Effect of hydroxypropyl-beta-cyclodextrin on the degradation of pentachlorophenol by potassium monopersulfate catalyzed with iron(III)-porphyrin complex

A novel biomimetic catalytic system containing a supramolecular complex between iron(III)-tetrakis(p-sulfonatophenyl)porphyrin [Fe(III)-TPPS] and hydroxypropyl-beta-cyclodextrin (HP-beta-CD) was examined for the potassium monopersulfate catalyzed oxidation of pentachlorophenol (PCP). In the absence of HP-beta-CD, the percentage of PCP disappearance and the numbers of chlorine atoms released from PCP increased to 50% and 1.5 for a 1-day reaction period, respectively. However, in the presence of HP-beta-CD, the PCP completely disappeared and the number of chlorine atoms from PCP was increased to 3.1. o-Tetrachloroquinone, 2- and 4-hydroxyl-nonachlorodiphenyl ethers, and octachlorodibenzo-p-dioxin were detected among the oxidation products. In the absence of HP-beta-CD, the percentage of PCP conversion to oxidation products increased and then reached plateau. In the presence of HP-beta-CD, the amount of oxidation products produced initially increased for the first 10 min and thereafter decreased gradually. These results suggest that the addition of HP-beta-CD results in the further degradation of oxidation products. In addition, the mineralization of PCP to CO2 was investigated using 14C6-labeled PCP. After a 1-day reaction period, 24% of the 14C6-labeled PCP was converted to 14CO2 in the presence of HP-beta-CD, although significant 14CO2 generation was not observed in its absence. The effect of HP-beta-CD on the facilitation of PCP degradation can be attributed to the fact that the self-oxidation of Fe(III)-TPPS is prevented by the formation of a stable supramolecular complex between HP-beta-CD and Fe(III)-TPPS.     

A nationwide survey of NDMA in raw and drinking water in Japan

A nationwide survey of N-nitrosodimethylamine (NDMA) in both raw and finished water samples from drinking water treatment plants (DWTPs) in Japan was conducted. NDMA was analyzed by solid-phase extraction (SPE) followed by ultra performance liquid chromatography (UPLC) coupled with tandem mass spectrometry (MS/MS). NDMA was detected in 15 of 31 raw water samples collected in the summer at concentrations up to 2.6 ng/L, and in 9 of 28 raw water samples collected in winter at concentrations up to 4.3 ng/L. The NDMA concentrations were higher in raw water samples collected from treatment plants with catchment areas that have high population densities. The NDMA concentrations were higher in river water samples collected from the east and west of Japan than in those collected from other areas. NDMA was detected in 10 of 31 finished samples collected in summer at reduced concentrations of up to 2.2 ng/L, while 5 of 28 finished samples collected in winter showed NDMA concentrations up to 10 ng/L. The highest NDMA levels were detected in finished water samples collected from the Yodo River basin DWTP, which uses ozonation. Furthermore, evaluation of the process water produced at six advanced water treatment plants was conducted. Influent from the Yodo River indicated that the NDMA concentration increased during ozonation to as high as 20 ng/L, and then decreased with subsequent biological activated carbon treatment. To our knowledge, this is the first nationwide evaluation of NDMA concentrations in water conducted in Japan to date.     

Isotopic evidence in tree rings for historical changes in atmospheric sulfur sources

Little is understood about the usefulness of sulfur isotopic ratios (sigma 34S) in tree rings because the sulfur content in rings is generally insufficient for analysis using conventional methods. We present sigma 34S values of the water-soluble and the organically bound sulfur fractions in rings of coniferous trees grown in Japan, analyzed using a large-volume oxygen bomb. Comparing the sigma 34S values of the organically bound fraction in tree rings with past atmospheric sulfur concentrations and with those of their sources, we find clear evidence that the sigma 34S values of the organically bound fraction in the rings are dependent upon the values of the atmospheric sulfur sources. The evidence suggests that the sigma 34S values in tree rings are a useful chronological proxy for evaluating possible causes of past atmospheric sulfur pollution.     

Ocular Effects of Exposure to 40, 75, and 95 GHz Millimeter Waves

The objective of this study was to develop a model of ocular damage induced by 40, 75, and 95 GHz continuous millimeter waves (MMW), thereby allowing assessment of the clinical course of ocular damage resulting from exposure to thermal damage-inducing MMW. This study also examined the dependence of ocular damage on incident power density. Pigmented rabbit eyes were exposed to 40, 75, and 95 GHz MMW from a spot-focus-type lens antenna. Slight ocular damage was observed 10 min after MMW exposure, including reduced cornea thickness and reduced transparency. Diffuse fluorescein staining around the pupillary area indicated corneal epithelial injury. Slit-lamp examination 1 day after MMW exposure revealed a round area of opacity, accompanied by fluorescence staining, in the central pupillary zone. Corneal edema, indicative of corneal stromal damage, peaked 1 day after MMW exposure, with thickness gradually subsiding to normal. Three days after exposure, ocular conditions had almost normalized, though corneal thickness was slightly greater than that before exposure. The 50% probability of ocular damage (DD₅₀) was in the order 40?>?95?≈?75 GHz at the same incident power densities.     

