Characterization and determination of linear alkylbenzenesulfonates in environmental water samples by high-performance liquid chromatography with a hydrophilic polymer column and electrospray ionization mass spectrometric detection.

A liquid chromatography-mass spectrometry (LC/MS) method was developed for the separation and determination of linear alkylbenzenesulfonates (C10-C14 LAS) in environmental water samples using a hydrophilic polymer column (Shodex Mspak GF-310 4D). This method involves a solid-phase extraction of the LAS samples with a Sep-Pak PS-2 cartridge. The LAS components were separated on the column with a mobile phase of 29% (w/v) acetonitrile-water containing 0.8 mM di-n-butylammonium acetate and 0.2 M acetic acid, and were detected by mass spectrometry with electrospray ionization. Detection limits of the developed method based on selected ion monitoring (SIM) technique for the C10-C14 LAS standards were 13-47 ng L(-1). The concentrations of the C10-C14 LAS in the environmental water samples ranged between 5-317 microg L(-1) for a river water sample and 0.4-6.4 microg L(-1) for a seawater sample. Linear relationships between the logarithms of retention factors and the alkyl chain lengths for each phenyl positional isomer of LAS could successfully be used for the identification of the isomer peaks.     

Polybenzimidazoles containing anthracene photodimer

Polybenzimidazoles that contained anthracene photodimer were prepared. The molecular weights of the polymers prepared by the photopolymerization of bis-anthrylbenzimidazoles were limited by the precipitation of the resulting polymers from the reaction organic solvents. Higher molecular weight polymers were obtained by the photopolymerization of bis-anthryl-Schiff's bases, followed by the oxidation of the resulting polymers. These polymers were soluble in acidic solvents such as formic and sulfuric acids but were insoluble in organic solvents.     

Synthesis and properties of polydiene and polypentenamer having formyl or hydroxymethyl groups and their photosensitive derivatives

cis-1,4-Polybutadiene and polypentenamer having pendant functional groups such as formyl, aldoxime, hydroxymethyl, or cinnamoyloxymethyl groups have been prepared, and some of their properties were investigated in terms of structural effect on physical properties of these polymers. cis-1, 4-Polybutadiene and polypentenamer having a different content of formyl group were prepared by the hydroformylation reaction with rhodium catalyst under mild conditions. The pendant formyl group was reduced to a hydroxymethyl group by using various reducing agents such as sodium borohydride or sodium trimethoxyborohydride which were effective to avoid a crosslinking reaction among the formyl groups. Glass transition temperature of polypentenamer having hydroxymethyl groups increased with increasing the content of the hydroxymethyl groups in the polymer. Cinnamoyl group was introduced into the polypentenamer having hydroxymethyl groups by reacting with cinnamoyl chloride so as to prepare a photosensitive rubber. The relationships between the photosensitivity of the cinnamoylated polypentenamer and the mobility of polymer main chains have been elucidated. A linear relationship between the photodimerization rate constant and the difference between ultraviolet (UV) irradiation temperature and the glass transition temperature of the polymer was found. It has become apparent that the photosensitivity of cinnamoylated polypentenamer can be estimated by the glass transition temperature of the original polymer, UV irradiation temperature, activation energy of the dimerization, and γ, which is a coefficient of the relationship between the photosensitive group concentration and the glass transition temperature of the polymer.     

Polymerization and copolymerization of methacrylic esters derived from glycidyl methacrylate

Copolymerization of methacrylic esters derived from glycidyl methacrylate and nucleophiles with styrene was carried out. The monomer reactivity ratios of these methacrylic esters were varied with the alkoxy groups of the esters and the solvent used.     

Polymerization of α-amino acid N-carboxy anhydride. IX. Copolymerization of α-amino acid N-carboxy anhydride in heterogeneous system

Copolymerization of NCA's was undertaken in a heterogeneous system in acetonitrile, which is not a solvent of the polypeptides. The reactivity ratio was calculated by using the Lewis-Mayo equation. Further, the conversion rate in the copolymerization and the configuration of the copolymer produced were compared with those of the copolymerization in the homogeneous system in nitrobenzene, in which the copolypeptides are swollen. The rate of copolymerization in acetonitrile was between the rates of polymerization of the individual monomers. It has been reported that the configuration of the copolymer obtained in dimethylformamide, in which the copolypeptides are swollen, is of the block type. On the other hand, many polypeptides obtained in acetonitrile, which is not a solvent of the copolypeptides, had a random configuration near to an alternating configuration.     

