We solved the problem of purification and successfully synthesized water-solubled hexaazatrinaphthylene with polyether and crown ether side chain under our biomimic and new material goal.

This study armed to develop a biofilter packed only with fern chips for the removal of air-borne propylene glycol monomethyl ether acetate (PGMEA). The fern chip biofilters could avoid the shortcomings of traditional media, such as compaction, drying, and breakdown, which lead to the performance failure of the biofilters. In the present study, a three stage down-flow biofilter (2.18 m in height and 0.4 m¡Ñ0.4 m in cross-sectional area) was constructed for the performance test. The first stage serviced as a humidifier for the incoming gas and the following two stages, both packed with fern chips of 0.30 m ¡Ñ 0.40 m ¡Ñ0.40 m, as trickling bed biofilters for the VOC removal. The experiment was divided into four phases. Operation conditions of an empty bed retention time (EBRT) of 1.60min and influent PGMEA concentrations of 9.33-329 (average 78.4) mg/m3 were used in the Phase I experiment which lasted for 99 days. An average PGMEA removal of only 68% was obtained in this phase. For improving the PGMEA removal in the following phases, a fixed dosage of milk powder of 1.0 g/(m3 media. day) added as aqueous milk suspension was added to the media for nutrition of the biofilms on the fern chip surfaces. After an additional operation time of 20 days (the 127th day from the startup time), a stable PGMEA removal of 91% was achieved. Following Phase II, PGMEA removals of 93 and 94% were obtained with EBRTs of 0.40 and 0.27 min, respectively, in Phases III and IV experiments. The results indicate that EBRT was not a key influencing factor to the PGMEA removal as long as the media had a high ability for the VOC degradation. Experimental data obtained from Phases II-IV reveal that with volumetric loadings (L) of less than 250 g PGMEA/(m3.h) to the up-streaming half of the whole media, 90% of the influent PGMEA could be removed in this half media. An additional 80% of the influent PGMEA to the following half media could be removed with L < 100 g PGMEA/(m3.h) to the half media. The PGMEA elimination capacities were proportional to the volumetric loadings of less than 250 g PGMEA/(m3.h). From the results, it could be proposed that for achieving over 93% of the PGMEA removal, appropriate operation conditions are media moisture content = 52-65%, media pH = 7.2-7.4, influent PGMEA concentration = 100-400 mg/Am3, EBRT = 0.27-0.40 min, and L to the whole media = 45-180 g PGMEA/(m3.h).

名古屋大学博士学位論文 学位の種類 : 博士(医学)(課程) 学位授与年月日:平成5年5月14日 雄山博文氏の博士論文として提出された

This study investigates the rate kinetics for BD and PGMEA oxidation by UV/O3 process. The reactor constructs of a 100 cm x 20 cm x 85 cm (L x W x H) stainless steel chamber, in which four vertical steel plates (20 cm x 65 cm, W x H) were inserted to establish a plug flow path for the flowing gas. The reactor has a total effective volume of 170 L. Each of the five compartments of the reactor is equipped with an individual UV irradiation system with a 3.0-cm x 15-cm (ID x L) quartz sheath that housed an UV lamp, and two electric UV power inputs of 0.147 or 0.294 W/L were obtained. The gas flows perpendicularly to the UV lamps in the reactor. The influent tested VOC concentration was adjusted to about 50 ppm, and the gas flows were controlled at the individual flow rate of 60 and 120 L/min. The effects of moisture content (relative humidity, RH), ozone dosage (initial molar ratio of ozone to the tested VOC, m) and UV volumetric electric power input on the removal of the tested VOCs are investigated in the study. Also, kinetic models of the tested VOCs by photolysis, ozonation and UV/O3 have been developed and confirmed with reference to the experimental data. According to the kinetic models, both photolysis rate and oxidation rate by UV/O3 are following the first order behavior with respect to the tested VOC concentrations which are low. The result reveals the absorbance for the reactions is weak absorbance under UV irradiation. The reaction rates are proportional to the UV electric power inputs in UV-initiated reactions. And the parameter, £i, which represents the ratio of OH radical consumption rate by the tested VOC to the total OH radical consumption rate, can be obtained by simulating the performance of experimental data of OH reactions. The experimental results reveal that for BD oxidation with a gas space time of 85 sec and RH = 40 ¡V 99%, BD photolysis did not occur at wavelength of 185 nm with UV electric power inputs of 0.147 and 0.294 W/L. The ozonation efficiency of BD reached 90% at m = 3.5, and RH had no influence on the removal efficiency of BD. The removal efficiencies by UV/O3 process reached 90% with m = 2.2 and 1.6 for UV power inputs of 0.147 and 0.294 W/L, respectively. The addition of ozone apparently encouraged BD removal efficiency by UV/O3 process. And the enhancement of ozone dosage (m = 0.5 ¡V 4.4) would promote the decomposition of BD more effectively than the enhancements of UV power input (from 0.147 to 0.294 W L-1) and RH (from 40 to 99%). For PGMEA photolysis in a batch reactor with volume of 1.188 L, the photolysis occurred at wavelength of 185 nm under UV irradiation. And the photolysis rate follows the first order behavior with respect to the concentration of PGMEA. But PGMEA photolysis did not occurred at UV wavelength of 254 nm. PGMEA ozonation was performed in the same batch reactor; and the removal efficiency of only 50% at m = 3.96 would take 35 min. So, PGMEA ozonation in the plug flow reactor did not be observed at the conditions of the gas space time of 85 sec and RH = 15 ¡V 99%. Besides, the photolysis of PGMEA was carried out at the above conditions. The removal efficiency of PGMEA by UV/O3 could reach 90% at the conditions of the gas space time of 170 sec, UV volumetric electric power input of 0.294 W/L and m = 2.9. And the enhancement of UV power input (from 0.147 to 0.294 W L-1) would promote the decomposition of PGMEA more effectively than the addition of ozone dosage (m = 1.05 ¡V 15.63) and RH = 15 ¡V 99%.

