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Mass spectrometry imaging (MSI) is a powerful scientific tool for understanding the spatial distribution of biochemical compounds in tissue structures. In this paper, we introduce three novel approaches in MSI data processing to perform the tasks of data augmentation, feature ranking, and image registration. We use these approaches in conjunction with non-negative matrix factorization (NMF) to resolve two of the biggest challenges in MSI data analysis, namely: 1) the large file sizes and associated computational resource requirements and 2) the complexity of interpreting the very high dimensional raw spectral data. There are many dimensionality reduction techniques that address the first challenge but do not necessarily result in readily interpretable features, leaving the second challenge unaddressed. We demonstrate that NMF is an effective dimensionality reduction algorithm that reduces the size of MSI datasets by three orders of magnitude with limited loss of information, yielding spatial and spectral components with meaningful correlation to tissue structure that may be used directly for subsequent data analysis without the need for additional clustering steps. This analysis is demonstrated on an MSI dataset from female Sprague-Dawley rats for an animal model of comorbid visceral pain hypersensitivity (CPH). We find that high-dimensional MSI data (∼ 100,000 ions per pixel) can be reduced to 20 spectral NMF components with < 20% loss in reconstruction accuracy. The resulting spatial NMF components are reproducible and correlate well with H&E-stained tissue images. These components may also be used to generate images with enhanced specificity for different tissue types. Small patches of NMF data (i.e., 20 spatial NMF components over 20 × 20 pixels) provide an accuracy of ∼ 87% in classifying CPH vs naïve control subjects. This paper presents the novel data processing methodologies that were used to produce these results, encompassing novel data processing pipelines for data augmentation to support training for classification, ranking of features according to their contribution to classification, and image registration to enhance tissue-specific imaging. 

Exposure to environmental contaminants can result in profound effects on the host immune system. One class of environmental toxicants, known as dioxins, are persistent environmental contaminants termed “forever chemicals”. The archetype toxicant from this group of chemicals is 2, 3, 7, 8-tetrachlorodibenzo-p-dioxin (TCDD), an immunotoxicant that activates the aryl-hydrocarbon receptor pathway leading to a variety of changes in immune cell responses. Immune cell functions are crucial to the development and maintenance of healthy reproduction. Immune cells facilitate tolerance between at the maternal-fetal interface between the parent and the semi-allogenic fetus and help defend the gravid reproductive tract from infectious assault. Epidemiological studies reveal that exposure to environmental contaminants (such as TCDD) are linked to adverse reproductive health outcomes including endometriosis, placental inflammation, and preterm birth. However, little is known about the molecular mechanisms that underpin h 

The nitrogen-interrupted Nazarov cyclization can be a powerful method for the stereocontrolled synthesis of sp 3 -rich N -heterocycles. However, due to the incompatibility between the basicity of nitrogen and the acidic reaction conditions, examples of this type of Nazarov cyclization are scarce. Herein, we report a one-pot nitrogen-interrupted halo -Prins/ halo -Nazarov coupling cascade that joins two simple building blocks, an enyne and a carbonyl partner, to furnish functionalized cyclopenta[ b ]indolines with up to four contiguous stereocenters. For the first time, we provide a general method for the alkynyl halo -Prins reaction of ketones, thus enabling the formation of quaternary stereocenters. Additionally, we describe the outcomes of secondary alcohol enyne couplings, which exhibit helical chirality transfer. Furthermore, we investigate the impact of aniline enyne substituents on the reaction and evaluate the tolerance of different functional groups. Finally, we discuss the reaction mechanism and demonstrate various transformations of the prepared indoline scaffolds, highlighting their applicability in drug discovery campaigns. 

Alternative polymer feedstocks are highly desirable to address environmental, social, and security concerns associated with petrochemical-based materials. Lignocellulosic biomass (LCB) has emerged as one critical feedstock in this regard because it is an abundant and ubiquitous renewable resource. LCB can be deconstructed to generate valuable fuels, chemicals, and small molecules/oligomers that are amenable to modification and polymerization. However, the diversity of LCB complicates the evaluation of biorefinery concepts in areas including process scale-up, production outputs, plant economics, and life-cycle management. We discuss aspects of current LCB biorefinery research with a focus on the major process stages, including feedstock selection, fractionation/deconstruction, and characterization, along with product purification, functionalization, and polymerization to manufacture valuable macromolecular materials. We highlight opportunities to valorize underutilized and complex feedstocks, leverage advanced characterization techniques to predict and manage biorefinery outputs, and increase the fraction of biomass converted into valuable products. 

Here we present length-weight relationships (LWR) for 11 reef fish species from eight islands in French Polynesia. A total of 1,930 fish were collected from five islands in the Society Archipelago (Moorea, Tahiti, Raiatea, Huahine, Tetiaroa) and in three atolls of the Tuamotu Archipelago (Takapoto, Tikehau, and Rangiroa). These fishes span trophic levels, including planktivores, herbivores, and carnivores, and are among the most abundant species for the region. Estimates include LWRs for species never previously published or available in the literature or accessible databases. Measurements of total length (TL: 0.1 cm precision) and total weight (W: 0.01 g precision) were taken. These estimates increase the number of available and robust LWRs for coral reef fishes, providing a better understanding of patterns of growth for these species. With a particular focus on small-bodied species, among the most abundant observed in underwater visual censuses, these estimates will allow marine resource managers and local scientists to characterize fish biomass in French Polynesia with greater precision. 

We report a Brønsted acid-catalyzed carbocyclization cascade, featuring condensation of an alcohol/sulfonamide with an aldehyde followed by an intramolecular three-component coupling involving an alkyne, an oxocarbenium/iminium ion, and an arene. A formal cycloaddition is embedded in the cationic cascade, which enables the synthesis of a wide range of fused heterotricycles. The diastereoselectivity of the cascade is studied using secondary alcohols/sulfonamides with different carbonyl partners. The described method results in the preparation of synthetically versatile scaffolds with ample opportunity for further derivatization at the resulting tetrasubstituted olefin, or by inclusion of other functionalizable motifs from the starting materials. It is worth noting that this chemistry also facilitates the synthesis of piperidines and 1,4-oxazepanes, as well as the inclusion of indoles and benzofurans, which are privileged motifs for medicinal chemistry. Herein we present the generality of this approach and some chemical transformations that can be achieved with our substrates.