Relative intensity noise transfer in higher-order distributed amplification through ultra-long fiber cavities

Among the different possible amplification solutions offered by Raman scattering in optical fibers, ultra-long Raman lasers are particularly promising as they can provide quasi-losless second order amplification with reduced complexity, displaying excellent potential in the design of low-noise long-distance communication systems. Still, some of their advantages can be partially offset by the transfer of relative intensity noise from the pump sources and cavity-generated Stokes to the transmitted signal. In this paper we study the effect of ultra-long cavity design (length, pumping, grating reflectivity) on the transfer of RIN to the signal, demonstrating how the impact of noise can be greatly reduced by carefully choosing appropriate cavity parameters depending on the intended application of the system. © 2010 Copyright SPIE - The International Society for Optical Engineering.

Collimation of a D-D Neutron Generator for Clinical Implementation of Neutron Stimulated Emission Computed Tomography: a Monte Carlo Study

This work is an investigation into collimator designs for a deuterium-deuterium (DD) neutron generator for an inexpensive and compact neutron imaging system that can be implemented in a hospital. The envisioned application is for a spectroscopic imaging technique called neutron stimulated emission computed tomography (NSECT).

Previous NSECT studies have been performed using a Van-de-Graaff accelerator at the Triangle Universities Nuclear Laboratory (TUNL) in Duke University. This facility has provided invaluable research into the development of NSECT. To transition the current imaging method into a clinically feasible system, there is a need for a high-intensity fast neutron source that can produce collimated beams. The DD neutron generator from Adelphi Technologies Inc. is being explored as a possible candidate to provide the uncollimated neutrons. This DD generator is a compact source that produces 2.5 MeV fast neutrons with intensities of 1012 n/s (4π). The neutron energy is sufficient to excite most isotopes of interest in the body with the exception of carbon and oxygen. However, a special collimator is needed to collimate the 4π neutron emission into a narrow beam. This work describes the development and evaluation of a series of collimator designs to collimate the DD generator for narrow beams suitable for NSECT imaging.

A neutron collimator made of high-density polyethylene (HDPE) and lead was modeled and simulated using the GEANT4 toolkit. The collimator was designed as a 52 x 52 x 52 cm3 HDPE block coupled with 1 cm lead shielding. Non-tapering (cylindrical) and tapering (conical) opening designs were modeled into the collimator to permit passage of neutrons. The shape, size, and geometry of the aperture were varied to assess the effects on the collimated neutron beam. Parameters varied were: inlet diameter (1-5 cm), outlet diameter (1-5 cm), aperture diameter (0.5-1.5 cm), and aperture placement (13-39 cm). For each combination of collimator parameters, the spatial and energy distributions of neutrons and gammas were tracked and analyzed to determine three performance parameters: neutron beam-width, primary neutron flux, and the output quality. To evaluate these parameters, the simulated neutron beams are then regenerated for a NSECT breast scan. Scan involved a realistic breast lesion implanted into an anthropomorphic female phantom.

This work indicates potential for collimating and shielding a DD neutron generator for use in a clinical NSECT system. The proposed collimator designs produced a well-collimated neutron beam that can be used for NSECT breast imaging. The aperture diameter showed a strong correlation to the beam-width, where the collimated neutron beam-width was about 10% larger than the physical aperture diameter. In addition, a collimator opening consisting of a tapering inlet and cylindrical outlet allowed greater neutron throughput when compared to a simple cylindrical opening. The tapering inlet design can allow additional neutron throughput when the neck is placed farther from the source. On the other hand, the tapering designs also decrease output quality (i.e. increase in stray neutrons outside the primary collimated beam). All collimators are cataloged in measures of beam-width, neutron flux, and output quality. For a particular NSECT application, an optimal choice should be based on the collimator specifications listed in this work.

[N]pT ensemble and finite-size-scaling study of the critical isostructural transition in the generalized exponential model of index 4.

First-order transitions of system where both lattice site occupancy and lattice spacing fluctuate, such as cluster crystals, cannot be efficiently studied by traditional simulation methods, which necessarily fix one of these two degrees of freedom. The difficulty, however, can be surmounted by the generalized [N]pT ensemble [J. Chem. Phys. 136, 214106 (2012)]. Here we show that histogram reweighting and the [N]pT ensemble can be used to study an isostructural transition between cluster crystals of different occupancy in the generalized exponential model of index 4 (GEM-4). Extending this scheme to finite-size scaling studies also allows us to accurately determine the critical point parameters and to verify that it belongs to the Ising universality class.

