Isobaric thermal behavior of glasses during uniform cooling and heating: Dependence of the characteristic temperatures on the relative contributions of temperature and structure to the rate of recovery. II. A one-parameter model approach

Isobaric variations of the characteristic temperatures T_g and T_max, obtained on uniform cooling and heating of glasses, are investigated in terms of their dependence on the relevant experimental variables, using a single retardation time model. The corresponding partial derivatives of T_g and T_max are derived as functions of the partition parameter x (ranging between zero and unity), which determines the relative contributions of temperature and structure to the retardation time. It is shown that the variation of T_g with the cooling rate is independent of x. In contrast, T_max critically depends on x, and its value as well as those of its three partial derivatives are linear functions of x^?1. The variations of T_max are analyzed in terms of a set of reduced variables, leading to simple reduction rules between any two of the experimental variables when the third is kept invariant. The reduction rules are further substantiated by investigating the behavior of glasses in two-step thermal cycles, which result in a unique set of inter-relationships between any pair of the partial derivatives of T_max, whatever the value of x. The results are discussed in terms of their relevance to the behavior of real glasses.     

Self-assembled shells composed of colloidal particles: fabrication and characterization

We construct shells with tunable morphology and mechanical response with colloidal particles that self-assemble at the interface of emulsion droplets. Particles self-assemble to minimize the total interfacial energy, spontaneously forming a particle layer that encapsulates the droplets. We stabilize these layers to form solid shells at the droplet interface by aggregating the particles, connecting the particles with adsorbed polymer, or fusing the particles. These techniques reproducibly yield shells with controllable properties such as elastic moduli and breaking forces. To enable diffusive exchange through the particle shells, we transfer them into solvents that are miscible with the encapsulant. We characterize the mechanical properties of the shells by measuring the response to deformation by calibrated microcantilevers.     

A duality principle for lattices and categories of modules

Let R be a ring with 1, R^op the opposite ring, and R-Mod the category of left unitary R-modules and R-linear maps. A characterization of well-powered abelian categories $\text{A}$ such that there exists an exact embedding functor $\text{A}$→R-Mod is given. Using this characterization and abelian category duality, the following duality principles can be established.Theorem. There exists an exact embedding functor $\text{A}$→R-Mod if and only if there exists an exact embedding functor $\text{A}$^op→R^op-Mod.Corollary. If R-Mod has a specified diagram-chasing property, then R^op-Mod has the dual property.A lattice L is representable by R-modules if it is embeddable in the lattice of submodules of some unitary left R-module; $\text{L}$(R) denotes the quasivariety of all lattices representable by R-modules.Theorem. A lattice L is representable by R-modules if and only if its order dual L¹ is representable by R^op-modules. That is, $\text{L}\text{(}\text{R}{}^{\mathrm{op}}\text{)={L}{}^1\text{:L?}\text{L}\text{(}\text{R}\text{)}}$.If $\text{R}$ is a commutative ring with 1 and a specified diagram-chasing result is satisfied in R-Mod, then the dual result is also satisfied in R-Mod. Furthermore, $\text{L}\text{(}\text{R}\text{)}$ is self-dual: $\text{L}\text{(}\text{R}\text{)= {L}{}^1\text{:L?}\text{L}\text{(}\text{R}\text{)}.}$     

Investigation of free base, Mg, Sn, and Zn substituted porphyrin LB films as gas sensors for organic analytes

The visible absorption spectra of various substituted porphyrin compounds both in chloroform solution and as Langmuir-Blodgett (LB) solid-state films have been investigated. The porphyrin compounds examined were the Zn, Sn, Mg, and free base derivatives of 5,10,15,20-tetrakis[3,4-bis(2-ethylhexyloxy)phenyl]-21H,23H-porphine (EHO). Changes in the absorption spectra of these materials induced by their exposure to various organic compounds are reported with a view toward determining whether this is a useful approach toward an optical gas sensor.     

