Synthesis, applications and phenomena of anisotropic inorganic colloids

We investigate the synthesis and application of anisotropic hollow silica colloids as air voided opacity modifiers in dry polymer films in Chapter 1, with the aim of improving upon the light scattering efficacy of the commercially used isotropic hollow latex particles, ROPAQUE™. In order to generate anisotropic hollow silica particles we utilized a sacrificial templating method, ultimately leading us to investigate the opacifying power of hollow silica particles derived from a calcium carbonate template known as SOCAL P3. Initial investigations indicated that shell fragmentation and collapse of our “1st generation” hollow silica particles (with thin shells) led to a loss of opacity, as few air voids remained intact. Tuning the reaction parameters afforded hollow silica particles with thicker shells that displayed enhanced light scattering over the 1st generation hollow SiO2 particles and to SOCAL P3 when film thickness was accounted for. Chapter 2 is an extension of the work done in Chapter 1, wherein we aim to improve pigment dispersion (and consequently opacity) by grafting negatively charged, hydrophilic, polymer brushes to CaCO3@SiO2 particles. This confers enhanced colloidal stability to the particles through electrosteric stabilization. For this we first functionalize the surface with a tertiary alkyl bromide atom transfer radical polymerization (ATRP) initiator to furnish a surface capable of growing polymer brushes from. The initiator is anchored to the surface through siloxane bonds and an amide group, the latter to enhance hydrolytic stability over a wide pH range. We then used a SI-ATRP (where SI = surface initiated) in order to grow the polymer brushes, which we found to generate highly colloidally stable hollow SiO2 particles that demonstrate an enhanced contrast ratio to the sterically stabilized hollow SiO2-PVP particles used in Chapter 1. In Chapter 3 we investigate the multiple orientations of hematite superellipsoids (pseudocubes stabilized with PVP) trapped at an oil-water interface, through a combination of experiments and simulations. We find three orientations in all; two of which are thermodynamic minima and one which corresponds to a kinetically-trapped orientation. The latter results from some particles going through a negligible free energy gradient upon reorientation. Experimental and computational results for the relative balance of particle populations are found to be in excellent agreement with one another. We show that the final position of the particle is both a function of the free energy landscape and the precise orientation of the particle at the point of contact with the interface. A modified silica rod synthesis from an oil-in-water emulsion is demonstrated in Chapter 4, whereby we manage to asymmetrically include a manganese oxide head at one end of the rod to generate a colloidal “matchstick” morphology. Placing these particles into a solution of hydrogen peroxide as fuel facilitates their propulsion as they form an asymmetrical gradient of the breakdown products of hydrogen peroxide; water and oxygen. Adjusting fuel concentration alters the effective diffusion coefficient with a 1st order relationship. Furthermore, we demonstrate that these particles can undergo chemotaxis towards a higher concentration of fuel when placed into a fuel gradient. We rule out convection and other external forces as the reason for directional motion by simultaneously imaging catalytically inert microspheres which travel under convection in the opposite direction to that of the rods

Adhesion signalling complexes

SummaryIntercellular communication in metazoa not only requires autocrine, paracrine and exocrine signalling systems, but it also relies on the structural and positional information encoded in extracellular matrices (ECMs). Most cells in tissues are structurally and functionally integrated with their surrounding ECM in a highly organised manner involving thousands of dynamic connections. On the intracellular face of these linkages, adhesion receptors — principally integrins and syndecans — link the cytoskeleton to the plasma membrane and compartmentalise cytoplasmic signalling events, whereas at the extracellular face the same receptors direct and organise the deposition of the ECM itself. Adhesion receptors transduce mechanical force bidirectionally across the plasma membrane by tethering variably deformable ECMs to the contractile cytoskeleton (Figure 1), and they translate the topography and composition of the ECM into chemical signals that determine behaviour. The membrane-proximal functions of adhesion receptors in turn trigger distal processes within cells, such as alterations in the direction of cell movement and the regulation of gene transcription, and long-range effects outside cells, such as the construction of ECM networks and consequent shaping of higher-order tissue structure. Given the diverse and fundamental roles attributed to adhesion, it is understandable that adhesion receptor engagement has been reported to alter the flux through virtually all major signalling pathways

Ambient DESI and LESA-MS analysis of proteins adsorbed to a biomaterial surface using in-situ surface tryptic digestion

