Total synthesis of (+)-yatakemycin

A convergent total synthesis of (+)-yatakemycin was accomplished in a 20-step sequence in an overall yield of 13%. The synthesis features the regioselective ring opening of (S)-epichlorohydrin with 2,6-dibromophenyllithium species, the mild copper-mediated aryl amination utilizing the combination of CuI and CsOAc, and the efficient deprotection of benzyl groups of aryl benzyl ether with BCl3 in the presence of pentamethylbenzene.     

Azotolane liquid-crystalline polymers: huge change in birefringence by photoinduced alignment change

Novel liquid-crystalline polymers (LCPs) containing a long azotolane moiety were synthesized, and the relationship between the chemical structures and the photoresponsive behavior was investigated. All homogeneously aligned LCP films exhibited extremely high values of birefringence (Deltan) in the wide wavelength range. Specifically, the azotolane LCP with two azobenzene units showed the most efficient change in the alignment of the azotolane moiety with a huge change in Deltan (>/=0.65). This means that the high value of Deltan in the homogeneously aligned state can be converted to the change in Deltan effectively.     

Synthesis of novel push-pull-type solvatochromic 2′-deoxyguanosine derivatives with longer wavelength emission

We synthesized novel push-pull-type fluorescent guanosine derivatives, ^CNG and ^AcG containing 1,6- and 2,7-disubstituted pyrene chromophores. 1,6-Disubstituted pyrene derivatives, 1,6-^CNG (3b) and 1,6-^AcG (3c), exhibited highly solvatochromic fluorescence emission at longer wavelength (∼540 nm). The environmentally sensitive fluorescent deoxyguanosines such as 3b and 3c can be used as powerful tools for structural studies of nucleic acids and molecular diagnostics.     

Dynamical LEED analyses of the clean and the NO-adsorbed Ir(111) surface

The adsorption structure of nitric oxide (NO) on Ir(111) was studied by thermal desorption spectroscopy (TDS) and dynamical analyses of low-energy electron diffraction (LEED). At the saturation coverage at about 100 K, a 2 × 2 pattern was observed by LEED and two peaks appeared at 365 and 415 K in TDS. No change in the LEED I–V curves was observed by annealing at 280 K, which means that the NO-saturated surface was retained at this temperature. On the contrary, partial desorption and changes of the LEED I–V curves were observed by annealing at 360 K. Combined with previous vibrational studies, it is suggested that one adsorption species is not affected, while another species is partially desorbed and the rest of them are dissociated by annealing at 360 K. Dynamical analyses of LEED were performed for the 280 K-annealed and the 360 K-annealed surfaces, which correspond to the NO-saturated and the NO-dissociated Ir(111) surfaces, respectively. These revealed that NO occupies the atop, fcc-hollow and hcp-hollow sites (atop-NO + fcc-NO + hcp-NO) for the NO-saturated Ir(111) surface with the saturation coverage of 0.75 ML. For the 360 K-annealed surface, the atop-NO is not affected but the fcc-NO and the hcp-NO are partially desorbed as NO and partially dissociated to N and O, both of which occupy the fcc-hollow site on the surface.     

Analysis of vertical coupling between a 2D photonic crystal cavity and a hydrogenated-amorphous-silicon-wire waveguide

We present an efficient means of light extraction from two-dimensional photonic crystal (2D PC) cavities with SiO₂ cladding. We propose a vertically coupled system consisting of a 2D PC cavity and a hydrogenated-amorphous-silicon (a-Si:H)-wire waveguide, which we theoretically investigate using the 3D finite-difference time-domain method. Light can be extracted with an efficiency of greater than 95% to both output ports of the a-Si:H-wire waveguide or extracted with an efficiency of greater than 90% to a single output port of the a-Si:H-wire waveguide with a reflector.     

Synthesis and biological evaluation of all A-ring stereoisomers of 5,6-trans-2-methyl-1,25-dihydroxyvitamin D(3) and their 20-epimers: possible binding modes of potent A-ring analogues to vitamin D receptor.

BACKGROUND: The secosteroid 1 alpha,25-dihydroxyvitamin D(3) (1) has a wide variety of biological activities, which makes it a promising therapeutic agent for the treatment of cancer, psoriasis and osteoporosis. Insight into the structure-activity relationships of the A-ring of 1 is still needed to assist the development of more potent and selective analogues as candidate chemotherapeutic agents, as well as to define the molecular mode of action. RESULTS: All possible A-ring stereoisomers of 5,6-trans-2-methyl-1,25-dihydroxyvitamin D(3) (6a-h) and their 20-epimers (7a-h) were designed and efficiently synthesized. The dependence of the affinities for vitamin D receptor (VDR) and vitamin D binding protein (DBP), as well as the HL-60 cell differentiation-inducing activity, upon the stereochemistry of the A-ring and at C20 in the side chain was evaluated. CONCLUSIONS: The binding affinities and potency of the 5,6-trans and 5,6-cis analogues were enhanced by a 2-methyl substituent in a certain orientation. Molecular docking studies based upon the X-ray crystal structure of VDR suggested that the axial 2-methyl group would be accommodated in a pocket surrounded by hydrophobic amino acid residues in the ligand binding domain, resulting in enhanced interaction.     

