Alexander Agassiz, 1835-1910

Biography with photograph

Assessing societal vulnerability of U.S. Pacific Northwest communities to storm induced coastal change

Progressive increases in storm intensities and extreme wave heights have been documented along the U.S. West Coast. Paired with global sea level rise and the potential for an increase in El Niño occurrences, these trends have substantial implications for the vulnerability of coastal communities to natural coastal hazards. Community vulnerability to hazards is characterized by the exposure, sensitivity, and adaptive capacity of human-environmental systems that influence potential impacts. To demonstrate how societal vulnerability to coastal hazards varies with both physical and social factors, we compared community exposure and sensitivity to storm-induced coastal change scenarios in Tillamook (Oregon) and Pacific (Washington) Counties. While both are backed by low-lying coastal dunes, communities in these two counties have experienced different shoreline change histories and have chosen to use the adjacent land in different ways. Therefore, community vulnerability varies significantly between the two counties. Identifying the reasons for this variability can help land-use managers make decisions to increase community resilience and reduce vulnerability in spite of a changing climate. (PDF contains 4 pages)

Improving reporting of uncertainties in sea level rise assessments

Sea level rise (SLR) assessments are commonly used to identify the extent that coastal populations are at risk to flooding. However, the data and assumptions used to develop these assessments contain numerous sources and types of uncertainty, which limit confidence in the accuracy of modeled results. This study illustrates how the intersection of uncertainty in digital elevation models (DEMs) and SLR lead to a wide range of modeled outcomes. SLR assessments are then reviewed to identify the extent that uncertainty is documented in peer-reviewed articles. The paper concludes by discussing priorities needed to further understand SLR impacts. (PDF contains 4 pages)

Palladium-catalyzed asymmetric allylic alkylation: insights, application toward cyclopentanoid and cycloheptanoid molecules, and the total synthesis of several daucane sesquiterpenes

The asymmetric construction of quaternary stereocenters is a topic of great interest in the organic chemistry community given their prevalence in natural products and biologically active molecules. Over the last decade, the Stoltz group has pursued the synthesis of this challenging motif via a palladium-catalyzed allylic alkylation using chiral phosphinooxazoline (PHOX) ligands. Recent results indicate that the alkylation of lactams and imides consistently proceeds with enantioselectivities substantially higher than any other substrate class previously examined in this system. This observation prompted exploration of the characteristics that distinguish these molecules as superior alkylation substrates, resulting in newfound insights and marked improvements in the allylic alkylation of carbocyclic compounds.

General routes to cyclopentanoid and cycloheptanoid core structures have been developed that incorporate the palladium-catalyzed allylic alkylation as a key transformation. The unique reactivity of α-quaternary vinylogous esters upon addition of hydride or organometallic reagents enables divergent access to γ-quaternary acylcyclopentenes or cycloheptenones through respective ring contraction or carbonyl transposition pathways. Derivatization of the resulting molecules provides a series of mono-, bi-, and tricyclic systems that can serve as valuable intermediates for the total synthesis of complex natural products.

The allylic alkylation and ring contraction methodology has been employed to prepare variably functionalized bicyclo[5.3.0]decane molecules and enables the enantioselective total syntheses of daucene, daucenal, epoxydaucenal B, and 14-p-anisoyloxydauc-4,8-diene. This route overcomes the challenge of accessing β-substituted acylcyclopentenes by employing a siloxyenone to effect the Grignard addition and ring opening in a single step. Subsequent ring-closing metathesis and aldol reactions form the hydroazulene core of these targets. Derivatization of a key enone intermediate allows access to either the daucane sesquiterpene or sphenobolane diterpene carbon skeletons, as well as other oxygenated scaffolds.

The theory of long distance electron transfer reactions

The rate of electron transport between distant sites was studied. The rate depends crucially on the chemical details of the donor, acceptor, and surrounding medium. These reactions involve electron tunneling through the intervening medium and are, therefore, profoundly influenced by the geometry and energetics of the intervening molecules. The dependence of rate on distance was considered for several rigid donor-acceptor "linkers" of experimental importance. Interpretation of existing experiments and predictions for new experiments were made.

The electronic and nuclear motion in molecules is correlated. A Born-Oppenheimer separation is usually employed in quantum chemistry to separate this motion. Long distance electron transfer rate calculations require the total donor wave function when the electron is very far from its binding nuclei. The Born-Oppenheimer wave functions at large electronic distance are shown to be qualitatively wrong. A model which correctly treats the coupling was proposed. The distance and energy dependence of the electron transfer rate was determined for such a model.

Stopping power of gases for heavy ions

Pulse-height and time-of-flight methods have been used to measure the electronic stopping cross sections for projectiles of ¹²C, ¹⁶O, ¹⁹F, ²³Na, ²⁴Mg, and ²⁷Al, slowing in helium, neon, argon, krypton, and xenon. The ion energies were in the range 185 keV ≤ E ≤ 2560 keV.

