The potential for monitoring and control of insect pests in Southern Hemisphere forestry plantations using semiochemicals

Southern Hemisphere plantation forestry has grown substantially over the past few decades and will play an increasing role in fibre production and carbon sequestration in future. The sustainability of these plantations is, however, increasingly under pressure from introduced pests. This pressure requires an urgent and matching increase in the speed and efficiency at which tools are developed to monitor and control these pests. To consider the potential role of semiochemicals to address the need for more efficient pest control in Southern Hemisphere plantations, particularly by drawing from research in other parts of the world. Semiochemical research in forestry has grown exponentially over the last 40 years but has been almost exclusively focussed on Northern Hemisphere forests. In these forests, semiochemicals have played an important role to enhance the efficiency of integrated pest management programmes. An analysis of semiochemical research from 1970 to 2010 showed a rapid increase over time. It also indicated that pheromones have been the most extensively studied type of semiochemical in forestry, contributing to 92% of the semiochemical literature over this period, compared with research on plant kairomones. This research has led to numerous applications in detection of new invasions, monitoring population levels and spread, in addition to controlling pests by mass trapping or disrupting of aggregation and mating signals. The value of semiochemicals as an environmentally benign and efficient approach to managing forest plantation pests in the Southern Hemisphere seems obvious. There is, however, a lack of research capacity and focus to optimally capture this opportunity. Given the pressure from increasing numbers of pests and reduced opportunities to use pesticides, there is some urgency to develop semiochemical research capacity.

Reciprocal and advanced generation hybrids between Corymbia citriodora and C-torelliana: forestry breeding and the risk of gene flow

Corymbia F1 hybrids have high potential for plantation forestry; however, little is known of their reproductive biology and potential for genetic pollution of native Corymbia populations. This study aims to quantify the influence of reproductive isolating barriers on the success of novel reciprocal and advanced generation Corymbia hybrids. Two maternal taxa, Corymbia citriodora subsp. citriodora and Corymbia torelliana, were pollinated using five paternal taxa, C. citriodora subsp. citriodora, C. torelliana, one C. torelliana x C. citriodora subsp. citriodora hybrid and two C. torelliana x C. citriodora subsp. variegata hybrids. Pollen tube, embryo and seed development were assessed. Reciprocal hybridisation between C. citriodora subsp. citriodora and C. torelliana was successful. Advanced generation hybrids were also created when C. citriodora subsp. citriodora or C. torelliana females were backcrossed with F1 hybrid taxa. Prezygotic reproductive isolation was identified via reduced pollen tube numbers in the style and reduced numbers of ovules penetrated by pollen tubes. Reproductive isolation was weakest within the C. citriodora subsp. citriodora maternal taxon, with two hybrid backcrosses producing equivalent capsule and seed yields to the intraspecific cross. High hybridising potential was identified between all Corymbia species and F1 taxa studied. This provides opportunities for advanced generation hybrid breeding, allowing desirable traits to be amplified. It also indicates risks of gene flow between plantation and native Corymbia populations.

Pond apple (Annona glabra L.) - Investigating novel mechanical control options

Pond apple usually occurs in swampy areas, but mechanical control may be a viable option in some locations during drier periods. Two machines, the Positrack™ and the Tracksaw™, have been trialled for initial kill rate, amount of follow-up control required, safety to field operators, cost-efficiency and selectivity (effect on native vegetation), compared to other control options. The Positrack™ is a tracked bobcat with a slasher-type attachment that cuts individual trees off near ground level and mulches them. It has no on-board herbicide application capability and requires an additional on-ground operator to apply herbicide by hand. The Tracksaw™ is a tracked mini-excavator with a chainsaw bar and spray applicator on the boom that cuts individual trees off near ground level and applies chemical immediately to the cut stump, requiring only a single operator. Initial trials were done in infestations of similar sizes and densities at the Daintree (Positrack™) and in Innisfail (Tracksaw™) in late 2009. Kill rates to date are 83% for Positrack™ mechanical, 95% for Positrack™ mechanical plus herbicide, and 78% for the Tracksaw™ combined treatment. If ongoing comparison proves either of these machines to be more cost effective, selective, and safer than traditional control methods, mechanical control methods may become more widely used.