Numerical detection of the Gardner transition in a mean-field glass former.

Recent theoretical advances predict the existence, deep into the glass phase, of a novel phase transition, the so-called Gardner transition. This transition is associated with the emergence of a complex free energy landscape composed of many marginally stable sub-basins within a glass metabasin. In this study, we explore several methods to detect numerically the Gardner transition in a simple structural glass former, the infinite-range Mari-Kurchan model. The transition point is robustly located from three independent approaches: (i) the divergence of the characteristic relaxation time, (ii) the divergence of the caging susceptibility, and (iii) the abnormal tail in the probability distribution function of cage order parameters. We show that the numerical results are fully consistent with the theoretical expectation. The methods we propose may also be generalized to more realistic numerical models as well as to experimental systems.

Intra-pulse transition between ion acceleration mechanisms in intense laser-foil interactions

Multiple ion acceleration mechanisms can occur when an ultrathin foil is irradiated with an intense laser pulse, with the dominant mechanism changing over the course of the interaction. Measurement of the spatial-intensity distribution of the beam of energetic protons is used to investigate the transition from radiation pressure acceleration to transparency-driven processes. It is shown numerically that radiation pressure drives an increased expansion of the target ions within the spatial extent of the laser focal spot, which induces a radial deflection of relatively low energy sheath-accelerated protons to form an annular distribution. Through variation of the target foil thickness, the opening angle of the ring is shown to be correlated to the point in time transparency occurs during the interaction and is maximized when it occurs at the peak of the laser intensity profile. Corresponding experimental measurements of the ring size variation with target thickness exhibit the same trends and provide insight into the intra-pulse laser-plasma evolution.

Dynamique des ambiances lumineuses - approche basée sur la photométrie vidéo d’espaces de transition

Les variations de la lumière naturelle lors du passage d’un espace à un autre caractérisent de manière complexe, mais importante le design d’un bâtiment. Cette adaptation visuelle s’inscrit dans un processus spatiotemporel et influe sur le confort et le bien-être de ses occupants. La littérature fait état du peu de connaissances de la relation lumière espace-temps. Cette recherche propose donc d’étudier cette relation spatio-temporelle existant entre la lumière et l’espace, afin de qualifier un parcours architectural au moyen d’une expérimentation in situ et de segments filmiques. La recherche combine l’utilisation d’un luminance-mètre, d’une caméra vidéo et d’une méthode d’analyse d’images numériques afin de permettre l’évaluation des qualités spatio-temporelles de la lumière. Le parcours architectural est analysé selon la diversité et l’intensité des ambiances lumineuses en fonction du temps permettant de décrire les perceptions visuelles d’espaces transitions. Cette méthode dynamique offre un potentiel d’analyse et de création aux concepteurs désireux d’enrichir le design de séquences spatiales en favorisant la diversité lumineuse dans l’expérience architecturale. Mots clefs: adaptation visuelle, analyse d’images, ambiance lumineuse, contraste, éclairage naturel, espaces transitions, lumière perception visuelle, vidéo, spatio-temporel.

Measurement of Training Intensity and Work During Submaximal Isokinetic Progressive Resistance Training Protocols

