Direct counting of submicrometer-sized photosynthetic apparatus dispersed in medium at cryogenic temperature by confocal laser fluorescence microscopy: estimation of the number of bacteriochlorophyll c in single light-harvesting antenna complexes chlorosomes of green photosynthetic bacteria

The number of pigments in single light-harvesting complexes (chlorosomes) were calculated by imaging single chlorosomes in a frozen buffer at cryogenic temperature with a confocal laser fluorescence microscope and pigment extraction. Chlorosomes were isolated from two types of green photosynthetic bacteria Chlorobium (Chl.) tepidum and Chloroflexus (Cfl.) aurantiacus and were individually imaged in the frozen medium. Each fluorescence spot observed mainly came from a single chlorosome and was ascribable to self-aggregates of bacteriochlorophyll (BChl) c molecules as core parts of chlorosomes. A three-dimensional distribution of fluorescence of single chlorosomes was analyzed, and the number of chlorosomes in a volume of 54,000 microm(3) was counted directly. On the basis of the results, averaged numbers of the BChl c molecules contained in a single chlorosome of Chl. tepidum and Cfl. aurantiacus were determined to be 1.4 x 10(5) and 9.6 x 10(4), respectively. The present numbers are almost comparable to those estimated by other methods (Martinez-Planells et al., Photosynth. Res. 2002, 71, 83 and Monta?o et al., Biophys. J. 2003, 85, 2560).     

New approaches to enantioselective fluorination: Cinchona alkaloids combinations and chiral ligands/metal complexes

The selective construction of carbon-fluorine bonds is of great interest to medicinal chemists because the replacement of a hydrogen or an oxygen atom with a fluorine atom in biologically active molecules can confer the molecules with improved physicochemical properties and biological activities. Since the first discovery of enantioselective fluorination using N-fluorocamphorsultam, our synthetic interest had been focused on the development of chiral N-fluorosulfonamide derivatives capable of enantioselective fluorination. However, these initial efforts revealed several limitations in both chemical yields and enantioselectivities of the fluorinated products. We present here the background of our personal story of the enantioselective fluorination reaction and some successful applications of the methods to the design and synthesis of biologically active products. Two novel approaches using cinchona alkaloid/Selectfluor^® combinations and chiral ligands/metal complexes have been pursued, respectively. In addition, the recent advances in this area by other groups are also described briefly.     

Synthesis and properties of thermoplastic propyl-etherified amylose

Amylose was etherified with 1-bromopropane in DMSO. The degree of substitution (DS) was varied by altering the feed ratio of 1-bromopropane. The structures of the products were characterized by IR and 1H-NMR spectroscopy. When the molar feed ratio of 1-bromopropane to hydroxyl groups of amylose was beyond 7.5, the hydroxyl groups were completely substituted with propyl ether groups. The etherified amylose with DS 1.9 showed a glass transition temperature (T_g), and that with DS 2.3 or 3.0 showed both T_g and melting temperature (T_m) (DS 3.0 means complete substitution). The etherification imparted melt processability and solubility in nonpolar organic solvent to amylose.     

Enhancement of Solar Hydrogen Evolution from Water by Surface Modification with CdS and TiO2 on Porous CuInS2 Photocathodes Prepared by an Electrodeposition–Sulfurization Method

Porous films of p‐type CuInS₂, prepared by sulfurization of electrodeposited metals, are surface‐modified with thin layers of CdS and TiO₂. This specific porous electrode evolved H₂ from photoelectrochemical water reduction under simulated sunlight. Modification with thin n‐type CdS and TiO₂ layers significantly increased the cathodic photocurrent and onset potential through the formation of a p–n junction on the surface. The modified photocathodes showed a relatively high efficiency and stable H₂ production under the present reaction conditions.     

Dithienylethenes with a novel photochromic performance

Dithienylethenes with low decoloration quantum yields and thermal reversibility at high temperature above 100 degrees C were prepared. Introduction of bulky alkoxy substituents at 2- and 2'-positions of the thiophene rings strongly suppressed the cycloreversion quantum yields. The quantum yields were lower than 10(-3), and the photogenerated color remained stable enough under room light. On the other hand, the bulky alkoxy substituent decreased the thermal stability of the colored closed-ring isomers at high temperature. The color of the dithienylethene with cyclohexyloxy substituents faded out in less than 1 min at 160 degrees C.     

Catalytic Pauson-Khand-type reaction using aldehydes as a CO source

[reaction: see text]. Rhodium complex-catalyzed carbonylative alkene-alkyne coupling proceeds using aldehydes as a CO source. Cinnamaldehyde is the best CO donor, and various cyclopentenones were provided in high isolated yields by a solvent-free system.     

Observation of B-->K(0)(S)pi(+)pi(-) and Evidence for B-->K(*+/-)pi(-/+)

We report on a search for charmless hadronic B decays to the three-body final states K(0)(S)h(+)pi(-), K(+)h(-)pi(0), K(0)(S)h(+)pi(0) (h(+/-) denotes a charged pion or kaon), and their charge conjugates, using 13.5 fb(-1) of integrated luminosity produced near sqrt[s]=10.6 GeV, and collected with the CLEO detector. We observe the decay B-->K0pi(+)pi(-) with a branching fraction (50(+10)(-9)(stat.)+/-7(syst.))x10(-6) and the decay B-->K(*+)(892)pi(-) with a branching fraction (16(+6)(-5)(stat.)+/-2(syst.))x10(-6).     

Thermolysis of vic-dihydroxybacteriochlorins: a new approach for the synthesis of chlorin-chlorin and chlorin-porphyrin dimers

[formula: see text] A novel approach for the preparation of symmetrical (chlorin-chlorin), and unsymmetrical (chlorin-porphyrin) dimers joined with carbon-carbon linkages as models to study the "intramolecular" charge transfer is discussed.