The influence of pre- and post-zygotic barriers on interspecific Corymbia hybridization

Corymbia species from different sections hybridize readily, with some of increasing economic importance to plantation forestry. This study explores the locations of reproductive barriers between interspecific Corymbia hybrids and investigates the reproductive success of a wide taxonomic range of C. torelliana hybrid crosses. Pollen, pistil and embryo development were investigated for four C. torelliana crosses (C. torelliana, C. citriodora subsp. citriodora, C. tessellaris and C. intermedia) using fluorescent and standard microscopy to identify the locations of interspecific reproductive isolating barriers. Corymbia torelliana was also crossed with 16 taxa, representing six of the seven Corymbia sections, both Corymbia subgenera and one species each from the related genera, Angophora and Eucalyptus. All crosses were assessed for capsule and seed yields. Interspecific C. torelliana hybridization was controlled by pre-zygotic reproductive isolating barriers inhibiting pollen adhesion to the stigma, pollen germination, pollen tube growth in the style and pollen tube penetration of the micropyle. Corymbia torelliana (subgenus Blakella, sect. Torellianae) was successfully hybridized with Corymbia species from subgenus Blakella, particularly C. citriodora subsp. citriodora, C. citriodora subsp. variegata, C. henryi (sect. Maculatae) and C. tessellaris (sect. Abbreviatae), and subgenus Corymbia, particularly C. clarksoniana and C. erythrophloia (sect. Septentrionales). Attempted intergeneric hybrids between C. torelliana and either Angophora floribunda or Eucalyptus pellita were unsuccessful. Corymbia hybrids were formed between species from different sections and subgenera, but not with species from the related genera Angophora or Eucalyptus. Reproductive isolation between the interspecific Corymbia hybrid crosses was controlled by early- and late-acting pre-zygotic isolating barriers, with reproductive success generally decreasing with increasing taxonomic distance between parent species. These findings support the monophyly of Corymbia and the close relationships of infrageneric clades. The hybridizing propensity of Corymbia species provides opportunities for breeding but suggests risks of environmental gene flow. © The Author 2012. Published by Oxford University Press on behalf of the Annals of Botany Company. All rights reserved. For Permissions, please email: journals.permissions@oup.com

