Abstract RF-gradients produced utilizing RF-field inhomogenity of conventional receiver/transmitter coil of NMR-probe can be used to mimic the effects of B0-gradients. This is done by placing long inhomogenous pulse in between two 90° pulses of appropriate phases (z-rotation cluster). B0-gradient based excitation sculpting can be converted into RF-gradient version. Selective one-dimensional TOCSY and NOESY using RF-gradient based excitation sculpting are described. In addition, non-selective two-dimensional experiments, TOCSY and NOESY, with RF-gradient based coherence selection are presented. Excitation sculpting using BIRD or BIRDR as inversion element results in isotope filter. Pre-suppression of non-13C-bound protons using RF-gradient BIRD prior to HSQC enables recording of spectrum of comparable quality to B0-gradient selected HSQC. This is beneficial for spectrometers lacking B0-gradient capabilities. Excitation sculpting using BIRDR can be used efficiently as low-pass filter in HMBC experiment. Furthermore, simultaneous elimination of protons bound to 15N and 13C can be accomplished with BIRDR based method.

Abstract This study was part of a project targeted at developing chemical sensors for organic cations and metal ions by exploiting the interactions between cations and anionic borate derivatives. As well, the chemical synthesis of thiophene monomers with charged or neutral ion-recognition sites was investigated. The primary task in the first part of the work was to prepare anionic receptor molecules based on synthesized borate derivatives and study their complexation with N-heteroaromatic and tropylium cations. The complexation was studied in solution by 1H NMR and ESIMS techniques and in solid state by X-ray crystallography. Crystal structures showed evidence of weak noncovalent interactions–hydrogen bonding, cation···π interactions, and π-stacking. In addition, the crystal structure of the alkali metal complex of tris[3-(2-pyridyl)pyrazolyl]hydroborate was determined. Stability constants of borate complexes were measured by 1H NMR titration in methanol/acetonitrile (1:1) solution at 30 °C. Various derivatives of aromatic borate anions synthesized within this project, some commercially available derivatives, and two neutral carriers containing aromatic anthryl groups were also studied as recognition sites for aromatic cations where N-methylpyridinium was used as primary ion in PVC membrane-based all-solid-state ion sensors. The results showed that borate derivatives offer new possibilities for molecular recognition by ion-selective electrodes (ISEs). The aim of the second part of the study was to develop chemical ion sensor materials where the ion-recognition unit and the charge-compensating ion are covalently coupled to the backbone of a conductive polymer. Sulfonated thiophenes were used as doping ions for the fabrication of Ag+-ISEs. More than 15 differently substituted monomers were synthesized. The materials differed with respect to the receptor unit, extent of oxidation, counteranion, and length of the chain.

We investigate "dual headquarters involvement", i.e., corporate and divisional headquarters' simultaneous involvement in innovation development projects hosted by subsidiaries of multibusiness firms. Drawing on selective hierarchical involvement theory and the literature on subsidiary network embeddedness, we analyze 83 innovation projects in 22 multibusiness firms and find that the number of partners in the projects, rather than subsidiary intra- and inter-divisional embeddedness acts as a driver of dual headquarters involvement. We do however find that intra- and inter-divisional embeddedness is positively related to dual headquarters involvement when the number of partners in the innovation project is relatively large. These results lend support to the idea that parenting in complex organizations entail complex headquarters structures. Our results suggest that we need to go beyond simple conceptualizations of headquarters and that considering different dimensions of the innovating subsidiary's network helps in explaining dual headquarters involvement.

