Cooperation between artificial receptors and supramolecular hydrogels for sensing and discriminating phosphate derivatives

This study has successfully demonstrated that the cooperative action of artificial receptors with semi-wet supramolecular hydrogels may produce a unique and efficient molecular recognition device not only for the simple sensing of phosphate derivatives, but also for discriminating among phosphate derivatives. We directly observed by confocal laser scanning microscopy that fluorescent artificial receptors can dynamically change the location between the aqueous cavity and the hydrophobic fibers upon guest-binding under semi-wet conditions provided by the supramolecular hydrogel. On the basis of such a guest-dependent dynamic redistribution of the receptor molecules, a sophisticated means for molecular recognition of phosphate derivatives can be rationally designed in the hydrogel matrix. That is, the elaborate utilization of the hydrophobic fibrous domains, as well as the water-rich hydrophilic cavities, enables us to establish three distinct signal transduction modes for phosphate sensing: the use of (i) a photoinduced electron transfer type of chemosensor, (ii) an environmentally sensitive probe, and (iii) an artificial receptor displaying a fluorescence resonance energy transfer type of fluorescent signal change. Thus, one can selectively sense and discriminate the various phosphate derivatives, such as phosphate, phospho-tyrosine, phenyl phosphate, and adenosine triphosphate, using a fluorescence wavelength shift and a seesaw type of ratiometric fluorescence change, as well as a simple fluorescence intensity change. It is also shown that an array of the miniaturized hydrogel is promising for the rapid and high-throughput sensing of these phosphate derivatives.     

Observation of cold, long-lived antiprotonic helium ions

Cold, two-body antiprotonic helium ions p 4He2+ and p 3He2+ with 100-ns-scale lifetimes, occupying circular states with the quantum numbers ni=28-32 and li=ni-1 have been observed. They were produced by cooling three-body antiprotonic helium atoms in an ultra-low-density helium target at temperature T approximately 10 K by atomic collisions, and then removing their electrons by inducing a laser transition to an autoionizing state. The lifetimes of p 3He2+ against annihilation induced by collisions were shorter than those of p 4He2+, and decreased for larger-ni states.     

Self-assembly of water-dispersed gold nanoparticles stabilized by a thiolated glycol derivative

Two-dimensional (2D) hexagonally close-packed arrays of water-dispersed gold nanoparticles (NPs) on highly hydrophilic sputter-deposited SiO₂ surfaces were fabricated via an evaporation-induced self-assembly process. Using a non-ionic amphiphilic glycol derivative with the thiol head group, 1-mercapto-3,6,9-trioxodecane, as a stabilization ligand, high-concentration Au NPs were stably dispersed in water, and self-assembled into μm-sized well-ordered 2D arrays on SiO₂ surfaces during the solvent evaporation on SiO₂ surfaces. Due to the non-ionic character of the ligand, the particle–particle interactions may only depend on the capillary and van der Waals forces, and not on the electric double-layer forces that change with ion/electrolyte concentrations during the solvent evaporation. This study provides an approach to fabrication of close-packed 2D arrays of water-dispersed NPs instead of using toxicological organic solvent or complex water-organic phase transfer process. Meanwhile, this approach will make it easier to study their self-assembly mechanisms in a variety of solvents by simplifying ambiguous particle–particle interactions.This revised version was published online in August 2005 with a corrected issue number.     

Local plasmon sensor with gold colloid monolayers deposited upon glass substrates

A new optical sensor that uses local plasmon resonance is proposed. A peak that is due to the local plasmon resonance appears in the absorption spectrum of a gold colloid suspension in the visible region, and its height and wavelength depend on the refractive index of the suspension. These properties are used for optical sensors. We used gold colloid monolayers in which colloidal gold particles a few tens of nanometers in diameter were immobilized upon a glass slide by a functional organic coupling agent. We measured the absorption spectra of the the gold colloid monolayers, which were immersed in liquid samples or coated with thin films. We observed increases of both the resonance wavelength and the absorbance as the refractive indices of the sample liquids or the thickness of the coated films increased. The proportional constants of the resonance wavelength to the film thickness were 3.6 and 5.7 for a 13.9- and a 20.2-nm gold colloid monolayer, respectively.     

Radiator effect on plastic nuclear track detectors for high-energy neutrons

The effect of radiators supplying charged particles to plastic nuclear track detectors has been investigated both experimentally and theoretically in order to apply them to personal dosimeters for high-energy neutrons. Performance of four types of radiator materials, CH₂, CD₂ (deuterized hydrocarbon), LiF (lithium fluoride) and C (graphite), was checked in a quasi-monoenergetic neutron field generated by p-Li reactions. The efficiency has been numerically calculated based on a model with a special attention to the angular dependence of cross sections and data of characteristic response to light ions. The effect of respective radiator candidates has been evaluated as a function of the neutron energy. A two-layer radiator has also been proposed to adjust the energy dependence of the relative sensitivity to conversion factor for dose-equivalent.     

Spectrophotometric determination of urinary protein with o-sulfophenylfluorone-metal complex.

A simple and sensitive spectrophotometric method for the determination of human serum albumin (HSA) was established based on the ternary complex-formation reaction of HSA with o-sulfophenylfluorone (SPF) as a xanthene dye and metal ion (niobium(V) and bismuth(III)) in the presence of a dispersion agent. This new method enabled the determination of HSA in the range of 1 - 15 microg/ml HSA by measuring the difference of the absorbance at 530 nm between HSA-SPF-metal ion and SPF-metal ion solutions. In the determination of HSA, this method is about 2-times more sensitive than the Pyrogallol Red-molybdenum(VI) method (PR method), which accounts for more than 80% of the quantification methods for urinary protein assays in Japan. There was no significant difference between the results obtained by the present method and the PR method for human urine samples. The binding process between the SPF-metal complex and HSA was studied by determining the binding parameters and the thermodynamic parameters.     

Mössbauer and infrared investigation of reactions of laser-evaporated iron atoms with ethylene

Reactions of laser-evaporated iron atoms with ethylene molecules were investigated. The reaction products were trapped in a low-temperature matrix observed by Mössbauer and infrared spectroscopies. Fe(C₂H₄) was produced at low ethylene concentration, and Fe(C₂H₄)₂ was obtained as the major product at higher ethylene concentration. The assignments were confirmed through molecular orbital calculations.