Selective determination of 2,4-xylenol by gas chromatography/supersonic jet/resonance-enhanced multiphoton ionization/time-of-flight mass spectrometry

Gas chromatography/supersonic jet/resonance-enhanced multiphoton ionization/time-of-flight mass spectrometry (GC/SSJ/REMPI/TOF-MS) was employed for isomer-selective determination of 2,4-xylenol in river and seawater samples. The sample containing 2,4-xylenol was measured using argon, rather than helium, as the GC carrier gas to cool the analyte molecule sufficiently. The instrumental detection limit (IDL) achieved at a flow rate of 1 mLmin(-1) was 14 pg. Although this value was comparable to the value (ca. 10 pg) obtained by gas chromatography/electron impact/quadrupole mass spectrometry (GC/EI/QMS). When the flow rate was increased to 8 mLmin(-1), interference from the 2,5-xylenol isomer was completely suppressed. The IDL was degraded to 83 or 160 pg at a flow rate of 5 or 8 mLmin(-1), respectively. The recovery of 2,4-xylenol from the river and the seawater samples was 85 and 93%, respectively. The time for analysis was only 10 min per one sample in GC/SSJ/REMPI/TOF-MS. These results suggest that GC/SSJ/REMPI/TOF-MS is useful for the selective measurement of 2,4-xylenol, which has been designated a Class I chemical substance in the Pollutant Release and Transfer Register (PRTR).     

Development of efficient photocatalytic systems for CO2 reduction using mononuclear and multinuclear metal complexes based on mechanistic studies

Photocatalytic systems for CO₂ reduction using metal complexes, especially rhenium(I) complexes as a main component, are reviewed: mononuclear Re(I) complexes, mixed systems with two different Re(I) complexes, and supramolecule systems with a Re(I) complex connected to a ruthenium(II) complex. We focus on the mechanistic studies and the architecture for constructing the photocatalytic systems based on the mechanism.     

Vernodalidimers A and B, novel orthoester elemanolide dimers from seeds of Vernonia anthelmintica

Two novel elemanolide dimers, vernodalidimers A (1) and B (2), possessing a rare tricyclic ortho ester moiety, were isolated from the seeds of Vernonia anthelmintica. Their structures were elucidated by 1D and 2D NMR data and CD spectra. Vernodalidimers A (1) and B (2) exhibited potent cell growth inhibitory activity against HL-60 cells (IC₅₀ 0.72 and 0.47 μM, respectively).     

Remarkable switch of regioselectivity in epoxide ring opening of 3-benzyl-7-oxa-3-azabicyclo[4.1.0]heptane with amines: practical synthesis of trans-4-amino-3-hydroxypiperidines and trans-3-amino-4-hydroxypiperidines

A simple and highly C3 selective ring-opening method for 3,4-epoxypiperidines has been developed. We also describe a practical improvement of the C4 selective ring-opening method using the same N-alkyl substituted 3,4-epoxypiperidines. This method provides access to pharmaceutically relevant trans-3-amino-4-hydroxypiperidines and trans-4-amino-3-hydroxypiperidines with simple procedures.     

Orientation Control of Photo‐Immobilized Antibodies on the Surface of Azobenzene‐Containing Polymers by the Introduction of Functional Groups

In our photo‐induced immobilization technique for an antibody (IgG) using azopolymers, the introduction of COOH and NMe₂ into the azopolymers, which can introduce surface charges, strongly affected the immobilization properties such as the efficiency of immobilization and the activity of the immobilized IgG (i.e., the orientation of the immobilized IgG). The introduction of COOH promoted a more active orientation of the immobilized IgG. The orientation was determined during the adsorption process onto the azopolymer surface in solution before photo‐immobilization, and was maintained during the photo‐immobilization. The surface charge of the azopolymer appears to be an important factor for IgG orientation, which involves electrostatic interactions between its Fab and the azopolymer surface.

     

Surface plasmon resonance study on binding interactions of multivalent cyclophane hosts with immobilized guests

Guest‐binding affinities of water‐soluble cyclophane heptadecamer (1) and pentamer (2) with immobilized guests such as 1‐pyrenylmethylamine (PMA) and 2‐(1‐ naphthyl)ethylamine (NEA) were investigated by surface plasmon resonance (SPR) measurements. As a typical example, the binding constants (K) for 1 and 2 with the immobilized PMA as a guest were evaluated to be 2.5 × 10⁷ and 2.7 × 10⁶ M^?1, respectively, and were much larger than that of a monocyclic reference cyclophane (K, 2.5 × 10⁴ M^?1). Interestingly, in the complexation of 1 and 2 with the immobilized guests, more favorable association and dissociation rate constant values (k_a and k_d, respectively) were observed in comparison with those for the monocyclic cyclophane, reflecting multivalent effects in macrocycles. The multivalent effects in macrocycles as well as molecular recognition abilities of the cyclophane oligomers were confirmed even when the guest molecules were immobilized on SPR sensor chip surfaces. Copyright © 2009 John Wiley & Sons, Ltd.     

Medicinal Flowers. XXXI. Acylated oleanane-type triterpene saponins, Sasanquasaponins I-V, with antiallergic activity from the flower buds of Camellia sasanqua

The methanolic extract and its 1-butanol-soluble fraction from the flower buds of Camellia sasanqua THUNB. were found to show inhibitory activities on the release of β-hexosaminidase from rat basophile leukemia (RBL-2H3) cells. From the 1-butanol-soluble fraction, five new acylated oleanane-type triterpene saponins, sasanquasaponins I-V, were isolated together with a known saponin and their chemical structures were elucidated on the basis of chemical and physicochemical evidence. The principal saponin constituents, sasanquasaponins I-III, with an acyl group at the 22-position of the aglycon part showed the inhibitory effects on the release of β-hexosaminidase and some structure-activity relationships were reported.     

Influence of head shape of solid body plunging into water on splash formation

Abstract  

We experimentally investigated the influence of a head shape of a solid body plunging into water on splash formation. Three different head shapes were tested: a hemisphere, cone, and circular cylinder. A hemisphere as a tail shape is common to all three head shapes. We captured images of splash formation using a high-speed CMOS camera. We found that a film flow generated at an early stage when a body impacts the water surface influences subsequent events until the splash sequence is completed. We explain the origin of the film flow according to the principle of conservation of momentum. The film flow as the primary splash originates from water displaced by the head. The meridian line, which connects the head to the tail of the body, affects separation of the film flow and causes the secondary splash. The air cavity generated when the body plunges into the water is also influenced by the head shape. The tertiary splash is formed by a reaction of the air cavity, which is detached from the body. We found that the secondary dome-type splash obstructs growth of the tertiary splash. Thus, we conclude that the head shape affects all events of the splash.     

Single-shot polarization-imaging digital holography based on simultaneous phase-shifting interferometry

We propose single-shot digital holography which is capable of simultaneously capturing both the information of multiple phase-shifted holograms and the distribution of the polarization. In this technique, a single image sensor records both the information required for phase-shifting interferometry and that of the polarization states of objects using an array of polarizers. The essence of the technique is the capability of imaging the distribution of the polarization of three-dimensional objects with a single-shot exposure by using the space-division multiplexing of holograms. The validity of the proposed technique was confirmed by the preliminary experiments.