Excited states of porphyrin isomers and porphycene derivatives: a SAC-CI study

Excited states of free-base porphyrin isomers, porphycene (Pc), corrphycene (Cor), and hemiporphycene (hPc), were studied by the Symmetry-Adapted Cluster (SAC)/SAC-Configuration Interaction (CI) method. The absorption peaks of the porphyrin isomers were assigned on the basis of the SAC-CI spectra. The X, Y, X', and Y' bands of the porphyrin isomers, which have weak intensities, are identified. The differences in the Q-band absorptions among the isomers were clearly explained by the four-orbital model. In Cor and hPc, the wave function of the B-band corresponds to the mixture of the four-orbital excitations and the optically forbidden excitation of free-base porphin (P), due to the molecular symmetry lowering in the isomers. The B-band character is described by the five-orbital model in Pc and the six-orbital model in Cor and hPc. Two tetrazaporphycenes and two ring-extended (dibenzo) porphycenes were designed, and the Q-band transition moment was successfully controlled. These examples show that the control of the four-orbital energy levels is the guiding principle for pigment design in porphyrin compounds.     

Practical synthesis of S-alkyl thiocarbamate herbicides by carbonylation of amines with carbon monoxide and sulfur

An industrial and economic carbonylation of amines with carbon monoxide and sulfur has been developed for the synthesis of S-alkyl thiocarbamate herbicides. In the presence of potassium carbonate and solvent DMSO, S-alkyl thiocarbamates, such as thiobencarb and orbencarb (herbicides) are synthesized in excellent yields from amines, carbon monoxide, sulfur, and alkyl halides under mild conditions (1 atm, 20 °C).     

Diversity-oriented synthesis of tamoxifen-type tetrasubstituted olefins

A general synthetic scheme for tamoxifen-type tetrasubstituted olefins based on the novel Cu-catalyzed carbomagnesation across alkynyl(2-pyridyl)silane has been developed. A wide array of electronically and structurally diverse tetrasubstituted olefins can be prepared in a regiocontrolled, stereocontrolled, and diversity-oriented manner. Noteworthy features are that (i) the three aryl groups, which are believed to be important (essential) for anti-estrogenic activity, can be varied at will because they all stem from readily available aryl iodides, and (ii) any stereo- and regioisomers can, in principle, be prepared by simply changing the applying order of aryl iodides into the sequence.     

The characteristic fragment ions and visualization of cationic starches on pulp fiber using ToF‐SIMS

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) was used to investigate the distribution of cationic starch on pulp fiber. To identify the characteristic fragment ions of the cationic starches, deuterium‐labeled cationic starches were prepared and analyzed using ToF‐SIMS. The starch 2‐hydroxypropyltrimethylammonium chloride derivative generated characteristic fragments at m/z 58 and 59, which were identified as [H₂C?N(CH₃)₂]⁺ and [N(CH₃)₃]^+·, respectively. The fragmentation patterns were also suggested. From the imaging analysis, the adsorption of the cationic starch on fibers was uneven on individual fibers, as well as between fibers. This may have been on account of fiber morphology and structure. On examining scanning electron microscope (SEM) images, the quaternary ammonium starch derivative (QS) did not penetrate the fiber. No migration of cationic starch was observed under various drying conditions. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis of polystyenes with different stereoregularities by anionic polymerization

The stereoregularity of polystyrene prepared by anionic polymerization was determined by means of ¹³C-NMR spectroscopy. The stereoregularity changed with such polymerization conditions as catalyst, solvent, and temperature. Sodium naphthalene as catalyst gave a syndiotactic-rich polystyrene of 66–68% syndiotactic dyads independently of solvent and temperature, while potassium and cesium naphthalenes as catalyst produced polystyrenes with different stereoregularities ranging from syndiotactic-rich to isotactic-rich configurations, depending on solvent and temperature. The mechanism of anionic polymerization which caused the difference in stereoregularity was discussed from the viewpoint of growing ionic species.     

