Chain-forming zintl antimonides as novel thermoelectric materials

Zintl phases, a subset of intermetallic compounds characterized by covalently-bonded "sub-structures," surrounded by highly electropositive cations, exhibit precisely the characteristics desired for thermoelectric applications. The requirement that Zintl compounds satisfy the valence of anions through the formation of covalent substructures leads to many unique, complex crystal structures. Such complexity often leads to exceptionally low lattice thermal conductivity due to the containment of heat in low velocity optical modes in the phonon dispersion. To date, excellent thermoelectric properties have been demonstrated in several Zintl compounds. However, compared with the large number of known Zintl phases, very few have been investigated as thermoelectric materials.

From this pool of uninvestigated compounds, we selected a class of Zintl antimonides that share a common structural motif: anionic moieties resembling infinite chains of linked MSb₄ tetrahedra, where $M$ is a triel element. The compounds discussed in this thesis (A₅M₂Sb₆ and A₃MSb₃, where A = Ca or Sr and M = Al, Ga and In) crystallize as four distinct, but closely related "chain-forming" structure types. This thesis describes the thermoelectric characterization and optimization of these phases, and explores the influence of their chemistry and structure on the thermal and electronic transport properties. Due to their large unit cells, each compound exhibits exceptionally low lattice thermal conductivity (0.4 - 0.6 W/mK at 1000 K), approaching the predicted glassy minimum at high temperatures. A combination of Density Functional calculations and classical transport models were used to explain the experimentally observed electronic transport properties of each compound. Consistent with the Zintl electron counting formalism, A₅M₂Sb₆ and A₃MSb₃ phases were found to have filled valence bands and exhibit intrinsic electronic properties. Doping with divalent transition metals (Zn²⁺ and Mn²⁺) on the M³⁺ site, or Na¹⁺ on the A³⁺ site allowed for rational control of the carrier concentration and a transition towards degenerate semiconducting behavior. In optimally-doped samples, promising peak zT values between 0.4 and 0.9 were obtained, highlighting the value of continued investigations of complex Zintl phases.

Economic Valuation of Ecosystem Services: Conflicts in Classification

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Mechanistic studies of reactions at the single-molecule level using microfluidics with applications in molecular diagnostics

Motivated by needs in molecular diagnostics and advances in microfabrication, researchers started to seek help from microfluidic technology, as it provides approaches to achieve high throughput, high sensitivity, and high resolution. One strategy applied in microfluidics to fulfill such requirements is to convert continuous analog signal into digitalized signal. One most commonly used example for this conversion is digital PCR, where by counting the number of reacted compartments (triggered by the presence of the target entity) out of the total number of compartments, one could use Poisson statistics to calculate the amount of input target.

However, there are still problems to be solved and assumptions to be validated before the technology is widely employed. In this dissertation, the digital quantification strategy has been examined from two angles: efficiency and robustness. The former is a critical factor for ensuring the accuracy of absolute quantification methods, and the latter is the premise for such technology to be practically implemented in diagnosis beyond the laboratory. The two angles are further framed into a “fate” and “rate” determination scheme, where the influence of different parameters is attributed to fate determination step or rate determination step. In this discussion, microfluidic platforms have been used to understand reaction mechanism at single molecule level. Although the discussion raises more challenges for digital assay development, it brings the problem to the attention of the scientific community for the first time.

This dissertation also contributes towards developing POC test in limited resource settings. On one hand, it adds ease of access to the tests by incorporating massively producible, low cost plastic material and by integrating new features that allow instant result acquisition and result feedback. On the other hand, it explores new isothermal chemistry and new strategies to address important global health concerns such as cyctatin C quantification, HIV/HCV detection and treatment monitoring as well as HCV genotyping.

