Few-mode fibre group-delays with intermediate coupling

We study the probability density function of the group-delay in few-mode fibres, validating for the first time an analytical estimation for the maximum group-delay spread as a function of linear mode coupling for fibres with more than three LP modes.

Advantages of strong mode coupling for suppression of nonlinear distortion in few-mode fibers

Nonlinear distortion in few-mode fibers for intermediate coupling is studied for the first time. Coupling strengths beyond -20 dB/100m give suppression of nonlinear distortion below the isolated mode without mode coupling.

Sonogashira cross-coupling and homocoupling on a silver surface:chlorobenzene and phenylacetylene on Ag(100)

Scanning tunneling microscopy, temperature-programmed reaction, near-edge X-ray absorption fine structure spectroscopy, and density functional theory calculations were used to study the adsorption and reactions of phenylacetylene and chlorobenzene on Ag(100). In the absence of solvent molecules and additives, these molecules underwent homocoupling and Sonogashira cross-coupling in an unambiguously heterogeneous mode. Of particular interest is the use of silver, previously unexplored, and chlorobenzene—normally regarded as relatively inert in such reactions. Both molecules adopt an essentially flat-lying conformation for which the observed and calculated adsorption energies are in reasonable agreement. Their magnitudes indicate that in both cases adsorption is predominantly due to dispersion forces for which interaction nevertheless leads to chemical activation and reaction. Both adsorbates exhibited pronounced island formation, thought to limit chemical activity under the conditions used and posited to occur at island boundaries, as was indeed observed in the case of phenylacetylene. The implications of these findings for the development of practical catalytic systems are considered.

Mitigating inconsistencies by coupling data cleaning, filtering, and contextual data validation in wireless sensor networks

With the advent of peer to peer networks, and more importantly sensor networks, the desire to extract useful information from continuous and unbounded streams of data has become more prominent. For example, in tele-health applications, sensor based data streaming systems are used to continuously and accurately monitor Alzheimer's patients and their surrounding environment. Typically, the requirements of such applications necessitate the cleaning and filtering of continuous, corrupted and incomplete data streams gathered wirelessly in dynamically varying conditions. Yet, existing data stream cleaning and filtering schemes are incapable of capturing the dynamics of the environment while simultaneously suppressing the losses and corruption introduced by uncertain environmental, hardware, and network conditions. Consequently, existing data cleaning and filtering paradigms are being challenged. This dissertation develops novel schemes for cleaning data streams received from a wireless sensor network operating under non-linear and dynamically varying conditions. The study establishes a paradigm for validating spatio-temporal associations among data sources to enhance data cleaning. To simplify the complexity of the validation process, the developed solution maps the requirements of the application on a geometrical space and identifies the potential sensor nodes of interest. Additionally, this dissertation models a wireless sensor network data reduction system by ascertaining that segregating data adaptation and prediction processes will augment the data reduction rates. The schemes presented in this study are evaluated using simulation and information theory concepts. The results demonstrate that dynamic conditions of the environment are better managed when validation is used for data cleaning. They also show that when a fast convergent adaptation process is deployed, data reduction rates are significantly improved. Targeted applications of the developed methodology include machine health monitoring, tele-health, environment and habitat monitoring, intermodal transportation and homeland security.

New organogermanium substrates for palladium-catalyzed cross-coupling reactions. Application of organogermanes towards the synthesis of carbon-5 modified uridine analogues