One of the overarching questions in the field of infant perceptual and cognitive development concerns how selective attention is organized during early development to facilitate learning. The following study examined how infants’ selective attention to properties of social events (i.e., prosody of speech and facial identity) changes in real time as a function of intersensory redundancy (redundant audiovisual, nonredundant unimodal visual) and exploratory time. Intersensory redundancy refers to the spatially coordinated and temporally synchronous occurrence of information across multiple senses. Real time macro- and micro-structural change in infants’ scanning patterns of dynamic faces was also examined. According to the Intersensory Redundancy Hypothesis, information presented redundantly and in temporal synchrony across two or more senses recruits infants’ selective attention and facilitates perceptual learning of highly salient amodal properties (properties that can be perceived across several sensory modalities such as the prosody of speech) at the expense of less salient modality specific properties. Conversely, information presented to only one sense facilitates infants’ learning of modality specific properties (properties that are specific to a particular sensory modality such as facial features) at the expense of amodal properties (Bahrick & Lickliter, 2000, 2002). Infants’ selective attention and discrimination of prosody of speech and facial configuration was assessed in a modified visual paired comparison paradigm. In redundant audiovisual stimulation, it was predicted infants would show discrimination of prosody of speech in the early phases of exploration and facial configuration in the later phases of exploration. Conversely, in nonredundant unimodal visual stimulation, it was predicted infants would show discrimination of facial identity in the early phases of exploration and prosody of speech in the later phases of exploration. Results provided support for the first prediction and indicated that following redundant audiovisual exposure, infants showed discrimination of prosody of speech earlier in processing time than discrimination of facial identity. Data from the nonredundant unimodal visual condition provided partial support for the second prediction and indicated that infants showed discrimination of facial identity, but not prosody of speech. The dissertation study contributes to the understanding of the nature of infants’ selective attention and processing of social events across exploratory time.

Cognition is dynamic and complex, requiring specific sets of brain areas to cooperate for specific tasks. Neural synchronization is a proposed mechanism for transient functional integration of specific neural populations, enabling feature flexible binding and dynamic assignment of functional connectivity in the brain according to task demands. This thesis addresses the role of neural synchronization in selective attention and perceptual consciousness. The goals of this thesis are to test the hypothesis that synchronization between brain regions is relevant to network dynamics in selective attention and for perceptual organization, and to elucidate the function of synchronization in different frequency ranges. Using a selective visuospatial cuing paradigm it is shown that deploying attention to one visual hemifield yields transient long-distance gamma-band synchronization between contralateral visual cortex and other, widespread, brain regions. This is interpreted as a mechanism for establishing anticipatory biasing of communication in the cortex. Long-distance gamma synchrony, moreover, is periodically 'refreshed' at a theta rate, possibly serving to maintain this gamma network. While local alpha-band activity was found to be greater ipsilateral to the attended visual hemifield, alpha-band synchronization between primary visual cortex and higher visual areas was greater contralateral to attended locations. This suggests that local alpha synchrony is relevant for inhibition, while long-range alpha synchronization enacts functional coupling. The onset of a new conscious percept during binocular rivalry coincides with large-scale gamma-band synchronization which recurs at a theta rate. This suggests that gamma synchronization integrates features into a unified conscious percept while the theta cycle maintains that network. Using an audiovisual speech integration paradigm it is shown that large-scale gamma synchronization is greater when incongruence is detected between auditory and visual streams. This highlights an important distinction: neural synchronization reflects neural integration, not perceptual integration. Perceptual integration typically requires neural integration (feature binding), however, in this case detection of audiovisual mismatches requires cooperation within a distributed network, whereas audiovisual speech integration is largely accomplished in superior temporal cortex. These studies indicate that long-distance gamma synchronization establishes neural integration, the theta cycle maintains gamma synchronous networks, and local and long-range alpha synchrony reflect sustained inhibition and functional coupling mechanisms, respectively. / Medicine, Faculty of / Graduate

Surficial geochemistry, particularly selective leach technology, has proven effective in revealing anomalous concentrations of ore indicator metals overlying zones of buried mineralization. This study focuses on the buried Zn-Cu-Au-Ag VMS deposit at McIlvenna Bay in the Flin Flon Greenstone Belt to determine whether the peat swamp at the surface contains any anomalies of ore indicator metals using simple surficial geochemical techniques. Three selective leaches were performed, ammonium acetate pH 5.0, hydroxylamine, and sodium pyrophosphate. The hydroxylamine leach, which selects for metals in the reducible phase often associated with Mn and Fe oxides, has the clearest anomaly for multiple metals observed simultaneously, at the greatest magnitude. The pyrophosphate leach, which selects for metals that are oxidizable, often associated with organics showed a clear anomaly only for Cu, despite the abundance of organic matter and its great affinity for binding metals, likely because the organic-metal complexes formed in this system are easily exchangeable and highly soluble, not allowing for the formation of clear anomalies. The use of selective leach technology on surficial soil or peat has shown to be effective for delineating ore indicator metal anomalies, giving surface projections of buried mineralization in various types of systems, as long as the dynamics of the system are well understood in order to determine the phase the metals are associated with.

