Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O) n − and (NH3) n −

The photodetachment spectra of (H₂O) _n ^=2?69/? and (NH₃) _n ^=41?1100/? have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly withn ^?1/3, extrapolating to a VDE (n=∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons.     

Activity concentrations of 210Po in the soft parts of cockle (Anadara granosa)at Kuala Selangor, Malaysia

Polonium-210 has been measured in the soft parts of Anadara granosa purchased at Kuala Selangor, West Coast of Malaysia in August 2001, April 2002 and September 2002. It is shown that ²¹⁰Po is non-uniformly distributed within cockles of various sizes (i.e., 2.5, 3.0, 3.5 and 4.0 cm of shell length) and the concentration of ²¹⁰Po in the soft parts of cockle was significantly different (p<0.05) due to sampling date. The highest value was observed in the smallest cockle with a shell length of 2.5 cm (411.6±26.16 Bq/g dry wt.). It is clear that there is an allometric relationship between ²¹⁰Po activity concentration and individual cockle weight. This may reflect on the differences of metabolic rate and growth age of cockles. The mean activity concentration of ²¹⁰Po measured in Kuala Selangor filtered water were 1.75±0.17, 0.79±0.08 and 1.13±0.20 Bq/kg for August 2001, April 2002 and September 2002, respectively. The yield concentration factors for ²¹⁰Po in the soft parts of cockles varies from 27.3^. 10³ to 106.9^. 10³. This revised version was published online in July 2006 with corrections to the Cover Date.     

Hypoxanthine,xanthine and theobromine complexes with palladium(II) and platinum(IV) chlorides

Summary Complexes of the general types Pd(L)(LH)Cl (LH=hxH, xnH, or tbH) and Pt(L)(LH)Cl₃ (LH=hxH, or xnH) are formed by boiling under reflux 21 molar mixtures of hypoxanthine (hxH), xanthine (xnH) or theobromine (tbH) and PdCl₂ or PtCl₄ in ethanol-triethyl orthoformate. These complexes appear to be linear chain polymeric species, characterized by single monoanionic L^– ligands bridging between adjacent Pd²⁺ or Pt⁴⁺ ions. Inclusion of one terminal neutral LH and one terminal chloro-ligand completes the coordination sphere in the square-planar Pd²⁺ complexes, while the Pt⁴⁺ complexes aretrans-octahedral, involving three terminal chloro and one terminal LH ligand per platinum. The possible binding sites of the bidentate bridging L^– and the unidentate terminal LH are discussed.     

Glucose-sensitive inverse opal hydrogels: analysis of optical diffraction response

A glucose-sensitive inverse opal hydrogel was synthesized through photopolymerization of 2-hydroxyethyl methacrylate and 3-acrylamidophenylboronic acid within the interstitial space of a dried poly(styrene) colloidal crystal template, followed by template removal. Charged complex formation between the phenylboronic acid functional group and the 1,2-cis-diol glucose resulted in reversible swelling of the inverse opal hydrogel, which was observed through shifts in the optical diffraction wavelength. The hydrogel was sensitive to glucose at physiological concentrations and ionic strength. The effects of phenylboronic acid concentration, ionic strength, and buffer pH on the equilibrium hydrogel swelling were also studied. The kinetics of hydrogel swelling was also examined, and it was found that the rate of diffraction shift matched well with diffusion-limited kinetics. Additionally, the diffraction response was compared with simulations using the scalar wave approximation and transfer matrix method.     

Active Chemical Constituents from Sauropus androgynus

This paper describes the chemical investigation on BuOH-soluble EtOH extract from the aerial part of Sauropus androgynus. This study led to the characterization of six bioactive ingredients including three nucleosides—adenosine (1), 5′-deoxy-5′-methylsulphinyl-adenosine ( 2 ), and uridine ( 3 ), two flavonol dioside — 3-O-β-D-glucosyl-7-O-α-L-rhamnosyl-kaempferol ( 4 ), 3-O-β-D-glucosyl-(1→6)-β-D-glucosyl-kaempferol ( 5 ), and one rare flavonol trioside — 3-O-β-D-glucosyl-(1→6)-β-D-glucosyl-7-O-α-L-rhamno-syl-kaempferol ( 6 ). Their structures were determined on the basis of spectral analysis.     