The detection and identification of proteins adsorbed onto biomaterial surfaces under ambient conditions has significant experimental advantages but has proven to be difficult to achieve with conventional measuring technologies. In this study, we present an adaptation of desorption electrospray ionization (DESI) and liquid extraction surface analysis (LESA) mass spectrometry (MS) coupled with in-situ surface tryptic digestion to identify protein species from a biomaterial surface. Cytochrome c, myoglobin, and BSA in a combination of single and mixture spots were printed in an array format onto Permanox slides, followed by in-situ surface digestion and detection via MS. Automated tandem MS performed on surface peptides was able to identify the proteins via MASCOT. Limits of detection were determined for DESI-MS and a comparison of DESI and LESA-MS peptide spectra characteristics and sensitivity was made. DESI-MS images of the arrays were produced and analyzed with imaging multivariate analysis to automatically separate peptide peaks for each of the proteins within a mixture into distinct components. This is the first time that DESI and LESA-MS have been used for the in-situ detection of surface digested proteins on biomaterial surfaces and presents a promising proof of concept for the use of ambient MS in the rapid and automated analysis of surface proteins

Dissecting a complex chemical stress: chemogenomic profiling of plant hydrolysates.

The efficient production of biofuels from cellulosic feedstocks will require the efficient fermentation of the sugars in hydrolyzed plant material. Unfortunately, plant hydrolysates also contain many compounds that inhibit microbial growth and fermentation. We used DNA-barcoded mutant libraries to identify genes that are important for hydrolysate tolerance in both Zymomonas mobilis (44 genes) and Saccharomyces cerevisiae (99 genes). Overexpression of a Z. mobilis tolerance gene of unknown function (ZMO1875) improved its specific ethanol productivity 2.4-fold in the presence of miscanthus hydrolysate. However, a mixture of 37 hydrolysate-derived inhibitors was not sufficient to explain the fitness profile of plant hydrolysate. To deconstruct the fitness profile of hydrolysate, we profiled the 37 inhibitors against a library of Z. mobilis mutants and we modeled fitness in hydrolysate as a mixture of fitness in its components. By examining outliers in this model, we identified methylglyoxal as a previously unknown component of hydrolysate. Our work provides a general strategy to dissect how microbes respond to a complex chemical stress and should enable further engineering of hydrolysate tolerance

Methodology for the synthesis of methacrylate monomers using designed single mode microwave applicators

© 2019 The Royal Society of Chemistry. A novel single-well prototype high throughput microwave reactor geometry has been produced and shown to be capable of synthesizing an array of non-commercially available methacrylate monomers. The reactor, which delivers the energy required via a dedicated coaxial line, has been shown experimentally to outperform other conventional/microwave formats. It is demonstrated to achieve significantly higher conversions than the alternative reactor types, whilst requiring (a) low levels of input power, (b) no additional energy for agitation/mass transfer, (c) no solvent and (d) no environmentally impacting thermos-fluids

An introduction to classical molecular dynamics simulation for experimental scattering users

Classical molecular dynamics simulations are a common component of multi-modal analyses from scattering measurements, such as small-angle scattering and diffraction. Users of these experimental techniques often have no formal training in the theory and practice of molecular dynamics simulation, leading to the possibility of these simulations being treated as a "black box" analysis technique. In this article, we describe an open educational resource (OER) designed to introduce classical molecular dynamics to users of scattering methods. This resource is available as a series of interactive web pages, which can be easily accessed by students, and as an open source software repository, which can be freely copied, modified, and redistributed by educators. The topic covered in this OER includes classical atomistic modelling, parameterising interatomic potentials, molecular dynamics simulations, typical sources of error, and some of the approaches to using simulations in the analysis of scattering data.Comment: Electronic Supplementary Information (ESI) available: All analysis/plotting scripts and figure files, allowing for a fully reproducible, and automated, analysis workflow for the work presented is available at \url{https://github.com/arm61/sim_and_scat_paper} (DOI: 10.5281/zenodo.2556826) under a CC BY-SA 4.0 licens