Physical exercise programmes are routinely prescribed in clinical practice to treat impairments, improve activity and participation in daily life because of their known physiological, health and psychological benefits (RCP, 2009). Progressive resistance exercise is a type of exercise prescribed specifically to improve skeletal muscle strength (Latham et al., 2004). The effectiveness of progressive resistance exercise varies considerably between studies and populations. This thesis focuses on how training parameters influence the delivery of progressive resistance exercise. In order to appropriately evaluate the influence of training parameters, this thesis argues the need to record training performance and the total work completed by participants as prescribed by training protocols. In the first study, participants were taken through a series of protocols differentiated by the intensity and volume of training. Training intensity was defined as a proportion of the mean peak torque achieved during maximal voluntary contractions and was set at 80% and 40% respectively of the MVC mean peak torque. Training volume was defined as the total external work achieved over the training period. Measures of training performance were developed to accurately report the intensity, repetitions and work completed during the training period. A second study evaluated training performance of the training protocols over repeated sessions. These protocols were then applied to 3 stroke survivors. Study 1 found sedentary participants could achieve a differentiated training intensity. Participants completing the high and low intensity protocols trained at 80% and 40% respectively of the MVC mean peak torque. The total work achieved in the high intensity low repetition protocol was lower than the total work achieved in the low intensity high repetition protocol. With repeated practice, study 2 found participants were able to improve in their ability to perform manoeuvres as shown by a reduction in the variation of the mean training intensity achieving total work as specified by the protocol to a lower margin of error. When these protocols were applied to 3 stroke survivors, they were able to achieve the specified training intensity but they were not able to achieve the total work as expected for the protocol. This is likely to be due to an inability in achieving a consistent force throughout the contraction. These results demonstrate evaluation of training characteristics and support the need to record and report training performance characteristics during progressive resistance exercise, including the total work achieved, in order to elucidate the influence of training parameters on progressive resistance exercise. The lack of accurate training performance may partly explain the inconsistencies between studies on optimal training parameters for progressive resistance exercise.

Physical and chemical kinetics of structural build-up of cement suspensions

Abstract : The structural build-up of fresh cement-based materials has a great impact on their structural performance after casting. Accordingly, the mixture design should be tailored to adapt the kinetics of build-up given the application on hand. The rate of structural build-up of cement-based suspensions at rest is a complex phenomenon affected by both physical and chemical structuration processes. The structuration kinetics are strongly dependent on the mixture’s composition, testing parameters, as well as the shear history. Accurate measurements of build-up rely on the efficiency of the applied pre-shear regime to achieve an initial well-dispersed state as well as the applied stress during the liquid-solid transition. Studying the physical and chemical mechanisms of build-up of cement suspensions at rest can enhance the fundamental understanding of this phenomenon. This can, therefore, allow a better control of the rheological and time-dependent properties of cement-based materials. The research focused on the use of dynamic rheology in investigating the kinetics of structural build-up of fresh cement pastes. The research program was conducted in three different phases. The first phase was devoted to evaluating the dispersing efficiency of various disruptive shear techniques. The investigated shearing profiles included rotational, oscillatory, and combination of both. The initial and final states of suspension’s structure, before and after disruption, were determined by applying a small-amplitude oscillatory shear (SAOS). The difference between the viscoelastic values before and after disruption was used to express the degree of dispersion. An efficient technique to disperse concentrated cement suspensions was developed. The second phase aimed to establish a rheometric approach to dissociate and monitor the individual physical and chemical mechanisms of build-up of cement paste. In this regard, the non-destructive dynamic rheometry was used to investigate the evolutions of both storage modulus and phase angle of inert calcium carbonate and cement suspensions. Two independent build-up indices were proposed. The structural build-up of various cement suspensions made with different cement contents, silica fume replacement percentages, and high-range water reducer dosages was evaluated using the proposed indices. These indices were then compared to the well-known thixotropic index (Athix.). Furthermore, the proposed indices were correlated to the decay in lateral pressure determined for various cement pastes cast in a pressure column. The proposed pre-shearing protocol and build-up indices (phases 1 and 2) were then used to investigate the effect of mixture’s parameters on the kinetics of structural build-up in phase 3. The investigated mixture’s parameters included cement content and fineness, alkali sulfate content, and temperature of cement suspension. Zeta potential, calorimetric, spectrometric measurements were performed to explore the corresponding microstructural changes in cement suspensions, such as inter-particle cohesion, rate of Brownian flocculation, and nucleation rate. A model linking the build-up indices and the microstructural characteristics was developed to predict the build-up behaviour of cement-based suspensions The obtained results showed that oscillatory shear may have a greater effect on dispersing concentrated cement suspension than the rotational shear. Furthermore, the increase in induced shear strain was found to enhance the breakdown of suspension’s structure until a critical point, after which thickening effects dominate. An effective dispersing method is then proposed. This consists of applying a rotational shear around the transitional value between the linear and non-linear variations of the apparent viscosity with shear rate, followed by an oscillatory shear at the crossover shear strain and high angular frequency of 100 rad/s. Investigating the evolutions of viscoelastic properties of inert calcite-based and cement suspensions and allowed establishing two independent build-up indices. The first one (the percolation time) can represent the rest time needed to form the elastic network. On the other hand, the second one (rigidification rate) can describe the increase in stress-bearing capacity of formed network due to cement hydration. In addition, results showed that combining the percolation time and the rigidification rate can provide deeper insight into the structuration process of cement suspensions. Furthermore, these indices were found to be well-correlated to the decay in the lateral pressure of cement suspensions. The variations of proposed build-up indices with mixture’s parameters showed that the percolation time is most likely controlled by the frequency of Brownian collisions, distance between dispersed particles, and intensity of cohesion between cement particles. On the other hand, a higher rigidification rate can be secured by increasing the number of contact points per unit volume of paste, nucleation rate of cement hydrates, and intensity of inter-particle cohesion.

