Chemical Differentiation Research Articles

53Mn-53Cr chronometry of ureilites: Implications for the timing of parent body accretion, differentiation and secondary reduction

Establishing the temporal evolution of the ureilite parent body(ies) is crucial for understanding the quantitative timescale of planetesimal formation and evolution in the protoplanetary disk. In order to establish a timeline for these early processes, age constraints on the accretion, differentiation and secondary reduction were obtained with the short-lived 53Mn-53Cr chronometer to whole-rock and sequentially digested fractions of main group ureilites. A whole-rock isochron dates the reservoir-scale Mn-Cr fractionation in the ureilite parent body(ies), associated with magmatic differentiation, to 2.89-0.51+0.56 Ma after CAI formation. This age implies that the ureilite parent body(ies) accreted no later than ∼1.5 Ma after CAI formation, at a time when the NC-CC dichotomy was already established. The 53Mn-53Cr systematics of fractions from chromite-bearing ureilites yield an age of 4.29-0.45+0.49 Ma after CAI formation for a secondary reduction event on the parent body. This event is commonly associated with the catastrophic disruption of the ureilite parent body while still hot. The chromite model ages are consistent with the isochron ages obtained from chromite-bearing ureilites. Collectively these ages indicate that chemical differentiation processes were underway on the ureilite parent body(ies) during the time interval when undifferentiated meteorite parent bodies were forming, and may have paused at the peak of planetesimal formation when planetary collisions were common.

Elemental differentiation and isotopic fractionation during space weathering of Chang’E-5 lunar soil

To investigate the chemical variation during space weathering of young mare basalts, here we report elemental, radiogenic Sr-Nd and stable Fe-Mg-Ca isotopic data of Chang’E-5 sieved soils and breccias. From the coarse fraction to the fine one, the sieved soils display increasing Al2O3 (10.34 wt%–13.36 wt%) and Sr (248 ppm–307 ppm) but decreasing FeO (23.50 wt%–20.22 wt%), MgO (6.88 wt%–5.78 wt%), FeO/Al2O3 (2.27–1.51) and MgO/Al2O3 (0.67–0.43). The contents of rare earth elements (except Eu) and high field strength trace elements do not vary with particle size but correlate with P2O5 contents. Given the limited contribution from contamination by meteorites and exotic materials ejected far away from the landing site, these elemental variations can be explained by differential comminution and distribution behaviors of plagioclase and mesostasis phases. These sieved soils yield a Sm-Nd isochron age (1.84 ± 0.83 Ga) comparable to that of basaltic clasts obtained by U-Pb dating (∼2.0 Ga). However, their Rb-Sr isotopic system is disturbed as indicated by their relatively homogeneous 87Sr/86Sr (0.701425–0.701592) despite variable Rb/Sr (0.017–0.028). These results suggest the Sm-Nd isotopic system is more robust to impact disturbance during space weathering compared to the Rb-Sr isotopic system. Given that the bulk soil still plots on the 2.03 Ga Rb-Sr reference isochron from the pristine plagioclases in CE-5 basalts, this disturbance did not affect the Rb-Sr isotopic system on the bulk scale. The CE-5 bulk soil has higher Mg# (33.6), 87Rb/86Sr (0.06) and present-day 87Sr/86Sr (0.701542) than the mean composition of reported basaltic clasts (Mg#: ∼28; 87Rb/86Sr: ∼0.038; 87Sr/86Sr: ∼0.700941), possibly implying that the bedrocks in CE-5 landing site consist of multiple magma pulses. The δ56Fe (0.122 ± 0.002 ‰ to 0.199 ± 0.008 ‰) and δ26Mg (−0.204 ± 0.016 ‰ to −0.109 ± 0.006 ‰) of sieved CE-5 soils increase with decreasing particle sizes but their δ44/42Ca (0.38 ± 0.04 ‰ to 0.44 ± 0.02 ‰) are relatively homogeneous. Mass balance modelling indicates that differential comminution has limited influence on the Fe-Mg-Ca stable isotopic compositions. We further dismiss the role of solar-wind sputtering, as Ca and Mg are more susceptible to sputtering and thus would be expected to show larger isotope fractionations compared to Fe, which is inconsistent with the observations. Free evaporation may explain the elevated δ56Fe and δ26Mg in fine fractions at given very limited depletion in FeO and MgO. The observed positive correlation between δ56Fe and δ26Mg, however, is much steeper than the slope expected for free evaporation, indicating also other mechanisms (e.g., Fe-Mg inter-diffusion). Since the CE-5 soil has a unique composition compared with Apollo and Luna soils, the chemical differentiation identified in this study provides new insights for establishing a connection between the chemistry and reflectance spectral properties of lunar soil. Our combined Fe-Mg-Ca isotopic study also provides a paradigm to distinguish the role of solar-wind sputtering and impact evaporation, and shows that the inter-particle diffusion process may be an important mechanism for the isotope fractionation among lunar soil components.