Polymerization of methacrylates. I. Polymerization reactivity of picryl methacrylate

The polymerization of picryl (PMA), 2,4-dinitrophenyl (2,4-DNMA),2,6-dinitrophenyl (2,6-DNMA), 2-methyl-4,6-dinitrophenyl (MDNMA), and 2,6-dimethylphenyl methacrylates (DMMA) was carried out in benzene at 60°C. PMA, 2,6-DNMA, and MDNMA did not undergo radical homopolymerization, while 2,4-DNMA and DMMA did. The results suggest that the growing radical readily attacks the oxygen atom of the nitro group at the 2 position of the terminal phenyl group due to the steric effect of the substituent at the 6 position, resulting in chain termination. PMA formed a charge-transfer complex with 2-naphthyl methacrylate (NMA). The stoichiometric composition of this complex was shown to be 1:1 molar complex. PMA was readily copolymerized with NMA. The amount of solvent affected the composition of the copolymer obtained at a given same mole fraction in feed. The results suggest that charge-transfer interaction between the ester groups affects the copolymerization mechanism.     

Electrochemical characterization of negative electrodes consisting of surface-modified Zr0.9Ti0.1(Ni1.1Co0.1Mn0.5V0.2Cr0.1)x Laves-phase alloys

Laves-phase hydrogen storage alloy has a high potential for use as negative electrode material as alternative for the misch-metal-based material. In order to improve the energy density and the rate capability of negative electrode, chemical and mechanical modification of Lavesphase alloy with different stoichiometric ratios was carried out. Discharge capacity and high-rate dischargeabilty was evaluated by electrochemical methods and the characterization of Laves-phase alloy was made by X-ray diffraction, SEM observation and PCT measurement. The best result in discharge capacity could be obtained for stoichiometric Laves-phase alloy with a composition of Zr_0.9Ti_0.1Ni_1.1Co_0.1Mn_0.5V_0.2Cr_0.1 by boiling in 10 M KOH solution. On the other hand, the high-rate dischargeability was increased remarkably by introducing mechanical grinding before alkali treatment. The cause for improved performance was discussed on the basis of thermodynamic stability of metal hydride and changes in crystal structure and surface morphology influencing on diffusion coefficient and diffusion path length of hydrogen.     

Photophysical and (photo)electrochemical properties of a coumarin dye

A new coumarin dye, cyano-{5,5-dimethyl-3-[2-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)vinyl]cyclohex-2-enylidene}-acetic acid (NKX-2753), was prepared and characterized with respect to photophysical and electrochemical properties. It was employed as a dye sensitizer in dye-sensitized solar cells and showed efficient photon-to-electron conversion properties. The photocurrent action spectrum exhibited a broad feature with a maximum incident photon-to-electron conversion efficiency (IPCE) of 84% at 540 nm, which is comparable to that for the famous red dye RuL2(NCS)2 (known as N3), where L stands for 2,2'-bipyridyl-4,4'-dicarboxylic acid. The sandwich-type solar cell with NKX-2753, under illumination of full sun (AM1.5, 100 mW cm(-2)), produced 16.1 mA cm(-2) of short-circuit photocurrent, 0.60 V of open-circuit photovoltage, and 0.69 of fill factor, corresponding to 6.7% of overall energy conversion efficiency using 0.1 M LiI, 0.05 M I2, 0.1 M guanidinium thiocyanate, and 0.6 M 1,2-dimethyl-3-n-propyl-imidazolium iodide in dry acetonitrile as redox electrolyte. In comparison with its analogue NKX-2586 (Langmuir 2004, 20, 4205), NKX-2753 with an extra side ring on the alkene chain produced much higher IPCE values at the same conditions. The side ring acted as a spacer to efficiently prevent dye aggregation when adsorbed on the TiO2 surface, resulting in significant improvements of short-circuit photocurrent, open-circuit photovoltage, and fill factor compared with NKX-2586 that aggregated on the TiO2 surface.     

Substrate dependence in aqueous Diels-Alder reactions of cyclohexadiene derivatives with 1,4-benzoquinone

A reactivity difference based on the position of substituents on cyclohexa-1,3- diene was observed for the title reaction. The effect of water as solvent was more distinct for 1-methyl-4-isopropylcyclohexa-1,3-diene than for 2-methyl-5-isopropylcyclohexa- 1,3-diene or non-substituted cyclohexa-1,3-diene. The effect of NaCl (salting-out) and guanidium chloride (salting-in) was also large for 1-methyl-4-isopropylcyclohexa-1,3- diene.