Crystals that count! Physical principles and experimental investigations of DNA tile self-assembly

Algorithmic DNA tiles systems are fascinating. From a theoretical perspective, they can result in simple systems that assemble themselves into beautiful, complex structures through fundamental interactions and logical rules. As an experimental technique, they provide a promising method for programmably assembling complex, precise crystals that can grow to considerable size while retaining nanoscale resolution. In the journey from theoretical abstractions to experimental demonstrations, however, lie numerous challenges and complications.

In this thesis, to examine these challenges, we consider the physical principles behind DNA tile self-assembly. We survey recent progress in experimental algorithmic self-assembly, and explain the simple physical models behind this progress. Using direct observation of individual tile attachments and detachments with an atomic force microscope, we test some of the fundamental assumptions of the widely-used kinetic Tile Assembly Model, obtaining results that fit the model to within error. We then depart from the simplest form of that model, examining the effects of DNA sticky end sequence energetics on tile system behavior. We develop theoretical models, sequence assignment algorithms, and a software package, StickyDesign, for sticky end sequence design.

As a demonstration of a specific tile system, we design a binary counting ribbon that can accurately count from a programmable starting value and stop growing after overflowing, resulting in a single system that can construct ribbons of precise and programmable length. In the process of designing the system, we explain numerous considerations that provide insight into more general tile system design, particularly with regards to tile concentrations, facet nucleation, the construction of finite assemblies, and design beyond the abstract Tile Assembly Model.

Finally, we present our crystals that count: experimental results with our binary counting system that represent a significant improvement in the accuracy of experimental algorithmic self-assembly, including crystals that count perfectly with 5 bits from 0 to 31. We show some preliminary experimental results on the construction of our capping system to stop growth after counters overflow, and offer some speculation on potential future directions of the field.

Dinâmica de crescimento de Cedrela odorata L. (Meliaceae) na Floresta Atlântica do Estado do Rio de Janeiro: fenologia, atividade cambial e dendrocronologia

Ao longo do século XX, poucos estudos de dendrocronologia foram desenvolvidos com espécies de ambientes tropicais, em função da crença de que as condições climáticas nessas regiões não apresentavam variações suficientemente marcantes e regulares para induzir um ritmo anual de crescimento radial. A realização de trabalhos sobre esse tema nas últimas décadas revelou que a formação de anéis de crescimento anuais nos trópicos pode estar associada a fatores diversos, como: existência de estação seca bem definida, ocorrência de inundações sazonais, respostas ao comportamento fenológico, respostas ao fotoperíodo e a ritmos endógenos. O presente estudo tem por objetivo compreender a dinâmica de crescimento radial de uma espécie da Mata Atlântica se desenvolvendo em ambiente natural. Para tanto, propôs-se: i) investigar a periodicidade da atividade cambial e dos fatores que a influenciam; ii) estimar a idade e taxa de crescimento diamétrico e iii) correlacionar os fatores ambientais com os anéis de crescimento, em indivíduos de Cedrela odorata L. Para o estudo da atividade cambial, foram obtidas amostras de caule a 1,30 m do solo, contendo periderme, faixa cambial e xilema e floema secundários, por métodos não destrutivos. A fenologia vegetativa e a frutificação dos indivíduos amostrados foram acompanhadas durante todo o período do experimento. O material coletado foi processado segundo técnicas usuais em Anatomia Vegetal e analisado sob microscopia óptica e de fluorescência. Os dados de fotoperíodo, precipitação, temperatura e fenologia vegetativa foram correlacionados à atividade cambial. Para o estudo dos anéis de crescimento, as coletas também foram realizadas a 1,30 m do solo, por meio de sonda de Pressler. As amostras obtidas foram polidas e analisadas sob microscópio estereoscópio, para demarcação e aferição do número de anéis de crescimento, e a largura dos anéis foi mensurada para a determinação das taxas de crescimento radial. A série histórica de temperatura e precipitação foi correlacionada à cronologia dos anéis de crescimento. Os resultados indicaram que a atividade cambial segue um ritmo anual de crescimento, correlacionado à sazonalidade do fotoperíodo, da precipitação e da fenologia vegetativa. A análise dos anéis de crescimento permitiu estimar a idade dos indivíduos e determinar a taxa média de incremento e as taxas de incremento diamétrico acumulado e incremento médio anual para a espécie no sítio de estudo. Os dados de incremento radial evidenciaram a ausência de relação entre a idade e o diâmetro das árvores. A análise da variação na largura dos anéis não apresentou correlações significativas com os fatores climáticos analisados.