Hydrogel-Integrated Millifluidic Systems: Advancing the Fabrication of Mucus-Producing Human Intestinal Models.

The luminal surface of the intestinal epithelium is protected by a vital mucus layer, which is essential for lubrication, hydration, and fostering symbiotic bacterial relationships. Replicating and studying this complex mucus structure in vitro presents considerable challenges. To address this, we developed a hydrogel-integrated millifluidic tissue chamber capable of applying precise apical shear stress to intestinal models cultured on flat or 3D structured hydrogel scaffolds with adjustable stiffness. The chamber is designed to accommodate nine hydrogel scaffolds, 3D-printed as flat disks with a storage modulus matching the physiological range of intestinal tissue stiffness (~3.7 kPa) from bioactive decellularized and methacrylated small intestinal submucosa (dSIS-MA). Computational fluid dynamics simulations were conducted to confirm a laminar flow profile for both flat and 3D villi-comprising scaffolds in the physiologically relevant regime. The system was initially validated with HT29-MTX seeded hydrogel scaffolds, demonstrating accelerated differentiation, increased mucus production, and enhanced 3D organization under shear stress. These characteristic intestinal tissue features are essential for advanced in vitro models as they critically contribute to a functional barrier. Subsequently, the chamber was challenged with human intestinal stem cells (ISCs) from the terminal ileum. Our findings indicate that biomimicking hydrogel scaffolds, in combination with physiological shear stress, promote multi-lineage differentiation, as evidenced by a gene and protein expression analysis of basic markers and the 3D structural organization of ISCs in the absence of chemical differentiation triggers. The quantitative analysis of the alkaline phosphatase (ALP) activity and secreted mucus demonstrates the functional differentiation of the cells into enterocyte and goblet cell lineages. The millifluidic system, which has been developed and optimized for performance and cost efficiency, enables the creation and modulation of advanced intestinal models under biomimicking conditions, including tunable matrix stiffness and varying fluid shear stresses. Moreover, the readily accessible and scalable mucus-producing cellular tissue models permit comprehensive mucus analysis and the investigation of pathogen interactions and penetration, thereby offering the potential to advance our understanding of intestinal mucus in health and disease.

Chemical Differentiation and Gas Kinematics around Massive Young Stellar Objects in RCW 120

Chemical Differentiation and Gas Kinematics around Massive Young Stellar Objects in RCW 120

Patterns of Genetic Variation of Nepeta nuda L. from the Central Balkans: Understanding Drivers of Chemical Diversity.

Nepeta nuda L., a notable medicinal species in the tradition of the Balkan region, is a rich source of bioactive iridoids and phenolics previously described as high-resolution taxonomical classifiers for the genus Nepeta. However, their potential in investigating intra-species differentiation is here described for the first time. The aim was to recognize the sources of natural chemical diversity and their association with the genetic variability both within and among N. nuda populations in the Central Balkans. Chemical diversity was assessed from methanol extracts and essential oils through untargeted and targeted metabolomics using state-of-the-art analytical tools, covering a broad spectrum of compounds that represent the N. nuda metabolome. We found that chemodiversity primarily resides within populations of N. nuda, and similar results were obtained at the DNA level using microsatellite markers. The low genetic and chemical differentiation of the studied N. nuda populations implies that their metabolomic profiles may be less influenced by geographic distance and variable environmental conditions within the Central Balkans, as they are under the pivotal control of their genetic backgrounds. Screening the distribution of the major bioactive compounds belonging to phenolics (phenolic acids and flavonoids) and iridoids (both aglycones and glycosylated forms), within and among N. nuda populations, is able to guarantee mass spectrometry-based tools for the selection of elite representative genotypes with practical importance. The knowledge acquired will allow us to delve deeper into the molecular background of N. nuda chemical diversity, which is the course of our further work.

Untargeted Metabolomic to Access Chemical Differences Induced by Dual Endophyte Cultures Isolated from Euphorbia Umbellata.

Endophytic fungi live asymptomatically inside vegetal tissues, and such uncommon habitat contributes to their exceptional chemical diversity. Isolating natural products from endophytic fungi could fail due to silent biosynthetic gene clusters under ordinary in vitro culture conditions, and co-culturing has been assayed to trigger their metabolism. We carried out single and dual cultures with 13 endophyte strains isolated from Euphorbia umbellata leaves. Multivariate statistics applied to untargeted metabolomics compared the chemical profiles of all endophyte cultures. PCA analysis guided the selection of the Aspergillus pseudonomiae J1 - Porogramme brasiliensis J9 dual culture for its most significant chemical differentiation: Five compounds were putatively annotated in the J1-J9 culture according to UHPLC-HRMS data, kojic acid, haliclonol and its diastereoisomer, caffeic acid, and 2-(3,4-dihydroxyphenyl)acetaldehyde. Analysis by PLS-DA using VIP score showed that kojic acid displayed the most significative importance in discriminating single and dual J1-J9 cultures.

