Conformation of substituted polyacetylenes in solution : relationship between electronic properties and local order

A study of the chain conformation in solutions of polyphenylacetylene and poly(2-octyne) has been performed. The two polymers differ in many ways : polyphenylacetylene gives a red solution while poly(2-octyne) is transparent and, a marked difference on the chain rigidity is observed : the statistical length are 45 Å and 135 Å respectively. From the study of these two systems, one deduces that curvature fluctuations play a minor role on the π electrons localization, and that the torsion between monomer units is the pertinent parameter to understand the chain conformation and the π electrons localization.

(Dimethylamino)borylene and Related Complexes of Electron-Rich Metal Fragments: Generation of Nucleophile-Resistant Cations by Spontaneous Halide Ejection

Spontaneous halide ejection from a three-coordinate Lewis acid has been shown to offer a remarkable new route to cationic metal complexes featuring a linear, multiply bonded boron-donor Ligand. The exploitation of electron-rich [CpM(PR3)(2)] fragments within boryl systems of the type LnMB(hal)NR2 leads to the spontaneous formation in polar solvents of chemically robust borylene complexes, [LnM(BNR2)](+), with exceptionally low electrophilicity and short M-B bonds. This is reflected by M-B distances (ca. 1.80 angstrom for FeB systems) which are more akin to alkyl-/aryl-substituted borylene complexes and, perhaps most strikingly, by the very low exothermicity associated with the binding of pyridine to the two-coordinate boron center (Delta H = -7.4 kcal mol(-1), cf. -40.7 kcal mol(-1) for BCl3). Despite the strong pi electron release from the metal fragment implied by this suppressed reactivity and by such short M-B bonds, the barrier to rotation about the Fe=B bond in the unsymmetrical variant [CpFe(dmpe)(BN{C6H4OMe-4}Me)](+) is found to be very small (ca. 2.9 kcal mol(-1)). This apparent contradiction is rationalized by the orthogonal orientations of the HOMO and HOMO-2 orbitals of the [CpML2](+) fragment, which mean that the M-B pi interaction does not fall to zero even in the highest energy conformation.

Toxicity and imaging of multi-walled carbon nanotubes in human macrophage cells.

Multi-walled carbon nanotubes (MWNTs) have been proposed for use in many applications and concerns about their potential effect on human health have led to the interest in understanding the interactions between MWNTs and human cells. One important technique is the visualisation of the intracellular distribution of MWNTs. We exposed human macrophage cells to unpurified MWNTs and found that a decrease in cell viability was correlated with uptake of MWNTs due to mainly necrosis. Cells treated with purified MWNTs and the main contaminant Fe(2)O(3) itself yielded toxicity only from the nanotubes and not from the Fe(2)O(3). We used 3-D dark-field scanning transmission electron microscopy (DF-STEM) tomography of freeze-dried whole cells as well as confocal and scanning electron microscopy (SEM) to image the cellular uptake and distribution of unpurified MWNTs. We observed that unpurified MWNTs entered the cell both actively and passively frequently inserting through the plasma membrane into the cytoplasm and the nucleus. These suggest that MWNTs may cause incomplete phagocytosis or mechanically pierce through the plasma membrane and result in oxidative stress and cell death.

Efecto de biofertilizantes sobre el desarrollo y rendimiento del maíz (Zea mays L.) variedad NB-6