Análise de fadiga em pontes rodoviárias de concreto armado

As pontes rodoviárias de concreto armado estão sujeitas às ações dinâmicas variáveis devido ao tráfego de veículos sobre o tabuleiro. Estas ações dinâmicas podem gerar o surgimento das fraturas ou mesmo a sua propagação na estrutura. A correta consideração destes aspectos objetivou o desenvolvimento de um estudo, de forma a avaliar os esforços do tráfego de veículos pesados sobre o tabuleiro. As técnicas para a contagem de ciclos de esforços e a aplicação das regras de dano acumulado foram analisadas através das curvas S-N de diversas normas estudadas. A ponte rodoviária investigada é constituída por quatro vigas longitudinais, três transversinas e por um tabuleiro de concreto armado. O modelo computacional, desenvolvido para a análise dinâmica da ponte, foi concebido com base no emprego de técnicas usuais de discretização através do método dos elementos finitos. O modelo estrutural da obra de arte rodoviária estudada foi simulado com base no emprego de elementos finitos sólidos tridimensionais. Os veículos são representados a partir de sistemas massa-mola-amortecedor. O tráfego dessas viaturas é considerado mediante a simulação de comboios semi-infinitos, deslocando-se com velocidade constante sobre o tabuleiro da ponte. As conclusões deste trabalho versam acerca da vida útil de serviço dos elementos estruturais de pontes rodoviárias de concreto armado submetidas às ações dinâmicas provenientes do tráfego de veículos pesados sobre o tabuleiro.

Cavity Optomechanics at Millikelvin Temperatures

The field of cavity optomechanics, which concerns the coupling of a mechanical object's motion to the electromagnetic field of a high finesse cavity, allows for exquisitely sensitive measurements of mechanical motion, from large-scale gravitational wave detection to microscale accelerometers. Moreover, it provides a potential means to control and engineer the state of a macroscopic mechanical object at the quantum level, provided one can realize sufficiently strong interaction strengths relative to the ambient thermal noise. Recent experiments utilizing the optomechanical interaction to cool mechanical resonators to their motional quantum ground state allow for a variety of quantum engineering applications, including preparation of non-classical mechanical states and coherent optical to microwave conversion. Optomechanical crystals (OMCs), in which bandgaps for both optical and mechanical waves can be introduced through patterning of a material, provide one particularly attractive means for realizing strong interactions between high-frequency mechanical resonators and near-infrared light. Beyond the usual paradigm of cavity optomechanics involving isolated single mechanical elements, OMCs can also be fashioned into planar circuits for photons and phonons, and arrays of optomechanical elements can be interconnected via optical and acoustic waveguides. Such coupled OMC arrays have been proposed as a way to realize quantum optomechanical memories, nanomechanical circuits for continuous variable quantum information processing and phononic quantum networks, and as a platform for engineering and studying quantum many-body physics of optomechanical meta-materials.

However, while ground state occupancies (that is, average phonon occupancies less than one) have been achieved in OMC cavities utilizing laser cooling techniques, parasitic absorption and the concomitant degradation of the mechanical quality factor fundamentally limit this approach. On the other hand, the high mechanical frequency of these systems allows for the possibility of using a dilution refrigerator to simultaneously achieve low thermal occupancy and long mechanical coherence time by passively cooling the device to the millikelvin regime. This thesis describes efforts to realize the measurement of OMC cavities inside a dilution refrigerator, including the development of fridge-compatible optical coupling schemes and the characterization of the heating dynamics of the mechanical resonator at sub-kelvin temperatures.