Assessment and control of Bacillus cereus emetic toxin in food

Despite of improving levels of hygiene, the incidence of registered food borne disease has been at the same level for many years: there were 40 to 90 epidemics in which 1000-9000 persons contracted food poisoning through food or drinking water in Finland. Until the year 2004 salmonella and campylobacter were the most common bacterial causes of food borne diseases, but in years 2005-2006 Bacillus cereus was the most common. Similar developement has been published i.e. in Germany already in the 1990´s. One reason for this can be Bacillus cereus and its emetic toxin, cereulide. Bacillus cereus is a common environmental bacterium that contaminates raw materials of food. Otherwise than salmonella and campylobacter, Bacillus cereus is a heat resistant bacterium, capable of surviving most cooking procedures due to the production of highly thermo resistant spores. The food involved has usually been heat treated and surviving spores are the source of the food poisoning. The heat treatment induces germination of the spore and the vegetative cells then produce toxins. This doctoral thesis research focuses on developing methods for assessing and eliminating risks to food safety by cereulide producing Bacillus cereus. The biochemistry and physiology of cereulide production was investigated and the results were targeted to offer tools for minimizing toxin risk in food during the production. I developed methods for the extraction and quantitative analysis of cereulide directly from food. A prerequisite for that is knowledge of the chemical and physical properties of the toxin. Because cereulide is practically insoluble in water, I used organic solvents; methanol, ethanol and pentane for the extraction. For extraction of bakery products I used high temperature (100C) and pressure (103.4 bars). Alternaties for effective extraction is to flood the plain food with ethanol, followed by stationary equilibration at room temperature. I used this protocol for extracting cereulide from potato puree and penne. Using this extraction method it is also possible also extract cereulide from liquid food, like milk. These extraction methods are important improvement steps for studying of Bacillus cereus emetic food poisonings. Prior my work, cereulide extraction was done using water. As the result, the yield was poor and variable. To investigate suspected food poisonings, it is important to show actual toxicity of the incriminated food. Many toxins, but not cereulide, inactivate during food processing like heating. The next step is to identify toxin by chemical methods. I developed with my colleague Maria Andesson a rapid assay for the detection of cereulide toxicity, within 5 to 15 minutes. By applying this test it is possible to rapidly detect which food was causing the food poisoning. The chemical identification of cereulide was achieved using mass spectrometry. I used cereulide specific molecular ions, m/z (+/-0.3) 1153.8 (M+H+), 1171.0 (M+NH4+), 1176.0 (M+Na+) and 1191.7 (M+K+) for reliable identification. I investigated foods to find out their amenability to accumulate cereulide. Cereulide was formed high amounts (0.3 to 5.5 microg/g wet wt) when of cereulide producing B. cereus strains were present in beans, rice, rice-pastry and meat-pastry, if stored at non refrigerated temperatures (21-23C). Rice and meat pastries are frequently consumed under conditions where no cooled storage is available e.g. picnics and outdoor events. Bacillus cereus is a ubiquitous spore former and is therefore difficult to eliminate from foods. It is therefore important to know which conditions will affect the formation of cereulide in foods. My research showed that the cereulide content was strongly (10 to 1000 fold differences in toxin content) affected by the growth environment of the bacterium. Storage of foods under nitrogen atmosphere (> 99.5 %) prevented the production of cereulide. But when also carbon dioxide was present, minimizing the oxygen contant (< 1%) did not protect the food from formation of cereulide in preliminary experiments. Also food supplements affected cereulide production at least in the laboratory. Adding free amino acids, leucine and valine, stimulated cereulide production 10 to 20 fold. In peptide bonded form these amino acids are natural constituents in all proteins. Interestingly, adding peptide bonded leucine and valine had no significant effect on cereulide production. Free amino acids leucine and valine are approved food supplements and widely used as flawour modifiers in food technology. My research showed that these food supplements may increase food poisoning risk even though they are not toxic themselves.

New nondestructive method for three-dimensional photoelasticity

A new set of equations describing completely the optical phenomena in a model involving continuous rotation of secondary axes and secondary principal-stress differences are obtained. These are solved by Peano-Baker method using experimentally determined characteristic parameters for several wavelengths of light. Experimental verifications are obtained for a rectangular bar subjected to combined torsion and tension. Paper was presented at Third SESA International Congress on Experimental Mechanics held in Los Angeles, CA on May 13–18, 1973.

Boronia heterophylla vase life is influenced more by ethylene than by bacterial numbers or vase solution pH

