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Semiochemicals released from logs infested by southern pine beetle (SPB), <i>Dendroctonus frontalis</i>, from a total of eight infestations located in Texas, South Carolina, and Virginia were collected four to eight days after initial attack. The quantities and chiralities of most semiochemicals, as analyzed by gas-liquid chromatography, showed geographic and temporal variations. Changes in the quantities of α-pinene (aP), frontalin (F), and <i>endo</i>-brevicomin (eB), are believed to result from responses of the host and the beetle to each other's activity at a given time and differences in their respective health. The chiralities of aP, F, and eB at all locations generally remained stable over time, yet variation across the insect's geographic range, particularly for aP and F, is believed to be due to genetic variation of individuals. Geographic and temporal variations in the quantities and chiralities of <i>cis</i>-verbenol (cV), <i>trans</i>-verbenol (tV), and verbenone (V) are presumed to be due to the multiple pathways of origin (SPB, autoxidation, and microorganisms). Analysis of the same semiochemicals isolated from hindguts of individual beetles from Texas, South Carolina, and North Carolina showed quantities of cV and tV to be substantially greater in females than in males; whereas, males contained much greater amounts of V. Geographic differences were found in quantities of tV and V in both sexes and in aP and F in males only. The chiralities of most semiochemicals present in SPB hindguts differed markedly from those released from infested logs. Males produced predominantly (+)-F and (-)-eB, (-)-cV, and (-)-V; however, the chirality of tV varied considerably among areas. In contrast, females produced predominantly (+)-cV and (+)-V and (-)-F, (-)-eB, and (-)-tV. The (+) enantiomer of aP predominated in both sexes, but the proportion of (+ )-aP was generally lower than that released from SPB-infested logs from the same areas. Geographic differences in chirality of tV and V were significant in males and for eB in females. In laboratory trials, aP autoxidized under ambient temperatures to form tV, myrtenol (M), V and to a lesser extent, cv. Both the quantities and chiralities of these compounds were dependent on the chirality of the aP precursor. Significantly greater amounts and proportions of the (+) enantiomer of each compound were produced when (+)-aP was predominant than when the antipode of the precursor was predominant. The extent to which autoxidation products playa role in bark beetle behavior is expected to be dependent on the proportion of aP in pine resin and its chirality present in a pine species. The information gained from this research was used to elaborate on previously proposed behavioral sequences occurring during the mass attack of host trees by SPB and to suggest new avenues to improve the use of semiochemicals in pest management efforts. / Ph. D.

The protic acid-catalyzed polymerization of 1,6-anhydro-6-D-glucopyranose (I) was first reported one-half century ago; however, the mechanism of this reaction has not been resolved and is the topic under investigation in this thesis. In an attempt to resolve this mechanism, a number of 1,6-anhydrides structurally related to 1,6-anhydro-B-D-glucopyranose (I) were prepared and polymerized. The C-2, C-3, or C-4 hydroxyl group was either specifically blocked, replaced by a hydrogen atom or positioned different sterically. The relative rates of disappearance of monomer in the polymerization reaction were measured and this information used to propose a reaction mechanism.