We will begin by summarizing the theoretical framework used to describe cavity optomechanical systems, as well as a handful of the quantum applications envisioned for such devices. Then, we will present background on the design of the nanobeam OMC cavities used for this work, along with details of the design and characterization of tapered fiber couplers for optical coupling inside the fridge. Finally, we will present measurements of the devices at fridge base temperatures of T_f = 10 mK, using both heterodyne spectroscopy and time-resolved sideband photon counting, as well as detailed analysis of the prospects for future quantum applications based on the observed optically-induced heating.

Fiber-optic integration and efficient detection schemes for optomechanical resonators

With the advent of the laser in the year 1960, the field of optics experienced a renaissance from what was considered to be a dull, solved subject to an active area of development, with applications and discoveries which are yet to be exhausted 55 years later. Light is now nearly ubiquitous not only in cutting-edge research in physics, chemistry, and biology, but also in modern technology and infrastructure. One quality of light, that of the imparted radiation pressure force upon reflection from an object, has attracted intense interest from researchers seeking to precisely monitor and control the motional degrees of freedom of an object using light. These optomechanical interactions have inspired myriad proposals, ranging from quantum memories and transducers in quantum information networks to precision metrology of classical forces. Alongside advances in micro- and nano-fabrication, the burgeoning field of optomechanics has yielded a class of highly engineered systems designed to produce strong interactions between light and motion.

Optomechanical crystals are one such system in which the patterning of periodic holes in thin dielectric films traps both light and sound waves to a micro-scale volume. These devices feature strong radiation pressure coupling between high-quality optical cavity modes and internal nanomechanical resonances. Whether for applications in the quantum or classical domain, the utility of optomechanical crystals hinges on the degree to which light radiating from the device, having interacted with mechanical motion, can be collected and detected in an experimental apparatus consisting of conventional optical components such as lenses and optical fibers. While several efficient methods of optical coupling exist to meet this task, most are unsuitable for the cryogenic or vacuum integration required for many applications. The first portion of this dissertation will detail the development of robust and efficient methods of optically coupling optomechanical resonators to optical fibers, with an emphasis on fabrication processes and optical characterization.

I will then proceed to describe a few experiments enabled by the fiber couplers. The first studies the performance of an optomechanical resonator as a precise sensor for continuous position measurement. The sensitivity of the measurement, limited by the detection efficiency of intracavity photons, is compared to the standard quantum limit imposed by the quantum properties of the laser probe light. The added noise of the measurement is seen to fall within a factor of 3 of the standard quantum limit, representing an order of magnitude improvement over previous experiments utilizing optomechanical crystals, and matching the performance of similar measurements in the microwave domain.

The next experiment uses single photon counting to detect individual phonon emission and absorption events within the nanomechanical oscillator. The scattering of laser light from mechanical motion produces correlated photon-phonon pairs, and detection of the emitted photon corresponds to an effective phonon counting scheme. In the process of scattering, the coherence properties of the mechanical oscillation are mapped onto the reflected light. Intensity interferometry of the reflected light then allows measurement of the temporal coherence of the acoustic field. These correlations are measured for a range of experimental conditions, including the optomechanical amplification of the mechanics to a self-oscillation regime, and comparisons are drawn to a laser system for phonons. Finally, prospects for using phonon counting and intensity interferometry to produce non-classical mechanical states are detailed following recent proposals in literature.

Radioautographic method of determination of number of bacteria in water-bodies [Translation from: Informatsionnyi Byulleten Biologiya Vnutrennikh Vod No.26, 65-67, 1975]

The radioautographic method of determination of the number of autotrophic microorganisms was initially suggested for counting methane-oxidizing bacteria. With the help of this method colonies of hydrogen-oxidizing bacteria are differentiated even more clearly from heterotrophic. Under laboratory conditions it was shown that colonies grown on membrane filters from a pure culture of thionic bacteria on a nutrient medium with radio- active carbonate, give better prints on film. This method was tested by the authors for determining the number of these bacteria in the meromictic Lake Vae de San Juan during the expedition to Cuba in the summer of 1973. The study showed that that the thionic bacteria are found throughout the pelagial. It proved that the thionic bacteria can be well considered in water-bodies by the radioautographic method.