Substances of natural and synthetic origin were studied using analytical, bioassay guided isolation, metabolomics and medicinal chemistry techniques. In a section focused on the plant family Marcgraviaceae, a validated method for the quantification of six pentacyclic triterpenes (α and β Amyrin lupeol, ursolic acid, betulin and betulinic acid) in the Souroubea spp was developed. Quantification of the triterpenes in the crude extracts was achieved using HPLC-APCI mass selective detection. The calibration curves for the five triterpenes evaluated were highly linear (r2 >0.993) and percentage recovery from spiked samples were greater than 94% for all compounds. The LOD for betulinic acid was 0.01 µg for betulinic acid on column and LOQ was 0.03 µg. The method was successfully applied to 41 crude extracts from leaf and stem of Souroubea spp, from two locations in Costa Rica. The method is suitable for quality control of raw materials used in the manufacture of natural health products. The use of modern metabolomic techniques, UHPLC-QTOF allowed the identification of five putative makers that can potentially be used in distinguishing between the two Souroubea species. The validated method was used in the quantification of the above triterpenes in a total of thirteen Marcgraviaceae species collected in Costa Rica. It was established that betulinic acid and β- Amyrin could be used as makers for this family of tropical vines. These same thirteen plants extracts were evaluated in antifungal and quorum sensing inhibition bioassays. Marcgravia nervosa was the only species that showed significant activity in both bioassays. Bioassay guided fractionation of the crude ethanolic extract of M. nervosa led to the identification of 2-methoxynaphthoquinone as the bioactive compound responsible for the bioactivity. The crude leaf ethanolic extract from M. nervosa showed a significant inhibition of QS comparable or somewhat better than D. pulchra extracts with the M. nervosa extract showing stronger inhibiting QS with a halo of 21.8mm, more than D. pulcra extracts which generated a halo of 15.9mm. The active quinone has a MIC of 85 µM against Saccharomyces cerevisiaBY4741 (haploid) and 100 µM against Saccharomyces cerevisiae BY4743 (diploid) compared to berberine (positive control) with a MIC 600 µM for both strains. This quinone is not present in any of the other twelve species of Marcgraviaceae available to us. In work focusing on organic synthesis, a total of 57 semi-synthetic derivatives of dillapiol, safrol and piperonal were prepared and evaluated for their inhibitory activity in a CYP 3A4 bioassay to assess their potential use as pesticide synergists. The synergistic activity of dillapiol has been improved 45 fold; analog 31 has an IC50 = 0.2 µM compared with dillapiol IC50= 9.18 µM. A number of other compounds structurally related to 31 showed similar levels of activity. A screening of a compound library identified the amino sulfoxide 3 as a potential lead for the design of a selective connexin blocker with potential application in the treatment of spinal cord injuries. The use of X-ray crystallography permitted the correction of the original structure assigned to 3. Once the structure was corrected a total of 6 analogs were prepared. Compound 3 has the highest inhibition of GJIC whereas compound 8 and compound 2, reduced anionic hemi-channel activity. Compound 2 also reduced the cationic activity of the hemi-channels.

The Selective Service system of the First World War was based on an attempt to reconcile the military necessity of conscription with American civic values. General Enoch Crowder and others in the War Department, with the disastrous Civil War experience in mind, were determined to produce a system of conscription that would incorporate such values. Because of this concern, a chief feature of Selective Service was a framework of decentralized administration: the local boards. The complete success of the local boards, though, was predicated on their operation in the sort of society that General Crowder and his associates had known, and indeed idealized. This was the homogeneous, inclusive, and participatory group characterized by the strong social bonds of "community." Selective Service was consciously intended to fit into and take advantage of the dynamics of closely-knit local society, of which the small country town was the American model. Beyond that, some viewed it as a means to strengthen the bonds of community and help unify society on both local and national levels. The major part of this study is concerned with Selective Service in a potentially difficult social context: that of racial segregation in one Southern city, Montgomery, Alabama. Society in Montgomery exhibited general Southern characteristics of segregation, but in Montgomery the social distance between black and white was perhaps greater than elsewhere. Relations between the two groups were governed by the basic conservatism of both, a not entirely vicious arrangement. Though officials had worried about full black participation, Selective Service got a strong start in Montgomery at the first registration in 1917. In such a setting, the question arises as to how Selective Service was affected in operation by segregation. In Montgomery the members of the local board were city officials, intelligent, competent, but unremarkable representatives of the white community. In dealing with white registrants, the board, not surprisingly, fulfilled all the expectations of the War Department. Above all the local board was absolutely fair in its judgments. The situation of the blacks was naturally somewhat different. The local board did not know or represent them in any real sense. Local customs (and a segregated army) dictated the maintenance of segregation in most, though not all, aspects of official proceedings. Yet in substantive terms the board was just as fair to the blacks as to the whites. The main disparities between the treatment of black and white was the unavoidable etiquette of segregation symbolized by the use of the word "Boy." The board's actions, though, left little room for complaint. If habits of segregation did not substantially influence the operation of Selective Service, did Selective Service in turn have any effect on segregation? In the case of Montgomery it is clear that conservatism was too strong and the forces of change too weak to produce much change in local society. Segregation was always maintained at public events. The races went their separate ways, the whites largely ignoring black activities. By the end of the war no change had taken place in racial attitudes. The war effort, while unsettling, simply was not a sufficiently pressing situation to compel an alteration in the views of conservative people. Also, things got done quite well under segregation, with the help of black leaders, so that there was no operational need to re-examine local lociety. And finally, there was no pressure from blacks, although in wartime circumstances they were beginning to develop some community organization. Selective Service came, did its work, and departed, leaving segregation in Montgomery as well established as before the war. Selective Service in Montgomery was thus both a success and a failure. It-succeeded in that there was a just administration of conscription, supported by public participation. It failed in that, although both the white and black people of the city participated in a common institution, the barriers of segregation remained untouched by the war experience. Despite the high social goals which some had had for it, Selective Service in Montgomery was only segregation at its best—and nothing more. / Arts, Faculty of / History, Department of / Graduate