Данная работа предполагает разработку методики анализа остаточных органических растворителей (ООР) в субстанциях натрия 3,8-диэтоксикарбонил-4-оксо-4Н-пиразоло[5,1-c][1,2,4]триазинид моногидрата (AB-19) и натрия 7-метилтио-4-оксо-3-циано-4Н-[1,2,4]триазоло[5,1-c][1,2,4]триазинида тригидрата (MNR-857). Анализ литературных данных показал, что наиболее предпочтительным методом определения ООР является метод газожидкостной хроматографии с парофазным вводом пробы. Для определения целевых аналитов в исследуемых субстанциях рассмотрены схемы синтеза и строение соединений, и определено, что образцы могут содержать органические растворители II (гексан, пиридин, метанол) и III (этанол, этилацетат, 2-пропанол) классов опасности. Однако опытные данные показали наличие в образцах субстанций только этанола и пропан-2-ола. В связи с этим проводили количественное определение только указанных растворителей. На основе литературных данных были определены исходные условия проведения хроматографического анализа. На практике исходная методика была скорректирована: изменение массы навески, разведения образца, времени выдерживания виалы, установление диапазона концентраций применения методики и метода количественного определения. Разработанную методику анализа подвергали испытаниям на пригодность по таким показателям как специфичность, линейность, предел количественного определения, сходимость, промежуточная прецизионность и правильность. Согласно проведенным исследованиям была доказана достоверность и надежность получаемых с использованием данной методики результатов. Количественное определение ООР с помощью разработанной методики в образцах субстанций AB-19 (3 партии синтеза) и MNR-857 (5 партий синтеза) подтвердило их соответствие требованиям ОФС.1.1.0008.15 по показателю остаточные органические растворители (не более 0,5 % для растворителей III класса опасности). / This paper discusses the development of a method for assay of residual organic solvents in substances in substances such as sodium 3,8-diethoxycarbonyl-4-oxo-4H-pyrazolo[5,1-c][1,2,4]triazinide monohydrate (AB-19) and sodium 7-methylthio-4-oxo-3-cyano-4H-[1,2,4]triazolo[5,1-c][1,2,4]triazinide trihydrate (MNR-857). An analysis of the literature data showed that the most preferred method for determining residual organic solvents is headspace gas-liquid chromatography. To determine the target analytes in the studied substances, synthesis schemes and the structure of compounds are considered. Thanks to this, it was decided that the samples might contain organic solvents of hazard classes II and III. Class II includes hexane, pyridine, methanol, and сlass III includes ethanol, ethyl acetate, 2-propanol. However, experimental data showed the presence of only ethanol and propan-2-ol in the samples of substances. In this regard, an assay was carried out only for these two solvents. Based on literature data, the initial conditions for the chromatographic analysis were determined. The original method was adjusted by changing the test portion of sample, diluting the samples, the holdup time of the vial, as well as by establishing ranges of concentrations and the method of quantitative measurement. The developed analysis method was tested for suitability by such indicators as specificity, linearity, limit of quantification, repeatability, intermediate precision, and accuracy. According to the research, it was demonstrated that the analytical technique is acceptable for solving the task. The residual organic solvents were quantified using the developed procedure for three batches of synthesis of substance AB-19 and for five batches of synthesis of substance MNR-857. The percentage of residual organic solvents in all samples was less than 0.5%. Thus, the results obtained satisfy the requirements of the article OFS.1.1.0008.15 of the State Pharmacopoeia of the Russian Federation in terms of residual organic solvents.

This study was conducted to identify and characterize rumen bacteria that are able to degrade the toxic compound, 3-hydroxy-4(lH)-pyridone (3,4 DHP), that is produced in the rumen from mimosine. Mimosine is a non-protein amino acid that is found in leaves and seeds of Leucaena leucocephala, a leguminous tree used as a forage crop for ruminants in the tropics, and degradation of 3,4 DHP by ruminal microbes is critical for protection of animals from leucaena toxicity. Microbes with this capacity are, however, not ubiquitous and microbial populations in the rumens of animals in some parts of the world are unable to metabolize 3,4 DHP. Four strains of obligately anaerobic, gram-negative, rod-shaped bacteria that degrade 3,4 DHP were isolated from rumen contents from a goat in Hawaii. The isolates do not ferment carbohydrates, but are able to use both 3,4 DHP and its isomer, 3-hydroxy-2(lH)-pyridone (2,3 DHP), as well as arginine and histidine as substrates for growth. Comparisons of the 16S rRNA sequence from one of these isolates with sequences from a widely diverse group of bacteria agree with other information indicating that these isolates do not fit into any existing taxon. Thus, we are hereby proposing a new genus and species designation, Synergistes jonesii, for these organisms.