FUZZY SOLID SETS FOR MATHEMATICAL MORPHOLOGY AND OPTICAL IMPLEMENTATION

Fuzzy sets in the subject space are transformed to fuzzy solid sets in an increased object space on the basis of the development of the local umbra concept. Further, a counting transform is defined for reconstructing the fuzzy sets from the fuzzy solid sets, and the dilation and erosion operators in mathematical morphology are redefined in the fuzzy solid-set space. The algebraic structures of fuzzy solid sets can lead not only to fuzzy logic but also to arithmetic operations. Thus a fuzzy solid-set image algebra of two image transforms and five set operators is defined that can formulate binary and gray-scale morphological image-processing functions consisting of dilation, erosion, intersection, union, complement, addition, subtraction, and reflection in a unified form. A cellular set-logic array architecture is suggested for executing this image algebra. The optical implementation of the architecture, based on area coding of gray-scale values, is demonstrated. (C) 1995 Optical Society of America

Automatic identification and enumeration of algae

A good understanding of the population dynamics of algal communities is vital in many ecological and pollution studies of freshwater and oceanic systems. Present methods require manual counting and identification of algae and can take up to 90 min to obtain a statistically reliable count on a complex population. Several alternative techniques to accelerate the process have been tried on marine samples but none have been completely successful because insufficient effort has been put into verifying the technique before field trials. The objective of the present study has been to assess the potential of in vivo fluorescence of algal pigments as a means of automatically identifying algae. For this work total fluorescence spectroscopy was chosen as the observation technique.

Theoretical investigations of experimental gravitation

This thesis has two basic themes: the investigation of new experiments which can be used to test relativistic gravity, and the investigation of new technologies and new experimental techniques which can be applied to make gravitational wave astronomy a reality.

Advancing technology will soon make possible a new class of gravitation experiments: pure laboratory experiments with laboratory sources of non-Newtonian gravity and laboratory detectors. The key advance in techno1ogy is the development of resonant sensing systems with very low levels of dissipation. Chapter 1 considers three such systems (torque balances, dielectric monocrystals, and superconducting microwave resonators), and it proposes eight laboratory experiments which use these systems as detectors. For each experiment it describes the dominant sources of noise and the technology required.

The coupled electro-mechanical system consisting of a microwave cavity and its walls can serve as a gravitational radiation detector. A gravitational wave interacts with the walls, and the resulting motion induces transitions from a highly excited cavity mode to a nearly unexcited mode. Chapter 2 describes briefly a formalism for analyzing such a detector, and it proposes a particular design.

The monitoring of a quantum mechanical harmonic oscillator on which a classical force acts is important in a variety of high-precision experiments, such as the attempt to detect gravitational radiation. Chapter 3 reviews the standard techniques for monitoring the oscillator; and it introduces a new technique which, in principle, can determine the details of the force with arbitrary accuracy, despite the quantum properties of the oscillator.

The standard method for monitoring the oscillator is the "amplitude- and-phase" method (position or momentum transducer with output fed through a linear amplifier). The accuracy obtainable by this method is limited by the uncertainty principle. To do better requires a measurement of the type which Braginsky has called "quantum nondemolition." A well-known quantum nondemolition technique is "quantum counting," which can detect an arbitrarily weak force, but which cannot provide good accuracy in determining its precise time-dependence. Chapter 3 considers extensively a new type of quantum nondemolition measurement - a "back-action-evading" measurement of the real part X₁ (or the imaginary part X₂) of the oscillator's complex amplitude. In principle X₁ can be measured arbitrarily quickly and arbitrarily accurately, and a sequence of such measurements can lead to an arbitrarily accurate monitoring of the classical force.

