Raman spectral analysis in the CHx-stretching region as a guiding beacon for non-targeted, disruption-free monitoring of germination and biofilm formation in the green seaweed Ulva.

Raman spectroscopy was used to study the complex interactions and morphogenesis of the green seaweed Ulva (Chlorophyta) and its associated bacteria under controlled conditions in a reductionist model system. Integrating multiple imaging techniques contributes to a more comprehensive understanding of these biological processes. Therefore, Raman spectroscopy was introduced as a non-invasive, label-free tool for examining chemical information of the tripartite community Ulva mutabilis-Roseovarius sp.-Maribacter sp. The study explored cell differentiation, cell wall protrusion, and bacterial-macroalgae interactions of intact algal thalli. Using Raman spectroscopy, the analysis of the CHx-stretching wavenumber region distinguished spatial regions in Ulva germination and cellular malformations under axenic conditions and upon inoculation with a specific bacterium in bipartite communities. The spectral information was used to guide in-depth analyses within the fingerprint region and to identify substance classes such as proteins, lipids, and polysaccharides, including evidence for ulvan found in cell wall protrusions.

Morpho-mechanical mapping of human dura mater microstructure.

The human dura mater is known to impact vastly traumatic brain injury mechanopathology. In spite of this involvement, dura mater is typically neglected in computational and physical human head models. The lack of location-dependent microstructural and related mechanical data of dura mater may be considered a rationale behind this simplification. The anisotropic nature of dura mater under various loading conditions so far remains unelucidated. Furthermore, principal collagen fiber orientation is yet to be quantified for a morpho-mechanically-informed material model on the dura mater. This study aims to assess how location-dependent mechanical anisotropy is linked to principal collagen fiber orientation. Uniaxial extension tests were performed in a heated tissue bath for 60 samples from six individuals and correlated to the three-dimensional collagen structure in four individuals using second-harmonic generation (SHG) imaging. Failure stress and stretch at failure, elastic modulus, and a microstructurally motivated material model were integrated to examine local differences in dura mater morpho-mechanics. The quantitative observation of collagen fiber orientation and dispersion confirmed that collagen is highly aligned in the human dura mater and that both fiber orientation and dispersion differ depending on the location investigated. This observation provides a possible explanation for the previously observed isotropic mechanical behavior, as the main collagen fiber direction is not oriented along the anterior-posterior or medial-lateral direction at most of the mapped locations. Additionally, these site-dependent structural properties have implications for the mechanical load response and therefore potentially for the regional functions dura mater has to fulfill. The here chosen non-symmetrical fiber dispersion material model fits the data well and provides a comprehensive parameter base for further studies and future finite element models. STATEMENT OF SIGNIFICANCE: The human dura mater greatly affects traumatic brain injury mechanisms, but it is often ignored in computational and physical head models. This is because there is a lack of detailed microstructural and mechanical data specific to the dura mater. Its anisotropic nature and collagen fiber orientation have not been fully understood, hindering the development of an accurate material model. Hence, this study combines morphological data on collagen fiber orientation and dispersion at multiple locations of human cranial dura mater, and links microstructure to location-specific load-displacement behavior. It provides microstructurally informed mechanical information towards realistic head models for predicting location-dependent tissue behavior and failure for assessing brain injury and graft material development.

Latent Nucleophiles in Lewis Base Catalyzed Enantioselective N-Allylations of N-Heterocycles.

Latent nucleophiles are compounds that are themselves not nucleophilic but can produce a strong nucleophile when activated. Such nucleophiles can expand the scope of Lewis base catalyzed reactions. As a proof of concept, we report that N-silyl pyrroles, indoles, and carbazoles serve as latent N-centered nucleophiles in substitution reactions of allylic fluorides catalyzed by Lewis bases. The reactions feature broad scopes for both reaction partners, excellent regioselectivities, and produce enantioenriched N-allyl pyrroles, indoles, and carbazoles when chiral cinchona alkaloid catalysts are used.