Aggregation behavior of polypropylene oxide with electric charges at both ends in aqueous solution

The aggregation behavior of polypropylene oxide (PPO) with positive charges at both ends was investigated in aqueous solution by means of the measurements of solution turbidity, dynamic light-scattering, differential scanning calorimetry, and dye solubilization. The positive charges were produced by protonation of terminal NH(2) groups attached to the polymer composed of 33 PO units. It was found that the aggregation behavior is quite sensitive to temperature. At low temperature, the polymer dissolves in water as a unimer. When temperature is increased, the unimer solution undergoes a phase separation to give a turbid solution. Further increase in temperature produces a transparent micellar solution. The aggregation of the polymer molecules must be induced by the dehydration of PPO chain caused by temperature increase. According to the analysis of heat absorptions associated with the melting of the solid mixture and the phase separation of the unimer solution, it is suggested that approximately 10% dehydration of PPO chain causes the phase separation. The temperature-composition phase diagram of aqueous mixture of this polymer was constructed on the basis of turbidity and DSC experiments, which reveals the aggregation behavior of this polymer in aqueous medium as a function of concentration and temperature.     

Counterion specificity in the phase behavior of tetradecyldimethylamine oxides at different degrees of protonation

Effects of counterion species on the aggregate structure of tetradecyldimethylamine oxide (C14DMAO) accompanying the protonation were examined by viscoelastic properties and phase behavior observations. Different extents of the synergetic behavior between protonated and non-protonated amine oxides were observed depending on the counterion species, which follow the Hofmeister, or the lyotropic, series. The efficacy of monovalent anions with respect to the increasing the surfactant packing parameter was as follows: salicylate>perchlorate>nitrate>bromide>chloride, formate. Vesicle formation was found in the case of salicylate and perchlorate anions and elongation of rodlike micelles was observed for nitrate, bromide, sulfate, tartronate and tartrate anions but little effects in the case of chloride and formate anions. The observed ionic specificity is well correlated with the free energy of hydration of counterions.     

Simultaneous measurement of ionization and scintillation from nuclear recoils in liquid xenon for a dark matter experiment

We report the first measurements of the absolute ionization yield of nuclear recoils in liquid xenon, as a function of energy and electric field. Independent experiments were carried out with two dual-phase time-projection chamber prototypes, developed for the XENON dark matter project. We find that the charge yield increases with decreasing recoil energy, and exhibits only a weak field dependence. These results are the first unambiguous demonstration of the capability of dual-phase xenon detectors to discriminate between electron and nuclear recoils down to 20 keV, a key requirement for a sensitive dark matter search.     

Enantioseparation of DL-isocitric acid by a chiral ligand exchange CE with Ni(II)-D-quinic acid system

The ratio of citric acid to D ‐isocitric acid can be used to distinguish authentic and adulterated fruit juices. To separate DL ‐isocitric acid enantiomers, we used ligand exchange CE. D ‐Quinic acid was used as a chiral selector ligand and Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions were used as the central ions of the chiral selector in the BGE. DL ‐Isocitric acid was found to be enantioseparated with the above metal ions except for Mn(II) ion. The optimum running conditions for the analysis of D ‐ and L ‐isocitric acids along with citric acid, an isomer of isocitric acid, were found to be a BGE (pH 5.0) containing 30% ACN, 20 mM acetic acid, 20 mM NiSO₄, and 80 mM D ‐quinic acid. Under these conditions, DL ‐isocitric and citric acids in fruit juices were analyzed successfully.     

