Crystallization on the Mesoscale : Self-Assembly of Iron Oxide Nanocubes into Mesocrystals

Self-assembly of nanoparticles is a promising route to form complex, nanostructured materials with functional properties. Nanoparticle assemblies characterized by a crystallographic alignment of the nanoparticles on the atomic scale, i.e. mesocrystals, are commonly found in nature with outstanding functional and mechanical properties. This thesis aims to investigate and understand the formation mechanisms of mesocrystals formed by self-assembling iron oxide nanocubes. We have used the thermal decomposition method to synthesize monodisperse, oleate-capped iron oxide nanocubes with average edge lengths between 7 nm and 12 nm and studied the evaporation-induced self-assembly in dilute toluene-based nanocube dispersions. The influence of packing constraints on the alignment of the nanocubes in nanofluidic containers has been investigated with small and wide angle X-ray scattering (SAXS and WAXS, respectively). We found that the nanocubes preferentially orient one of their {100} faces with the confining channel wall and display mesocrystalline alignment irrespective of the channel widths.  We manipulated the solvent evaporation rate of drop-cast dispersions on fluorosilane-functionalized silica substrates in a custom-designed cell. The growth stages of the assembly process were investigated using light microscopy and quartz crystal microbalance with dissipation monitoring (QCM-D). We found that particle transport phenomena, e.g. the coffee ring effect and Marangoni flow, result in complex-shaped arrays near the three-phase contact line of a drying colloidal drop when the nitrogen flow rate is high. Diffusion-driven nanoparticle assembly into large mesocrystals with a well-defined morphology dominates at much lower nitrogen flow rates. Analysis of the time-resolved video microscopy data was used to quantify the mesocrystal growth and establish a particle diffusion-based, three-dimensional growth model. The dissipation obtained from the QCM-D signal reached its maximum value when the microscopy-observed lateral growth of the mesocrystals ceased, which we address to the fluid-like behavior of the mesocrystals and their weak binding to the substrate. Analysis of electron microscopy images and diffraction patterns showed that the formed arrays display significant nanoparticle ordering, regardless of the distinctive formation process.  We followed the two-stage formation mechanism of mesocrystals in levitating colloidal drops with real-time SAXS. Modelling of the SAXS data with the square-well potential together with calculations of van der Waals interactions suggests that the nanocubes initially form disordered clusters, which quickly transform into an ordered phase.

Shape and chemically anisotropic colloidal particles: A theoretical study of their structure, phase behavior, and slow dynamics

A detailed non-equilibrium state diagram of shape-anisotropic particle fluids is constructed. The effects of particle shape are explored using Naive Mode Coupling Theory (NMCT), and a single particle Non-linear Langevin Equation (NLE) theory. The dynamical behavior of non-ergodic fluids are discussed. We employ a rotationally frozen approach to NMCT in order to determine a transition to center of mass (translational) localization. Both ideal and kinetic glass transitions are found to be highly shape dependent, and uniformly increase with particle dimensionality. The glass transition volume fraction of quasi 1- and 2- dimensional particles fall monotonically with the number of sites (aspect ratio), while 3-dimensional particles display a non-monotonic dependence of glassy vitrification on the number of sites. Introducing interparticle attractions results in a far more complex state diagram. The ideal non-ergodic boundary shows a glass-fluid-gel re-entrance previously predicted for spherical particle fluids. The non-ergodic region of the state diagram presents qualitatively different dynamics in different regimes. They are qualified by the different behaviors of the NLE dynamic free energy. The caging dominated, repulsive glass regime is characterized by long localization lengths and barrier locations, dictated by repulsive hard core interactions, while the bonding dominated gel region has short localization lengths (commensurate with the attraction range), and barrier locations. There exists a small region of the state diagram which is qualified by both glassy and gel localization lengths in the dynamic free energy. A much larger (high volume fraction, and high attraction strength) region of phase space is characterized by short gel-like localization lengths, and long barrier locations. The region is called the attractive glass and represents a 2-step relaxation process whereby a particle first breaks attractive physical bonds, and then escapes its topological cage. The dynamic fragility of fluids are highly particle shape dependent. It increases with particle dimensionality and falls with aspect ratio for quasi 1- and 2- dimentional particles. An ultralocal limit analysis of the NLE theory predicts universalities in the behavior of relaxation times, and elastic moduli. The equlibrium phase diagram of chemically anisotropic Janus spheres and Janus rods are calculated employing a mean field Random Phase Approximation. The calculations for Janus rods are corroborated by the full liquid state Reference Interaction Site Model theory. The Janus particles consist of attractive and repulsive regions. Both rods and spheres display rich phase behavior. The phase diagrams of these systems display fluid, macrophase separated, attraction driven microphase separated, repulsion driven microphase separated and crystalline regimes. Macrophase separation is predicted in highly attractive low volume fraction systems. Attraction driven microphase separation is charaterized by long length scale divergences, where the ordering length scale determines the microphase ordered structures. The ordering length scale of repulsion driven microphase separation is determined by the repulsive range. At the high volume fractions, particles forgo the enthalpic considerations of attractions and repulsions to satisfy hard core constraints and maximize vibrational entropy. This results in site length scale ordering in rods, and the sphere length scale ordering in Janus spheres, i.e., crystallization. A change in the Janus balance of both rods and spheres results in quantitative changes in spinodal temperatures and the position of phase boundaries. However, a change in the block sequence of Janus rods causes qualitative changes in the type of microphase ordered state, and induces prominent features (such as the Lifshitz point) in the phase diagrams of these systems. A detailed study of the number of nearest neighbors in Janus rod systems reflect a deep connection between this local measure of structure, and the structure factor which represents the most global measure of order.