Bacterial proliferation in both vase solutions and in cut flower stems has been implicated in reducing the vase life of numerous genera. Boronia heterophylla F. Muell. (Red Boronia) vase life was assessed at two stages of floral maturity for nine vase solution treatments covering a pH range of 2.5-5.7. Vase life for advanced harvest maturity stems ranged from 4.2 d in 10 mM citric acid + 50 mg L-1 chlorine (pH 2.5) to 12.9 d after STS pulsing (pH 5.7). For normal harvest maturity stems, the corresponding range was 5.8-19.0 d, respectively. Vase solutions containing 50 mg L-1 chlorine biocide resulted in decreased longevity. In contrast, pulsing with the ethylene-binding inhibitor, STS, significantly increased vase life. The number of bacteria in the vase solutions after 11 d was determined in stems of advanced maturity. The solution with the greatest number of bacteria, 4.0 x 10(10) cfu mL(-1), was water used after STS pulsing and in which the flowers lasted longest. Vase solution bacteria were enumerated on days 0,3, 6, 9 and 12 of the vase period with stems of normal harvest maturity. There was no relationship between vase life and vase solution bacterial numbers ((R) over bar (2) = 0.000). Moreover, there was a negative relationship between numbers of bacteria in basal 0-5 cm stem segments and vase life. As no correlations were evident between longevity and either the pH or vase solution bacterial numbers, B. heterophylla vase life was evidently limited principally by ethylene action. (C) 2013 Elsevier B.V. All rights reserved.

To Greta: The Biography of Kurt Tauber 1914-1995

The memoir contains poems, eulogies and family photos and was written in 1995 in Connecticut. Recollections of the author's childhood in an orthodox Jewish family in the Leopoldstadt, the second district in Vienna. He was the third of four children. His father was a businessman who was dealing with clothing and textile. Kurt was enrolled in the same class as his older brother Hans at Gymnasium. Memories of his Bar Mitzvah celebration. Cello lessons and concerts with his brother Hans. After graduation Kurt started to study medicine at the Anatomic Institute of Julius Tandler at the Vienna University. Member of the liberal medical students' union "Wiener Mediziner". Acquaintance with his future-wife Greta. Skiing trip in the mountains. Antisemitic attacks at University, particularly within the faculties of law and medicine. Arrest under the false accusation of distributing illegal literature. In January 1938 Greta and Kurt Tauber were married. Worsening of political situation and rising of the illegal Nazi movement in Austria. Recollections of the "Anschluss" (Nazi take-over) in March 1938. Affidavit for Greta and Kurt from her brother in the United States. In June 1938 they went to London, where they waited for their visas to the US. Fervent attempts to arrange exit permits for their families in Vienna. Greta and Kurt Tauber arrived in New York in October of 1938. Difficult start at the beginning. Kurt started to work in a bakery. Greta and Kurt moved to a small apartment in the Lower East Side. Move to Queens with Greta's parents. Kurt's parents arrived in 1940 and moved to Washington Heights. Kurt and Greta started a baking business in Kew Gardens, Queens. Birth of their daughters Judy in 1941 and Ellen in 1944. Recollections of Passover family celebrations and vacations in the mountains and at Fleischmann's in the Catskills. Description of business encounters and family events, such as the birth of their grandchildren. Journey to Israel. Retirement and

How do you like America? 1800-1940

The memoirs were written in 2000 in California and contains some of the author's diary entries during the years of the family's emigration and reminiscences of the author's father. Detailed description of family history going back to the early 19th century. The author's grandfather Moses Stern had a rawproduct business in Gelsenkirchen, Westphalia. His father Max Stern took his graduate exam (Abitur) at the Jacobsohn boarding school in 1904 and was sent to a business school in Brussles, Belgium. Work in the family business M. Stern AG. World War One and rise of the family business with branches throughout Germany and offices in New York, London, Milan and Stockholm. Due to political unrest at the end of the war the business administration moved to Essen. Description of the family background of Beate Herzberg, the author's mother. Courtship of his parents and marriage in 1922. Birth of his sister Annelore in 1923. Martin Stern was born in 1924. Description of the family household and domestic life in a well-to-do family the 1920s. Friday visits to the synagogue and celebration of Jewish holidays. Vacations at the North sea and skiinig in the Alps. Martin attended a Jewish elementary school. Rising National Socialism. After Hitler came to power in 1933 the author's father immediately started preparations for the family's emigration, but was persuaded to stay by his family. Life under National Socialism. Martin attended Gymnasium and was one of only two Jewish students in his class. Antisemitic incidents. Private lessons in piano and Hebrew. Bar Mitzvah in 1937. Recollections of performances of the Kulturbund.