Se estudió el efecto de mezclas de biofertilizantes (microorganismos efectivos (ME), cascarilla de arroz, aserrín, estiércol de ganado, gallinaza y pulpa de café) en el crecimiento, desarrollo y rendimiento del maíz, variedad NB-6. La fertilización química (N, P, K y Urea 46%) fue utilizada como tratamiento de comparación. Se evaluó biomasa de hojas, biomasa de tallos, biomasa de panoja y espiga (bracteas, raquis y granos), así como biomasa total y área foliar. Se correlacionó cada indicador con la edad del cultivo, para ello se seleccionaron, en la mayoria de los casos, ecuaciones cuadráticas .. Se efectuó análisis de varianza para los indicadores del crecimiento en cada momento de muestreo. Se utilizo la prueba de Duncan en los casos requeridos. El tratamiento 5 (NPK: 12-24-12, Urea 46%}, tuvo el mayor incremento en los indicadores de crecimiento. El tratamiento 4 (cascarilla de arroz, gallinaza, estiércol de ganado y ME) ocupó el segundo lugar. El tratamiento 2 (cascarilla de arroz, estiércol de ganado, aserrín y ME) tuvo el menor efecto sobre el desarrollo. El tratamiento 4 (cascarilla de arroz, gallinaza, estiércol de ganado y ME) produjo los mayores rendimientos del grano(2 101 kg ha·l ), significativamente superior a los tratamientos 6 (testigo absoluto) y 2 (cascarilla de arroz. estiércol de ganado, aserrin y ME). En los restantes tratamientos no se encontraron diferencias significativas. El tratamiento 2 (cascarilla de arroz, estiércol de ganado, aserrin y ME} produjo los menores rendimientos del grano ( 1240.6 kg ha-1), significativamente inferior al resto de tratamientos, excepto el 6 (testigo absoluto).

Análisis estratégico de la industria de la construcción en España

[ES] El sector de la construcción tiene, en España, una notable importancia, por su aportación al PIB (del entorno del 10%) y al empleo (en torno al 10%) y porque aglutina un amplio tejido empresarial. El deterioro de la situación económica y la saturación del mercado residencial han llevado a una fuerte contracción de la actividad constructiva, después una larga época de crecimiento.

Enpresaren estrategia konpetitiboa errendimendu handiko lan-sistemen faktore baldintzatzaile gisa

Lan honen helburua enpresaren estrategia konpetitiboak Errendimendu Altuko Lan-Sistemen (EALS) ezarpenean zeresanik izan dezakeen aztertzea da, hau da, sistema hauen ezarpenean faktore baldintzatzaile bezala jokatu dezakeen edo ez analizatzea. Giza Baliabideen Zuzendaritza Estrategikoaren esparruan ikerketa asko egin dira “praktika onenen” potentzialtasunean estrategia konpetitiboaren jokaera aztertu dutenak, zehazki, Giza Baliabideen Zuzendaritza-Errendimendua binomioan duen eragina ikertu dutenak. Baina hauetan batez ere bere izaera moderatzailea aztertu da ikuspegi kontingentean oinarrituz. Izaera baldintzatzaile hau aztertzeko helburuarekin, lehenik eta behin literaturaren azterketa egiten dugu. Giza Baliabideen Zuzendaritza eta estrategia konpetitiboen arteko harremana lant zen duten ereduak berrikusten ditugu eta estrategia hauek EALS-kin erlazionat zen dituzten lanak ere kontutan hartzen dira. Ondoren, eta bereziki Porter-ek (1985) proposatutako estrategia konpetitiboei buruzko tipologian oinarritzen den eredua aztertuz, bertatik eratortzen diren konklusioak proposatzen dira. Horrez gain, aurrera begira EALS-n ikerketa ildo honetan sakondu beharko liratekeen urratsak proposatzen dira.

Proceedings of the Nineteenth Annual Symposium on Sea Turtle Conservation and Biology, 2-6 March 1999 South Padre Island, Texas, U.S.A.