A semiempirical calculation of the electronic stopping cross section for projectiles with atomic numbers between 6 and 13 passing through the inert gases has been performed using a modification of the Firsov model. Using Hartree-Slater-Fock orbitals, and summing over the losses for the individual charge states of the projectiles, good agreement has been obtained with the experimental data. The main features of the stopping cross section seen in the data, such as the Z₁ oscillation and the variation of the velocity dependence on Z₁ and Z₂, are present in the calculation. The inclusion of a modified form of the Bethe-Bloch formula as an additional term allows the increase of the velocity dependence for projectile velocities above v_o to be reproduced in the calculation.

An experimental study of a stellar neutron source: ^(13)C(α, n)^(16)O

Described in this thesis are measurements made of the thick-target neutron yield from the reaction ¹³C(α, n)¹⁶O. The yield was determined for laboratory bombarding energies between 0.475 and 0.700 MeV, using a stilbene crystal neutron detector and pulse-shape discrimination to eliminate gamma rays. Stellar temperatures between 2.5 and 4.5 x 10^{8 o}K are involved in this energy region. From the neutron yield was extracted the astrophysical cross-section factor S(E), which was found to fit a linear function: S(E) = [(5.48 ± 1.77) + (12.05 ± 3.91)E] x 10⁵ MeV-barns, center-of-mass system. The stellar rate of the ¹³C(α, n)¹⁶O reaction if calculated, and discussed with reference to helium burning and neutron production in the core of a giant star.

Results are also presented of measurements carried out on the reaction ⁹Be(α, n)¹²C, taken with a thin Be target. The bombarding energy-range covered was from 0.340 to 0.680 MeV, with excitation curves for the ground- and first excited-state neutrons being reported. Some angular distributions were also measured. Resonances were found at bombarding energies of E_LAB = 0.520 MeV (E_CM = 0.360 MeV, Γ ~ 55 keV CM, ωγ = 3.79 eV CM) and E_LAB = 0.600 MeV (E_CM = 0.415 MeV, Γ ˂ 4 keV CM, ωγ = 0.88 eV CM). The astrophysical rate of the ⁹Be(α, n)¹²C reaction due to these resonances is calculated.

Cloning and analysis of laccases from acinetobacter baumannii isolates

Laccases (benzenediol : oxygen oxi doreductases; EC 1.10.3.2) are wide spread i n nature. They are usually found in higher plants and fungi (Thurston 19 94; Mayer and Staples 2002), but recently some bacterial laccases have also been found . The first laccase studied was from Rhus vernicifera in 1883, a Japanese lacquer tree, fr om which the name laccase was derived (Yoshida , 1883). These enzymes belong to the group of bl ue multi - copper oxidases (MCOs) . They usually contain four copper atoms located in three distinct sites. Each site reacts differently to light. The Type 1 (T1) site copper atom absorbs intensely at 600 nm and emits the blue light , the Type 2 (T2) site copper atom is not visible in the absorption spectr um and last, the Type 3 (T3) site has two c opper atoms and absorbs at 330 nm ( Santhanam et al . , 2011; Quintanar et al . , 2007 ) . The protei n structure acts as a complex ligand for the catalytic coppers, providing them the right structure where changes between the reduction states are thermodynamically possible (Dub é , 2008 ) . These enzymes oxidize a surprisingly wide variety of organic and inorganic compounds like, diphenols, polyphenols, substituted phenols, diamines and a romatic amines, with concomitant reduction of molecular oxygen to water (Thurston , 1

O laboratório analítico: a psicologia de C.G. Jung examinada pela teoria do ator-rede

O psiquiatra suíço Carl Gustav Jung (1875-1961) é um dos principais nomes da psicologia e da psicoterapia do século XX. Algumas de suas maiores contribuições teórico-metodológicas são as idéias de realidade psíquica, complexo, arquétipo (inconsciente coletivo), processo de individuação, método dialético, método construtivo e imaginação ativa. A psicologia analítica de Jung, ao longo de sua formação, foi influenciada por diversas disciplinas, dentre elas a etnologia (ciências sociais). Este trabalho buscou dar continuidade a este processo de construção epistêmica, mediante exame das concepções de Jung por intermédio da teoria do ator-rede (TAR), uma importante corrente da sociologia contemporânea. Pretendeu-se também saber se a psicologia analítica se mantém atual ou se já é uma teoria e prática clínica anacrônicas. O principal autor relacionado à TAR a quem se recorreu neste trabalho foi o sociólogo francês Bruno Latour. De sua perspectiva, o acordo moderno, disjuntor de Natureza e Cultura, é insuficiente para explicar a complicação inerente às entidades que compõem a realidade. Para escapar das armadilhas conceptuais da modernidade, Latour opera com constructos tais como coletivo (social), ator-rede, proposição, vínculo e plasma. Além do pensamento de Latour, este trabalho valeu-se das idéias sociológicas de Gabriel Tarde e da influenciologia etnopsicanalítica de Tobie Nathan, aproveitando-se da afinidade teórica que compartilham com Latour. Nathan, por desenvolver uma prática em psicoterapia, permitiu propor à psicologia clínica de Jung determinadas questões que o enfoque mais estritamente sociológico de Latour não possibilitava. Uma vez expostas as concepções de Latour, Tarde e Nathan, apresentaram-se os elementos da psicologia analítica com os quais se esperava que elas fossem compatíveis. Concluiu-se que, apesar das diferenças, muitas aproximações são plausíveis entre psicologia analítica e TAR. Constatou-se que a concepção de Jung de um psiquismo multifacetado, em devir, cujos componentes se relacionam de diferentes maneiras, é comparável à noção de ator-rede trabalhada por Latour e à monadologia de Tarde. Verificou-se também que a abordagem pragmática e construtiva identificada na psicoterapia junguiana é em muitos aspectos análoga à prática da etnopsicanálise. Assim, foi possível afirmar que a TAR e a psicologia analítica podem formar aliança.