Microfluidic platforms for the characterization of in meso membrane protein crystallization

Membrane proteins, which reside in the membranes of cells, play a critical role in many important biological processes including cellular signaling, immune response, and material and energy transduction. Because of their key role in maintaining the environment within cells and facilitating intercellular interactions, understanding the function of these proteins is of tremendous medical and biochemical significance. Indeed, the malfunction of membrane proteins has been linked to numerous diseases including diabetes, cirrhosis of the liver, cystic fibrosis, cancer, Alzheimer's disease, hypertension, epilepsy, cataracts, tubulopathy, leukodystrophy, Leigh syndrome, anemia, sensorineural deafness, and hypertrophic cardiomyopathy.1-3 However, the structure of many of these proteins and the changes in their structure that lead to disease-related malfunctions are not well understood. Additionally, at least 60% of the pharmaceuticals currently available are thought to target membrane proteins, despite the fact that their exact mode of operation is not known.4-6 Developing a detailed understanding of the function of a protein is achieved by coupling biochemical experiments with knowledge of the structure of the protein. Currently the most common method for obtaining three-dimensional structure information is X-ray crystallography. However, no a priori methods are currently available to predict crystallization conditions for a given protein.7-14 This limitation is currently overcome by screening a large number of possible combinations of precipitants, buffer, salt, and pH conditions to identify conditions that are conducive to crystal nucleation and growth.7,9,11,15-24 Unfortunately, these screening efforts are often limited by difficulties associated with quantity and purity of available protein samples. While the two most significant bottlenecks for protein structure determination in general are the (i) obtaining sufficient quantities of high quality protein samples and (ii) growing high quality protein crystals that are suitable for X-ray structure determination,7,20,21,23,25-47 membrane proteins present additional challenges. For crystallization it is necessary to extract the membrane proteins from the cellular membrane. However, this process often leads to denaturation. In fact, membrane proteins have proven to be so difficult to crystallize that of the more than 66,000 structures deposited in the Protein Data Bank,48 less than 1% are for membrane proteins, with even fewer present at high resolution (< 2Å)4,6,49 and only a handful are human membrane proteins.49 A variety of strategies including detergent solubilization50-53 and the use of artificial membrane-like environments have been developed to circumvent this challenge.43,53-55 In recent years, the use of a lipidic mesophase as a medium for crystallizing membrane proteins has been demonstrated to increase success for a wide range of membrane proteins, including human receptor proteins.54,56-62 This in meso method for membrane protein crystallization, however, is still by no means routine due to challenges related to sample preparation at sub-microliter volumes and to crystal harvesting and X-ray data collection. This dissertation presents various aspects of the development of a microfluidic platform to enable high throughput in meso membrane protein crystallization at a level beyond the capabilities of current technologies. Microfluidic platforms for protein crystallization and other lab-on-a-chip applications have been well demonstrated.9,63-66 These integrated chips provide fine control over transport phenomena and the ability to perform high throughput analyses via highly integrated fluid networks. However, the development of microfluidic platforms for in meso protein crystallization required the development of strategies to cope with extremely viscous and non-Newtonian fluids. A theoretical treatment of highly viscous fluids in microfluidic devices is presented in Chapter 3, followed by the application of these strategies for the development of a microfluidic mixer capable of preparing a mesophase sample for in meso crystallization at a scale of less than 20 nL in Chapter 4. This approach was validated with the successful on chip in meso crystallization of the membrane protein bacteriorhodopsin. In summary, this is the first report of a microfluidic platform capable of performing in meso crystallization on-chip, representing a 1000x reduction in the scale at which mesophase trials can be prepared. Once protein crystals have formed, they are typically harvested from the droplet they were grown in and mounted for crystallographic analysis. Despite the high throughput automation present in nearly all other aspects of protein structure determination, the harvesting and mounting of crystals is still largely a manual process. Furthermore, during mounting the fragile protein crystals can potentially be damaged, both from physical and environmental shock. To circumvent these challenges an X-ray transparent microfluidic device architecture was developed to couple the benefits of