Preparation of Various Nanomaterials via Controlled Gelation of a Hydrophilic Polymer Bearing Metal-Coordination Units with Metal Ions.

We investigated the gelation of a hydrophilic polymer with metal-coordination units (HPMC) and metal ions (PdII or AuIII). Gelation proceeded by addition of an HPMC solution in N-methyl-2-pyrrolidone (NMP) to a metal ion aqueous solution. An increase in the composition ratio of the metal-coordination units from 10 mol% to 34 mol% (HPMC-34) increased the cross-linking rate with AuIII. Cross-linking immediately occurred after dropwise addition of an HPMC-34 solution to the AuIII solution, generating the separation between the phases of HPMC-34 and AuIII. The cross-linking of AuIII proceeded from the surface to the inside of the HPMC-34 droplets, affording spherical gels. In contrast, a decrease in the ratio of metal-coordination units from 10 mol% to 4 mol% (HPMC-4) decreased the PdII cross-linking rate. The cross-linking occurred gradually and the gels extended to the bottom of the vessel, forming fibrous gels. On the basis of the mechanism for the formation of gels with different morphologies, the gelation of HPMC-34 and AuIII provided nanosheets via gelation at the interface between the AuIII solution and the HPMC-34 solution. The gelation of HPMC-4 and PdII afforded nanofibers by a facile method, i.e., dropwise addition of the HPMC-4 solution to the PdII solution. These results demonstrated that changing the composition ratio of the metal-coordination units in HPMC can control the gelation behavior, resulting in different types of nanomaterials.

A trail of dark-matter-free galaxies from a bullet-dwarf collision.

The ultra-diffuse galaxies DF2 and DF4 in the NGC 1052 group share several unusual properties: they both have large sizes1, rich populations of overluminous and large globular clusters2-6, and very low velocity dispersions that indicate little or no dark matter7-10. It has been suggested that these galaxies were formed in the aftermath of high-velocity collisions of gas-rich galaxies11-13, events that resemble the collision that created the bullet cluster14 but on much smaller scales. The gas separates from the dark matter in the collision and subsequent star formation leads to the formation of one or more dark-matter-free galaxies12. Here we show that the present-day line-of-sight distances and radial velocities of DF2 and DF4 are consistent with their joint formation in the aftermath of a single bullet-dwarf collision, around eight billion years ago. Moreover, we find that DF2 and DF4 are part of an apparent linear substructure of seven to eleven large, low-luminosity objects. We propose that these all originated in the same event, forming a trail of dark-matter-free galaxies that is roughly more than two megaparsecs long and angled 7° ± 2° from the line of sight. We also tentatively identify the highly dark-matter-dominated remnants of the two progenitor galaxies that are expected11 at the leading edges of the trail.

Synthesis of Nanosheets Containing Uniformly Dispersed PdII Ions at an Aqueous/Aqueous Interface: Development of a Highly Active Nanosheet Catalyst for Mizoroki-Heck Reaction.

A method was developed to synthesize a nanosheet at the interface of an aqueous layer of PdII ions and an aqueous layer of hydrophilic polymer bearing a metal coordination unit (HPMC). The nanosheet was synthesized through generation of an interface by the addition of an aqueous solution of PdII ions with a low specific gravity (1.03 g/cm3) to a dispersed aqueous solution of HPMC with a high specific gravity (1.50 g/cm3), resulting in rapid cross-linking at the interface. An electron probe microanalysis mapping image showed that the PdII ions were uniformly dispersed in the nanosheet. The nanosheet showed a high catalyst activity for the Mizoroki-Heck cross-coupling reaction with a turnover number (TON) and turnover frequency (TOF) greater than 3,333,333 and 138,889 h-1, respectively. These are the greatest TON and TOF values reported for heterogeneous polymeric catalysts for the Mizoroki-Heck reaction.

Thermoelectric Array Sensors with Selective Combustion Catalysts for Breath Gas Monitoring.

