Monitoring nano-flow rate of water by atomic emission detection using helium radio-frequency plasma

Recently, high-performance nano-scale flow pumping systems have been developed for micro and miniaturized analysis systems. A novel device capable of measuring and monitoring nanoliter scale flow rates has been required for the further development of the pumping system. In this study, an atomic emission detector using helium radio-frequency plasma (RFP-AED) was used for the measurement of the nanoliter scale flow rate of water by quantitatively detecting the emission from hydrogen in the water molecules. Monitoring nano-flow rates of water in the range up to 1.0 microl min(-1), and the change in the flow rate by the indication of the ratio of the emissions of H (656.3 nm) and He (667.8 nm) were successful. At present, the lowest flow rate that could be determined reproducibly was 4 nl min(-1) calculated as five times the standard deviation of the background noise. Additionally, similar evaluations for the deviation of each flow rate by using the RFP-AED and a flow-injection system were produced.     

Synthesis of (--)-Muricatacin via alpha- and alpha'-C-H bond functionalization of tetrahydrofuran

(--)-Muricatacin, a potent cytotoxic (4R,5R)-5-hydroxyheptadecan-4-olide, has been synthesized through alpha-C--H hydroxyalkylation and alpha'-C--H oxidation of tetrahydrofuran. This study presents a novel method for C--H bond functionalization as a means for preparing gamma-(hydroxyalkyl)-gamma-butyrolactones.     

Concentration-dependence of faradaic currents and conductivity in a polystyrene sulfonic latex suspension

The conductivity, κ, in a suspension of polystyrene sulfonic latex without supporting electrolyte showed a linear dependence on the volume fraction, v_f, of the latex for v_f<0.03 with a finite intercept. In contrast, this deviated upward from the linear line for v_f>0.03. These variations were qualitatively consistent with the dependence of the voltammetric reduction current of H⁺ on v_f without supporting electrolyte. The current values were only a few percent of the theoretical diffusion-controlled current that could be observed in the suspension with supporting electrolyte. This fact indicates the electrostatic immobilization of the hydrogen ions by sulfonic latex particles. A plot of the current against κ at common values of v_f showed that the current for v_f>0.07 was smaller than the value predicted from the conductivity. This can be explained in terms of a combination of the increase in electrostatically unbounded H⁺ estimated by conductance measurements and electric migration in which the electrochemical depletion of [H⁺] also causes the depletion of the latex.     

Influence of nano-structure on electrolytic properties in CeO2 based system

Doped ceria (CeO₂) compounds are fluorite type oxides that show oxygen ionic conductivity higher than yttria stabilized zirconia, in oxidizing atmosphere. In order to improve the conductivity, the effective index was suggested to maximize the oxygen ionic conductivity in doped CeO₂ based oxides. In addition, the true microstructure of doped CeO₂ was observed at atomic scale for conclusion of conduction mechanism. Doped CeO₂ had small domains (10-50 nm) with ordered structure in a grain. It is found that the electrolytic properties strongly depended on the nano-structural feature at atomic scale in doped CeO₂ electrolyte. This revised version was published online in August 2006 with corrections to the Cover Date.     

Fluorometric sensing of alkaline Earth metal cations by new lariat ethers having plural pyrenylmethyl groups on the electron-donating sidearms

[structure: see text] New fluorescent compounds (1), lariat ethers having plural pyrenylmethyl groups on the sidearms, were prepared, and their complexation behavior with alkaline earth metal cations was examined by fluorescence spectrometry. The pyrene excimer emission decreased accompanied with an increase in the monomer emission upon complexation with the metal ion. This finding is ascribed to the cooperative participation of one of the two sidearms in the complexation of the crown ring with the metal ion.     

