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).

Propylene oxide (PO) is an important raw material for the chemical industry, which is produced commercially by the chlorohydrin process and hydroperoxide process. However the deficiencies in these processes have given rise to considerable interest in the development of a direct route to PO that does not produce by-products or coproducts. The development of novel, active and selective catalysts for gas phase oxidation of propylene using molecular oxygen were studied via testing a large number of catalysts by high-throughput screening method over combinatorially prepared different catalytic system in this study. v The promoted and un-promoted silver (Ag), copper (Cu), manganese (Mn) mono and bimetallic catalytic system over high and low surface area silica, alumina, titanium oxide and titanium-silicate supports were prepared by single step sol-gel method and by incipient wetness method. The study to determine the most effective catalyst and promoter in the epoxidation reaction with different reaction conditions, showed that potassium (K)- promoted Cu metal supported over high surface area silica favored the PO production at a high reaction temperature (350 &deg / C) and oxygen rich atmosphere (C3H6/O2=1.0). The catalyst showed high and low propylene oxide productivity was investigated by some of the characterization techniques. The highlydispersed copper particle over silica support was determined by XRD, TEM and XPS techniques. The only change between promoted and un-promoted catalyst was found out in the temperature dependence of propylene consumption and PO production rate. It was inferred that potassium (K) only neutralizes the acid sites of silica.

Propylene epoxidation reaction was investigated on catalytic surfaces of chlorinated copper(I) oxide and ruthenium(IV) oxide using periodic density functional theory (DFT). Cu2O(001) and (110) surface of RuO2 was selected to generate chlorinated surfaces to be used in the study. Besides epoxidation, other reactions that compete with epoxidation were also studied such as formations of allyl-radical, acrolein, acetone on chlorinated Cu2O(001) and formations of propionaldehyde, allyl-radical and acetone on chlorinated RuO2(110) surface. Path of each reaction was determined by CI-NEB method and transition state analyses. Generally accepted stable surface intermediate mechanism was utilized in reactions to final products. The surface intermediate favorable on the surfaces in this study was determined to be the intermediate that is not preferable on metallic surfaces under low oxygen. On chlorinated Cu2O(001) surface, formation of propylene oxide, acetone and acrolein have higher probability than gas phase allyl-radical since the desorption energy of allyl-radical was calculated to be 70kcal/mol which is a relatively high value. In fact it is desirable since gas phase allyl-radical is known to be the precursor of combustion products. On chlorinated RuO2(110) surface, desorption Propylene epoxidation reaction was investigated on catalytic surfaces of chlorinated copper(I) oxide and ruthenium(IV) oxide using periodic density functional theory (DFT). Cu2O(001) and (110) surface of RuO2 was selected to generate chlorinated surfaces to be used in the study. Besides epoxidation, other reactions that compete with epoxidation were also studied such as formations of allyl-radical, acrolein, acetone on chlorinated Cu2O(001) and formations of propionaldehyde, allyl-radical and acetone on chlorinated RuO2(110) surface. Path of each reaction was determined by CI-NEB method and transition state analyses. Generally accepted stable surface intermediate mechanism was utilized in reactions to final products. The surface intermediate favorable on the surfaces in this study was determined to be the intermediate that is not preferable on metallic surfaces under low oxygen. On chlorinated Cu2O(001) surface, formation of propylene oxide, acetone and acrolein have higher probability than gas phase allyl-radical since the desorption energy of allyl-radical was calculated to be 70kcal/mol which is a relatively high value. In fact it is desirable since gas phase allyl-radical is known to be the precursor of combustion products. On chlorinated RuO2(110) surface, desorption observed to be possible on chlorinated RuO2(110) surface but not possible on chlorinated Cu2O(001). When activation barriers and desorption energies of all possible reactions are compared on chlorinated RuO2(110) surface / gas phase propylene oxide generated directly seems as the preferable product with allylradical although it was computed to have high desorption energy. Comparison of activation barriers obtained in this study on chlorinated Cu2O(001) with the barriers of nonchlorinated surface revealed chlorine slightly increases the activation barrier of unwanted allylic hydrogen stripping and hence slightly decreases the probability of occurance. When chlorine is placed closer to reaction site, activation barrier of allylic hydrogen stripping reaction increases further. The effect of chlorine might be electronic since the charge of oxygen at reaction site slightly becomes less negative when the place of chlorine gets closer to the reaction site on the surface. Similar comparison between chlorinated and nonchlorinated RuO2(110) surfaces revealed that chlorine addition does not improve the surface toward propylene oxide formation, rather it is detrimental as chlorine addition caused a decrease in unwanted allylic hydrogen stripping reaction.

