CH double-pulsed PLIF measurement in turbulent premixed flame

The flame displacement speeds in turbulent premixed flames have been measured directly by the CH double-pulsed planar laser-induced fluorescence (PLIF). The CH double-pulsed PLIF systems consist of two independent conventional CH PLIF measurement systems and laser beams from each laser system are led to same optical pass using the difference of polarization. The highly time-resolved measurements are conducted in relatively high Reynolds number turbulent premixed flames on a swirl-stabilized combustor. Since the time interval of the successive CH PLIF can be selected to any optimum value for the purpose intended, both of the large scale dynamics and local displacement of the flame front can be discussed. By selecting an appropriate time interval (100–200 μs), deformations of the flame front are captured clearly. Successive CH fluorescence images reveal the burning/generating process of the unburned mixtures or the handgrip structures in burnt gas, which have been predicted by three-dimensional direct numerical simulations of turbulent premixed flames. To evaluate the local flame displacement speed directly from the successive CH images, a flame front identification scheme and a displacement vector evaluation scheme are developed. Direct measurements of flame displacement speed are conducted by selecting a minute time interval (≈30 μs) for different Reynolds number (Re _λ = 63.1–115.0). Local flame displacement speeds coincide well for different Reynolds number cases. Furthermore, comparisons of the mean flame displacement speed and the mean fluid velocity show that the convection in the turbulent flames will affect the flame displacement speed for high Reynolds number flames.     

Base-discriminating fluorescent (BDF) nucleoside: distinction of thymine by fluorescence quenching

A novel fluorescence BDF probe containing pyrene-labeled 7-deaza-2[prime or minute]-deoxyadenosine has been developed for the detection of thymine base on a target DNA.     

A Convenient and Efficient Synthesis of SLeX Analogs

Described is the preparation and use of tetrasaccharide 1, which enables a rapid and preparative scale synthesis of sialyl Lewis X (SLeX) analogs having 1-O- and 2-N-disubstituted glucosamine (GlcN) moieties. Such modifications should bring a dramatic change of the physical and pharmacological properties of the SLeX analogs. Therefore, tetrasaccharide 1 is a convenient intermediate for the synthesis of various SLeX analogs, since it has convertible 2-(trimethylsilyl)ethyl (SE) glycoside and the free amino group on GlcN moiety. The intermediate 1 was constructed from a glucosamine derivative by a highly efficient combined use of enzymatic galactosylation/sialylation and chemical fucosylation. Thus obtained 1 was converted into SLeX analogs by N-substitution followed by transformation of SE glycoside into other glycosides and deprotection. These synthesized analogs were found to inhibit cell adhesion of HL-60 cells to recombinant soluble human E-selectin.     

Biosynthetic pathway of iridoid glucosides in Gardenia jasminoides f. grandiflora cell suspension cultures after iridodial cation formation

Administration of ²H- or ¹³C-labeled monoterpenes to $\text{Gardenia}$$\text{jasminoides}$ f. $\text{grandiflora}$ cell suspension cultures demonstrated that iridoid glucosides of the suspension cultures are biosynthesized, after iridodial cation formation from 10-oxocitral (3), via 8-epiiridodial (13), 8-epiiridotrial (14), boschnaloside (8-epiiridotrial glucoside) (12) and dehydroiridotrial glucoside (8). In addition, the coexistence of a route via iridodial cation (4), dehydroiridodial (6), dehydroiridotrial (15) and dehydroiridotrial glucoside (8) is conceivable.     

High-performance affinity chromatography of oligonucleotides on nucleic acid analogue immobilized silica gel columns.

The nucleic acid analogues poly(9-vinyladenine) (PVAd), poly(9-adenylethyl methacrylate) and poly(thymylethyl methacrylate) (PTM) were chemically bonded to porous silica gel, which had been pretreated with 3-trimethoxysilylpropyl methacrylate, by free radical copolymerization to produce novel packing materials for affinity chromatographic columns. The columns separated nucleosides and nucleotide dimers on the basis of hydrophobic interaction using an aqueous buffer and complementary hydrogen bonding interaction in methanol as an eluent. The PVAd- and PTM-silica gel columns gave a nucleobase-selective separation of oligonucleotides differing in length from mixtures of oligoadenylic and oligouridylic acids. On the PVAd-silica gel column terminal phosphate isomers of oligouridylic acid up to seven mer were resolved and the elution order of the isomers was different from that on an ODS column.     