Biotreatment for air pollution control can generally be categorized as biofilter, bioscrubbing and biotrickling filter systems. Generally, biotreatments could be effective and more economical treatment for containment waste gas if designed and operated properly. A two stage down-flow biofilter (2.18 m in height and 0.4 m¡Ñ0.4 m in cross-sectional area) was constructed to develop a biofilter packed only with fern chips for the removal of air-borne propylene glycol monomethyl ether acetate (PGMEA). Both stages were packed with fern chips of 0.30 m in height and 0.40 m ¡Ñ0.40 m in cross section. Fern chips could avoid the shortcomings of traditional media, such as compaction, drying, and breakdown, which lead to the performance failure of the biofilters. In addition, the fern chip medium has the following merits: (1) simplicity in composition, (2) low pressure drop for gas flow (< 20 mmH2O m-1), (3) simple in humidification, nutrient addition, pH control, and metabolite removal, (4) economical (USD$ 174 ¡V 385 m-3), and (5) low weight (wet basis around 290 kg m-3). Results indicate that with operation conditions of media moisture content controlled in the range of 50 ¡V 74%, media pH of 6.5 ¡V 8.3, EBRT (empty bed retention time) of 0.27 ¡V 0.4 min, influent PGMEA concentrations of 100 to 750 mg m-3, volumetric organic loading of < 170 g m-3 h-1, and nutrition rates of Urea-N 66.0 g m-3.day-1, KH2PO4-P 13.3 g m-3.day-1 and milk powder 1.0 g m-3 day-1, the fern-chip packed biofilter could achieve an overall PGMEA removal efficacy of around 94%. Instant milk powder or liquid milk was essential to the good and stable performance of the biofilter for PGMEA removal. An activated sludge aeration basin (20 cm i.d., 140 cm height) equipped with either a coarse air diffuser (a plastic pipe perforated with 56 orifices of 2 mm in diameter) or a fine diffuser (porous plastic type with 100-micrometer pores) was utilized to treat an air-borne hydrophobic VOC (toluene, 700 ¡V 800 mg m-3). The purposes of this study were to test the influences of both MLSS and diffuser type on the VOC removal efficiency. Results show that higher MLSS (mixed liquor suspended solids) such as 10,000 ¡V 40,000 mg L-1 in the mixed liquor did not enhance greatly the transfer and removal of the introduced toluene. Instead, activated sludge basins with a normal MLSS (e.g., 2,000 ¡V 4,000 mg L-1) in the mixed liquor and an efficient gas diffusion system with volumetric VOC transfer coefficient of around 10 ¡V 15 h-1 can be used for the removal of hydrophobic VOCs from the introduced gas. For achieving a removal of over 95% of the introduced toluene or similar hydrophobic VOCs, commercial air diffusers for aerobic biological wastewater treatment basins can be used with a submerged liquid depth of over 0.40 m over the diffusers and an aeration intensity (air flow rate/basin cross-sectional area) of lower than 5.0 m3 m-2 h-1.