Simultaneous and group determination methods for designated substances by HPLC with multi-channel electrochemical detection and their application to real samples

Many psychotropic substances are illegally available on the streets and/or via the Internet. This wide distribution has become a serious social problem. To control this problem, many substances have been controlled as ‘designated substances’ (Shitei‐Yakubutsu) in Japan since April 2007 by the Pharmaceutical Affairs Law, including tryptamines, phenethylamines and piperazines. In the present study, simultaneous determination methods using HPLC with multi‐channel electrochemical detection (MECD) were developed for the designated substances. The proposed methods utilizing online electrochemical oxidation are the first report on the simultaneous determination of various designated substances. The methods involve direct determination and require no complicated pretreatments such as fluorescence labeling. The designated substances were separated by reversed‐phase chromatography using a TSK‐gel ODS‐100V (4.6 × 250 mm, i.d., 3 µm) and gradient elution by a mixture of potassium phosphate buffer, methanol and acetonitrile. The total separation of 31 designated substances was successfully performed but required long chromatographic run times. Thus, the designated substances were divided into three groups: (1) tryptamines, (2) phenethylamines and (3) piperazines and others. They were then analyzed by HPLC‐MECD as another separation method. The suitable applied voltages for each designated substance were determined based upon the hydrodynamic voltammogram. The limits of detection (signal‐to‐noise ratio of 3) of the designated substances for the most suitable voltages were in the range of 17.1 pg (5‐MeO‐MIPT) to 117 ng (indan‐2‐amine). The calibration curves based on the peak heights were linearly related to the amounts of the designated substances (R² > 0.999). Good accuracy and precision by intra‐day assay and inter‐day assay were also obtained using the present procedures. The proposed methods were applied to the analyses of the designated substance in several real samples. Copyright © 2010 John Wiley & Sons, Ltd.     

A method for DNA detection in a microchannel: fluid dynamics phenomena and optimization of microchannel structure

A simple DNA diagnosis method using microfluidics has been developed which requires simple and straightforward procedures such as injection of sample and probe DNA solutions. This method takes advantage of the highly accurate control of fluids in microchannels, and is superior to DNA microarray diagnosis methods due to its simplicity, highly quantitative determination, and high-sensitivity. The method is capable of detecting DNA hybridization for molecules as small as a 20 mer. This suggests the difference in microfluidic behavior between single strand DNA (ssDNA) and double stranded DNA (dsDNA). In this work, influence of both the inertial force exerted on DNA molecules and the diffusion of DNA molecules was investigated. Based on the determination of these parameters for both ssDNA and dsDNA by experiments, a numerical model describing the phenomena in the microchannel was designed. Computational simulation results using this model were in good agreement with previously reported experimental results. The simulation results showed that appropriate selection of the analysis point and the design of microchannel structure are important to bring out the diffusion and inertial force effects suitably and increase the sensitivity of the detection of DNA hybridization, that is, the analytical performance of the microfluidic DNA chip.     

Non-derivatized analysis of methiin and alliin in vegetables by capillary electrophoresis

Methiin and alliin are important components of flavors or the precursors of flavors and odors of Allium vegetables. Moreover, they are thought to be beneficial to health. A non-derivative method was developed to analyze these compounds in vegetables by capillary electrophoresis. These compounds in the extracts of Allium and Brassica vegetables were detected indirectly at 225 nm. The analysis of each sample required less than 25 min, and the linear detection range was 5-5000 mg/l. This method was simple compared to the other published methods using high performance liquid chromatography. Moreover, it was possible to detect the peak of pyruvate simultaneously with methiin and alliin using this method. The presence of pyruvate peak is a useful indicator if the blanching of the samples has been insufficient.     

Highly Oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations,Biradical Properties and Decreases in Magnetic Anisotropy

Presented here is a comprehensive study of highly oxidized multiple-decker complexes composed of Tb^III and Cd^II ions and two to five phthalocyaninato ligands, which are stabilized by electron-donating n-butoxy groups. From X-ray structural analyses, all the complexes become axially compressed upon ligand oxidation, resulting in bowl-shaped distortions of the ligands. In addition, unusual coexistence of square antiprism and square prism geometries around metal ions was observed in +4e charged species. From paramagnetic ¹H NMR studies on the resulting series of triple, quadruple and quintuple-decker complexes, ligand oxidation leads to a decrease in the magnetic anisotropy, as predicted from theoretical calculations. Unusual paramagnetic shifts were observed in the spectra of the +2e charged quadruple and quintuple-decker complexes, indicating that those two species are actually unexpected triplet biradicals. Magnetic measurements revealed that the series of complexes show single-molecule magnet properties, which are controlled by the multi-step redox induced structural changes.