Highly planar amphiphilic porphyrins

A first synthesis of an asymmetric and amphiphilic β-substituted porphyrin is reported. The porphyrin can be integrated into various types of nanostructures with the amphiphilic characters in hydrophilic solvents. The one-dimensional integration may induce a magnetic interaction between the central metals.     

Beam profile measurement with CR-39 track detector for low-energy ions

A CR-39 track detector was successfully used to measure the outline of thin low-energy ion beams. After the etching, the surface of the detector was examined with an observation system composed of a Normarski microscope, a CCD camera and a digital image processing computer. Beam images obtained with the system were in good agreement on the outline of the beam formed with a beam aperture. Also, the resolving power in the beam outline measurement was roughly explained from the consideration of the ion range and the etch-pit growth in the chemical etching for the CR-39 detector.     

Bonding properties and structures of titanium clusters on (10, 0) single wall carbon nano capsule

We optimize whole structures of Ti clusters, Ti_n (n=1, 3 and 7), on a zigzag-type (10, 0) single wall carbon nano capsule, C₁₆₀, by using the first principles molecular dynamics within the spin density functional approximation, and discuss the bonding properties of Ti clusters on the C₁₆₀. For all the clusters, the most stable configuration includes a site above a center of C-hexagonal or pentagonal ring. The shape of Ti₇ cluster is very different by the located site. The cluster in which Ti atoms are located around centers of hexagon has a flat bottom and flatten the curvature of C wall below it.     

57Fe and57Co Mössbauer studies of highT c Y-Ba-Cu oxides

The⁵⁷Co emission Mössbauer spectra from YBa₂Cu₃O_6.92 (1-2-307) and YBa₂Cu₃O_6.00 (1-2-306) have been measured and compared with the⁵⁷Fe absorption spectra from YBa₂Cu_2.95Fe_0.05O_7?δ in order to clarify decisively the site assignments for the⁵⁷Fe quadrupole-split doublets in these compounds. Mössbauer spectra obtained from both specimens consist of four components whose hyperfine interaction parameters well agree with each other. It is shown that the Co and Fe atoms mainly substitute at Cu1 chain sites in 1-2-307, but in 1-2-306 the Co atoms occupy randomly the Cu2 plane sites and indicate magnetically-split sextet which converts to a paramagnetic doublet of S-state Fe³⁺ in 1-2-307 by a post-annealing in O₂ gas.     

Interaction and arrangement of nitrogen and carbon atoms in fcc γ-iron

A Mössbauer effect measurement has been done for Fe?N, Fe?Al?C and Fe?Ni?C austenite in order to study the interaction between the interstitial atoms and their distribution among the octahedral sites of the fcc lattice, together with the influence of Al and Ni atoms. The spectra for Fe?N and Fe?Al?C austenite are decomposed into three components; one singlet γ₀, and two sets of doublet γ₁ and γ₂, with different quadrupole splittings, while no γ₂ component is found in the spectrum for Fe?Ni?C. By analyzing the component ratio in each spectrum, it is concluded that, in Fe?N and Fe?Al?C, the interaction between 2nd nearest neighboring nitrogen or carbon atoms is attractive, and is repulsive between 1st nearest for Fe?N, and that the interaction between 2nd nearest atoms is repulsive for Fe?Ni?C. By measuring the spectra of Fe?Ni?C in magnetic field, the sign of EFG for most of the γ₁ component is determined to be negative.     

Duplicated ring enlargement of 4,9-methanothia[11]annulene to 6,11-methanothia[15]annulene

3,10-Dipyrrolidinyl-4,9-methanothia[11]annulene reacts with excess dimethyl acetylenedicarboxylate (DMAD) in refluxing toluene to give ring-enlarged 6,11-methanothia[15]annulene. X-ray crystallographic analysis of the product shows two different cis,trans-dienyl parts in the ring system. Product formation possibly involves π-facial selective addition of the enamine with DMAD and torque-selective ring opening of the intermediate cyclobutenes.     

Preparation of highly dispersible and tumor-accumulative, iron oxide nanoparticles Multi-point anchoring of PEG-b-poly(4-vinylbenzylphosphonate) improves performance significantly

This paper describes the preparation of iron oxide nanoparticles, surface of which was coated with extremely high immobilization stability and relatively higher density of poly(ethylene glycol) (PEG), which are referred to as PEG protected iron oxide nanoparticles (PEG-PIONs). The PEG-PIONs were obtained through alkali coprecipitation of iron salts in the presence of the PEG-poly(4-vinylbenzylphosphonate) block copolymer (PEG-b-PVBP). In this system, PEG-b-PVBP served as a surface coating that was bound to the iron oxide surface via multipoint anchoring of the phosphonate groups in the PVBP segment of PEG-b-PVBP. The binding of PEG-b-PVBP onto the iron oxide nanoparticle surface and the subsequent formation of a PEG brush layer were proved by FT-IR, zeta potential, and thermogravimetric measurements. The surface PEG-chain density of the PEG-PIONs varied depending on the [PEG-b-PVBP]/[iron salts] feed-weight ratio in the coprecipitation reaction. PEG-PIONs prepared at an optimal feed-weight ratio in this study showed a high surface PEG-chain surface density (≈0.8 chainsnm(-2)) and small hydrodynamic diameter (<50 nm). Furthermore, these PEG-PIONs could be dispersed in phosphate-buffered saline (PBS) that contains 10% serum without any change in their hydrodynamic diameters over a period of one week, indicating that PEG-PIONs would provide high dispersion stability under in vivo physiological conditions as well as excellent anti-biofouling properties. In fact we have confirmed the prolong blood circulation time and facilitate tumor accumulation (more than 15% IDg(-1) tumor) of PEG-PIONs without the aid of any target ligand in mouse tumor models. The majority of the PEG-PIONs accumulated in the tumor by 96 h after administration, whereas those in normal tissues were smoothly eliminated by 96 h, proving the enhancement of tumor selectivity in the PEG-PION localization. The results obtained here strongly suggest that originally synthesized PEG-b-PVBP, having multipoint anchoring character by the phosphonate groups, is rational design for improvement in nanoparticle as in vivo application. Two major points, viz., extremely stable anchoring character and dense PEG chains tethered on the nanoparticle surface, worked simultaneously to become PEG-PIONs as an ideal biomedical devices intact for prolonged periods in harsh biological environments.     

Inverted micelle formation of cell-penetrating peptide studied by coarse-grained simulation: importance of attractive force between cell-penetrating peptides and lipid head group

Arginine-rich peptide and Antennapedia are cell-penetrating peptides (CPPs) which have the ability to permeate plasma membrane. Deformation of the plasma membrane with CPPs is the key to understand permeation mechanism. We investigate the dynamics of CPP and the lipid bilayer membrane by coarse-grained simulation. We found that the peptide makes inverted micelle in the lipid bilayer membrane, when the attractive potential between the peptide and lipid heads is strong. The inverted micelle is formed to minimize potential energy of the peptide. For vesicle membrane, the peptide moves from the outer vesicle to the inner vesicle through the membrane. The translocation of the peptide suggests inverted micelle model as a possible mechanism of CPPs.