scale, integration, and precise fluid control with the ability to perform in situ X-ray analysis (Chapter 5). This approach was validated successfully by crystallization and subsequent on-chip analysis of the soluble proteins lysozyme, thaumatin, and ribonuclease A and will be extended to microfluidic platforms for in meso membrane protein crystallization. The ability to perform in situ X-ray analysis was shown to provide extremely high quality diffraction data, in part as a result of not being affected by damage due to physical handling of the crystals. As part of the work described in this thesis, a variety of data collection strategies for in situ data analysis were also tested, including merging of small slices of data from a large number of crystals grown on a single chip, to allow for diffraction analysis at biologically relevant temperatures. While such strategies have been applied previously,57,59,61,67 they are potentially challenging when applied via traditional methods due to the need to grow and then mount a large number of crystals with minimal crystal-to-crystal variability. The integrated nature of microfluidic platforms easily enables the generation of a large number of reproducible crystallization trials. This, coupled with in situ analysis capabilities has the potential of being able to acquire high resolution structural data of proteins at biologically relevant conditions for which only small crystals, or crystals which are adversely affected by standard cryocooling techniques, could be obtained (Chapters 5 and 6). While the main focus of protein crystallography is to obtain three-dimensional protein structures, the results of typical experiments provide only a static picture of the protein. The use of polychromatic or Laue X-ray diffraction methods enables the collection of time resolved structural information. These experiments are very sensitive to crystal quality, however, and often suffer from severe radiation damage due to the intense polychromatic X-ray beams. Here, as before, the ability to perform in situ X-ray analysis on many small protein crystals within a microfluidic crystallization platform has the potential to overcome these challenges. An automated method for collecting a "single-shot" of data from a large number of crystals was developed in collaboration with the BioCARS team at the Advanced Photon Source at Argonne National Laboratory (Chapter 6). The work described in this thesis shows that, even more so than for traditional structure determination efforts, the ability to grow and analyze a large number of high quality crystals is critical to enable time resolved structural studies of novel proteins. In addition to enabling X-ray crystallography experiments, the development of X-ray transparent microfluidic platforms also has tremendous potential to answer other scientific questions, such as unraveling the mechanism of in meso crystallization. For instance, the lipidic mesophases utilized during in meso membrane protein crystallization can be characterized by small angle X-ray diffraction analysis. Coupling in situ analysis with microfluidic platforms capable of preparing these difficult mesophase samples at very small volumes has tremendous potential to enable the high throughput analysis of these systems on a scale that is not reasonably achievable using conventional sample preparation strategies (Chapter 7). In collaboration with the LS-CAT team at the Advanced Photon Source, an experimental station for small angle X-ray analysis coupled with the high quality visualization capabilities needed to target specific microfluidic samples on a highly integrated chip is under development. Characterizing the phase behavior of these mesophase systems and the effects of various additives present in crystallization trials is key for developing an understanding of how in meso crystallization occurs. A long term goal of these studies is to enable the rational design of in meso crystallization experiments so as to avoid or limit the need for high throughput screening efforts. In summary, this thesis describes the development of microfluidic platforms for protein crystallization with in situ analysis capabilities. Coupling the ability to perform in situ analysis with the small scale, fine control, and the high throughput nature of microfluidic platforms has tremendous potential to enable a new generation of crystallographic studies and facilitate the structure determination of important biological targets. The development of platforms for in meso membrane protein crystallization is particularly significant because they enable the preparation of highly viscous mixtures at a previously unachievable scale. Work in these areas is ongoing and has tremendous potential to improve not only current the methods of protein crystallization and crystallography, but also to enhance our knowledge of the structure and function of proteins which could have a significant scientific and medical impact on society as a whole. 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Water sorption-induced crystallization, structural relaxations and strength analysis of relaxation times in amorphous lactose/whey protein systems

