Applications of artificial intelligence for chemical inference—X : Intsum. A data interpretation and summary program applied to the collected mass spectra of estrogenic steroids

A method for systematic interpretation and summary of evidence found for all possible mass spectral fragmentations of a molecule or set of related molecules is described. The method is embodied in a computer program (INTSUM) which interprets, in terms of fragmentation processes, mass spectral data collected on known compounds. Utilizing high resolution mass spectra from 47 estrogenic steroids, the method is verified and new findings are discussed. Finally, the method is used to explore the fragmentations of equilenins and several acetate and benzoate ester derivatives.     

Novel heteroaromatic silanes in the gas phase

The appearance of intense peaks, due to the (P—30)²⁺ ions, in the mass spectra of 8-trimethylsiloxyquinoline, 2-methyl-8-trimethylsiloxyquinoline, 2-trimethylsiloxymethylpyridine and 2-trimethylsiloxymethyl-6-methylpyridine suggests that these ions have considerable heteroaromatic character.     

A comparison of broadband models for sand sediments

Chotiros and Isakson [J. Acoust. Soc. Am. 116(4), 2011-2022 (2004)] recently proposed an extension of the Biot-Stoll model for poroelastic sediments that makes predictions for compressional wave speed and attenuation, which are in much better accord with the experimental measurements of these quantities extant in the literature than either those of the conventional Biot-Stoll model or the rival model of Buckingham [J. Acoust. Soc. Am. 108(6), 2796-2815 (2000)]. Using a local minimizer, the Nelder-Mead simplex method, it is shown that there are generally at least two choices of the Chotiros-Isakson parameters which produce good agreement with experimental measurements. Since one postulate of the Chotiros-Isakson model is that, due to the presence of air bubbles in the pore space, the pore fluid compressibility is greater than that of water, an alternative model based on a conjecture by Biot [J. Acoust. Soc. Am. 34(5), 1254-1264 (1962)], air bubble resonance, is considered. While this model does as well or better than the Chotiros-Isakson model in predicting measured values of wave speed and attenuation, the Rayleigh-Plesset theory of bubble oscillation casts doubt on its plausibility as a general explanation of large dispersion of velocity with respect to frequency.     

The Walden cycle revisited: a computational study of competitive ring closure to alpha- and beta-lactones

The text-book Walden cycle which interconverts the stereochemical configurations of chlorosuccinic and malic acids involves a beta-lactone intermediate in preference to an alpha-lactone intermediate because the O(nuc) C Cl angle in the transition structure for the former (174 degrees) is more favourable than that for the latter (139 degrees), as determined by PCM(epsilon = 78.4)/B3LYP/6-31+G* calculations; the smaller ring-strain energy of the beta-lactone contributes little to the reactivity difference.     

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.     

Imprinting vortices into antiferromagnets

The effect of imprinting symmetric and displaced vortex structures into an antiferromagnetic material is investigated in micron-sized disks consisting of exchange coupled ferromagnetic-antiferromagnetic bilayers. The imprint of displaced vortices manifests itself by the occurrence of a new type of asymmetric hysteresis loops characterized by curved, reversible, central sections with nonzero remanent magnetization. Such an imprint is achieved by cooling the disks through the blocking temperature of the system in small fields. Micromagnetic simulations reveal that asymmetric vortexlike loops naturally result from the competition between the different energies involved in the system.     

PRESSURE-VELOCITY EQUILIBRIUM HYDRODYNAMIC MODELS

This article describes mathematical models for phase separated mixtures of materials that are in pressure and velocity equilibrium but not necessarily temperature equilibrium. General conditions for constitutive models for such mixtures that exhibit a single mixture sound speed are discussed and specific examples are described.     

Simultaneous detection of ultraviolet and infrared radiation in a single GaN/GaAlN heterojunction

Results are presented for a dual-band detector that simultaneously detects UV radiation in the 250-360 nm and IR radiation in the 5-14 microm regions with near zero spectral cross talk. In this detector having separate UV- and IR-active regions with three contacts (one common contact for both regions) allows the separation of the UV and IR generated photocurrent components, identifying the relative strength of each component. This will be an important development in UV-IR dual-band applications such as fire-flame detection, solar astronomy, and military sensing, eliminating the difficulties of employing several individual detectors with separate electronics-cooling mechanisms.