Synthesis of pyrrolo[1,2-a]quinoxalines by 1,3-dipolar cycloaddition reaction. An additional reaction mechanism via an aziridine intermediate

The reaction of the 2-substituted 6-chloroquinoxaline 4-oxides 1a or 1b with 2-fold molar amount of methyl propiolate resulted in the 1,3-dipolar cycloaddition reaction to give 8-chloro-1,3-bismethoxycarbonyl-4-(piperidin-1-yl)pyrrolo[1,2-a]quinoxaline 4a or 8-chloro-1,3-bismethoxycarbonyl-4-(morpholin-4-yl)pyrrolo-[1,2-a]quinoxaline 4b , respectively. Compound 4a or 4b was transformed into 8-chloro-3-methoxycarbonyl-4-(piperidin-1-yl)pyrrolo[1,2-a]quinoxaline 5a or 8-chloro-3-methoxycarbonyl-4-(morpholin-4-yl)pyrrolo[1,2-a]-quinoxaline 5b , respectively. The structure of 4a,b was confirmed by the NOE measurement among the C₁ -H , C ₂-H and C ₉-H proton signals of 5a,b . An additional reaction mechanism was proposed for the ring transformation of isoxazolo[2,3-a]quinoxalines into pyrrolo[1,2-a]quinoxalines.     

Absolute asymmetric photoreactions of aliphatic amino acids by circularly polarized synchrotron radiation: critically pH-dependent photobehavior

The absolute asymmetric photoreaction (AAP) of racemic aliphatic amino acids, such as alanine (Ala) and leucine (Leu), by left- and right-handed circularly polarized light (l- and r-CPL) irradiation was investigated in aqueous solutions at various pHs, by using the Onuki-type polarizing undulator installed in an electron storage ring. The magnitude of the optical purity (op) generated and the enantiomer-enriching mechanism operative in the AAP were found to be entirely dependent on the ionic state (and thus pH) of the amino/carboxylic acid moieties. At pH 1, the op of Ala and Leu determined by circular dichroism (CD) spectral measurement gradually developed with CPL irradiation, according to Kagan's equation. In contrast, irradiation at pH 7 gave op's much smaller than the theoretical values predicted by Kagan's equation. However, it turned out that the photodecomposition at pH 7 produces the corresponding alpha-hydroxycarboxylic acids stereoselectively, the CD sign of which is just opposite to that of the remaining amino acid, thus affording the apparently small op. It is concluded that, irrespective of solution pH, the AAP of amino acid proceeds upon CPL irradiation. At pH 1, the photodecomposition of valine, Leu, and isoleucine occurs via a Norrish type II mechanism, which is also applicable to other amino acids possessing a gamma-hydrogen. In the case of amino acids lacking a gamma-hydrogen, such as glycine and Ala, the photodecomposition mechanism is a photodeamination/hydroxylation and a Norrish type I reaction. At pH 7, the main photoproducts were ammonia and alpha-hydroxycarboxylic acids that were produced via photodeamination.     

One-pot synthesis of macrocyclic compounds possessing two cyclobutane rings by sequential inter- and intramolecular [2+2] photocycloaddition reactions

Sensitized photocycloaddition reactions of 6,6′-dimethyl-4,4′-[1,3-bis(methylenoxy)phenylene]-di-2-pyrone (1) with electron-poor α,ω-diolefins such as ethylene diacrylate (2a) and polyoxyethylene dimethacrylates (2b-d) afforded site- and stereoselective macrocyclic dioxatetralactones (3a-d) and (4b) having 18- to 25-membered rings across the C5-C6 and C5′-C6′ double bonds, or C5-C6 and C3′-C4′ double bonds in 1, respectively. Similar photoreactions of 1 with electron-rich α,ω-diolefins such as poly(ethylene glycol)divinyl ether (2e and 2f) afforded crown ether-type macrocyclic compounds (5e and 5f) having 18- and 21-membered rings across the C3-C4 and C3′-C4′ double bonds in 1, respectively. The stereochemical features of 3b, 5e-xx, and 5e-nn were determined by the X-ray crystal analysis. The reaction mechanism was inferred by MO methods.     

A planar chiral six-membered cyclic (amino)(ferrocenyl)carbene and its sulfur adduct

A planar chiral ferrocene-fused cyclic aldimine was synthesized and a series of iminium salts were divergently prepared from it. The new carbene was generated from a salt by simple deprotonation with a strong base and identified by a carbene trapping experiment with sulfur. The sulfur adduct was fully characterized and its crystal structure implied that the new carbene would create an excellent chiral environment when used as a catalyst or a ligand in catalytic asymmetric synthesis.