6 resultados para alkylation pattern
em Brock University, Canada
Resumo:
Young soybean plants (Glycine ~. L. cultivar Harosoy '63), grown under controlled conditions, were exposed to gamma radiation on a single occasion. One hour following exposure to 3,750 rads, the mature trifoliate leaf of the soybean plant was isolated in a closed system and permitted to photoassimilate approximately 1-5 pCi of 14C02 for 15 minutes. After an additional 45 minute-period, the plant was sacrificed and the magnitude of translocation and distribution pattern of 14C determined. In the non-irradiated plants 18~ of the total 14C recovered was outside the fed leaf blades and of this translocated 14c, 28~ was above the node of the fed leaf, 38~ in the stem below the node, 28~ in the roots and 7~ in the petiole. As well, in the irradiated plants, a smaller per cent (6~) of the total 14 C recovered was exported out of the source leaf blades. Of this translocated 14c , a smaller per cent (20~) was found in the apical region above the node of the source leaf and a higher per cent (45~) was recovered from the stem below the node and in the petiole (11~). The per cent of exported 14 C recovered from the root was unaffected by the radiation. Replacement of the shoot apex with 20 ppm IAA immediately following irradiation, only J partially increased the magnitude of translocation but did completely restore the pattern of distribution to that observed in the non-irradiated plants. From supplementary studies showing a radiationinduced reduction of photosynthetic rates in the source leaf and a reduction of the cumulative stem and leaf lengths in the apical sink region, the observed effects of radiation on the translocation process have been correlated to damage incurred by the source and sink regions. These data suggest that the reduction in the magnitude of translocation is the result of damage to both the source and sink regions rather than the phloem conducting tissue itself, whereas the change in the pattern of translocation is probably the result of a reduced rate of 14C-assimilate movement caused by a radiation-induced decrease of sink metabolism, especially the decrease in the metabolism of the apical sink.
Resumo:
Linear alkylbenzenes, LAB, formed by the Alel3 or HF catalyzed alkylation of benzene are common raw materials for surfactant manufacture. Normally they are sulphonated using S03 or oleum to give the corresponding linear alkylbenzene sulphonates In >95 % yield. As concern has grown about the environmental impact of surfactants,' questions have been raised about the trace levels of unreacted raw materials, linear alkylbenzenes and minor impurities present in them. With the advent of modem analytical instruments and techniques, namely GCIMS, the opportunity has arisen to identify the exact nature of these impurities and to determine the actual levels of them present in the commercial linear ,alkylbenzenes. The object of the proposed study was to separate, identify and quantify major and minor components (1-10%) in commercial linear alkylbenzenes. The focus of this study was on the structure elucidation and determination of impurities and on the qualitative determination of them in all analyzed linear alkylbenzene samples. A gas chromatography/mass spectrometry, (GCIMS) study was performed o~ five samples from the same manufacturer (different production dates) and then it was followed by the analyses of ten commercial linear alkylbenzenes from four different suppliers. All the major components, namely linear alkylbenzene isomers, followed the same elution pattern with the 2-phenyl isomer eluting last. The individual isomers were identified by interpretation of their electron impact and chemical ionization mass spectra. The percent isomer distribution was found to be different from sample to sample. Average molecular weights were calculated using two methods, GC and GCIMS, and compared with the results reported on the Certificate of Analyses (C.O.A.) provided by the manufacturers of commercial linear alkylbenzenes. The GC results in most cases agreed with the reported values, whereas GC/MS results were significantly lower, between 0.41 and 3.29 amu. The minor components, impurities such as branched alkylbenzenes and dialkyltetralins eluted according to their molecular weights. Their fragmentation patterns were studied using electron impact ionization mode and their molecular weight ions confirmed by a 'soft ionization technique', chemical ionization. The level of impurities present i~ the analyzed commercial linear alkylbenzenes was expressed as the percent of the total sample weight, as well as, in mg/g. The percent of impurities was observed to vary between 4.5 % and 16.8 % with the highest being in sample "I". Quantitation (mg/g) of impurities such as branched alkylbenzenes and dialkyltetralins was done using cis/trans-l,4,6,7-tetramethyltetralin as an internal standard. Samples were analyzed using .GC/MS system operating under full scan and single ion monitoring data acquisition modes. The latter data acquisition mode, which offers higher sensitivity, was used to analyze all samples under investigation for presence of linear dialkyltetralins. Dialkyltetralins were reported quantitatively, whereas branched alkylbenzenes were reported semi-qualitatively. The GC/MS method that was developed during the course of this study allowed identification of some other trace impurities present in commercial LABs. Compounds such as non-linear dialkyltetralins, dialkylindanes, diphenylalkanes and alkylnaphthalenes were identified but their detailed structure elucidation and the quantitation was beyond the scope of this study. However, further investigation of these compounds will be the subject of a future study.