Die Biosynthese von Chlorophyll ist komplex und umfasst mehr als ein Dutzend enzymatische Schritte. Es ist nur allzu selbstverständlich, dass eine Deregulation der Chlorophyllsynthese globale Effekte auf die Zelle hat. Um diese Konsequenzen näher zu beleuchten, wurden Arabidopsis thaliana Pflanzen mit chemisch induzierter Deaktivierung von zwei Chlorophyllbiosynthesegenen (CHLH bzw. CHL27) erzeugt sowie photoautotophe Zellsuspensionskulturen von Arabidopsis thaliana hinsichtlich kurzzeitig induzierter Signalprozesse untersucht. Die Resultate verdeutlichen, dass durch Fehlregulationen innerhalb der Chlorophyllbiosynthese erzeugte reaktive Sauerstoffspezies die Transkriptionskontrolle kernkodierter Gene beeinflussen. Die Untersuchung eines enzymatischen Schrittes der Chlorophyllbiosynthese trat in dieser Arbeit in den Hauptfokus: Die Bildung des fünften, isozyklischen Ringes im Chlorophyllmolekül, katalysiert durch das bisher unzureichend erforschte Enzym Mg-Protoporphyrin-IX-monomethylester-Cyclase (Cyclase). Anhand von transgenen Cyanobakterien und Pflanzen sollte das noch unbekannte Gen ycf54 hinsichtlich seiner physiologischen Funktion in dem Cyclase-Enzymschritt analysiert werden. Das Fehlen von Ycf54 in Synechocystis sp. PCC6803 bzw. des homologen LCAA-Proteins in Nicotiana tabacum und Arabidopsis thaliana führt zu starken Cyclase-Substrat-Akkumulationen, verringerten Chlorophyllgehalten und reduzierten Ycf59- bzw. CHL27-Proteingehalten. Ein Mangel von Ycf54/LCAA beeinträchtigt daher die Funktionalität des Cyclase-Komplexes und scheint sich zudem interessanterweise auch auf die Stabilität photosynthetischer Antennenkomplexe auszuwirken. Mittels Pulldown-Assays konnte für Arabidopsis thaliana die direkte physikalische Interaktion zwischen LCAA und CHL27 bestätigt werden. Darüber hinaus sind erste Hinweise für die Ferredoxin-NADP-Reduktase als potenziellen Interaktionspartner gezeigt. / Synthesis of chlorophyll is a complex metabolic process and encompasses more than a dozen enzymatic reactions. It is self-evident that a deregulation of chlorophyll biosynthesis evokes global cellular impacts. To elucidate these consequences Arabidopsis thaliana plants with chemically inducible deactivation of two chlorophyll biosynthesis genes (CHLH and CHL27, respectively) were generated and photoautotrophic cell suspension cultures of Arabidopsis thaliana were used for short induced signal processes. The results illustrate that reactive oxygen species provoked by a deregulated chlorophyll synthesis affect the control of transcription of nuclear genes. The investigation of one enzymatic step of chlorophyll biosynthesis was placed as main focus: The formation of the isocyclic ring of the chlorophyll molecule catalyzed by the Mg protoporphyrin IX monomethyl ester cyclase (short: cyclase), an enzyme which is not fully investigated so far. The still unknown hypothetical chloroplast open reading frame (ycf) ycf54 should be analyzed concerning it’s physiological function in the enzymatic step of the cyclase using transgenic cyanobacteria and plants. Lack of Ycf54 in Synechocystis sp. PCC6803 and the homologous LCAA protein in Nicotiana tabacum and Arabidopsis thaliana, respectively, leads to chlorophyll deficiency, a strong accumulation of the cyclase substrate and reduced protein contents of Ycf59 and CHL27, respectively. A deficit of Ycf54/LCAA impairs the functionality of the cyclase complex and also might compromise the stability of photosynthetic antenna complexes. Using pull-down assays a direct physical interaction between LCAA and CHL27 could be confirmed. Additionally, first evidences for ferredoxin NADP reductase as a potential interaction partner was given.