Novel photodegradation of the antifungal antibiotic pyrrolnitrin in anhydrous and aqueous aprotic solvents

The UV irradiation of pyrrolnitrin (1a), which is an antibiotic clinically useful against dermatophytosis and possesses a unique 2-(pyrrol-3-yl)nitrobenzene moiety in the molecule, in an anhydrous aprotic solvent resulted in the exclusive formation of transient 7,4'-dichlorospiro[1,3-dihydrobenzo(c)isoxazole-3,3'-pyrrolin-2'-one] (2a) via the intramolecular oxidation of the juxtaposed pyrrole ring by the triplet-excited nitro group. The irradiation in an aqueous aprotic solvent, however, allowed the concurrent occurrence of intramolecular cyclization by the singlet-excited nitro group in 1a and the hydroxylation at the 2-position of the pyrrole ring by water to afford 3,7-dichloro-8-hydroxy-8,8a-dihydropyrrolo[2,3-b]indol-2-one (3a), accompanied by the formation of 2a. Elongation of the irradiation time in these photoreactions caused a rapid consumption of the products, 2a and 3a, to give undetermined polar polymeric products. The present results indicate that the photodegradation of 1a is significantly influenced by the presence of water in the reaction media and by the nature of its excited state. Thus, the loss of the antifungal activities by the photosensitive antibiotic 1a was chemically proved.     

Shape Rememorization of an Organosuperelastic Crystal through Superelasticity–Ferroelasticity Interconversion

As altering permanent shapes without loss of material function is of practical importance for material molding, especially for elastic materials, shape‐rememorization ability would enhance the utility of elastic crystalline materials. Since diffusionless plastic deformability can preserve the crystallinity of materials, the interconversion of diffusionless mechanical deformability between superelasticity and ferroelasticity could enable shape rememorization of superelastic single crystals. This study demonstrates the shape rememorization of an organosuperelastic single crystal of 1,4‐dicyanobenzene through time‐reversible interconversion of superelasticity–ferroelasticity relaxation by holding the mechanically twinned crystal without heating. The shape‐rememorization ability of the organosuperelastic crystal indicates the compatibility of superelasticity (antiferroelasticity) and ferroelasticity as well as the intrinsic workability of organic crystalline materials capable of recovering their crystal functions under mild conditions.     

Electrolytic synthesis of ammonia in molten salts under atmospheric pressure

Ammonia was successfully synthesized by using a new electrochemical reaction with high current efficiency at atmospheric pressure and at lower temperatures than the Haber-Bosch process. In this method, nitride ion (N3-), which is produced by the reduction from nitrogen gas at the cathode, is anodically oxidized and reacts with hydrogen to produce ammonia at the anode.     

Synthesis and cation-binding properties of poly-and bis(thiacrown ether)s

Poly- and bis(thiacrown ether) derivatives in which some oxygen atoms of benzocrown ether moiety are replaced by sulfur atoms have been synthesized. Their cation-binding abilities were investigated by using the solvent extraction method. The poly- and bis(benzothiacrown ether)s showed great affinity for silver ion, being more excellent in the affinity than the corresponding monocyclic analogs. They, however, possess very poor cation-binding ability for alkali and alkaline-earth metal ions. The poly- and bis(thiacrown ether)s also bind mercuric ions effectively, whereas the corresponding monomeric analogs do not at all.     

Synthesis and properties of photochromic liquid‐crystalline copolymers containing both spironaphthoxazine and cholesteryl groups

Photochromic liquid‐crystalline copolymers consisting of a photochromic monomeric unit containing both a spironaphthoxazine group and an undecamethylene spacer, and a liquid‐crystalline monomeric unit containing both a cholesteryl group and a decamethylene spacer were prepared to investigate the effect of the thermal properties of the photochromic monomeric unit on the mesomorphic order of the side chain of the related copolymers. The photochromic liquid‐crystalline copolymers containing a photochromic liquid‐crystalline monomeric unit showed only a smectic phase. On the other hand, the photochromic liquid‐crystalline copolymers containing a photochromic non‐liquid‐crystalline monomeric unit showed a chiral nematic phase (cholesteric phase). The photochromic chiral nematic liquid‐crystalline copolymer containing 14 mol % photochromic monomeric unit reflected visible light around 104 °C. To lower the temperature range of reflection of visible light, cholesteryl oleyl carbonate was used as a chiral nematic plasticizer for the photochromic chiral liquid‐crystalline polymer systems. Photo‐induced pitch change of the mixture by means of UV irradiation was investigated and it was concluded that the pitch change observed under UV irradiation was mainly induced by thermal effect in the case of our system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 887–894, 2000