Under Swastika and the French flag.

The memoirs were originally written for the Harvard University competition in 1940 and were translated by the author in 2001. Reflections on his childhood in Germany and Austria. His parents were both from Poland. They moved to Vienna in 1921, where his father opened a haberdashery store in the Second district (Leopoldstadt). Otto attended primary school in Czerningasse. Birth of his sister Cecile in 1924. After his failing business endeavors his father decided to move back to Germany, where the family opened a department store in Elbing, East Prussia. Otto attended Gymnasium, where he was one of only two Jewish students in his class. Growing Nazi movement among students. Summer vacations on the Baltic Sea. Private piano lessons. Hitler’s rise in Germany and life under National Socialism. Bar mitzvah in 1933. Anti-Jewish boycotts. His father fled to Vienna in order to escape a rounding up of Jews. The family followed soon after to Austria. Otto attended Gymnasium in the Zirkusgasse and started to work as a tutor. Member of a youth group and hiking tours in the mountains. Recollections of the Anschluss in 1938. Fervent attempts to obtain an exit visa for the United States, where they had a relative in New York. Description of discriminations and frequent attacks on Jewish friends and relatives in the weeks after the Anschluss. Otto was picked up by Nazi stormtroops. He was forced to hold up an anti-Jewish sign and was walked up and down, receiving beatings and spittings in front of a jeering crowd. Detailed account of the atmosphere within the Jewish population. The Gymnasium Zirkusgasse was transferred into a Jewish school. Frequent attacks of Hitler Youths on the students. Preparations for the “Matura” despite the turmoil. In June of 1938 his father was arrested and sent to Dachau concentration camp. After passing the final exams, Otto planned on leaving the country illegally, since he was subject to the Polish quota for the United States with

My First 6701 Days : July 31 1921 to December 1939 /

The memoirs contain photocopies of documents and photos as well as extracts from letters and were written in October 1989 in the United States. Description of life in Baden, a famous health resort near Vienna. The family lived in Vienna in the second district (Leopoldstadt). Recollections of schoolteachers and childhood friends. Occasional Friday night services in the Leopoldstadt temple. Theater and opera visits and cultural life in Vienna. Private piano and music lessons. Description of the family apartment and Jewish life in the Leopoldstadt. The family celebrated Christmas and observed the high Jewish holidays. Recollections of the author's bar mitzvah celebration. His mother Charlotte, nee Schwadron, was an artistic woman, who studied painting at the Frauenakademie with Tina Blau. Walter's father Leo Schaffir was born in Byalistock, Russia and studied in Berlin. He was a travelling businessmen. His family lived in Lemberg, Galicia. Leo and Charlotte Schaffir got married in 1919 in Vienna by rabbi Dr. Grunwald. Recollections of a family trip to Poland and to the World Fair in Posen in 1930. Suicide of the author's father due to business failure in 1930. Schaffir and Schwadron family history. Both families originated in Galicia, Poland. Family and social life. Summer vacation at the Semmering. Austrian politics in the 1930's and rising National Socialism. Life in Vienna after the "Anschluss" in 1938. Walter had to leave school and took lessons in graphic arts with the artist Heinrich Koerner. Preparations to emigrate. Walter was picked up in the streets in the days after Kristallnacht and released due to his mother's intervention. He was sent with his brother Kurt on a "Kindertransport" to Holland. They were sent to a quarantine camp at Heyplaat. Reunition with their mother in the United States in December 1939. Reflections on life as an emigre.