The diverse biological properties exhibited by uridine analogues modified at carbon-5 of the uracil base have attracted special interest to the development of efficient methodologies for their synthesis. This study aimed to evaluate the possible application of vinyl tris(trimethylsilyl)germanes in the synthesis of conjugated 5-modified uridine analogues via Pd-catalyzed cross-coupling reactions. The stereoselective synthesis of 5-[(2-tris(trimethylsilyl)germyl)ethenyl]uridine derivatives was achieved by the radical-mediated hydrogermylation of the protected 5-alkynyluridine precursors with tris(trimethylsilyl)germane [(TMS)3GeH]. The hydrogermylation with Ph3GeH afforded in addition to the expected 5-vinylgermane, novel 5-(2-triphenylgermyl)acetyl derivatives. Also, the treatment with Me3GeH provided access to 5-vinylgermane uridine analogues with potential biological applications. Since the Pd-catalyzed cross-coupling of organogermanes has received much less attention than the couplings involving organostannanes and organosilanes, we were prompted to develop novel organogermane precursors suitable for transfer of aryl and/or alkenyl groups. The allyl(phenyl)germanes were found to transfer allyl groups to aryl iodides in the presence of sodium hydroxide or tetrabutylammonium fluoride (TBAF) via a Heck arylation mechanism. On the other hand, the treatment of allyl(phenyl)germanes with tetracyanoethylene (TCNE) effectively cleaved the Ge-C(allyl) bonds and promoted the transfer of the phenyl groups upon fluoride activation in toluene. It was discovered that the trichlorophenyl,- dichlorodiphenyl,- and chlorotriphenylgermanes undergo Pd-catalyzed cross-couplings with aryl bromides and iodides in the presence of TBAF in toluene with addition of the measured amount of water. One chloride ligand on the Ge center allows efficient activation by fluoride to promote transfer of one, two or three phenyl groups from the organogermane precursors. The methodology shows that organogermanes can render a coupling efficiency comparable to the more established stannane and silane counterparts. Our coupling methodology (TBAF/moist toluene) was also found to promote the transfer of multiple phenyl groups from analogous chloro(phenyl)silanes and stannanes.

Stable isotopes reveal complex changes in trophic relationships following nutrient addition in a coastal marine ecosystem

Complex links between the top-down and bottomup forces that structure communities can be disrupted by anthropogenic alterations of natural habitats.We used relative abundance and stable isotopes to examine changes in epifaunal food webs in seagrass (Thalassia testudinum) beds following 6 months of experimental nutrient addition at two sites in Florida Bay (USA) with different ambient fertility. At a eutrophic site, nutrient addition did not strongly affect food web structure, but at a nutrient-poor site, enrichment increased the abundances of crustacean epiphyte grazers, and the diets of these grazers became more varied. Benthic grazers did not change in abundance but shifted their diet away from green macroalgae + associated epiphytes and towards an opportunistic seagrass (Halodule wrightii) that occurred only in nutrient addition treatments. Benthic predators did not change in abundance, but their diets were more varied in enriched plots. Food chain length was short and unaffected by site or nutrient treatment, but increased food web complexity in enriched plots was suggested by increasingly mixed diets. Strong bottom-up modifications of food web structure in the nutrient-limited site and the limited top-down influences of grazers on seagrass epiphyte biomass suggest that, in this system, the bottom-up role of nutrient enrichment can have substantial impacts on community structure, trophic relationships, and, ultimately, the productivity values of the ecosystem.

Exploring the role of large predators in marsh food webs: evidence for a behaviorally-mediated trophic cascade

The influence of large predators on lower trophic levels in oligotrophic, structurally complex, and frequently disturbed aquatic environments is generally thought to be limited. We looked for effects of large predators in two semi-permanent, spikerush-dominated marshes by excluding large fish (>12 mm body depth) and similarly sized herpetofauna from 1 m2 cages (exclosures) for 2 weeks. The exclosures allowed for colonization by intermediate (in size and trophic position) consumers, such as small fish, shrimp, and crayfish. Exclosures were compared to control cages that allowed large fish to move freely in and out. At the end of the experiment, intermediate-consumer densities were higher in exclosures than in controls at both sites. Decapod crustaceans, especially the riverine grass shrimp (Palaemonetes paludosus), accounted for the majority of the response. Effects of large fish on shrimp were generally consistent across sites, but per capita effects were sensitive to estimates of predator density. Densities of intermediate consumers in our exclosures were similar to marsh densities, while the open controls had lower densities. This suggests that these animals avoided our experimental controls because they were risky relative to the surrounding environment, while the exclosures were neither avoided nor preferred. Although illuminating about the dynamics of open-cage experiments, this finding does not influence the main results of the study. Small primary consumers (mostly small snails, amphipods, and midges) living on floating periphyton mats and in flocculent detritus (“floc”) were less abundant in the exclosures, indicative of a trophic cascade. Periphyton mat characteristics (i.e., biomass, chlorophyll a, TP) were not clearly or consistently affected by the exclosure, but TP in the floc was lower in exclosures. The collective cascading effects of large predators were consistent at both sites despite differences in drought frequency, stem density, and productivity.