Inflammable breath gases such as H2 and CH4 are used as bio markers for monitoring the condition of the colon. However, their typical concentrations of below 100 ppm pose sensitivity and selectivity challenges to current gas sensing systems without the use of chromatography. We fabricated a compact, gas-selective thermoelectric array sensor (TAS) that uses micro-machined sensor devices with three different combustion catalysts to detect gases such as H2, CO, and CH4 in breath. Using Pt/Pt-W thin-film micro-heater meanders, Pd/Al2O3, Pt,Pd,Au/Co3O4, and Pt/Al2O3 catalysts were heated to 320, 200, and 125 °C, respectively, and the gas sensing performances of the TAS for each gas and for a model breath gas mixture of 100 ppm H2, 25 ppm CO, 50 ppm CH4, and 199 ppm CO2 in air were investigated. Owing to its high catalyst temperature, the Pd/Al2O3 catalyst burned all three gases, while the Pt,Pd,Au/Co3O4 burned CO and H2 and the Pt/Al2O3 burned H2 selectively. To calibrate the gas concentration of the mixture gas without the use of a gas separation tool, linear discriminant analysis was applied to measure the sensing performance of TAS. To enhance the gas selectivity against H2, a double catalyst structure was integrated into the TAS sensor.

Adsorption dynamics of tannin on deacetylated electrospun Konjac glucomannan fabric.

A nonwoven fabric of Konjac glucomannan (KGM) for the adsorption of tannin was fabricated by using electrospinning and then followed by deacetylation with alkaline solution. To analyze the adsorption dynamics of tannin, the time course of the adsorption of tannin on the nonwoven KGM fabric was measured by immersing the fabric in tannin solution at different concentrations of tannin and amounts of the fabric. The initial and late stages of the adsorption behavior could be expressed, respectively, by using a diffusion-limited equation and a stoichiometric equation. A discussion on the dependence of the control parameters on the adsorption behavior is presented. The results represent the first step to provide an effective adsorption procedure for tannin in the use of modified KGM fabric.

Temperature Dependence of Electrophoretic Mobility and Hydrodynamic Radius of Microgels of Poly(N-isopropylacrylamide).

Electrostatic interactions in charged microgels, which are dominated by the microgel net charge, play a crucial role in colloidal stabilization and loading of small, charged molecules. In this study, the temperature dependences of electrophoretic mobility µ and hydrodynamic radius Rh were measured for a slightly ionized poly(N-isopropylacrylamide) (PNIPA) microgel in a dilute suspension. A decrease in Rh was observed in the temperature range between 30 °C and 35 °C, corresponding to the lower critical solution temperature of PNIPA, and an increase in |µ| was observed in a higher temperature range between 34 °C and 37 °C. The analysis based on electrophoresis theory for spherical polyelectrolytes indicated that the net charge of the microgel decreased as the microgel was deswollen.

Heavy metal adsorptivity of calcium-alginate-modified diethylenetriamine-silica gel and its application to a flow analytical system using flame atomic absorption spectrometry.

This study aimed to evaluate the heavy metal adsorptivity of calcium-alginate-modified diethylenetriamine-silica gel (CaAD) and incorporate this biosorbent into a flow analytical system for heavy metal ions using flame atomic absorption spectrometry (FAAS). The biosorbent was synthesized by electrostatically coating calcium alginate onto diethylenetriamine (dien)-silica gel. Copper ion adsorption tests by a batch method showed that CaAD exhibited a higher adsorption rate compared with other biosorbents despite its low maximum adsorption capacity. Next, CaAD was packed into a 1mL microcolumn, which was connected to a flow analytical system equipped with an FAAS instrument. The flow system quantitatively adsorbed heavy metals and enriched their concentrations. This quantitative adsorption was achieved for pH 3-4 solutions containing 1.0×10(-6) M of heavy metal ions at a flow rate of 5.0 mL min(-1). Furthermore, the metal ions were successfully desorbed from CaAD at low nitric acid concentrations (0.05-0.15 M) than from the polyaminecarboxylic acid chelating resin (Chelex 100). Therefore, CaAD may be considered as a biosorbent that quickly adsorbs and easily desorbs analyte metal ions. In addition, the flow system enhanced the concentrations of heavy metals such as Cu(2+), Zn(2+), and Pb(2+) by 50-fold. This new enrichment system successfully performed the separation and determination of Cu(2+) (5.0×10(-8)M) and Zn(2+) (5.7×10(-8) M) in a river water sample and Pb(2+) (3.8×10(-9) M) in a ground water sample.

Thermal balance analysis of a micro-thermoelectric gas sensor using catalytic combustion of hydrogen.

A thermoelectric gas sensor (TGS) with a combustion catalyst is a calorimetric sensor that changes the small heat of catalytic combustion into a signal voltage. We analyzed the thermal balance of a TGS to quantitatively estimate the sensor parameters. The voltage signal of a TGS was simulated, and the heat balance was calculated at two sections across the thermoelectric film of a TGS. The thermal resistances in the two sections were estimated from the thermal time constants of the experimental signal curves of the TGS. The catalytic combustion heat Q(catalyst) required for 1 mV of ∆V(gas) was calculated to be 46.1 µW. Using these parameters, we find from simulations for the device performance that the expected Q(catalyst) for 200 and 1,000 ppm H2 was 3.69 µW and 11.7 µW, respectively.