Predictions of the Intersensory Redundancy Hypothesis (IRH) state that early in development information presented to a single sense modality (unimodal) selectively recruits attention to and enhances perceptual learning of modality-specific properties of stimulation at the expense of amodal properties, while information presented redundantly across two or more modalities (bimodal) results in enhanced perceptual learning of amodal properties. The present study explored these predictions during prenatal development by assessing bobwhite quail embryos’ detection of pitch, a modality-specific property, under conditions of unimodal and redundant bimodal stimulation. Chicks’ postnatal auditory preferences between the familiarized call and the same call with altered pitch were assessed following hatching. Unimodally-exposed chicks significantly preferred the familiarized call over the pitch-modified call, whereas bimodally-exposed chicks did not prefer the familiar call over the pitch-modified call. Results confirm IRH predictions, demonstrating unimodal exposure facilitates learning of modality-specific properties, whereas redundant bimodal stimulation interferes with learning of modality-specific properties.

The Intersensory Redundancy Hypothesis (IRH; Bahrick & Lickliter, 2000, 2002, 2012) predicts that early in development information presented to a single sense modality will selectively recruit attention to modality-specific properties of stimulation and facilitate learning of those properties at the expense of amodal properties (unimodal facilitation). Vaillant (2010) demonstrated that bobwhite quail chicks prenatally exposed to a maternal call alone (unimodal stimulation) are able to detect a pitch change, a modality-specific property, in subsequent postnatal testing between the familiarized call and the same call with altered pitch. In contrast, chicks prenatally exposed to a maternal call paired with a temporally synchronous light (redundant audiovisual stimulation) were unable to detect a pitch change. According to the IRH (Bahrick & Lickliter, 2012), as development proceeds and the individual’s perceptual abilities increase, the individual should detect modality-specific properties in both nonredundant, unimodal and redundant, bimodal conditions. However, when the perceiver is presented with a difficult task, relative to their level of expertise, unimodal facilitation should become evident. The first experiment of the present study exposed bobwhite quail chicks 24 hr after hatching to unimodal auditory, nonredundant audiovisual, or redundant audiovisual presentations of a maternal call for 10min/hr for 24 hours. All chicks were subsequently tested 24 hr after the completion of the stimulation (72 hr following hatching) between the familiarized maternal call and the same call with altered pitch. Chicks from all experimental groups (unimodal, nonredundant audiovisual, and redundant audiovisual exposure) significantly preferred the familiarized call over the pitch-modified call. The second experiment exposed chicks to the same exposure conditions, but created a more difficult task by narrowing the pitch range between the two maternal calls with which they were tested. Chicks in the unimodal and nonredundant audiovisual conditions demonstrated detection of the pitch change, whereas the redundant audiovisual exposure group did not show detection of the pitch change, providing evidence of unimodal facilitation. These results are consistent with predictions of the IRH and provide further support for the effects of unimodal facilitation and the role of task difficulty across early development.