Segregation of Palaemonid Shrimp Along an Everglades Estuarine Gradient: Do Multiple Species Have Similar Trophic Function?

Variation in physical gradients and production along estuaries can alter species compositions. Spatiotemporal variation in abundance and distribution of palaemonid shrimp species was investigated in relation to seasonal freshwater inputs and salinity in the Shark River Estuary, Everglades National Park, Florida, USA. Using trapping techniques, multiple sites were sampled repeatedly extending from the headwaters to the Gulf of Mexico. Stable isotope analyses were also performed on a subset of samples. Five palaemonid species occurred in the samples: Palaemonetes paludosus (Gibbes, 1850), Palaemonetes pugio (Holthuis, 1949), Palaemonetes intermedius (Holthuis, 1949), Palaemon floridanus (Chace, 1942), and Leander paulensis(Ortmann, 1897). Overall, shrimp catches in traps doubled in the dry season. Catches in the upper estuary were dominated by P.paludosus, particularly in the wet season, while catch per unit effort at the most downstream and highest salinity sites were dominated by P. floridanus. At mid-estuary, several species co-occurred. δ15n analyses revealed that most species filled similar roles in the community, with the exception of P. paludosus, which shifted from enrichment in the dry season to depletion in the wet season as it expanded downstream in the estuary. Palaemonid δ13C values varied between sites and seasons, with shrimp in upstream sites being more depleted. These data suggest that changes in salinity regimes resulting from Everglades restoration efforts may result in species replacement, with potential implications for trophic dynamics.

Does variation in movement tactics and trophic interactions among American alligators create habitat linkages?

1. Highly mobile top predators are hypothesized to spatially and/or temporally link disparate habitats through the combination of their movement and feeding patterns, but recent studies suggest that individual specialization in habitat use and feeding could keep habitats compartmentalized. 2.  We used passive acoustic telemetry and stable isotope analysis to investigate whether specialization in movement and feeding patterns of American alligators (Alligator mississippiensis) in an oligotrophic subtropical estuary created habitat linkages between marine and estuarine/freshwater food webs. 3.  Individual alligators adopted one of the three relatively distinct movement tactics that were linked to variation in diets. Fifty-six per cent of alligators regularly travelled from the upstream (freshwater/mid-estuary) areas into the downstream (marine-influenced) areas where salinities exceed those typically tolerated by alligators. Thirty-one per cent of the alligators made regular trips from the mid-estuarine habitat into the upstream habitat; 13% remained in the mid-estuary zone year-round. 4.  Stable isotopic analysis indicated that, unlike individuals remaining in the mid-estuary and upstream zones, alligators that used the downstream zone fed at least partially from marine food webs and likely moved to access higher prey abundance at the expense of salt stress. Therefore, ‘commuting’ alligators may link marine food webs with those of the estuary and marshes in the coastal Everglades and create an upstream vector for allochthonous nutrient inputs into the estuary. 5.  This study lends further support to the hypothesis that large-bodied highly mobile predators faced with trade-offs are likely to exhibit individual specialization leading to habitat linkages, rather than compartmentalization. However, the conditions under which this scenario occurs require further investigation.