Interaction between charged soft microcapsules and red blood cells: effects of PEGylation of microcapsule membranes upon their surface properties

Four types of hydrophilic gel microcapsules containing water have been prepared by an interfacial polymerization method. Each type of microcapsules has a membrane of different composition. Using three kinds of monomers, N,N-dimethylacrylamide (DMAAm), 4-(aminomethyl)styrene (AmSt), and N,N-dimethylaminopropylacrylamide (DMAPAA), one type of aqueous copolymer having primary and tertiary amino groups was obtained. By the polymerization of three kinds of monomers, DMAAm, AmSt, and 2-[(methacryloyloxy)ethyl] trimethylammoniumchloride (METAC), another type of aqueous copolymer having primary and quaternary ammonium groups was also obtained. Two more types of copolymers were synthesized by copolymerization of -acryloxy-ω-methoxy-poly(ethylene glycol) (a-PEG) with the above two kinds of monomer mixture. These copolymers were polymerized with terephthaloyldichloride at the water/oil interface to prepare four types of microcapsules containing water, i.e., poly(DMAAm-co-DMAPAA-co-AmSt-alt-terephthalic acid) microcapsules, poly(DMAAm-co-DMAPAA-co-AmSt-co-PEG-alt-terephthalic acid) microcapsules, poly (DMAAm-co-METAC-co-AmSt-alt-terephthalic acid) microcapsules, and poly (DMAAm-co-METAC-co-AmSt-co-PEG-alt-terephthalic acid) microcapsules, which will be abbreviated to MC 1, MC 2, MC 3, and MC 4, respectively. It has been predicted that the microcapsule membranes are hydrophilic and soft and have two-sublayer structures from electrophoretic mobility measurements and from the analysis of the data with Ohshima’s electrokinetic theory for soft particles. The outer sublayers of MC 1 and MC 2 are negatively charged and those of MC 3 and 4 are slightly positively charged. Also, the surfaces of MC 1 and MC 2 are harder than those of MC 3 and 4. By PEGylation, the surface charge density in the membranes decreases and the surface becomes softer. It has been found that the membrane of red blood cells (RBC) is also soft and is composed of two-sublayers, the outer sublayer of which is negatively charged and the inner one is positively charged. The interaction of four types of microcapsules with RBC has been studied. It was found that microcapsules with soft surfaces (MC 3 and MC 4) do not interact with RBC, even though the microcapsule surfaces are positively charged and the surface of RBC is negatively charged. On the other hand, microcapsules with negatively charged but harder surfaces (MC 1) interact with RBC to introduce hemolysis. The membrane surface of MC 2, which is obtained by PEGylation of MC 1, becomes softer than that of MC 1 so that the interaction with RBC was weakly suppressed. From these, it was concluded that the dominant factor to control the interaction between synthetic polymer surfaces and biological cell surfaces is not the surface charges carried by the polymer surfaces but the softness of the polymer surfaces.     

Photoluminescence properties of size-selected Si nanocluster films prepared by laser ablation

Size-dispersed Si nanocluster films have been synthesized by a method of crossing an Ar gas beam perpendicularly to a silicon cluster beam that is produced by a laser ablation technique. Flight directions of the nanoclusters are changed due to Ar gas collisions, and smaller nanoclusters are deflected further from the axis of the primary cluster beam. The size-dispersed nanocluster films exhibit strong red photoluminescence (PL) after exposure to the air. The PL peak energy changes between 1.42 and 1.72 eV depending on the sample position. The average diameter of the oxidized nanoclusters characterized by transmission electron microscopy is 10 nm at the position of the primary cluster beam axis and becomes smaller as deviated from the axis. The relation between the PL peak energy and the size of the oxidized Si nanoclusters is discussed. Received: 4 May 2000 / Accepted: 9 May 2000 / Published online: 13 July 2000     

Temperature-responsive,polymer-modified surfaces for green chromatography

Thermoresponsive poly(N-isopropylacrylamide) (PIPAAm) and its derivatives were utilized as chromatography column matrix modifiers to develop novel supports for thermoresponsive hydrophobic chromatography with aqueous mobile phase. In the column, matrix surfaces show thermoresponsive hydrophilic/hydrophobic property alterations, which alter interaction with and retention of solutes to be separated. We have also demonstrated that the electrostatic interaction of ionic solutes and charged, thermoresponsive polymer-modified surfaces can be modulated temperature changes in the aqueous mobile phase alone.     

Cell sheet engineering: intelligent polymer patterned surfaces for tissue engineered liver

We describe a new culture system utilizing the temperature-responsive polymer grafted surface for designing of cell position and layered tissue reconstruction. Organizing of the hepatic tissue structure by controlling the culture system, that is patterned co-culture and layered cell sheet co-culture achieved by moving the cultured cells from the culture surface, resulted in regulation of the hepatocyte function. The technique for cell sheet manipulation would promote the liver tissue engineering in quality.