Cyanide-catalyzed aldimine coupling was employed to synthesize compounds with 1,2-ene-diamine and α-imine-amine structural motifs: 1,2,N,N'- tetraphenyletheylene-1,2-diamine (13) and (+/-)-2,3-di-(2-hydroxyphenyl)-1,2- dihydroquinoxaline (17), respectively. Single crystal X-ray diffraction provided solidstate structures and density functional theory calculations were used to probe isomeric preferences within this and the related hydroxy-ketone/ene-diol system. The enediamine and imine-amine core structures were calculated to be essentially identical in energy. However, additional effects-such as π conjugation-in 13 render an enediamine structure that is slightly more stable than the imine-amine tautomer (14). In contrast, the intramolecular hydrogen bonding present in 17 significantly favors the imine-amine isomer over the ene-diamine tautomer (18). Aldimine coupling (AIC) is the nitrogen analogue of the benzoin condensation and has been applied to dialdimines, providing the first examples of cyclizations effected by cyanide-catalyzed AIC. Sodium cyanide promoted the facile, intramolecular cyclization of several dialdimines in N,N-dimethylformamide, methanol, or dichloromethane/water (phase-transfer conditions) yielding a variety of six-membered heterocycles. Under aerobic conditions, an oxidative cyclization occurs to provide the diimine heterocycle. Cyanide-catalyzed aldimine coupling was employed as a new synthetic method for oligomerization. Nine rigidly spaced dialdimines were oxidatively coupled under aerobic conditions to yield conjugated oligoketimines and polyketimines with unprecedented structure and molecular weight (DP = 2 - 23, ~700 -8200 g/mol). The α- diimine linkage was established based on IR spectroscopy, NMR spectroscopy, size exclusion chromatography, and X-ray crystallographic characterization of the model oxidized dimer of N-benzylidene-(p-phenoxy)-aniline. Cyclic voltammetry indicates ptype electrical conductivity, suggesting they are promising candidates for plastic electronic devices. The cyanide-catalyzed benzoin condensation reaction of 4-substituted benzaldehydes followed by oxidation to the diketone, and the Schiff Base condensation of two equivalents of o-aminophenol provides 2,3-(4-X-phenyl)2-1,4-(2- hydroxyphenyl)2-1,4-diazabutadiene. The ligand is given the moniker X-dabphol. These ligands are readily metallated to form M-X-dabphol complexes. The copper complexes catalytically fix CO2 with propylene oxide to yield propylene carbonate. DFT studies along with a comparison with Hammet parameters help validate and elaborate on the catalytic cycle and the catalytic results obtained. The nickel complex is competent for olefin epoxidation. Synthesis, characterization, X-ray structure, DFT analysis, and catalytic activity of the parent nickel dabphol complex are reported.