An integrated mass spectrometry imaging and digital pathology workflow for objective detection of colorectal tumours by unique atomic signatures

Tumours are abnormal growths of cells that reproduce by redirecting essential nutrients and resources from surrounding tissue. Changes to cell metabolism that trigger the growth of tumours are reflected in subtle differences between the chemical composition of healthy and malignant cells. We used LA-ICP-MS imaging to investigate whether these chemical differences can be used to spatially identify tumours and support detection of primary colorectal tumours in anatomical pathology. First, we generated quantitative LA-ICP-MS images of three colorectal surgical resections with case-matched normal intestinal wall tissue and used this data in a Monte Carlo optimisation experiment to develop an algorithm that can classify pixels as tumour positive or negative. Blinded testing and interrogation of LA-ICP-MS images with micrographs of haematoxylin and eosin stained and Ki67 immunolabelled sections revealed Monte Carlo optimisation accurately identified primary tumour cells, as well as returning false positive pixels in areas of high cell proliferation. We analysed an additional 11 surgical resections of primary colorectal tumours and re-developed our image processing method to include a random forest regression machine learning model to correctly identify heterogenous tumours and exclude false positive pixels in images of non-malignant tissue. Our final model used over 1.6 billion calculations to correctly discern healthy cells from various types and stages of invasive colorectal tumours. The imaging mass spectrometry and data analysis methods described, developed in partnership with clinical cancer researchers, have the potential to further support cancer detection as part of a comprehensive digital pathology approach to cancer care through validation of a new chemical biomarker of tumour cells.

Digital pathology and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) imaging reveals a unique elemental signature of colorectal cancer.     

Tunable ultraviolet laser source based on solid-state dye laser technology and CsLiB(6)O(10) harmonic generation

Tunable UV radiation centered at 289nm was obtained from a 532-nm Nd:YAG pumped high-brightness solid-state dye laser, frequency doubled in CsLiB(6)O(10). Frequency doubling to 284-294 nm was demonstrated from a singly doped, rotating pyrromethene dye plastic disk with damage threshold >3 J/cm(2) . UV energies up to 44 mJ at 10 Hz were obtained with a 15% absolute conversion efficiency from 532 nm.     

Investigation of Catalytic Chain Transfer Copolymerization of Methacrylates

Batch experiments were carried out to investigate the kinetics of catalytic chain transfer copolymerization of methyl methacrylate and n‐butyl methacrylate. The Predici® model developed to represent the system describes the numerous experimental data measured at high concentrations of Co(II ) catalyst, taking into account the chain‐length dependencies of termination, propagation and catalytic chain transfer. The constants for catalytic chain transfer are determined as 2.3 × 10⁴ for both methyl methacrylate and n‐butyl methacrylate from fitting the experimental data. Two inhibition mechanisms are shown to describe the decrease of the polymerization rate in the presence of catalyst equally well, with an unknown impurity dissolved in initiator introduced to explain experimental profiles measured at high initiator concentrations.

     

Recent Advances in the Study of High‐Temperature Free Radical Acrylic Solution Copolymerization

Semibatch starved‐feed solution copolymerization is used to produce acrylic resins for coatings formulations. Mechanisms and rate coefficients for polymerization of methacrylates, acrylates, and styrene (ST) under these high‐temperature conditions are reviewed. An extended set of experimental results at 138 °C is used to refine a model describing the solution copolymerization of ST and methacrylates. The data suggest that both changing initiator efficiency and transfer reactions of oxygen‐centered radicals to polymer affect the development of polymer molecular weight. A penultimate model is used to describe the variation in termination rate coefficient with copolymer composition. Significant progress has been made to develop an extended model capable of representing multicomponent high‐temperature acrylic polymerizations.

     

On list‐coloring outerplanar graphs

We prove that a 2‐connected, outerplanar bipartite graph (respectively, outerplanar near‐triangulation) with a list of colors L (v ) for each vertex v such that (resp., ) can be L‐list‐colored (except when the graph is K₃ with identical 2‐lists). These results are best possible for each condition in the hypotheses and bounds. © 2008 Wiley Periodicals, Inc. J Graph Theory 59: 59–74, 2008