ℓ2 Gain Estimation and Visualization of A Control Parameter Set in 3D Space Using Plant Response Data

In this paper, a novel parameter space approach that uses volume rendering is proposed to visualize controller parameter sets that consist of three controller parameters. An off‐line design method for robust control using plant response data is also studied. A solution set with equal ?₂ gain can be visualized as isosurfaces in three‐dimensional space, and the designer can visually select an appropriate parameter. This numerical method is applicable to many practical specifications, in contrast to analytical methods based on solving equations. An estimation method based on the extension theorem and a method using bandpass filters are both considered as possible methods for estimating the ?₂ gain of the sensitivity functions when using grid points on the order of tens of thousands to create the volume data.The former method is superior to the latter with respect to accuracy but impractical with respect to computational load. The latter method is hence practical, because the computing time is reduced to less than 0.05 s for about 300,000 grid points by parallel computation with a graphical processing unit.     

L1 synthesis of a static output controller for positive systems by LMI iteration

An approach to find a static output feedback gain that makes the feedback system positive and minimizes the L₁ gain is proposed. The problem of finding a static output feedback gain has 3 aspects: stabilizing the system, making the system positive, and then minimizing the L₁ gain. Each subproblem is described by bilinear matrix inequality with respect to the feedback gain and the Lyapunov matrix or vector. Linear matrix inequality (LMI) that is sufficient to satisfy bilinear matrix inequality is derived using a convex‐concave decomposition, and the feedback gain sequence is calculated by an iterative solution of LMI. The sequence of the upper bounds on the design parameter is guaranteed to be monotonically nonincreasing for each algorithm. Similarly, 2 other LMIs are derived for each subproblem using another convex‐concave decomposition and PK iteration. The effectiveness of these algorithms is illustrated via several numerical examples.     

Crystallization Controlled by Silicate Surfaces in Nylon 6‐Clay Nanocomposites

The crystallization behavior of pure nylon 6 (N6) and its nanocomposite with montmorillonite has been studied in detail. The crystallization rate of N6 is faster in the presence of clay compared to pure N6, as revealed by light scattering experiments. Nylon 6 crystallizes exclusively in the γ‐form in the nanocomposite because of the epitaxial crystallization, which is also revealed from the transmission electron microscopic images (sandwiched structure) of the crystallized sample. The storage modulus of the nanocomposite is always higher than the pure nylon 6, irrespective of crystallization temperatures. Much higher increment of storage modulus for pure nylon 6 with increasing crystallization temperature is explained by the higher amount of the thermally stable α‐form at higher temperature. A unique mechanism has been proposed to illustrate the crystallization behavior of nylon 6 in the presence of the clay particles.

Transmission electron micrograph of N6C3.7 crystallized at 210 °C, showing the typical shish‐kebab type of structure.     

Measurement of mobile-phase volume in reversed-phase liquid chromatography and evaluation of the composition of liquid layer formed by solvation of packing materials

The mobile-phase volumes (Vm) in reversed-phase liquid chromatography (RPLC) with alkyl-bonded silica, defined as the difference between the total volume of eluent in the column (V0) and the volume of the eluent solvent layer formed by solvation of the bonded phase (VL), are determined by the method derived from the eluent electrolyte effect on the retention of ionic analytes. The validity of the Vm values obtained is evaluated by comparing them with the retention volumes of various organic compounds and inorganic ions, which have been suggested as unretained markers, and those obtained from a linear dependence of the logarithmic retention factor on the carbon numbers of homologous series. From the results obtained, it has been concluded that the solvated liquid phase on a column packing material should be assigned to a part of the stationary phase and the method developed for determination of the Vm value based on the ion partition model gives the most reasonable value as the mobile-phase volume in RPLC. The volume and the solvent composition of the solvated liquid phase on C1, C8, and C18 bonded silica are estimated, and the effects of organic modifiers and the physicochemical structures of the packing materials on these values are discussed.     

Convenient preparative method for lactones from 3-hydroxy propanoic acids using iodine under solvent-free conditions

Intramolecular cyclization of 3-hydroxy acids was investigated using iodine as a catalyst under solvent-free conditions. The reaction proceeded to completion in the heterogeneous system. Lactones were obtained by intramolecular cyclization of 3-hydroxy acids. Propella lactone (11-oxatricyclo[4.4.3.0(1,6)]tridecan-12-one) was conveniently synthesized from 3-hydroxy acid ((6-hydroxyspiro[4.5]dec-6-yl)acetic acid) in 88% yield with carbon skeleton rearrangement. Spiro lactones and bicyclic lactones were also obtained from the corresponding 3-hydroxy acids in yields of over 75%. The most suitable reaction conditions were a temperature of 80 degrees C, a molar ratio of 3-hydroxy acid:iodine = 1:0.1, and a time period of 6 h. In addition, terpenic lactones were efficiently synthesized from the corresponding 3-hydroxy acids, derived from (+)-camphor, (-)-fencone, and (-)-pulegone, with skeleton rearrangement. The yield of the solvent-free reaction was as high as that of the corresponding reaction in solution.