IoT Based Pain Management using Physiological Parameters

The continuous technology evaluation is benefiting our lives to a great extent. The evolution of Internet of things and deployment of wireless sensor networks is making it possible to have more connectivity between people and devices used extensively in our daily lives. Almost every discipline of daily life including health sector, transportation, agriculture etc. is benefiting from these technologies. There is a great potential of research and refinement of health sector as the current system is very often dependent on manual evaluations conducted by the clinicians. There is no automatic system for patient health monitoring and assessment which results to incomplete and less reliable heath information. Internet of things has a great potential to benefit health care applications by automated and remote assessment, monitoring and identification of diseases. Acute pain is the main cause of people visiting to hospitals. An automatic pain detection system based on internet of things with wireless devices can make the assessment and redemption significantly more efficient. The contribution of this research work is proposing pain assessment method based on physiological parameters. The physiological parameters chosen for this study are heart rate, electrocardiography, breathing rate and galvanic skin response. As a first step, the relation between these physiological parameters and acute pain experienced by the test persons is evaluated. The electrocardiography data collected from the test persons is analyzed to extract interbeat intervals. This evaluation clearly demonstrates specific patterns and trends in these parameters as a consequence of pain. This parametric behavior is then used to assess and identify the pain intensity by implementing machine learning algorithms. Support vector machines are used for classifying these parameters influenced by different pain intensities and classification results are achieved. The classification results with good accuracy rates between two and three levels of pain intensities shows clear indication of pain and the feasibility of this pain assessment method. An improved approach on the basis of this research work can be implemented by using both physiological parameters and electromyography data of facial muscles for classification.

Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.

Investigations into the mechanism of orotidine 5'-monophosphate decarboxylase: Sources of substrate destabilization and transition state stabilization

Orotidine 5′-monophosphate decarboxylase (OMPDC) achieves a rarely paralleled rate acceleration, yet the catalytic basis prompting this enhancement have yet to be fully elucidated. To accomplish decarboxylation, OMPDC must overcome the high energy barrier due to the localized anionic charge of the intermediate. Mechanistic studies employing enzyme mutagenesis and product or intermediate analogues were used to investigate possible transition state stabilization by a carbene resonance structure. Viability of the carbene structure depends upon a key hydrogen bond between O4 of the substrate and the amide backbone of a conserved serine or threonine. Substitution of the conserved residue with Pro resulted in a kcat/KM of 1 M-1s-1; deletion of the FUMP O4 resulted in a product analogue that does not undergo H6 exchange or inhibit decarboxylation. Hence, indirect evidence reveals the O4-backbone interaction plays an important role for binding and catalysis. OMPDC likely has honed multiple mechanisms to attain its remarkable catalysis. The successful crystallizations of OMPDC a decade ago sparked hypotheses that structure and sequence conserved residues induced productive strain on the substrate-enzyme complex. Here, we demonstrate a new source of stress: a hydrophobic pocket adjacent to the OMP carboxylate that exhibits kinetic parameters characteristic of substrate destabilization. Substitution of these residues with hydrophilic side-chains, by providing hydrogen-bonding partners, decreased kcat by 10 to 10^4–fold. The same substitutions display very little change in the rate of product H6 exchange, supporting that this hydrophobic pocket affects the substrate-enzyme complex before the transition state. We also provide evidence that hydrophilic residues can insert water molecules into the pocket with detrimental effects to catalysis.

