Elongation and contraction of molecular springs. Synthesis, structures, and properties of bridged [7]thiaheterohelicenes

A series of bridged [7]thiaheterohelicenes 3a-c and 4 with a variety of helical pitches have been prepared from racemic and optical pure 2,13-bis(hydroxymethyl)dithieno[3,2-e:3',2'-e']benzo[1,2-b:4,3-b']bis[1]benzothiophene (1) in order to investigate the helical structures in solution. Recrystallizations of (PM)-3a, (PM)-3b, (PM)-3c, and (P)-4 from hexane-dichloromethane gave crystals suitable for X-ray crystallography, while recrystallization of (PM)-4 with benzene gave an inclusion complex with a stoichiometry of (PM-4)(4).(C(6)H(6)). X-ray analyses of (PM)-3a-c, (PM-4)(4).(C(6)H(6)), and (P)-4 indicate that the dihedral angles between terminal thiophene rings of the helical framework significantly vary from 22 degrees for 4 to 59 degrees for 3c. This represents as increase of 37 degrees or 168%. Although the (13)C NMR and UV absorption spectra of bridged helicenes 3a-c and unbridged helicene 5 are essentially the same, the molar rotation of 5 is very large compared with those of 3a-c and 4. A red shift (15 nm) in the circular dichroism (CD) spectrum is observed for 4, suggesting that this compound is more planar than 3a-c in solution. In the series of [7]thiaheterohelicenes studied, the minimum helical pitch is 2.70 A for 4.     

Carbazoledioxazines having long alkyl groups. 2. Synthesis of carbazoledioxazines with angular type structure

Carbazoledioxazines with an angular type structure (5,15-dialkyl-7,17-dialkyloxy-9,19-dichloro-5,15-dihydrodiindolo[2,3-c:2′,3′-n]triphenodioxazines) were selectively synthesized by electrochemical oxidative ring closure of precursors (2,5-bis(9-alkyl-2-alkyloxy-3-carbazolylamino)-3,6-dichloro-1,4-benzoquinones). The structure was confirmed by ¹H-nmr and other instrumental analyses. Their thermal properties and solubilities were investigated and were compared with those of carbazoledioxazines with a linear type structure.     

Synthesis and Odor Evaluation of Stereoisomers of Imine Derivatives in Roasted Spotted Shrimp

All possible stereoisomers of imine derivatives 1 – 4 , which have the characteristic roast odor of seafood, were synthesized. As a result of odor evaluation of all isomers, we found that each isomer has a different and characteristic odor of roasted seafood.     

Memory effects on the quantum diffusion of a particle in a fluctuating medium

We introduce a phenomenological Hamiltonian for a particle in a medium with sitediagonal and off-diagonal disorder. Without assuming the usual white noise expression for the correlation between fluctuating variables, we arrive at a master equation using second order perturbation theory. This expression is expanded in powers of the correlation time. The mean square displacement and velocity are discussed and corrections to the diffusion coefficient are given.Partially supported by the grant of the Ministry of Education of the Japanese Government and by Sakkokai Foundation     

EPMA line analysis of chemical states of chromium

A novel technique for determining the chemical states of elements with a heterogeneous distribution in samples involving EPMA line analysis is proposed. LLS (linear least squares) calculation was applied to a set of reduced spectra measured in the line analysis. The reduced spectra which have several energy points (including two points for backgrounds) were measured in order to save measuring time. The LLS calculation gives the mole fraction of each chemical state. We applied this method to the analysis of corrosion products formed on Cr-containing steel after corrosion tests. EPMA mapping revealed that Cr is enriched only in the inner layer of the corrosion products. From the results of the LLS calculation, it was determined that Cr in the corrosion products exists in the trivalent Cr state whereas in the steel Cr is in the metallic state. This result corresponds to the spectra of characteristic x-rays from the corroded steel. Copyright © 2001 John Wiley & Sons, Ltd.     

Chemistry and antiproliferative activities of 3-methoxyflavones isolated from <Emphasis Type="Italic">Varthemia iphionoides</Emphasis>

A new isolated flavone, 4′-hydroxy-3,5,6,7-tetramethoxyflavone (6), together with seven known 3-O-methylated flavones isolated from the ethanol extract of the aerial parts of Varthemia iphionoides, were studied for DPPH free radical-scavenging and cytotoxic activities. Flavones 2, 3, 4, and 8 were the most active DPPH free-radical scavengers with inhibition percentage of 63.5, 42.9, 47.9, and 55.6, respectively, at a concentration of 100 μg/mL. Flavones 2 and 8 were the most active as inhibitor for human leukemia HL-60 cells; the IC₅₀ values after 48 h incubation were 20.5 and 23.9 μg/mL, respectively.     

HPLC separation of all aldopentoses and aldohexoses on an anion-exchange stationary phase prepared from polystyrene-based copolymer and diamine: the effect of NaOH eluent concentration

To investigate the separations of all aldopentoses (ribose, arabinose, xylose and lyxose) and aldohexoses (glucose, galactose, allose, altrose, mannose, gulose, idose and talose) on the D? stationary phase prepared by the reaction of chloromethylated styrene-divinylbenzene copolymer and N,N,N',N'-tetramethyl-1,6-diaminohexane, we examined the effect of varying the concentration of the NaOH eluent on the elution orders. Separations of these aldoses were achieved using a 20 mM NaOH eluent. The elution behaviors of the aldoses were probably due to not only the individual pK(a) values, but also the chemical structures of the cyclic aldoses.