Influence of the characteristics of soil and fly ash on the supercritical carbon dioxide extraction of dioxins.

Several investigations on the extraction of dioxins from soil and fly ash with supercritical fluid have been reported; however, few of them describe the influence of components on the extraction. We extracted dioxins from eight samples with different values of organic carbon content and surface area with supercritical CO(2) at a temperature of 463 K, a pressure of 40 MPa, and using 10% toluene as an entrainer. We researched the influence of the characteristics of soil and fly ash on supercritical CO(2) extraction of dioxins. The results revealed that the extraction efficiencies of PCDD/DFs and PCBs were high for all soil samples, while that of fly ash samples decreased with the increase in organic carbon content and surface area. The extraction efficiencies of dioxins from four standard samples, activated carbon, humic acid, alumina, and florisil, were also examined. The results revealed that the extraction efficiencies were strongly influenced by activated carbon like components present in the samples.     

Preparation of benzoylchitosans and their chiroptical properties in dilute solutions

Two benzoyl substituted chitosan derivatives, 3,6‐O‐dibenzoylchitosan (DBC) and 2‐N‐3,6‐O‐tribenzoylchitosan (TBC), were prepared, and their optical activities in organic solvent were investigated by circular dichroism (CD). For TBC, two splitting bands (a negative one at 288 nm and a positive one at 274 nm) corresponding to the ¹L_b transition of the benzoyl group were observed in chloroform and dichloromethane, while only a negative CD band was recorded in N, N‐dimethylformamide (DMF). These results indicated that the transition moments of benzoyl groups were orderly arranged along the helical polymer chain when TBC was dissolved in a solvent with low polarity, but the same ordered structure did not appear in a polar solvent of DMF. For DBC, only negative CD signals corresponding to the ¹L_b transition of the benzoyl group were observed, regardless of the solvent property, which indicated that the chromophores were not arranged in an ordered fashion with appropriate geometry to interact with one another to induce bi‐signate CD signals. Adding methanol or DMF to the solution of TBC/chloroform resulted in a progressive decrease of the intensity of the positive split band at 274 nm. The intensity of the positive band was weakened upon heating a solution of TBC/chloroform from 20 to 60 °C. The results suggested that the ordered arrangement of the chromophores in the TBC system was dependent on solvent and sensitive to temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4107–4115, 2004     

Electroneutrality coupling of electron transfer at an electrode surface and ion transfer across the interface between thin-layer of 1-octyl-3-methylimidazolium bis(perfluoroalkylsulfonyl)imide covering the electrode surface and an outer electrolyte solution.

The electrode reaction of decamethylferrocene (DMFc) dissolved in a thin layer of a room-temperature molten salt (RTMS), 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C8mimC1C1N) or 1-octyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide (C8mimC2C2N), on a self-assembled monolayer-modified gold electrode is coupled with the ion transfer across the interface between the RTMS and the outer aqueous solution (W) to give a voltammogram whose shape resembles a voltammogram of a simple one-electron transfer process. The electroneutrality of the RTMS layer during the oxidation of DMFc to decamethylferricenium ion is maintained by the concomitant dissolution of C8mim+ ion from the RTMS phase to the W phase, and the reduction of decamethylferricenium ion to DMFc is accompanied by the transfer of either C1C1N- or C2C2N- from RTMS to W. The midpoint potential of the voltammogram varies with the concentration of the salt in the aqueous phase, C8mimCl or LiCnCnN (n = 1 or 2), in a Nernstian manner, showing that the phase-boundary potential between the RTMS and the W is controlled by the partition of these ions. Although the phase-boundary potential across the RTMS / W interface is Nernstian with respect to the ions common to both phases at the equilibrium, the polarization at the RTMS / W interface under current flow distorts the shape of the voltammograms, resulting in a wider peak separation in the voltammogram.     

Simultaneous determination of serotonin and 5-hydroxyindole-3-acetic acid in human urine by automated precolumn derivatization and semi-microbore column liquid chromatography with fluorescence detection.

An improved high-performance liquid-chromatographic (HPLC) assay for the simultaneous determination of serotonin (5-HT) and 5-hydroxyindole-3-acetic acid (5-HIAA) in human urine is reported. Following the automated precolumn derivatization of urinary 5-HT and 5-HIAA with benzylamine, the derivatives are separated by isocratic elution on a reversed-phase C18 semi-microbore column, and are fluorometrically detected at an excitation wavelength of 345 nm and an emission wavelength of 480 nm. The detection limits of 5-HT and 5-HIAA are 7 and 5 nmol/l in urine (0.7 and 0.5 fmol/20-microl injection). The proposed automatic method permits a highly selective and sensitive determination of 5-HT and 5-HIAA in human urine without any sample purification.     