Giza-erlazioen psikologia: adimen emozionala eta gizarte harremanak

[eus] Egungo gizartean, konpetentzia emozional maila baxuak “analfabetismo emozionala” jarri du agerian (Goleman, 1996). Arrazoi honengatik, adimen emozionala jorratu beharra dago, bai familia eta baita hezkuntza arloan ere. Hau guztiagatik, ikerketa honen xede nagusia, 7-11 urte tarteko umeen trebetasun sozialak kooperazioaren bitartez sustatzea da; izan ere, garai horretan, gizabanakoaren bizitza soziala goreneko intentsitatera heltzen da. Honetarako, Bilboko Pagasarribide ikastetxean (Lehen Hezkuntzako 5.maila) jorratzeko unitate didaktikoa aurkezten da. Beraz, bertako bi jardueratan lortutako emaitzak kontuan hartuz, baieztatu ahal da, honi esker, ikasleen trebetasun sozialak garatu direla eta emozionalki adimentsuagoak izatea lortuko dutela unitate didaktiko hau bere osotasunean jorratu ondoren.

Variation in movement patterns of red drum (Sciaenops ocellatus) inferred from conventional tagging and ultrasonic telemetry

We used 25 years of conventional tagging data (n= 6173 recoveries) and 3 years of ultrasonic telemetry data (n=105 transmitters deployed) to examine movement rates and directional preferences of four age classes of red drum (Sciaenops ocellatus) in estuarine and coastal waters of North Carolina. Movement rates of conventionally tagged red drum were dependent on the age, region, and season of tagging. Age-1 and age-2 red drum tagged along the coast generally moved along the coast, whereas fish tagged in oligohaline waters far from the coast were primarily recovered in coastal regions in fall months. Adult (age-4+) red drum moved from overwintering grounds on the continental shelf through inlets into Pamlico Sound in spring and summer months and departed in fall. Few tagged red drum were recovered in adjacent states (0.6% of all recoveries); however, some adult red drum migrated seasonally from overwintering grounds in coastal North Carolina northward to Virginia in spring, returning in fall. Age-2 transmitter-tracked red drum displayed seasonal emigration from a small tributary, but upstream and downstream movements within the tributary were correlated with fluctuating salinity regimes and not season. Large-scale conventional tagging and ultrasonic telemetry programs can provide valuable insights into the complex movement patterns of estuarine fish.

Effects of a large fishing closure on benthic communities in the western Gulf of Maine: recovery from the effects of gillnets and otter trawls

The recovery of benthic communities inside the western Gulf of Maine fishing closure area was evaluated by comparing invertebrate assemblages at sites inside and outside of the closure four to six years after the closure was established. The major restriction imposed by the closure was a year-round prohibition of bottom gillnets and otter trawls. A total of 163 seafloor sites (~half inside and half outside the closure) within a 515-km2 study area were sampled with some combination of Shipek grab, Wildco box corer, or underwater video. Bottom types ranged from mud (silt and clay) to boulders, and the effects of the closure on univariate measures (total density, biomass, taxonomic richness) of benthos varied widely among sediment types. For sites with predominantly mud sediments, there were mixed effects on inside and outside infauna and no effect on epifauna. For sites with mainly sand sediments, there were higher density, biomass, and taxonomic richness for infauna inside the closure, but no significant effects on epifauna. For sites dominated by gravel (which included boulders in some areas), there were no effects on infauna but strong effects on epifaunal density and taxonomic richness. For fishing gear, the data indicated that infauna recovered in sand from the impacts of otter trawls operated inside the closure but that they did not recover in mud, and that epifauna recovered on gravel bottoms from the impact of gillnets used inside the closure. The magnitudes of impact and recovery, however, cannot be inferred directly from our data because of a confounding factor of different fishing intensities outside the closure for a direct comparison of preclosure and postclosure data. The overall negative impact of trawls is likely underestimated by our data, whereas the negative impact of gillnets is likely overestimated.