The goal of this project was to develop a mixed matrix membrane with enhanced properties for propylene/propane separations. To start with the project, one of the high performance 6FDA based polyimides was identified as the polymer matrix for the rest of the project. The chosen polymer (6FDA-6FpDA) was successfully synthesized in the laboratory. During the synthesis process the key objectives for high molecular weight and low polydispersity index polymer were identified. High molecular weight 6FDA-6FpDA was achieved via laboratory synthesis and was tested successfully. After successful synthesis of the high performance polymer, pure polymer dense films were tested for transport properties. One problem identified with 6FDA-6FpDA polymer films for propylene/propane separations was plasticization. A major objective of this research was to develop a method for plasticization suppression. A carefully controlled annealing procedure with high temperature permeation experiments was used in this research to suppress plasticization in a mixed gas environment. To the best of our knowledge, this is for the first time plasticization suppression was achieved with pure polymeric membrane material for propylene/propane separations with pure and mixed gases. The observed mixed gas experimental selectivity was lower than the pure gas selectivity which was explained by the combination effect of dual mode and bulk flow effect. The last objective of this project was to successfully incorporate molecular sieve materials to form a mixed matrix membrane hybrid material with enhanced transport properties First, an ideal molecular sieve for propylene/propane separation was identified and characterized. AlPO-14 was chosen for this research following its success with propylene/propane pressure swing adsorption. Mixed matrix membranes were successfully produced and tested for enhanced transport properties. Both pure and mixed gas results showed promising results with enhanced propylene permeability and propylene/propane selectivity. The experimental results were modeled with the Cussler and Maxwell models. A modified Cussler model was presented in this work. This is the first time an enhancement in the transport properties with mixed matrix membrane for propylene/propane separations has been observed. This fundamental dense film work holds a bright future for the scale up of propylene/propane separations.

The Deepwater Horizon blowout in 2010 released an estimated 4.9 million barrels of crude oil into the Gulf of Mexico in the 83 days between the initial explosion and the capping of the well. Response included extensive use of Corexit© oil dispersant. Although South Florida was spared exposure by currents, this event highlights the need for effective bioassay organisms for coral reefs. Amphistegina spp. are benthic foraminifers that host diatom symbionts in a relationship similar to that of coral and their zooxanthellae. Amphistegina spp. occur abundantly in reef communities nearly worldwide, are easily collected and maintained in culture, and are a key component of the FoRAM Index, a indicator of water and sediment quality in coastal waters. The major goals of this project were to develop protocols to test the acute and chronic responses of A. gibbosa to potentially toxic organic chemicals. Initial objectives were to determine lethal concentrations and effects ranges, as defined by the US Environmental Protection Agency, of two components of the Corexit© dispersants. Preliminary experiments indicated that many specimens exposed to propylene glycol (v/v) at concentrations of 2% or higher appeared to be dead following 48-hour exposure, resulting in apparent LC50 of 3% and an initial effects range of 2-4%. When placed in filtered seawater, after 72-hours the observed LC50 was 6%. All parameters assessed, including sub-lethal chronic effects (differences in growth and visible responses after 40 days), revealed an effects range of 0.5% to 12%, above which there was 100% mortality. For 2-butoxyethanol, the apparent LC50 after 48-hour exposure was 0.2%; after 72-hour recovery the LC50 was 1%. In all experiments, a 72-hour recovery period was sufficient to determine acute effects. A key discovery was the observation of inactivity during exposure to toxic substances, followed by recovery when placed in filtered seawater. This observation indicates the potential for dormancy in adult foraminifers exposed to toxic substances that has not previously been reported.

Darbe tirtos struktūrinės ir spektroskopinės dviejų šeimų nematinių skystakristalinių dendrimerų ištirpintų chloroforme savybės. Taip pat struktūrinės, spektroskopinės ir magnetooptinės dendrimerų su įterptomis Co nanodalelėmis savybės. Dviejų šeimų skystakristalinių dendrimerų ištirpintų chloroforme optiniai tyrimai parodė, kad pirmos šeimos skystakristalinių dendrimerų vidinę dalį nusakanti sugerties juosta antros ir penktos generacijų atžvilgiu yra paslinkusi per 8nm, tuo tarpu antros šeimos atitinkamai pirmos ir penktos generacijų atžvilgiu per 19nm. Dendrimerų su įterptomis Co nanodalelėmis magnetooptiniai tyrimai parodė, kad Co nanodalelės gali būti valdomos magnetiniais laukais. / Dendritic structure is one of the prevalent topologies on our planet [1]. Dendrimers is generally described as monodispersed low viscosity macromolecules with highly branched, well defined 3D structure, first reported in 1978 by Vögtle. They are always composed of a core molecule and dendritic branches extended from core to terminal groups [26]. The number of functional groups on the dendrimer surface increases exponentially as a function of generation, of that in the higher generations they become much more spherical and amplified highly ordered architectures. Liquid crystalline dendrimers of their unique structural and physical properties have attached considerable attention. Because of their hyper branched spherical structure, interior inside dendrimers have fixed cavities. Strong interaction forces in the terminal mesogenic units determine that in the interior can be incorporated atoms, ions, guest molecules or nanoparticles. They are particularly well suited materials for hosting nanoparticles of the following reasons: nanoparticles are stabilized and don’t agglomerate, dendrimer branches can be use as selective gates to control access of small molecules [19]. As result of their architecture, dendrimers can possess essential physical, chemical and biological properties and whole range of applications in energy, medicine, engineering, information technology and ect. We present optical and structural studies of liquid crystalline poly(propylene imine) (PPI) dendrimers... [to full text]