Titanium Complexes for the Polymerisation of Ethene and Caprolactone

The literature part of the thesis mainly reviews the results of the use of titanium catalysts for ethene and caprolactone polymerisation. The behaviour of titanium catalysts bearing phenoxy-imino ligands has been the focus of more detailed investigations in ethene polymerisation. Reasons for the production of multimodal polyethene for a range of catalysts are also given. The experimental part of the thesis is divided into two sections based on the monomers used in the polymerisations: Part A (ethene) and part B (caprolactone). Part A: Titanium(IV) complexes bearing phenoxy-imino ligands are known to possess high ethene polymerisation activities after MAO activation. Depending on the ligand, the activities of the catalysts in polymerisation can vary between 1 and 44000 kgPE/(mol*cat*h*bar). Depending on the polymerisation temperature and the electronic and steric properties of the catalyst ligands, low to high molar mass values and uni- and multimodal polydispersity values can been observed. In order to discover the reasons for these differences, 22 titanium(IV) complexes containing differently substituted phenoxy-imino derivatives as di- and tetradentate ligands were synthesised with high yields and used as homogeneous catalysts in ethene polymerisations. Computational methods were used to predict the geometry of the synthesised complexes and their configuration after activation. Based on the results obtained, the geometry of the catalyst together with the ligand substituents seem to play a major role in defining the catalytic activity. Novel titanium(IV) complexes bearing malonate ligands were also synthesised. Malonates are considered to be suitable ligand pre-cursors since they can be produced by the simple reaction of any primary or secondary alcohol with malonylchloride, and thus they are easily modifiable. After treatment with MAO these complexes had polymerisation activities between 10 and 50 kgPE/(mol*cat*h*bar) and surprisingly low polydispersity values when compared with similar types of catalysts bearing the O?O chelate ligand. Part B: One of the synthesis routes in the preparation of the above mentioned phenoxy-imino titanium dichloride complexes involved the use of Ti(NMe2)4 with a range of salicylaldimine type compounds. On reaction, these two compounds formed an intermediate product selectively and quantitatively which was active in the ring-opening polymerisation of caprolactone. Several mono-anionic alcoholates were also combined with Ti(NMe2)4 in different molar ratios and used as catalysts. Full conversion of the monomer was achieved within 15 minutes with catalysts having a co-ordination number of 4 while after 22 hours full conversion was achieved with catalysts having a co-ordination number of 6.

Tailoring polyolefin properties by metallocene catalysis

This doctoral thesis deals with the syntheses of olefin homo- and copolymers using different kind of metallocene catalyst. Ethene, propene, 1-hexene, 1-hexadecene, vinylcyclohexane and phenylnorbornene were homo- or copolymerized with the catalysts. The unbridged benzyl substituted zirconium dichloride catalysts (1-4), ansa- bridged acenaphtyl substituted zirconium dichloride catalysts, ( 5, 6), rac- and meso-ethylene-bis(1-indenyl)zirconium dichlorides, (rac- and meso-8), rac-ethylene-bis(1-indenyl)hafnium dichloride, ( 12), bis(9-fluorenyl)hafnium dichloride (14 ) enantiomerically pure (R)- phenylethyl[(9-fluorenyl-1-indenyl)]ZrCl2, (11), 14 and asymmetric dimethylsilyl[(3-benzylindenyl-(2-methylbenzen[e]indenyl)] zirconium dichloride, (13), were prepared in our laboratory. Dimethylsilyl-bis(1-indenyl)zirconium dichloride, (9), isopropylidene(9-fluorenyl-cyclopentadienyl)zirconium dichloride, (10), and were obtained commercially. The solid-state structures of the catalysts rac- and meso-1 were determined by X-ray crystallography. Computational methods were used for the structure optimization of the catalyst rac- and meso-1 in order to compare the theoretical calculations with the experimental results. Polymerization experiments were conducted in a highly purified autoclave system using low pressures (< 5 bar) of gaseous monomers. The experiments were designed to attain the optimal catalytic activity and a uniform copolymer composition. The prepared homo- and copolymers were characterized by the gel permeation chromatography, GPC, differential scanning calorimetry, DSC, nuclear magnetic resonance, NMR, and Fourier transform infrared spectrometry, FTIR . Molar mass (Mw, Mn), molar mass distribution (Mw/Mn), tacticity, comonomer content, melting temperature, glass transition temperature, and end group structures and content were determined. A special attention was paid on the correlation of the polymer properties with the catalyst structures and polymerization conditions. An intramolecular phenyl coordination was found in phenyl substituted benzyl zirconocenes 1-3 explaining the decreased activity of the catalysts. Novel copolymers poly(propene-co-phenylnorbornene) and poly(propene co-vinylcyclohexane), were synthesized and high molar mass poly(ethene-co-1-hexene) and poly(ethene-co-1-hexadecene) copolymers with elastic properties were prepared. Activation of a hafnocene catalyst was studied with UV-Vis spectrometry and activation process for the synthesis of ultra high molar mass poly(1-hexene) was found out.

