Simultaneous determination of silicate and phosphate in environmental waters using pre-column derivatization ion-pair liquid chromatography

A highly sensitive HPLC method for the simultaneous determination of soluble silicate and phosphate in environmental waters was developed, using ion-pair liquid chromatography preceded by the formation of their yellow α-heteropolymolybdates. The moderate-pH mobile phase enabled to use a highly efficient reversed-phase silica column. The pre-column coloring reactions at moderate-pH were reproducible for both silicate and phosphate in all quantification ranges with R.S.D.s less than 2% and 5%, respectively. The linear calibration lines between concentrations (mg-SiO₂/L and mg-PO₄/L) and peak area intensities were obtained for silicate and phosphate both with acceptable determination coefficients (r²) of 0.9999. The limits of determination for both analytes were 0.007 mg-SiO₂/L and 0.003 mg-PO₄/L, which were calculated theoretically using 10σ/slope. The four-digit dynamic ranges were obtained for 0.007-10 mg-SiO₂/L and 0.003-20 mg-PO₄/L. The developed method was applied for the analysis of tap water, river water, coastal seawater, well water, hot-spring water, commercial mineral water, and laboratory water. The results were very reasonable and acceptable from the environmental viewpoints, which were well correlated with those confirmed by the molybdenum-blue spectrophotometry.     

Structural study of self-assembled monolayers of ferrocenylalkanethiols on gold by angleresolved X-ray photoelectron spectroscopy

An angle-resolved X-ray photoelectron spectroscopic study has been performed on structures of self-assembling systems, viz ferrocenylthiols on a gold (111) crystal. The angular dependence of the intensities of photoemission reveals that ferrocenyl groups are on the outermost layer, separated from the gold substrate by hydrocarbon chains of the thiol groups.     

Parallel vs. anti-parallel orientation in a curdlan/oligo(dA) complex as estimated by a FRET technique

We already found that beta-1,3-glucan polysaccharides form polymeric complexes with certain polynucleotides, but the parallel vs. anti-parallel orientation in those complexes had remained unsolved. In this paper, this controversial problem has been discussed for curdlan/oligo(dA) complexes utilizing two different energy transfer techniques. The first system consists of a combination of fluorescein-labeled curdlan and 3'-(or 5'-)tetramethyl-rhodamine (TAMRA)-labeled oligo(dA). The second system utilizes gold nanoparticles: that is, two curdlan chains were linked by a disulfide bond and after complexation with oligo(dA), the complex was immobilized on gold nanoparticles. In this system, TAMRA was attached to the 3'(or 5') end of oligo(dA) and the gold particle acted as a fluorescence quencher (energy acceptor). These experiments have led us to conclude that in the curdlan/oligo(dA) complex, parallel orientation is more favourable than anti-parallel orientation. These findings have enabled us to envision a clearer image for the complexation mode between beta-1,3-glucan polysaccharides and polynucleotides.     

Quantitative analysis of alcohol-water binary solutions using Raman spectroscopy

Raman spectroscopy was used for rapid and in situ measurements of alcohols in alcohol-water binary systems. An external standard was used to eliminate factors such as laser power or instrumental effects. Band ratios between the Raman bands of the target molecule and that of acetonitrile as external standard were calculated and found to be proportional to the mass fraction of alcohol. Better linearity was achieved as compared with that in the calibration curve obtained by plotting the Raman intensity alone. The equations of the calibration curves were y=0.2747x with R² of 0.9996 and y=0.2189x+1.340×10⁻³ with an R² of 1.000 in methanol-water and in ethanol-water binary systems, with y and x denoting the Raman intensity ratio and the mass fraction of alcohol, respectively.     

Thermal cured epoxy resins using certain calixarenes and their esterified derivatives as curing agents

The acetyl esterified calixarene (CA) derivatives were prepared from calix[4]resorcinarene (CRA), and p‐tert‐butylcalixarene (BCA[n], n = 4, 6, 8), respectively. Using these CA derivatives as curing agents, the thermal curing reactions of two multifunctional epoxy resins (jER 828, 186 g/equiv., and ESCN, 193.7 g/equiv.) were investigated. The temperatures of glass transition (T_g) and decomposition (T) were measured by DSC and TGA, respectively. Based on the yields, T_gs, and T_ds of the thermal cured jER 828 epoxy resin with CRA‐E100, the curing conditions were optimized to be tetrabutylphosphonium bromide (TBPB) as catalyst in NMP at 160 °C for 15 h. Under this curing condition, the cured materials of jER 828 or ESCN using various CA derivatives as curing agents were prepared. Except for BCA4 derivatives, the yields of thermal curing reaction were higher than 90%. T_gs and Ts of the resultant cured materials were in the range of 113–248 °C and 363–404 °C, respectively. These results mean that the cured epoxy resins with excellent T_gs were successfully formed by using CA derivatives as curing agents. It was also found that the T_gs of cured epoxy resins were strongly affected by the degree of esterification of CA derivatives. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1931–1942, 2010     

Copper-Free Sonogashira coupling in water with an amphiphilic resin-supported palladium complex

The palladium-catalyzed coupling reaction of aryl halides with terminal alkynes, the Sonogashira coupling, took place in water under copper-free conditions by use of an amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported palladium-phosphine complex to give the corresponding aryl-substituted alkynes in high yields. The PS-PEG resin-supported palladium catalyst was recovered by simple filtration and reused four times without any loss of catalytic activity.     

Synthesis of dihydroxyoligophenylenes containing π-deficient or π-excess hetero-aromatic rings and their solvatochromic behavior

Dihydroxyoligophenylenes (HO-ArPh(m)-OHs) with 9,9-dihexyl-2,7-fluorene (Ar=Flu), 2,5-dioctyloxy-1,4-benzene (Ar=Dob), pyridine (Ar=Py), or thiophene (Ar=Th) rings were synthesized by the Suzuki coupling reaction. Absorption maxima (λ_max) of HO-ArPh(m)-OHs shifted progressively toward long wavelengths due to the expansion of the π-conjugation system with an increase in the number of benzene rings. Deprotonation of the OH groups of HO-ArPh(m)-OHs by treatment with NaH caused a bathochromic shift of λ_max. The bathochromic shift of the deprotonated species increased with the donor numbers (DNs) of the solvents. The emission peak positions of NaO-ArPh(m)-ONas depended on the DNs of the solvents; therefore, the emission color could be tuned by changing the solvent.     

Characterization of certified reference material for quantification of polychlorinated biphenyls and organochlorine pesticides in fish

Fish certified reference material (CRM), NMIJ CRM 7404-a, for the analysis of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) was developed by the National Metrology Institute of Japan, part of the National Institute of Advanced Industrial Science and Technology. Fish samples (Japanese seabass) used for the preparation of the CRM were collected from Tokyo Bay, and the edible part was freeze-dried, pulverized, sieved, homogenized, and sterilized by γ-irradiation. This sample is in the form of a powder comprising approximately 10 g stored in a brown glass bottle. The certification was carried out using multiple analytical methods such as pressurized liquid extraction, Soxhlet extraction, saponification, and homogenization to ensure the reliability of analytical results; the certified values of target PCBs (PCB 28, PCB 70, PCB 105, PCB 153, and PCB 170) and OCPs (trans-nonachlor, dieldrin, p,p′-DDE, p,p′-DDT, and p,p′-DDD) were 1.05–14.0 μg kg⁻¹ and 1.57–18.0 μg kg⁻¹ for PCBs and OCPs, respectively. This is the first fish powder CRM in which PCBs and OCPs were determined by isotope dilution mass spectrometry.