Automation for continuous analysis on microchip electrophoresis using flow-through sampling

Automation of electrophoretic microchips for sequential analysis of different samples is demonstrated. This system used an autosampler, which was on-line connected to the microchip and the whole process including sample loading and injection, analysis and data acquisition as well as washing were all automated. Rhodamin B at different concentrations was first loaded into a hydrodynamic flow stream by an autosampler, delivered to the microchip, and then sequentially injected into the electrophoretic microchannel for analysis and detection. Automation was achieved by running two independent programs, one for sample loading by an autosampler and the other one for electrophoretic injection by voltage switching, on the same computer. Using this sampling chip, each loaded volume (0.2-1 microL) can be injected for dozens of electrophoretic analyses (1-10 nL for each injection). The variances caused by the external connections, which did not affect the electrophoretic analysis but would cause band broadening of the loaded sample in the hydrodynamic flow stream, were theoretically deduced. Results indicate that the dead volume (approximately 300 nL) due to the connection fitting on the chip could lead to dilution of the loaded sample by a factor of one when 0.2 microL of sample was loaded. Such a design allows sequential analysis of a series of samples while the running buffer is continuously pumped into the connection capillary as well as microchannels for washing between two loaded samples to minimize cross contamination without human intervention. Using this sampling chip, the required sample amount and handling time can be greatly reduced compared to the manual method.     

Unusual solid-state behavior in a neutral [2]catenane bearing a hydrolyzable component

A template-directed strategy to forming a bis(diimide) macrocycle through an intermediate asymmetric [2]catenane is reported. Saponification of the ester linkages within the crown ether component is much slower in the mechanically interlocked structure when compared to the free crown. The predominance of a single translational isomer leads to a dimeric structure, resulting in the generation of infinite channels within the crystal lattice. [structure: see text]     

Catalyst Design for Methacrolein Oxidation to Methacrylic Acid

Heteropoly compounds (HPCs) with the general formula CsMHPVMo₁₁O₄₀are prepared and tested as catalysts. The influence of elements entering the formula on the catalyst properties is studied: Cs defines the acidity and specific area, V controls the selectivity, and the transition metal M defines the mobility of oxygen in the bulk and the catalyst activity. The mechanism of methacrolein oxidation over HPCs is investigated. Using the response method and mass spectrometry of the reaction mixture, it is shown that only the catalyst oxygen atoms take part in the formation of methacrylic acid and that the transport of active oxygen to adsorbed methacrolein plays a key role in the oxidation process. A correlation between the HPC activity and the redox ability of the metal cation M ⁿ⁺ M ^{n+ i} (i= 1 or 2) is found. New catalysts for methacrolein oxidation to methacrylic acid are developed on the basis of this correlation. These are the salts of PVMo-poly acid with Cs, Cu, and the transition metal M as cations. These catalysts are more active (a conversion of up to 91%) and selective (up to 98%) compared to conventional catalysts for methacrolein oxidation to methacrylic acid.     

Ligand exchange reactions with η6-arene-η5-cyclopentadienyliron cations under thermal or photochemical conditions

Reactions of various η⁶-arene-η⁵-cyclopentadienyliron or substituted cyclopentadienyliron cations with trimethyl, triethyl or triphenyl phosphite under either thermal or photochemical conditions all resulted in the replacement of the arene ligand with three phosphite ligands to give η⁵-tris(trimethyl, triethyl or triphenyl phosphite)-η⁵-cyclopentadienyliron or substituted cyclopentadienyliron cations. The yields of the phosphite complexes were higher from photolysis than from the analogous thermolysis. Photolysis of the η⁶-chlorobenzene-η⁵-cyclopentadienyliron cation (IX) carried out in the presence of a more basic or more electron-rich aromatic ligand resulted in the exchange of the chlorobenzene of IX with the more basic arene, thus providing synthetic routes to cyclopentadienyliron complexes that may be difficult to prepare by other means. New complexes synthesized in this way are the η⁶-2-phenylethyl tosylate-η⁵-cyclopentadienyliron cation and the CpFe⁺ complexes of thiophene, 2-methylthiophene, 3-methylthiophene and 2,5-dimethylthiophene.     

Spectrophotometric Determination of Zirconium in Monazite Sand

A sensitive spectrophotometric method was developed for the determination of zirconium in monazite sand. The zirconium ion was previously separated from the other interfering elements by a 0.5 M thenoyltrifluoroacetone (TTA)-xylene extraction, then determined with Arsenazo III in 9 M HCl medium. Zirconium reacted with Arsenazo III to form an emeraled green coloured complex having maximum absorbance at 665 nm in 9 M HCl medium. The color was stable for at least 2 hours. Effects of time, HCl concentration, gelatine and various ions have been studied. The system confirms the Beer's law over the concentration range investigated. Optimum condition range for measurement in 1.0 cm quartz cell is 0.1–0.5 μg/ml of zirconium. The molar absorptivity is 1.51×10⁵ liter mole^?1 cm^?1. The metal-ligand ratio of 1:4 was confirmed by Job's Continuous Variation method and the conditional stability constant of Zirconium-Arsenazo III Complex in 4 M HCl and 9 M HCl were also determined by this method.