The kinetics and reactivity of several polyatomic free radicals in reactions with NO2, O2, Cl2, and HCl

In this thesis, the kinetics of several alkyl, halogenated alkyl, and alkenyl free radical reactions with NO2, O2, Cl2, and HCl reactants were studied over a wide temperature range in time resolved conditions. Laser photolysis photoionisation mass spectrometer coupled to a flow reactor was the experimental method employed and this thesis present the first measurements performed with the experimental system constructed. During this thesis a great amount of work was devoted to the designing, building, testing, and improving the experimental apparatus. Carbon-centred free radicals were generated by the pulsed 193 or 248 nm photolysis of suitable precursors along the tubular reactor. The kinetics was studied under pseudo-first-order conditions using either He or N2 buffer gas. The temperature and pressure ranges employed were between 190 and 500 K, and 0.5 45 torr, respectively. The possible role of heterogeneous wall reactions was investigated employing reactor tubes with different sizes, i.e. to significantly vary the surface to volume ratio. In this thesis, significant new contributions to the kinetics of carbon-centred free radical reactions with nitrogen dioxide were obtained. Altogether eight substituted alkyl (CH2Cl, CHCl2, CCl3, CH2I, CH2Br, CHBr2, CHBrCl, and CHBrCH3) and two alkenyl (C2H3, C3H3) free radical reactions with NO2 were investigated as a function of temperature. The bimolecular rate coefficients of all these reactions were observed to possess negative temperature dependencies, while pressure dependencies were not noticed for any of these reactions. Halogen substitution was observed to moderately reduce the reactivity of substituted alkyl radicals in the reaction with NO2, while the resonance stabilisation of the alkenyl radical lowers its reactivity with respect to NO2 only slightly. Two reactions relevant to atmospheric chemistry, CH2Br + O2 and CH2I + O2, were also investigated. It was noticed that while CH2Br + O2 reaction shows pronounced pressure dependence, characteristic of peroxy radical formation, no such dependence was observed for the CH2I + O2 reaction. Observed primary products of the CH2I + O2 reaction were the I-atom and the IO radical. Kinetics of CH3 + HCl, CD3 + HCl, CH3 + DCl, and CD3 + DCl reactions were also studied. While all these reactions possess positive activation energies, in contrast to the other systems investigated in this thesis, the CH3 + HCl and CD3 + HCl reactions show a non-linear temperature dependency on the Arrhenius plot. The reactivity of substituted methyl radicals toward NO2 was observed to increase with decreasing electron affinity of the radical. The same trend was observed for the reactions of substituted methyl radicals with Cl2. It is proposed that interactions of frontier orbitals are responsible to these observations and Frontier Orbital Theory could be used to explain the observed reactivity trends of these highly exothermic reactions having reactant-like transition states.

Jerusalem Commemorative Medal

Obverse: Stylized picture of Jerusalem atop mountains surrounded by clouds. Reverse: Bar Kochba coin from Jerusalem, in the center four columns, an arc, a symbol of the Torah.