Riffe und fazielle Entwicklung der florigemma-Bank (Korallenoolith, Oxfordium) im Süntel und östlichen Wesergebirge (NW-Deutschland

During the Sedimentation of the platform carbonate deposits of the Korallenoolith Formation (middle Oxfordian to early Kimmeridgian) small buildups ofcorals formed in the Lower Saxony Basin. These bioconstructions are restricted to particular horizons (Untere Korallenbank,ßorigenuna-Bank Member etc.) and represent patch reefs and biostromes. In this study, the development of facies, fossil assemblages, spatial distribution of fossils, and reefs of the ßorigenuna-Bank Member (upper Middle Oxfordian) in the Süntel Mts and the eastern Wesergebirge Mts is described; the formation of reefs is discussed in detail. Twelve facies types are described and interpreted. They vary between high-energy deposits as well winnowed oolites and quiet-water lagoonal mudstones. Owing to the significance of biota, micro- and macrofossils are systematically described. The reefs are preserved in growth position, are characterized by numerous corresponding features and belong to a certain reef type. According to their size, shape and framework, they represent patch reefs, coral knobs (sensu James, 1983), coral thrombolite reefs (sensu Leinfelder et al., 1994) or “Klein- and Mitteldickichte” (sensu Laternser, 2001). Their growth fabric corresponds to the superstratal (dense) pillarstone (sensu Insalaco, 1998). As the top of the ßorigenuna-Bank displays an erosional unconformity (so-called Hauptdiskontinuität), the top of the reefs are erosionally capped. Their maximum height amounts to at least the maximum thickness of the ßorigenuna-Bank which does not exceed 4 metres. The diversity of coral fauna of the reefs is relatively low; a total of 13 species is recorded. The coral community is over- whelmingly dominated by the thin-branched ramose Thamnasteria dendroidea (Lamouroux) that forms aggregations of colonies (77?. dendroidea thickets). Leafy to platy Fungiastrea arachnoides (Parkinson) and Thamnasteria concinna (Goldfuss) occur subordinately, other species are only of minor importance. In a few cases, the reef-core consisting of Th. dendroidea thickets is laterally encrusted by platy F. arachnoides and Th. concinna colonies, and microbial carbonates. This zonation reflects probably a succession of different reef builders as a result of changing environmental conditions (allogenic succession). Moreover, some reefs are overlain by a biostrome made of large Solenopora jurassica nodules passing laterally in a nerinean bed. Mikrobial carbonates promoted reef growth and favoured the preservation of reef organismn in their growth position or in situ. They exhibit a platy, dendroid, or reticulate growth form or occur as downward-facing hemispheroids. According to their microstructure, they consist of a peloidal, clotted, or unstructured fabric (predominately layered and poorly structured thrombolite as well as clotted leiolite) (sensu Schmid, 1996). Abundant endo- and epibiontic organisms (bivalves, gastropods, echinoids, asteroids, ophiuroids, crabs etc) are linked to the reefs. With regard to their guild structure, the reefs represent occurrences at which only a few coral species serve as builder. Moreover, microbial carbonates contribute to both building and binding of the reefs. Additional binder as well as baffler are present, but not abundant. According to the species diversity, the dweller guild comprises by far the highest number of invertebrate taxa. The destroyer guild chiefly encompasses bivalves. The composition of the reef community was influenced by the habitat structure of the Th. dendroidea thickets. Owing to the increase in encrusting organisms and other inhabitants of the thickets, the locational factors changed, since light intensity and hydrodynamic energy level and combined parameters as oxygen supply declined in the crowded habitat. Therefore a characteristic succession of organisms is developed that depends on and responds to changing environmental conditions („community replacement sequence“). The succession allows the differentiation of different stages. It started after the cessation of the polyps with boring organisms and photoautotrophic micro-encrusters (calcareous algae, Lithocodium aggregatum). Following the death of these pioneer organisms, encrusting and adherent organisms (serpulids, „Terebella“ species, bryozoans, foraminifers, thecideidinids, sklerospongid and pharetronid sponges, terebratulids), small mobile organisms (limpets), and microbial induced carbonates developed. The final stage in the community replacement sequence gave rise to small cryptic habitats and organisms that belong to these caves (cryptobionts, coelobites). The habitat conditions especially favoured small non-rigid demosponges (“soft sponges”) that