Characterizing Online Vandalism: A Rational Choice Perspective

What factors influence the decision to vandalize? Although the harm is clear, the benefit to the vandal is less clear. In many cases, the thing being damaged may itself be something the vandal uses or enjoys. Vandalism holds communicative value: perhaps to the vandal themselves, to some audience at whom the vandalism is aimed, and to the general public. Viewing vandals as rational community participants despite their antinormative behavior offers the possibility of engaging with or countering their choices in novel ways. Rational choice theory (RCT) as applied in value expectancy theory (VET) offers a strategy for characterizing behaviors in a framework of rational choices, and begins with the supposition that subject to some weighting of personal preferences and constraints, individuals maximize their own utility by committing acts of vandalism. This study applies the framework of RCT and VET to gain insight into vandals' preferences and constraints. Using a mixed-methods analysis of Wikipedia, I combine social computing and criminological perspectives on vandalism to propose an ontology of vandalism for online content communities. I use this ontology to categorize 141 instances of vandalism and find that the character of vandalistic acts varies by vandals' relative identifiability, policy history with Wikipedia, and the effort required to vandalize

The Panchromatic Hubble Andromeda Treasury XI: The Spatially-Resolved Recent Star Formation History of M31

We measure the recent star formation history (SFH) across M31 using optical images taken with the \texit{Hubble Space Telescope} as part of the Panchromatic Hubble Andromeda Treasury (PHAT). We fit the color-magnitude diagrams in ~9000 regions that are ~100 pc $\times$ 100 pc in projected size, covering a 0.5 square degree area (~380 kpc$^2$, deprojected) in the NE quadrant of M31. We show that the SFHs vary significantly on these small spatial scales but that there are also coherent galaxy-wide fluctuations in the SFH back to ~500 Myr, most notably in M31's 10-kpc star-forming ring. We find that the 10-kpc ring is at least 400 Myr old, showing ongoing star formation over the past ~500 Myr. This indicates the presence of molecular gas in the ring over at least 2 dynamical times at this radius. We also find that the ring's position is constant throughout this time, and is stationary at the level of 1 km/s, although there is evidence for broadening of the ring due to diffusion of stars into the disk. Based on existing models of M31's ring features, the lack of evolution in the ring's position makes a purely collisional ring origin highly unlikely. We find that the global SFR has been fairly constant over the last ~500 Myr, though it does show a small increase at 50 Myr that is 1.3 times the average SFR over the past 100 Myr. During the last ~500 Myr, ~60% of all SF occurs in the 10-kpc ring. Finally, we find that in the past 100 Myr, the average SFR over the PHAT survey area is $0.28\pm0.03$ M$_\odot$ yr$^{-1}$ with an average deprojected intensity of $7.3 \times 10^{-4}$ M$_\odot$ yr$^{-1}$ kpc$^{-2}$, which yields a total SFR of ~0.7 M$_\odot$ yr$^{-1}$ when extrapolated to the entire area of M31's disk. This SFR is consistent with measurements from broadband estimates. [abridged]Comment: 23 pages, 17 figures, 2 tables, accepted for publication in Ap

CfAIR2: Near Infrared Light Curves of 94 Type Ia Supernovae

CfAIR2 is a large homogeneously reduced set of near-infrared (NIR) light curves for Type Ia supernovae (SN Ia) obtained with the 1.3m Peters Automated InfraRed Imaging TELescope (PAIRITEL). This data set includes 4607 measurements of 94 SN Ia and 4 additional SN Iax observed from 2005-2011 at the Fred Lawrence Whipple Observatory on Mount Hopkins, Arizona. CfAIR2 includes JHKs photometric measurements for 88 normal and 6 spectroscopically peculiar SN Ia in the nearby universe, with a median redshift of z~0.021 for the normal SN Ia. CfAIR2 data span the range from -13 days to +127 days from B-band maximum. More than half of the light curves begin before the time of maximum and the coverage typically contains ~13-18 epochs of observation, depending on the filter. We present extensive tests that verify the fidelity of the CfAIR2 data pipeline, including comparison to the excellent data of the Carnegie Supernova Project. CfAIR2 contributes to a firm local anchor for supernova cosmology studies in the NIR. Because SN Ia are more nearly standard candles in the NIR and are less vulnerable to the vexing problems of extinction by dust, CfAIR2 will help the supernova cosmology community develop more precise and accurate extragalactic distance probes to improve our knowledge of cosmological parameters, including dark energy and its potential time variation.Comment: 31 pages, 15 figures, 10 tables. Accepted to ApJS. v2 modified to more closely match journal versio