Biotic and abiotic determinants of intermediate-consumer trophic diversity in the Florida everglades

Food-web structure can shape population dynamics and ecosystem functioning and stability. We investigated the structure of a food-web fragment consisting of dominant intermediate consumers (fishes and crayfishes) in the Florida Everglades, using stable isotope analysis to quantify trophic diversity along gradients of primary production (periphyton), disturbance (marsh drying) and intermediate-consumer density (a possible indicator of competition). We predicted that trophic diversity would increase with resource availability and decrease after disturbance, and that competition could result in greater trophic diversity by favouring resource partitioning. Total trophic diversity, measured by niche area, decreased with periphyton biomass and an ordination axis representing several bluegreen algae species. Consumers’ basal resource diversity, estimated by δ13C values, was similarly related to algal community structure. The range of trophic levels (δ15N range) increased with time since the most recent drying and reflooding event, but decreased with intermediate-consumer density, and was positively related to the ordination axis reflecting increases in green algae and decreases in filamentous bluegreen algae. Our findings suggest that algal quality, independent of quantity, influences food-web structure and demonstrate an indirect role of nutrient enrichment mediated by its effects on periphyton palatability and biomass. These results reveal potential mechanisms for anthropogenic effects on Everglades communities.

Indirect and direct controls of macroinvertebrates and small fish by abiotic factors and trophic interactions in the Florida Everglades

1. The roles of nutrients, disturbance and predation in regulating consumer densities have long been of interest, but their indirect effects have rarely been quantified in wetland ecosystems. The Florida Everglades contains gradients of hydrological disturbance (marsh drying) and nutrient enrichment (phosphorus), often correlated with densities of macroinvertebrate infauna (macroinvertebrates inhabiting periphyton), small fish and larger invertebrates, such as snails, grass shrimp, insects and crayfish. However, most causal relationships have yet to be quantified. 2.  We sampled periphyton (content and community structure) and consumer (small omnivores, carnivores and herbivores, and infaunal macroinvertebrates inhabiting periphyton) density at 28 sites spanning a range of hydrological and nutrient conditions and compared our data to seven a priori structural equation models. 3.  The best model included bottom-up and top-down effects among trophic groups and supported top-down control of infauna by omnivores and predators that cascaded to periphyton biomass. The next best model included bottom-up paths only and allowed direct effects of periphyton on omnivore density. Both models suggested a positive relationship between small herbivores and small omnivores, indicating that predation was unable to limit herbivore numbers. Total effects of time following flooding were negative for all three consumer groups even when both preferred models suggested positive direct effects for some groups. Total effects of nutrient levels (phosphorus) were positive for consumers and generally larger than those of hydrological disturbance and were mediated by changes in periphyton content. 4.  Our findings provide quantitative support for indirect effects of nutrient enrichment on consumers, and the importance of both algal community structure and periphyton biomass to Everglades food webs. Evidence for top-down control of infauna by omnivores was noted, though without substantially greater support than a competing bottom-up-only model.

Stereoselective synthesis of vinyl germanes and silanes. Applications of tris(trimethyl)germanes and silanes in Pd-catalyzed cross -coupling reactions

Although group 14 organometallic compounds (Si, Sn) have been well developed as transmetallation reagents in cross-coupling reactions, the application of organogermanium compounds as cross-coupling reagents is still a relatively new area with few papers published. This study aimed to develop methods for the synthesis of new classes of vinyl germane and vinyl silane compounds, mainly Z and E tris(trimethylsilyl)germanes and silanes, which were then applied to Pd-catalyzed cross-couplings with aryl and alkenyl halides. The stereoselective radical-mediated desulfonylation of vinyl sulfones with tris(trimethyl)germanium or silane hydrides provided access to the synthesis of trans vinyl germanes or silanes. Alternatively hydrogermylation or hydrosilylation of terminal alkynes gave cis vinyl germanes or silanes. The application of these new classes of organometallic compounds in cross-coupling reactions with various aryl and alkenyl halides under aqueous [NaOH/H2O2/Pd(PPh 3)4] and anhydrous [KH/t-BuOOH/Pd(PPh 3)4] oxidative conditions were investigated. ^ It was found that the vinyl tris(trimethylsilyl)germanes successfully underwent Pd-catalyzed cross-couplings with aryl and alkenyl halides and aryl triflates under aqueous and anhydrous oxidative conditions. These procedures provided examples of "ligand-free" Pd-catalyzed coupling of organogermanes with aryl and alkenyl halides. Interestingly, couplings with fluorinated vinyl germanes appeared to occur more easily than with the corresponding (α-fluoro)vinyl stannanes and silanes since neither addition of an extra ligand nor activation with fluoride was necessary. The vinyl tris(trimethyl)silanes were found to be alternative substrates for the Hiyama reaction. The coupling of TTMS-silanes with various aryl, heteroaryl as well as alkenyl halides proceeded smoothly upon treatment with hydrogen peroxide in the presence of sodium hydroxide and fluoride ion. ^