tolerate reduced water circulation. Reef rubble is negligible, so that the reefs are bordered by fossiliferous micritic limestone passing laterally in micritic limestone. Approximately 10% of the study area (outcropping florigemma-Bank) corresponds to reefal deposits whereas the remaining 90% encompass lagoonal inter-reefal deposits. The reef development is a good example for the interaction between reef growth, facies development and sea-level changes. It was initiated by a sea-level rise (transgression) and corresponding decrease in the hydrodynamic energy level. Colonization and reef growth took place on a coarse-grained Substrate composed of oncoids, larger foraminifers and bioclasts. Reef growth took place in a calm marine lagoonal setting. Increasing abundance of spherical coral morphs towards the Northeast (section Kessiehausen, northwestem Süntel Mts) reflects higher turbidity and a facies transition to coral occurrences of the ßorigenuna-Bank Member in the adjacent Deister Mts. The reef growth was neither influenced by stonns nor by input of siliciclastic deposits, and took place in short time - probably in only a thousand years under most probably mesotrophic conditions. The mass appearance of solenoporids and nerineids in the upper part of the ßorigenuna-Bank Member point to enhanced nutrient level as a result of regression. In addition, this scenario of fluctuations in nutrient availability seems to be responsible for the cessation of reef corals. The sea level fall reached its climax in the subaerial exposure and palaeokarst development of the florigemma-Bank. The reef building corals are typical pioneer species. The blade-like, flattened F. amchnoides colonies are characterized by their light porous calcium carbonate skeleton, which is a distinct advantage in soft bottom environment. Thus, they settled on soft bottom exposing the large parts of its surface to the incoming light. On the other hand, in response to their light requirements they were also able to settle shaded canopy structures or reef caves. Th. dendroidea is an opportunistic coral species in very shallow, well illuminated marine environment. Their thin and densely spaced branches led to a very high surface/volume ratio of the colonies that were capable to exploit incoming light due to their small thamasterioid calices characterized by “highly integrated polyps”. In addition, sideward coalescence of branches during colony growth led to a wave-resistant framework and favoured the authochthonous preservation of the reefs. Asexual reproduction by fragmented colonies promoted reef development as Th. dendroidea thickets laterally extend over the sea floor or new reefs have developed from broken fragments of parent colonies. Similar build ups with Th. dendroidea as a dominant or frequent reef building coral species are known from the Paris Basin and elsewhere from the Lower Saxony Basin (Kleiner Deister Mts). These buildups developed in well-illuminated shallow water and encompass coral reefs or coral thrombolite reefs. Intra- and inter-reef deposits vary between well-winnowed reef debris limestone and mudstones representing considerably calmer conditions. Solenoporid, nerineids and diceratides belong to the characteristic fossils of these occurrences. However, diceratides are missing in theflorigemma-Bank Member. Th. dendroidea differs in its colonization of low- to high-energy environment from recent ramose scleractinian corals (e.g., Acropora and Porites sp.). The latter are restricted to agitated water habitats creating coral thickets and carpets. According to the morphologic plasticity of Th. dendroidea, thick-branched colonies developed in a milieu of high water energy, whereas fragile, wide- and thin-branched colonies prevail in low-energy settings. Due to its relatively rapid growth, Th. dendroidea was able to keep pace with increased Sedimentation rates. 68 benthonic foraminiferan species/taxa have been recognized in thin sections. Agglutinated foraminifers (textulariids) predominate when compared with rotaliids and milioliids. Numerous species are restricted to a certain facies type or occur in higher population densities, in particular Everticyclammina sp., a larger agglutinated foraminifer that occurs in rock building amounts. Among the 25 reef dwelling foraminiferal species, a few were so far only known from Late Jurassic sponge reefs. Another striking feature is the frequency of adherent foraminiferal species. Fauna and flora, in particular dasycladaleans and agglutinated foraminifers, document palaeobiogeographic relationships to the Tethys and point to (sub)tropical conditions. Moreover, in Germany this foraminiferan assemblage is yet uncompared. In Southern Germany similar tethyan type assemblages are not present in strata as young as Middle Tithonian.