The 19th Annual Symposium on Sea Turtle Biology and Conservation was the largest to date. The beautiful venue was the South Padre Island Convention Centre on South Padre Island, Texas from March 2-6, 1999. Key features of the 19th were invited talks on the theme The Promise, the Pain, and the Progress of 50 years of Sea Turtle Research and Conservation, a mini-symposium on the Kemp's ridley and an increased emphasis on high quality poster sessions. Hosts for the meeting included Texas A&M University, the Texas Sea Grant College Program, The Gladys Porter Zoo and Sea Turtle, Inc. Co-sponsors included the National Marine Fisheries Service-Southeast Fisheries Science Center, the National Marine Fisheries Service-Protected Resources Branch, Padre Island National Seashore and the U.S. Fish and Wildlife Service. With the assistance of Jack Frazier, we were fortunate to obtain a $30,000 grant from the David and Lucile Packard Foundation. This grant provided travel support to 49 individuals from 24 nations who presented a total of 50 presentations. (PDF contains 309 pages)

The economic contribution of whalewatching to regional economies: Perspectives from two National Marine Sanctuaries

Whenever human beings have looked out on the sea, they have seen whales. First from the shore and later from ships when humanity entered the ocean realm as seafarers, we have responded to seeing these creatures with awe and wonder. Even when we hunted whales, a period well chronicled both in history and in literature, the sight of a whale brought an adrenaline rush that was not totally linked to potential economic gain. The first trips on boats specifically to watch, rather than hunt, whales began around 45 years ago in Southern California where the migrating gray whales, seen in the distance from land, drew vessels out for a closer look. Since that time whalewatching has boomed, currently conducted in over 40 countries around the world, including Antarctica, and estimated by economists at the Whale and Dolphin Conservation Society to have a 1999 worldwide economic value of around $800 million USD. The economic contribution to local coastal communities is particularly significant in developing countries and those where declining fish populations (and in some cases like the Japanese, international bans on whaling) have driven harvesters to look for viable alternatives. Clearly, whalewatching is now, in many places around the world, a small but thriving part of the regional economy. Like in the days of whaling, we still get the rush, but for some, money is back contributing to the physiological response. (PDF contains 90 pages.)

Bis(thiophenolate)pyridine pincer ligands and trivalent zirconocene complexes relevant to early transition metal polymerization catalysts

Two major topics are covered: the first chapter is focused on the development of post-metallocene complexes for propylene polymerization. The second and third chapters investigate the consequences of diisobutylaluminum hydride (HAlⁱBu₂) additives in zirconocene based polymerization systems.

The synthesis, structure, and solution behavior of early metal complexes with a new tridentate LX₂ type ligand, bis(thiophenolate)pyridine ((SNS) = (2-C₆H₄S)₂-2,6-C₅H₃N) are investigated. SNS complexes of Ti, Zr, and Ta having dialkylamido coligands were synthesized and structurally characterized. The zirconium complex, (SNS)Zr(NMe₂)₂, displays C₂ symmetry in the solid state. Solid-state structures of tantalum complexes (SNS)Ta(NMe₂)₃ and (SNS)TaCl(NEt₂)₂ also display pronounced C₂ twisting of the SNS ligand. 1D and 2D NMR experiments show that (SNS)Ta(NMe₂)₃ is fluxional with rotation about the Ta N(amide) bonds occurring on the NMR timescale. The fluxional behavior of (SNS)TaCl(NEt₂)₂ in solution was also studied by variable temperature ¹H NMR. Observation of separate signals for the diastereotopic protons of the methylene unit of the diethylamide indicates that the complex remains locked on the NMR timescale in one diastereomeric conformation at temperatures below -50 °C.

Reduction of Zr(IV) metallocenium cations with sodium amalgam (NaHg) produces EPR signals assignable to Zr(III) metallocene complexes. Thus, chloro-bridged heterobinuclear ansa-zirconocenium cation [((SBI))Zr(μ-Cl)₂AlMe₂]⁺B(C₆F₅)_4¯ (SBI = rac-dimethylsilylbis(1-indenyl)), gives rise to an EPR signal assignable to the complex (SBI)Zr^III(μ-Cl)₂AlMe₂, while (SBI)Zr^III-Me and (SBI)Zr^III(-H)2AlⁱBu₂ are formed by reduction of [(SBI)Zr(μ-Me)₂AlMe₂]⁺B(C₆F₅)_4¯ and [(SBI)Zr(μ-H)₃(AlⁱBu₂)₂]⁺B(C₆F₅)4¯, respectively. These products are also formed, along with (SBI)Zr^III-ⁱBu and [(SBI)Zr^III]⁺ AlR4¯ when (SBI)ZrMe₂ reacts with HAlⁱBu₂, eliminating isobutane en route to the Zr(III) complex. Studies concerning the interconversion reactions between these and other (SBI)Zr(III) complexes and reaction mechanisms involved in their formation are also reported.