Water sorption-induced crystallization, α-relaxations and relaxation times of freeze-dried lactose/whey protein isolate (WPI) systems were studied using dynamic dewpoint isotherms (DDI) method and dielectric analysis (DEA), respectively. The fractional water sorption behavior of lactose/WPI mixtures shown at aw ≤ 0.44 and the critical aw for water sorption-related crystallization (aw(cr)) of lactose were strongly affected by protein content based on DDI data. DEA results showed that the α-relaxation temperatures of amorphous lactose at various relaxation times were affected by the presence of water and WPI. The α-relaxation-derived strength parameter (S) of amorphous lactose decreased with aw up to 0.44 aw but the presence of WPI increased S. The linear relationship for aw(cr) and S for lactose/WPI mixtures was also established with R2 > 0.98. Therefore, DDI offers another structural investigation of water sorption-related crystallization as governed by aw(cr), and S may be used to describe real time effects of structural relaxations in noncrystalline multicomponent solids.

Hafnocene catalyst for polyethylene and its nanocomposites with SBA-15 by in situ polymerization: immobilization approaches, catalytic behavior and properties evaluation

A hafnocene catalyst combined with methylaluminoxane (MAO) has been used as catalytic complex for the preparation of a set of polyethylene homopolymers by in situ polymerization under homogenous conditions and of different nanocomposites with mesoporous SBA- 15 particles, the latter playing the dual role of catalyst support and nanofiller. Distinct immobilization approaches have been explored for obtainment of these nanocomposites. Moreover, catalytic features, thermal stability, melting and crystallization transitions and mechanical behavior have been evaluated for those materials.

The Behavior of Hydroxyl Units of Synthetic Goethite and its Dehydroxylated Product Hematite

The behavior of the hydroxyl units of synthetic goethite and its dehydroxylated product hematite was characterized using a combination of Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) during the thermal transformation over a temperature range of 180-270 degrees C. Hematite was detected at temperatures above 200 degrees C by XRD while goethite was not observed above 230 degrees C. Five intense OH vibrations at 3212-3194, 1687-1674, 1643-1640, 888-884 and 800-798 cm(-1), and a H2O vibration at 3450-3445 cm(-1) were observed for goethite. The intensity of hydroxyl stretching and bending vibrations decreased with the extent of dehydroxylation of goethite. Infrared absorption bands clearly show the phase transformation between goethite and hematite: in particular. the migration of excess hydroxyl units from goethite to hematite. Two bands at 536-533 and 454-452 cm(-1) are the low wavenumber vibrations of Fe-O in the hematite structure. Band component analysis data of FTIR spectra support the fact that the hydroxyl units mainly affect the a plane in goethite and the equivalent c plane in hematite.

Let's Dance: A Language for Service Behavior Modeling

In Service-Oriented Architectures (SOAs), software systems are decomposed into independent units, namely services, that interact with one another through message exchanges. To promote reuse and evolvability, these interactions are explicitly described right from the early phases of the development lifecycle. Up to now, emphasis has been placed on capturing structural aspects of service interactions. Gradually though, the description of behavioral dependencies between service interactions is gaining increasing attention as a means to push forward the SOA vision. This paper deals with the description of these behavioral dependencies during the analysis and design phases. The paper outlines a set of requirements that a language for modeling service interactions at this level should fulfill, and proposes a language whose design is driven by these requirements.

Multiple-choice versus short-response items: Differences in omit behavior

The overall rate of omission of items for 28,331 17 year old Australian students on a high stakes test of achievement in the common elements or cognitive skills of the senior school curriculum is reported for a subtest in multiple choice format and a subtest in short response format. For the former, the omit rates were minuscule and there was no significant difference by gender or by type of school attended. For the latter, where an item can be 'worth' up to five times that of a single multiple choice item, the omit rates were between 10 and 20 times that for multiple choice and the difference between male and female omit rate was significant as was the difference between students from government and non-government schools. For both formats, females from single sex schools omitted significantly fewer items than did females from co-educational schools. Some possible explanations of omit behaviour are alluded to.

Examining the antecedents and consequences of ritualized fan behavior [Abstract]