Chapter 3 describes explicit gedanken experiments which demonstrate that X₁ can be measured arbitrarily quickly and arbitrarily accurately, it considers approximate back-action-evading measurements, and it develops a theory of quantum nondemolition measurement for arbitrary quantum mechanical systems.

In Rosen's "bimetric" theory of gravity the (local) speed of gravitational radiation v_g is determined by the combined effects of cosmological boundary values and nearby concentrations of matter. It is possible for v_g to be less than the speed of light. Chapter 4 shows that emission of gravitational radiation prevents particles of nonzero rest mass from exceeding the speed of gravitational radiation. Observations of relativistic particles place limits on v_g and the cosmological boundary values today, and observations of synchrotron radiation from compact radio sources place limits on the cosmological boundary values in the past.

Recent progress in the identification and determination of freshwater phytoplankton in the natural environment

The biomass of the phytoplankton and its composition is one of the most important factors in water quality control. Determination of the phytoplankton assemblage is usually done by microscopic analysis (Utermöhl's method). Quantitative estimations of the biovolume, by cell counting and cell size measurements, are time-consuming and normally are not done in routine water quality control. Several alternatives have been tried: computer-based image analysis, spectral fluorescence signatures, flow cytometry and pigment fingerprinting aided by high performance liquid chromatography (HPLC). The latter method is based on the fact that each major algal group of taxa contains a specific carotenoid which can be used for identification and relative quantification of the taxa in the total assemblage. This article gives a brief comparative introduction to the different techniques available and presents some recent results obtained by HPLC-based pigment fingerprinting, applied to three lakes of different trophic status. The results show that this technique yields reliable results from different lake types and is a powerful tool for studying the distribution pattern of the phytoplankton community in relation to water depth. However, some restrictions should be taken into account for the interpretation of routine data.

一种新的光学非球面度计算方法

提出了一种新的、能完全统一二次非球面与高次非球面的非球面度计算,且能直接得出最接近球的球心位置的计算方法面积长度法.该方法的计算内涵是两条相似曲线分别与某一固定点围成的面积应相等,且两条曲线的长度应非常接近.计算实例表明该方法计算结果准确,且易于编程,运算速度快.

Verificação à fadiga de pontes rodoviárias mistas (aço-concreto)

As pontes rodoviárias mistas (aço-concreto) estão sujeitadas às ações dinâmicas variáveis, por exemplo, devido ao tráfego de veículos sobre a superfície irregular do pavimento. Estas ações dinâmicas podem gerar a nucleação de fraturas ou mesmo a sua propagação sobre a estrutura. A correta consideração desses aspectos objetivou o desenvolvimento de uma metodologia de análise, com a finalidade de avaliar os níveis dos esforços e tensões oriundos do tráfego dos veículos sobre a superfície irregular do pavimento e, bem como, proceder uma verificação à fadiga de obras de arte rodoviárias em aço e mistas (aço-concreto). Para tal, as técnicas para a contagem de ciclos de tensão e a aplicação das regras de dano acumulado foram analisadas através de curvas do tipo S-N, associadas a diversas normas de projeto. A ponte rodoviária mista (aço-concreto) investigada neste estudo é constituída por quatro vigas de aço longitudinais e por um tabuleiro de concreto armado. O modelo numérico-computacional, desenvolvido para a análise dinâmica da ponte, foi concebido com base em técnicas usuais de discretização através do método dos elementos finitos. Simulam-se as almas das vigas de aço e as lajes de concreto do tabuleiro através de elementos finitos de casca. As mesas dessas vigas, transversinas e os enrijecedores são modelados por elementos de viga tridimensionais. Os veículos são representados a partir de sistemas "massa-mola-amortecedor". O tráfego dessas viaturas é considerado mediante a simulação de comboios semi-infinitos, deslocando-se com velocidade constante sobre a ponte. As conclusões da presente investigação versam acerca da vida útil de serviço dos elementos estruturais de pontes mistas (aço-concreto).