Seasonal variation in hatching pattern and chick survival in the ring-billed gull Larus delawarensis
Resumo:
The general objective of my study was to monitor proximate causes and seasonal patterns of hatching asynchrony and chick survival in the Ring-billed Gull (Larus delawarensis). Two different plots were set up at a Ring-billed Gull colony near Port Colborne, Ontario in the summer of 1992. One group was from 'peak' nesting pairs (clutches initiated between 15 April and 1 May); a second group was from 'late' nesting pairs (clutches initiated between 9 .. 22 May). Despite equal intra-clutch egg laying intervals between the peak and late periods, intra-clutch hatching intervals lengthened as the season progressed (ie. hatching became more asynchronous). Clutches from both periods were monitored for nocturnal attendance and brood patch development of parents was monitored during the egg laying period. Late nesters were characterized by an absence of nocturnal desertion, substantial brood patch defeatheration at clutch initiation and a reduction in the number of chicks fledged per pair. Chick survival to 25 days (taken as fledging) reflected patterns of chick mass at brood completion and five days post-brood completion, in peak clutches. In late clutches, survival was poor for all chicks and, was partially independent of hatching order, due in part to stochastic events such as Herring Gull predation and adverse weather. In both the peak and late periods, last-hatched C-chicks realized the poorest survival to fledging among brood mates. An artificial hatching pattern (manipulated synchrony) and an artificial hatching order were created, in three-chick broods, through a series of egg exchanges. In peak and late clutches manipulated to hatch synchronously (s; 24 h): C-chick survival to fledging did not differ from the survival of A- and B-chicks, in the peak period. In the late period, the survival of C-chicks was significantly lower than that of A-chicks. In peak clutches manipulated such that chicks from last-laid eggs (C-chicks) hatched 24 h - 48 h ahead of the A- and B- chicks, C-chick survival was greater than in controls. Within those broods, C-chicks survived better on average than both A- and B- chicks.
Resumo:
Aluminosilicate catalysts containing supported ZnCl2 and metal fluoride salts have been prepared using a sol-gel based route, tested and characterized. The activities of these ZnCl2 + metal fluoride catalysts, while greater than "Clayzic" (ZnCI2 supported on montmorillonite KIO) are not as good as supported ZnCl2 only supported on aluminosilicate. Alumina supports have also been prepared via a sol-gel route using various chemical additives to generate a mesoporous structure, loaded with ZnCl2 and tested for activity. The activities for these alumina-supported catalysts are also significantly higher than that of "Clayzic", an effective Friedel-Crafts catalyst. Characterizations of these two types of catalysts were done by magic angle spinning (MAS) NMR, diffuse reflectance infrared (DRIFT) spectroscopy and additionally for the alumina nitrogen adsorption studies were done. Supported aluminum trichloride was also investigated as an alternative to the traditional use of aluminum trichloride.
Resumo:
Hydrogen bond assisted alkylation of phenols is compared with the classical base assisted reactions. The influence of solvents on the fluoride assisted reactions is discussed,· with emphasis on the localization of hydrogen bond charge density. Polar aprotic solvents such as DMF favour a-alkylation, and nonpolar aprotic solvents such as toluene favourC-alkylation of phenol. For more reactive and soluble fluorides, such as tetrabu~ylammoniumfluoride, the polar aprotic solvent favours a-alkylation and nonpolar aprotic solvent favours fluorination. Freeze-dried potassium fluoride is a better catalytic agent in hydrogen bond assisted alkylation reactions of phenol than the oven-dried fluoride. The presence of water in the alkylation reactions reduces the expected yield drastically. The tolerance of the reaction to water has also been studied. The use ofa phase transfer catalyst such as tetrabutylammonium bromide in the alkylation reactions of phenol in the presence of potassium fluoride is very effective under anhydrous conditions. Sterically hindered phenols such as 2,6-ditertiarybutyl-4-methyl phenol could not be alkylated even by using the more reactive fluorides, such as tetrabutylammonium fluoride in either polar or nonpolar aprotic solvents. Attempts were also made to alkylate phenols in the presence of triphenylphosphine oxide.
Resumo:
Scientists have overwhelmingly concluded that global warming occurs as a consequence of human activities and that climate change, combined with the depletion of resources, could have catastrophic consequences for the human civilization later this century. However, in political circles and in the public sphere these conclusions are not taken seriously, or they are laid aside for future generations to deal with; at the same time, significant efforts are being deployed to discredit the scientific evidence. In this thesis I have studied the positions of climate scientists as well as those of climate change deniers, and I also examined how their points of view are likely to impact the interests and habits of corporations and citizens. The work of Thomas Homer-Dixon was used as an important source for analyzing the complex interaction between our natural, economic, and social systems, and John Dewey's pattern of inquiry provided the theoretical foundation for an analysis of the current crisis and its possible solutions. No concerted action to deal with climate change has yet been taken by the leaders of the Western world; I corroborated data from four reliable sources (Hansen, 2009; IPCC, 2007; Lynas, 2007; Steffen, 2011) regarding several development scenarios and their likely consequences on greenhouse gas emissions, and I concluded that a future temperature increase of more than 2°C appears now as unavoidable. In the light of this conclusion I argue that education for increasing the resilience of smaller communities is a realistic alternative that can offer some hope in dealing with the challenges ahead.