A facile and high-recovery material for rare-metals based on a water-soluble polyallylamine with side-chain thiourea groups.

We describe a facile and high-recovery material for rare metals based on a polymer combining amino groups for water solubility and thiourea groups for metal complexation. Good solubility in aqueous metal ion solutions allows for homogeneous and efficient adsorption by the polymer, and a maximum Pd(II) recovery amount (0.508 gPd gpolymer(-1)) greater than those of other polymers reported in the literature.

Reversible chain association/dissociation via a CO2 responsive crosslinking/decrosslinking system.

Reversible chain association/dissociation phenomenon via CO(2) responsive crosslinking/decrosslinking was detected in aqueous solutions of polyallylamine (PAA). The chain association/dissociation behavior was reversible and useful in the synthesis of porous crosslinked polystyrene, which suggested potential utility in the area of CO(2)-responsive separable adhesives, switches and sensors.

Synthesis of hydrogels from polyallylamine with carbon dioxide as gellant: development of reversible CO(2) absorbent.

Hydrogels were successfully synthesized utilizing CO(2) as a gellant. A cross-linking reaction of polyallylamine (PAA) with CO(2) in the presence of 1,8-Diazabicyclo[5,4,0]-undec-7-ene (DBU) provided hydrogels bearing urea cross-linking points and residual amino groups in the side chains. The obtained hydrogels absorbed CO(2) at 25 °C and gave a maximum absorption four times larger than that of PAA aqueous solution and 2.8 times larger than that of the most commonly used absorbent, monoethanolamine. The PAA hydrogels desorbed the absorbed CO(2) completely under a N(2) atmosphere at 120 °C, and could be repeatedly recycled without loss of efficiency, indicating their potential application as recyclable CO(2) absorption materials.

Imaging of forearm-muscle activities by CP-MCT and TR-DOT.

Chirp Pulse Microwave Computed Tomography (CP-MCT) has been developed to visualize activities of forearm muscles during exercise. The change in the gray levels between two images obtained before and after loading exercises showed position dependence. This was produced by physiological- or biochemical- changes in forearm muscles caused by grasping a rubber ball in the bolus tank that was filled with saline solution. However, nobody knows the truth how this change was produced. In order to infer the mechanism of the gray level change caused by the exercise, the forearm exercise was investigated also by using electromyography and Time-Resolved Diffuse Optical Tomography (TR-DOT). Measurements by CP-MCT and TR-DOT were not performed simultaneously, but both images obtained under the same experimental condition showed similar changes in each tomogram. They were characterized by activation of inner muscles needed for continuing the exercise.

Antibacterial properties of some cyclic organobismuth(III) compounds.

Bismuth compounds are known for their low levels of toxicity in mammals, and various types of bismuth salts have been used to treat medical disorders. As part of our program to probe this aspect of bismuth chemistry, cyclic organobismuth compounds 1 to 8 bearing a nitrogen or sulfur atom as an additional ring member have been synthesized, and their antimicrobial activities against five standard strains of gram-negative and gram-positive bacteria were assessed. The eight-membered-ring compounds, compounds 1 to 3, exhibited MICs of less than 0.5 microg/ml against Staphylococcus aureus and were more active than the six-membered ones, compounds 5 to 8 (MICs, 4.0 to 16 microg/ml). The gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis, and Enterococcus faecalis) were more susceptible to both types of ring compounds than the gram-negative ones (Escherichia coli and Pseudomonas aeruginosa). Treatment with polymyxin B nonapeptide increased the susceptibility of E. coli to cyclic organobismuth compounds, indicating the low permeability of the outer membrane of gram-negative bacteria to the compounds. Compound 1 also had activity against methicillin-resistant S. aureus, which had an MIC for 90% of the hospital stock strains of 1.25 microg/ml. The killing curves for S. aureus treated with compound 1 or 3 revealed a static effect at a low dose (2x the MIC). However, when S. aureus was treated with 10x the MIC of compound 1 or 3, there was an approximately 3-log reduction in the viable cell number after 48 h of treatment. Electron microscopic inspection demonstrated a considerable increase in the size of S. aureus and the proportion of cells undergoing cell division after treatment with compound 1 at 0.5x the MIC.