Synthesis of multisubstituted halo -olefins via Pd-catalyzed cross -coupling reactions. Applications in nucleoside chemistry

The enzyme S-adenosyl-L-homocysteine (AdoHcy) hydrolase effects hydrolytic cleavage of AdoHcy to adenosine (Ado) and L-homocysteine (Hcy). The cellular levels of AdoHcy and Hcy are critical because AdoHcy is a potent feedback inhibitor of crucial transmethylation enzymes. Also, elevated plasma levels of Hcy in humans have been shown to be a risk factor in coronary artery disease. ^ On the basis of the previous finding that AdoHcy hydrolase is able to add the enzyme-sequestered water molecule across the 5',6'-double bond of (halo or dihalohomovinyl)-adenosines causing covalent binding inhibition, we designed and synthesized AdoHcy analogues with the 5',6'-olefin motif incorporated in place of the carbon-5' and sulfur atoms. From the available synthetic methods we chose two independent approaches: the first approach was based on the construction of a new C5'-C6' double bond via metathesis reactions, and the second approach was based on the formation of a new C6'-C7' single bond via Pd-catalyzed cross-couplings. Cross-metathesis of the suitably protected 5'-deoxy-5'-methyleneadenosine with racemic 2-amino-5-hexenoate in the presence of Hoveyda-Grubb's catalyst followed by standard deprotection afforded the desired analogue as 5' E isomer of the inseparable mixture of 9'R/S diastereomers. Metathesis of chiral homoallylglycine [(2S)-amino-5-hexenoate] produced AdoHcy analogue with established stereochemistry E at C5'atom and S at C9' atom. The 5'-bromovinyl analogue was synthesized using the bromination-dehydrobromination strategy with pyridinium tribromide and DBU. ^ Since literature reports on the Pd-catalyzed monoalkylation of dihaloalkenes (Csp2-Csp3 coupling) were scarce, we were prompted to undertake model studies on Pd-catalyzed coupling between vinyl dihalides and alkyl organometallics. The 1-fluoro-1-haloalkenes were found to undergo Negishi couplings with alkylzinc bromides to give multisubstituted fluoroalkenes. The alkylation was trans-selective affording pure Z-fluoroalkenes. The highest yields were obtained with PdCl 2(dppb) catalyst, but the best stereochemical outcome was obtained with less reactive Pd(PPh3)4. Couplings of 1,1-dichloro-and 1,1-dibromoalkenes with organozinc reagents resulted in the formation of monocoupled 1-halovinyl product. ^

Trait Contributions to Fish Community Assembly Emerge From Trophic Interactions in an Individual-Based Model

Community ecology seeks to understand and predict the characteristics of communities that can develop under different environmental conditions, but most theory has been built on analytical models that are limited in the diversity of species traits that can be considered simultaneously. We address that limitation with an individual-based model to simulate assembly of fish communities characterized by life history and trophic interactions with multiple physiological tradeoffs as constraints on species performance. Simulation experiments were carried out to evaluate the distribution of 6 life history and 4 feeding traits along gradients of resource productivity and prey accessibility. These experiments revealed that traits differ greatly in importance for species sorting along the gradients. Body growth rate emerged as a key factor distinguishing community types and defining patterns of community stability and coexistence, followed by egg size and maximum body size. Dominance by fast-growing, relatively large, and fecund species occurred more frequently in cases where functional responses were saturated (i.e. high productivity and/or prey accessibility). Such dominance was associated with large biomass fluctuations and priority effects, which prevented richness from increasing with productivity and may have limited selection on secondary traits, such as spawning strategies and relative size at maturation. Our results illustrate that the distribution of species traits and the consequences for community dynamics are intimately linked and strictly dependent on how the benefits and costs of these traits are balanced across different conditions.