Rate coefficient for the reaction of CCl3 radicals with ozone

The rate coefficient for the reaction of CCl₃ radicals with ozone has been measured at 303 ± 2 K. The CCl₃ radicals were generated by the pulsed laser photolysis of carbon tetrachloride at 193 nm. The time profile of CCl₃ concentration was monitored with a photoionization mass spectrometer. Addition of the O₃–O₂ mixture to this system caused a decay of the CCl₃ concentration because of the reactions of CCl₃ + O₃ → products (5) and CCl₃ + O₂ → products (4). The decay of signals from the CCl₃ radical was measured in the presence and absence of ozone. In the absence of ozone, the O₃–O₂ mixture was passed through a heated quartz tube to convert the ozone to molecular oxygen. Since the rate coefficient for the reaction of CCl₃ + O₂ could be determined separately, the absolute rate coefficient for reaction ( 5 ) was obtained from the competition among these reactions. The rate coefficient determined for reaction ( 5 ) was (8.6 ± 0.5) × 10^?13 cm³ molecule^?1 s^?1 and was also found to be independent of the total pressure (253–880 Pa of N₂). This result shows that the reaction of CCl₃ with O₃ cannot compete with its reaction with O₂ in the ozone layer. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 310–316, 2003     

Discrimination of poly(vinyl chloride) samples with different plasticizers and prediction of plasticizer contents in poly(vinyl chloride) using near-infrared spectroscopy and neural-network analysis.

In the recycling of poly(vinyl chloride) (PVC), it is required to discriminate every plasticizer for quality control. For this purpose, the near-infrared spectra were measured for 41 kinds of PVC samples with different plasticizers (DINP, DOP, DOA, TOTM and Polyester) and different plasticizer contents (0-49%). A neural-network analysis was applied to the near-infrared spectra pretreated by second-derivative processing. They were discriminated from one another. The neural-network analysis also allowed us to propose a calibration model which predicts the contents of plasticizers in PVC. The correlation coefficient (R) and the root-mean-square error of prediction (RMSEP) for the DINP calibration model were found to be 0.999 and 0.41 wt%, respectively. In comparison, a partial least-squares regression analysis was carried out. The R and RMSEP of the DINP calibration model were calculated to be 0.993 and 1.27 wt%, respectively. It is found that a near-infrared spectra measurement combined with a neural-network analysis is useful for plastic recycling.     

Living anionic polymerization of N‐methoxymethyl‐N‐isopropylacrylamide: Synthesis of well‐defined poly(N‐isopropylacrylamide) having various stereoregularity

Anionic polymerization of N‐methoxymethyl‐N‐isopropylacrylamide ( 1 ) was carried out with 1,1‐diphenyl‐3‐methylpentyllithium and diphenylmethyllithium, ‐potassium, and ‐cesium in THF at ?78 °C for 2 h in the presence of Et₂Zn. The poly( 1 )s were quantitatively obtained and possessed the predicted molecular weights based on the feed molar ratios between monomer to initiators and narrow molecular weight distributions (M_w/M_n = 1.1). The living character of propagating carbanion of poly( 1 ) either at 0 or ?78 °C was confirmed by the quantitative efficiency of the sequential block copolymerization using N,N‐diethylacrylamide as a second monomer. The methoxymethyl group of the resulting poly( 1 ) was completely removed to give a well‐defined poly(N‐isopropylacrylamide), poly(NIPAM), via the acidic hydrolysis. The racemo diad contents in the poly(NIPAM)s could be widely changed from 15 to 83% by choosing the initiator systems for 1 . The poly(NIPAM)s obtained with Li⁺/Et₂Zn initiator system possessed syndiotactic‐rich configurations (r = 75–83%), while either atactic (r = 50%) or isotactic poly(NIPAM) (r = 15–22%) was generated with K⁺/Et₂Zn or Li⁺/LiCl initiator system, respectively. Atactic and syndiotactic poly(NIPAM)s (42 < r < 83%) were water‐soluble, whereas isotactic‐rich one (r < 31%) was insoluble in water. The cloud points of the aqueous solution of poly(NIPAM)s increased from 32 to 37 °C with the r‐contents. These indicated the significant effect of stereoregularity of the poly(NIPAM) on the water‐solubility and the cloud point in water © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4832–4845, 2006     

Synthesis of 3-substituted 4H-1-benzothiopyran-4-ones

3-Substituted 2-phenyl-4H-1-benzothiopyran-4-ones (thioflavones) were prepared to test antimicrobial activity. It was found that 3-(phenyl)thiochromone derivatives (isothioflavones) were prepared by the Meerwein reaction of thiochromone with p-nitrobenzenediazonium ion. 3-(Formyl)thioflavone exhibits weak antimicrobial activity against Trichophytons and Candida.     

Addition reactions of pendant epoxide group in poly(glycidyl methacrylate) with various active esters

Addition reactions of pendant epoxide groups in poly(glycidyl methacrylate) (PGMA) with various active esters such as 1-benzotriazolyl benzoate, S-(2-benzoxazolyl) thiobenzoate, S-(2-benzothiazolyl) thiobenzoate, 4-nitrophenyl benzoate (4NPB), and S-phenyl thiobenzoate (PTB) were carried out using quaternary salts as catalysts. The reactions of PGMA with those active esters proceeded in diglyme at 100°C for 24 h quantitatively without the formation of 2-hydroxyl pendant groups in the polymer when 10 mol % of tetraethylammonium bromide was used as a catalyst. Furthermore, it was found that the respective quaternary salts have higher catalytic activity than tertiary amines in the reaction of PGMA with the active esters, and the reaction of PGMA with 4NPB gave the corresponding polymer with the highest conversion by addition of tetrabutylammonium bromide as a catalyst, while tetraethylammonium chloride showed the highest activity for the reaction of PGMA with PTB. In addition, the rate of reaction of PGMA with 4NPB was proportional to third order kinetics of the epoxide concentration, the ester concentration and the catalyst concentration as follows: ?d[Epoxide]/dt = ?[Ester]/dt = k₃[Epoxide] [Ester] [Catalyst].     

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.