutron irradiation on the performance degradation of Si pin photodiodes together with the radiation-induced defects, observed by deep level transient spectroscopy. The degradation of the device performance and the introduction rate of the lattice defects decrease with increasing sample temperature during irradiation. For a 250°C irradiation, the reduction of the reverse current is only 20% of the starting value. This result suggests that the creation and recovery of the radiation damage proceeds simultaneously at high temperatures. Carbon-related complex as hole capture levels is also mainly responsible for the device degradation for high-temperature neutron irradiation.     

Population study of sizes and components of self-reproducing giant multilamellar vesicles

Population analysis of a system of self-reproducing giant multilamellar vesicles (GMVs) was carried out by means of flow cytometry. The multidimensional distribution of forward light scattering (FS), side light scattering (SS), and fluorescence (FL) intensities originating from each GMV provided information about changes in a population composed of 104 vesicles. FS-FL dot plots indicated that, after the addition of the membrane precursor, the size distribution of the newly generated vesicles was nearly the same as that of the original, but the catalyst content was reduced. This result can be interpreted as evidence for the occurrence of the self-reproduction of GMVs. Moreover, the new GMVs recovered the amount of catalyst to the initial value, keeping their size distribution constant, when a solution of the catalyst was added to the new GMVs. These results are the first experimental evidence for a novel phenomenon on GMV size distribution during their self-reproducing cycle.