The addition of HAlⁱBu₂ to precatalyst [(SBI)Zr(µ-H)₃(AlⁱBu₂)₂]⁺ significantly slows the polymerization of propylene and changes the kinetics of polymerization from 1st to 2nd order with respect to propylene. This is likely due to competitive inhibition by HAlⁱBu₂. When the same reaction is investigated using [(ⁿBuCp)₂Zr(μ-H)₃(AlⁱBu₂)₂]⁺, hydroalumination between propylene and HAlⁱBu₂ is observed instead of propylene polymerization.

Damping and saturation of a second order electron plasma wave echo

A description is given of experimental work on the damping of a second order electron plasma wave echo due to velocity space diffusion in a low temperature magnetoplasma. Sufficient precision was obtained to verify the theoretically predicted cubic rather than quadratic or quartic dependence of the damping on exciter separation. Compared to the damping predicted for Coulomb collisions in a thermal plasma in an infinite magnetic field, the magnitude of the damping was approximately as predicted, while the velocity dependence of the damping was weaker than predicted. The discrepancy is consistent with the actual non-Maxwellian electron distribution of the plasma.

In conjunction with the damping work, echo amplitude saturation was measured as a function of the velocity of the electrons contributing to the echo. Good agreement was obtained with the predicted J₁ Bessel function amplitude dependence, as well as a demonstration that saturation did not influence the damping results.

Paths Towards High Efficiency Silicon Photovoltaics

While photovoltaics hold much promise as a sustainable electricity source, continued cost reduction is necessary to continue the current growth in deployment. A promising path to continuing to reduce total system cost is by increasing device efficiency. This thesis explores several silicon-based photovoltaic technologies with the potential to reach high power conversion efficiencies. Silicon microwire arrays, formed by joining millions of micron diameter wires together, were developed as a low cost, low efficiency solar technology. The feasibility of transitioning this to a high efficiency technology was explored. In order to achieve high efficiency, high quality silicon material must be used. Lifetimes and diffusion lengths in these wires were measured and the action of various surface passivation treatments studied. While long lifetimes were not achieved, strong inversion at the silicon / hydrofluoric acid interface was measured, which is important for understanding a common measurement used in solar materials characterization.

Cryogenic deep reactive ion etching was then explored as a method for fabricating high quality wires and improved lifetimes were measured. As another way to reach high efficiency, growth of silicon-germanium alloy wires was explored as a substrate for a III-V on Si tandem device. Patterned arrays of wires with up to 12% germanium incorporation were grown. This alloy is more closely lattice matched to GaP than silicon and allows for improvements in III-V integration on silicon.

Heterojunctions of silicon are another promising path towards achieving high efficiency devices. The GaP/Si heterointerface and properties of GaP grown on silicon were studied. Additionally, a substrate removal process was developed which allows the formation of high quality free standing GaP films and has wide applications in the field of optics.

Finally, the effect of defects at the interface of the amorphous silicon heterojuction cell was studied. Excellent voltages, and thus efficiencies, are achievable with this system, but the voltage is very sensitive to growth conditions. We directly measured lateral transport lengths at the heterointerface on the order of tens to hundreds of microns, which allows carriers to travel towards any defects that are present and recombine. This measurement adds to the understanding of these types of high efficiency devices and may aid in future device design.