Engineering the transition from non-living to living matter

Re-creating and understanding the origin of life represents one of the major challenges facing the scientific community. We will never know exactly how life started on planet Earth, however, we can reconstruct the most likely chemical pathways that could have contributed to the formation of the first living systems. Traditionally, prebiotic chemistry has investigated the formation of modern life’s precursors and their self-organisation under very specific conditions thought to be ‘plausible’. So far, this approach has failed to produce a living system from the bottom-up. In the work presented herein, two different approaches are employed to explore the transition from inanimate to living matter. The development of microfluidic technology during the last decades has changed the way traditional chemical and biological experiments are performed. Microfluidics allows the handling of low volumes of reagents with very precise control. The use of micro-droplets generated within microfluidic devices is of particular interest to the field of Origins of Life and Artificial Life. Whilst many efforts have been made aiming to construct cell-like compartments from modern biological constituents, these are usually very difficult to handle. However, microdroplets can be easily generated and manipulated at kHz rates, making it suitable for high-throughput experimentation and analysis of compartmentalised chemical reactions. Therefore, we decided to develop a microfluidic device capable of manipulating microdroplets in such a way that they could be efficiently mixed, split and sorted within iterative cycles. Since no microfluidic technology had been developed before in the Cronin Group, the first chapter of this thesis describes the soft lithographic methods and techniques developed to fabricate microfluidic devices. Also, special attention is placed on the generation of water-in-oil microdroplets, and the subsequent modules required for the manipulation of the droplets such as: droplet fusers, splitters, sorters and single/multi-layer micromechanical valves. Whilst the first part of this thesis describes the development of a microfluidic platform to assist chemical evolution, finding a compatible set of chemical building blocks capable of reacting to form complex molecules with endowed replicating or catalytic activity was challenging. Abstract 10 Hence, the second part of this thesis focuses on potential chemistry that will ultimately possess the properties mentioned above. A special focus is placed on the formation of peptide bonds from unactivated amino acids, despite being one of the greatest challenges in prebiotic chemistry. As opposed to classic prebiotic experiments, in which a specific set of conditions is studied to fit a particular hypothesis, we took a different approach: we explored the effects of several parameters at once on a model polymerisation reaction, without constraints on hypotheses on the nature of optimum conditions or plausibility. This was facilitated by development of a new high-throughput automated platform, allowing the exploration of a much larger number of parameters. This led us to discover that peptide bond formation is less challenging than previously imagined. Having established the right set of conditions under which peptide bond formation was enhanced, we then explored the co-oligomerisation between different amino acids, aiming for the formation of heteropeptides with different structure or function. Finally, we studied the effect of various environmental conditions (rate of evaporation, presence of salts or minerals) in the final product distribution of our oligomeric products.

Optimization of the Ion Source-Mass Spectrometry Parameters in Non-Steroidal Anti-Inflammatory and Analgesic Pharmaceuticals Analysis by a Design of Experiments Approach

The flow rates of drying and nebulizing gas, heat block and desolvation line temperatures and interface voltage are potential electrospray ionization parameters as they may enhance sensitivity of the mass spectrometer. The conditions that give higher sensitivity of 13 pharmaceuticals were explored. First, Plackett-Burman design was implemented to screen significant factors, and it was concluded that interface voltage and nebulizing gas flow were the only factors that influence the intensity signal for all pharmaceuticals. This fractionated factorial design was projected to set a full 2(2) factorial design with center points. The lack-of-fit test proved to be significant. Then, a central composite face-centered design was conducted. Finally, a stepwise multiple linear regression and subsequently an optimization problem solving were carried out. Two main drug clusters were found concerning the signal intensities of all runs of the augmented factorial design. p-Aminophenol, salicylic acid, and nimesulide constitute one cluster as a result of showing much higher sensitivity than the remaining drugs. The other cluster is more homogeneous with some sub-clusters comprising one pharmaceutical and its respective metabolite. It was observed that instrumental signal increased when both significant factors increased with maximum signal occurring when both codified factors are set at level +1. It was also found that, for most of the pharmaceuticals, interface voltage influences the intensity of the instrument more than the nebulizing gas flowrate. The only exceptions refer to nimesulide where the relative importance of the factors is reversed and still salicylic acid where both factors equally influence the instrumental signal. Graphical Abstract ᅟ.