<p>In this thesis, I present the electrochemical studies of three dendrimeric polypropylene imine (PPI) nanomaterials and their applications as a platform in the development of a novel label free DNA nanobiosensor based on electrochemical impedance spectroscopy. Cyclic voltammetry (CV), differentia pulse voltammetry (DPV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivities of the nanomaterials on glassy carbon electrode (GCE) as the working electrode.</p>

Safripol is a South African polymer company producing mainly high density polyethylene and polypropylene for the South African market. Safripol used to be part of a global chemical company Dow Chemicals. Dow Chemical's divested in South Africa in 2006 and Safripol lost all the advantages of being part of a global corporate enterprise. The company is faced with a unique situation in that it is receiving monomer from Sasol, which is also its main competitor in the polymer market. The price of monomer and its low availability is putting pressure on Safripol's product margins, with a negative effect on the company's sustainability. The above was also defined as the research problem that threatens to undermine the company's competitive edge in the polymer market. It was clear from this research study that monomer and specifically propylene was the biggest burning point for Safripol regarding the price and availability thereof. Research into the South African polymer market has shown that Safripol will lose significant market share if the company is not showing additional growth in the market. The research problem is investigated through interviews, monomer availability investigations, plant capacity increasing and potential technology partner's discussions. A specific scenario planning process was also followed to help Safripol identify potential present and future scenarios that the company can investigate. The research problem was addressed by developing a strategy for Safripol to address the research objectives. Recommendations were done regarding the following: 1) Recommendations for additional propylene supply. 2) Recommendations to increase the polypropylene plant capacity. 3) Recommendations with regards to technology partners. 4) Recommendations regarding the scenario planning process. / Thesis (M.Ing. (Development and Management Engineering))--North-West University, Potchefstroom Campus, 2011. (Mag eers in 2014 gepubliseer word)

Safripol is a South African polymer company producing mainly high density polyethylene and polypropylene for the South African market. Safripol used to be part of a global chemical company Dow Chemicals. Dow Chemical's divested in South Africa in 2006 and Safripol lost all the advantages of being part of a global corporate enterprise. The company is faced with a unique situation in that it is receiving monomer from Sasol, which is also its main competitor in the polymer market. The price of monomer and its low availability is putting pressure on Safripol's product margins, with a negative effect on the company's sustainability. The above was also defined as the research problem that threatens to undermine the company's competitive edge in the polymer market. It was clear from this research study that monomer and specifically propylene was the biggest burning point for Safripol regarding the price and availability thereof. Research into the South African polymer market has shown that Safripol will lose significant market share if the company is not showing additional growth in the market. The research problem is investigated through interviews, monomer availability investigations, plant capacity increasing and potential technology partner's discussions. A specific scenario planning process was also followed to help Safripol identify potential present and future scenarios that the company can investigate. The research problem was addressed by developing a strategy for Safripol to address the research objectives. Recommendations were done regarding the following: 1) Recommendations for additional propylene supply. 2) Recommendations to increase the polypropylene plant capacity. 3) Recommendations with regards to technology partners. 4) Recommendations regarding the scenario planning process. / Thesis (M.Ing. (Development and Management Engineering))--North-West University, Potchefstroom Campus, 2011. (Mag eers in 2014 gepubliseer word)