One of the features of the sporting industry is the ritualized way in which it is consumed across the world. Fans of every sport have rituals and superstitions to help them enjoy the spectacle, socialize with other like-minded fans, and reduce some of the anxiety of watching their team play. These rituals include dress, barracking styles and pre and post match behaviors. What is not known are the factors that lead fans to engage in ritual behaviors and what relationship rituals have with desirable outcomes such as increased attendance, attitudinal loyalty or satisfaction. Given that some ritual behaviors are clearly undesirable, (e.g., hooliganism), understanding these relationships is important to managers who may be questioning whether rituals should be encouraged. Although ritualized behavior amongst fans is clearly visible, the symbolic and emotional nature of ritual poses challenges to researchers. Most previous ritual research is exploratory and qualitative in nature. This study, however, uses a behavior-based scale to measure fan ritual and relates it to desirable outcomes such as commitment and attendance. Over 2,000 season ticket holders of a football (soccer) team in Australia’s professional A-League competition were surveyed to investigate the antecedents and consequences of fan ritual behavior. Cluster analysis was used to explore the characteristics of respondents, and it revealed that those fans that engage in ritual behavior also differed on many other demographic and attitudinal dimensions. The associations between ritual and psychological commitment, and ritual and attendance are positive and significant. When used in conjunction with other constructs, fan ritual also improves the explanation of attendance behavior. The findings support previous research that found a significant and positive relationship between team identification, involvement and attendance, and extend previous research by finding a significant and positive relationship between rituals and attendance. For sports marketing practitioners, the results indicate the importance of developing and managing consumption rituals tied to game day attendance, with a view to generating uncommon loyalty.

Sharing knowledge at work : macro, social and relational individual influences on individual behavior

The impact of relations between an organization and its workers and the relations among workers on individual knowledge generation and sharing practices has not, to date, been addressed in an integrated way. This paper discusses the findings of a study analyzing issues at macro, locally-constructed and micro levels in a public sector organization, to identify and integrate the complex sets of mediators. Key factors were found to include (a) the contested nature of the process of knowledge construction, (b) the worker’s experience of the organization’s internal environment, (c) how the organization is understood to value knowledge sharing, (d) relations with colleagues, and (e) the perceived outcomes of knowledge sharing behaviors. Implications for practice are discussed.

Interpersonal pattern dynamics and adaptive behavior in multiagent neurobiological systems : conceptual model and data

Ecological dynamics characterizes adaptive behavior as an emergent, self-organizing property of interpersonal interactions in complex social systems. The authors conceptualize and investigate constraints on dynamics of decisions and actions in the multiagent system of team sports. They studied coadaptive interpersonal dynamics in rugby union to model potential control parameter and collective variable relations in attacker–defender dyads. A videogrammetry analysis revealed how some agents generated fluctuations by adapting displacement velocity to create phase transitions and destabilize dyadic subsystems near the try line. Agent interpersonal dynamics exhibited characteristics of chaotic attractors and informational constraints of rugby union boxed dyadic systems into a low dimensional attractor. Data suggests that decisions and actions of agents in sports teams may be characterized as emergent, self-organizing properties, governed by laws of dynamical systems at the ecological scale. Further research needs to generalize this conceptual model of adaptive behavior in performance to other multiagent populations.

Adaptive and phase transition behavior in performance of discrete multi-articular actions by degenerate neurobiological systems

The identification of attractors is one of the key tasks in studies of neurobiological coordination from a dynamical systems perspective, with a considerable body of literature resulting from this task. However, with regards to typical movement models investigated, the overwhelming majority of actions studied previously belong to the class of continuous, rhythmical movements. In contrast, very few studies have investigated coordination of discrete movements, particularly multi-articular discrete movements. In the present study, we investigated phase transition behavior in a basketball throwing task where participants were instructed to shoot at the basket from different distances. Adopting the ubiquitous scaling paradigm, throwing distance was manipulated as a candidate control parameter. Using a cluster analysis approach, clear phase transitions between different movement patterns were observed in performance of only two of eight participants. The remaining participants used a single movement pattern and varied it according to throwing distance, thereby exhibiting hysteresis effects. Results suggested that, in movement models involving many biomechanical degrees of freedom in degenerate systems, greater movement variation across individuals is available for exploitation. This observation stands in contrast to movement variation typically observed in studies using more constrained bi-manual movement models. This degenerate system behavior provides new insights and poses fresh challenges to the dynamical systems theoretical approach, requiring further research beyond conventional movement models.

Analyzing web multimedia query reformulation behavior

Current multimedia Web search engines still use keywords as the primary means to search. Due to the richness in multimedia contents, general users constantly experience some difficulties in formulating textual queries that are representative enough for their needs. As a result, query reformulation becomes part of an inevitable process in most multimedia searches. Previous Web query formulation studies did not investigate the modification sequences and thus can only report limited findings on the reformulation behavior. In this study, we propose an automatic approach to examine multimedia query reformulation using large-scale transaction logs. The key findings show that search term replacement is the most dominant type of modifications in visual searches but less important in audio searches. Image search users prefer the specified search strategy more than video and audio users. There is also a clear tendency to replace terms with synonyms or associated terms in visual queries. The analysis of the search strategies in different types of multimedia searching provides some insights into user’s searching behavior, which can contribute to the design of future query formulation assistance for keyword-based Web multimedia retrieval systems.