Collective coordinates and the mechanism for conformational transitions of complex molecules

Reduction of dimensionality is crucial for the deeper understanding of the mechanism for large-amplitude conformational transitions of complex molecules. By taking up a six-atomcluster as an illustrative example, we present a general methodology to understand conformational transitions of molecules in terms of the low-dimensional dynamics of molecular gyration radii. The dynamics of gyration radii is generally governed by the interplay between the ordinary potential force and a dynamical force called the internal centrifugal force. We show that the internal centrifugal force can be more important than the original potential barrier and gives rise to a new dynamical barrier that truly dominates the conformational transitions of the system. This kind of dynamical effect should be crucially important in a wide class of molecular reaction dynamics. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Chromatic aberration free liquid crystal adaptive optics for flood illuminated retinal camera

A high-resolution, flood-illumination retinal camera using liquid crystal (LC) adaptive optics (AO) is presented. The retinal camera uses light at 780 nm for ocular aberration measurement while light at 655 nm and 593 nm for retinal imaging. In order to avoid chromatic aberrations due to wavelength dependence of LC, we adopt an open-loop technique, in which dynamic correction of aberrations is applied only to the imaging light. A compensation pattern projected on the LC wavefront corrector is adjusted to provide phase wrapping of 2 π for illumination light. We confirmed feasibility of this technique by performing in vivo retinal imaging experiments. Photoreceptors were clearly revealed at both imaging light at 655 nm and 593 nm. Feasibility of the technique was also supported by comparison of the retinal images taken by the present open-loop technique with those taken by the conventional closed-loop one and by analysis of the spatial distribution of the photoreceptors.     

Modification of Spatial Coherence by Means of Low-Order Zernike-Mode Adaptive Optics

Spatial coherence of the field modified by low-order adaptive optics is analyzed to establish a theoretical basis for the recent idea of using adaptive optics as a spatial coherence modifier. In this context low-order adaptive optics has the ability to correct some of the low-order aberrations specified by Zernike polynomials. The initial field to be modified is assumed to be a spatially partially coherent one resulting from phase disturbance. It is demonstrated, as in the previous study, that low-order adaptive optics serves to enhance the spatial coherence of the resultant field and that the effect of the enhancement becomes stronger as the spatial coherence of the initially partially coherent field increases. Potential applications of low-order adaptive optics as a spatial coherence modifier are briefly discussed.     

In vivo multispectral imaging of the absorption and scattering properties of exposed brain using a digital red–green–blue camera

Optical Review - To evaluate multi-spectral images of the absorption and scattering properties in the cerebral cortex of rat brain, we investigated spectral reflectance images estimated by the...     

Optical modulator using metal-oxide-semiconductor type Si ring resonator

Electric-field drive optical modulators using a Si ring resonator were fabricated on silicon-on-insulator (SOI) wafers. The fabricated resonators consisted of Si waveguides with width and thickness of 1.0 and 0.3 μm, respectively. In order to induce the linear electro-optic (EO) effect in the Si core layer, the strain was applied by covering the layer with Si₃N₄ film (0.26 μm thick) deposited by low pressure chemical vapor deposition (LPCVD) at 750 °C. The vertical electric-field was applied to the Si waveguide through the top and bottom cladding layers, and the optical output from the drop port at the resonance wavelength was measured. At a wavelength of 1501.6 nm, the optical modulation of 33% was obtained at 200V (electric-field at the silicon surface ∼3 × 10⁵ V/cm, nearly the breakdown field). The resonance wavelength was shifted toward the short wavelength side by applying both positive and negative voltages, this shift was explained by carrier concentration modulation. The linear EO effect in the Si core layer was not observed, presumably because the strain in the Si core layer was too small.     

Anti-biofouling properties of an amphoteric polymer brush constructed on a glass substrate

An amphoteric copolymer brush of methacrylic acid (MA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) was prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization using both a free chain transfer agent (n-butylsulfanylthiocarbonylsulfanyl-2-methyl propionic acid) and a radical initiator (4,4'-azobis(4-cyanopentanoic acid)) covalently fixed to a glass substrate. An aqueous solution of the copolymer, Poly(MA-r-DMAEMA), which was simultaneously obtained in liquid phase, had a sufficiently small polydispersity in its molecular weight. The copolymer brush showed effective suppression of non-specific adsorption of bovine serum albumin and egg white lysozyme to the brush. In contrast, both negatively charged PolyMA and positively charged PolyDMAEMA brushes significantly adsorbed the proteins irrespective of their net charges. Upon ion beam irradiation, furthermore, a hollow space with a designed shape could be made on the glass substrate, and both HEK293 and HepG2 cells non-specifically adhered to the space, forming aggregates, while no adhesion to the non-treated area on the brush was observed. These results suggest that the amphoteric polymer brushes will be useful materials for biomedical applications.     

Enantioselective total synthesis of the potent anti-HIV nucleoside EFdA

A concise enantioselective total synthesis of 4'-ethynyl-2-fluoro-2'-deoxyadenosine (EFdA), an extremely potent anti-HIV agent, has been accomplished from (R)-glyceraldehyde acetonide in 18% overall yield by a 12-step sequence involving a highly diastereoselective ethynylation of an α-alkoxy ketone intermediate.     

Research on Liebeskind-Srogl coupling/intramolecular Diels-Alder reaction cascade

The Liebeskind-Srogl coupling/intramolecular Diels-Alder (IMDA) reaction cascade that stereoselectively affords a tricarbocyclic compound with a trans–trans-cis fused ring system including an all-carbon quaternary stereogenic center at the ring junction is described. The cascade reactions proceed quickly and stereoselectively afford the products within 2?h at room temperature in the presence of a suitable thioester. The developed protocol as well as the prepared chiral compounds are useful for the enantioselective total synthesis of terpenoids with the trans–trans-cis fused ring system.     

The first total synthesis of hibarimicinone,a potent v-Src tyrosine kinase inhibitor

The first total synthesis of hibarimicinone has been achieved. The polyhydroxydecalin moieties (AB and GH rings) have been synthesized from sulfonylenone 4 derived from d-arabinose. The chiral biaryl 20 was coupled with two polyhydroxydecalins 11 by Michael–Dieckmann type condensation to give the eight rings system. Aromatization and oxidation with Ag⁺ gave quinone 24, and the subsequential transannular etheration gave the hibarimicinone skeleton. Deprotection and tautomerization were performed in one pot to give hibarimicinone (1).