Fluorimetric assay for measuring Dns-His-Lys-Arg-His-Lys cleaving enzyme using high-performance liquid chromatography

A rapid and sensitive assay for the determination of Dns-His-Lys-Arg-His-Lys cleaving enzyme activity is reported. This assay is based on fluorimetric detection of a dansylated dipeptide, 5-dimethylaminonaphthalene-1-sulfonyl-His-Lys, enzymatically formed from the substrate 5-dimethylaminonaphthalene-1-sulfonyl-His-Lys-Arg-His-d-Lys, after separation by high-performance liquid chromatography (HPLC) using a C-18 reversed-phase column by isocratic elution. This assay is sensitive enough to measure 5-dimethylaminonaphthalene-1-sulfonyl-His-Lys at concentrations as low as 7 pmol, and yields highly reproducible results and requires less than 9.0 min per sample for separation and quantitation. The optimum pH for Dns-His-Lys-Arg-His-Lys cleaving enzyme activity was 7.5-8.0. The Michaelis constant (K_m) and the maximum velocity (V_max) values were 33.3 μM and 47.07 pmol/(μg h), respectively with the use of enzyme extract obtained from bovine pituitary. By using this assay, axonal transport of this enzyme activity was observed 48 h after double ligations of rat sciatic nerves. The high sensitivity and selectivity of this assay would be useful for clarification of the physiological role of this enzyme.     

Facile construction and divergent transformation of polycyclic isoxazoles: direct access to polyketide architectures

[reaction: see text] Base-promoted cyclocondensation of C-chloro oximes with cyclic 1,3-diketones affords functionalized isoxazoles in good yield and under convenient reaction conditions. This process enables the synthesis of highly substituted products with notable functional group tolerance. The products obtained are directly converted to a variety of polyketide-derived polycyclic structures including xanthenes, anthracenes, and benzophenones.     

Copper-catalyzed allylation of carbonyl derivatives using allyl(2-pyridyl)silanes

[reaction: see text] We have developed an efficient copper-catalyzed allylation of carbonyl derivatives using allyl(2-pyridyl)silanes, in which the strong directing effect of the 2-pyridyl group was observed. A useful synthesis and allylation of substituted allyl(2-pyridyl)silanes is also described.     

Separation and determination of some stereoisomers by capillary gel electrophoresis with cyclodextrin incorporated in polyacrylamide gel

Capillary gel electrophoresis (CGE) was successfully applied to the separation of optically active isomers and position isomers by incorporating a suitable cyclodextrin chiral selector in polyacrylamide gel. A commercially available ß-cyclodextrin (ß-CD) was used for enantioselectivity towards o-, m- and p-nitrobenzoic acid, o-, m- and p-hydroxybenzoic acid, o-, m- and p-toluic acid and the optical isomers of dansyl-D,L-leucine and R,S-1,1-binaphthyl-2,2-dihydrogenphosphate. Especially the effect of organic solvents, such as acetonitrile, methanol, dimethylsulphoxide and others were examined in detail. The resolution varied to some extent with the addition of the organic solvent to the polyacrylamide gel and the running buffer solution. The possible mechanism has also been discussed. In addition, quantitative aspects of the separation of stereoisomers using CGE have been studied, showing that both the resolution and accuracy of the determinations were affected by the ratio of the enantiomers.     

Polytheonamides A and B, highly cytotoxic, linear polypeptides with unprecedented structural features, from the marine sponge, Theonella swinhoei

Polytheonamides A and B are highly cytotoxic polypeptides with 48 amino acid residues isolated from the marine sponge, Theonella swinhoei. The structure of polytheonamide B was determined by spectral and chemical methods, especially extensive 2D NMR experiments, which resulted in the unprecedented polypeptide structure; the N-terminal glycine blocked with a 5,5-dimethyl-2-oxo-hexanoyl group, the presence of eight tert-leucine, three beta-hydroxyvaline, six gamma-N-methylasparagine, two gamma-N-methyl-beta-hydroxyasparagine, and beta,beta-dimethymethionine sulfoxide residues. More significantly, it has the sequence of alternating D- and L-amino acids. Polytheonamide A is an epimer of polytheonamide B differing only in the stereochemistry of the sulfoxide of the 44(th) residue.