Identification of the Sedimentary Sources and Origin of Uranium for Zhiluo Formation of the Tarangaole U Deposit, Northeastern Ordos Basin

The large-sized Tarangaole uranium deposit and its neighboring Daying and Nalinggou deposits, located in the northeastern margin of the Ordos Basin, constitutes a major uranium resource base in northern China. In order to further clarify the sedimentary material source, uranium source and regional sediment–tectonic setting of the uranium-fed clastic rocks (i.e., Zhiluo Formation(J2z)) in the district, this paper carried out whole-rock geochemistry, heavy minerals composition and in situ U-Pb dating of detrital zircons for sandstones from the lower section of the Zhiluo Formation. The results have shown that the average chemical differentiation index (CIA) for the host rocks is 73.16 and the chemical weathering degree is moderate. Heavy minerals are mainly composed of ilmenite, garnet, chlorpyrite, zircon, pyrite, apatite, hematite, etc. The U-Pb dating of detrital zircon generally indicates three age peaks, i.e., 260~Ma, 1850~Ma and 2450~Ma, respectively. In conclusion, the source rocks may have been formed at active continental margins, e.g., in a continental margin arc environment. The sedimentary materials mainly come from khondalite series, TTGs, granulite, and mafic–ultramafic intrusive rocks distributed among the Daqing–Ula Mountains and adjacent areas, etc. The Late Paleozoic U-rich intermediate and acidic magmatic rocks spreading over the eastern part of the Ula–Daqing and Wolf mountains have provided the main uranium sources for the formation of major U deposits in the northern Ordos Basin.

The Role of Peritectic Biotite for the Chemical and Mechanical Differentiation of Felsic Plutonic Rocks (Western Adamello, Italy)

Abstract The volcanic–plutonic connection plays a fundamental role for magmatic systems, linking crystallising plutons, volcanic activity, volatile exsolution and ore deposits. Nonetheless, our understanding of the nature of these links is limited by the scarcity of continuous outcrops exhibiting clear relationships between the plutonic roots that feed its volcanic counterpart. One way to better characterise the volcanic–plutonic connection is to quantify the amount of melt segregation within crystallising tonalitic to granodioritic plutonic rocks, and to compare those with recent silicic eruptions. Here we investigate the processes of interstitial melt segregation in the calc-alkaline Western Adamello pluton (Italy). The Western Adamello tonalite exhibits a coarse-grained, equigranular texture and is mainly composed of hornblende partially replaced by biotite, plagioclase, quartz and alkali feldspar. Within the tonalites, several types of schlieren textures, crystal accumulation zones and dikes are found, comprising: (i) hornblende-biotite-gabbros, spatially related to (ii) plagioclase- and quartz-rich leucotonalites; and (iii) quartz-, albite- and alkali-feldspar-rich domains forming aplitic to pegmatitic dikes indicative of melt segregation and extraction. Hornblende, biotite and plagioclase phenocrysts have essentially the same compositional range in the tonalites, gabbros and leucotonalites. Together with field observations, this indicates that deformation-driven crystal–melt segregation controls the modal variation within the host tonalite. The calculated melt in equilibrium with the primitive amphiboles has the same trace element composition as the host tonalite to within 5% to 10%, indicating that the tonalite did not experience substantial melt loss. Quantitative modal compositions and crystallisation–differentiation calculations suggest that the evolution of the tonalite is controlled by plagioclase and hornblende crystallisation followed by a biotite-forming peritectic reaction. This peritectic reaction can be written as melt1 + amphibole = melt2 + biotite + quartz + plagioclase and decreases the remaining interstitial melt fraction from 40% to 15% in a small temperature interval (~50°C), therefore, reducing the temperature window for large-scale melt segregation. The biotite-forming reaction initiates in weakly corundum-normative compositions in low to intermediate K calc-alkaline differentiation (e.g. Western Adamello and Peninsular Ranges Batholith, California), whereas it seems absent in intermediate to high K, clinopyroxene-normative melts (e.g. Tuolumne Intrusive Suite, California). This difference is likely controlled by the initial aluminium saturation index and the differentiation path of the parental melt within the middle to lower crust. Textural observations and mass balance models indicate that 75% to 88% plagioclase and quartz and 30% to 70% interstitial melt was mechanically removed from the Western Adamello tonalite to form hornblende-biotite-gabbros, whereas the leucotonalites result from the accumulation of 40% to 80% plagioclase and quartz. Of the emplaced 300 to 400 km3 of Western Adamello tonalite, only about 0.8 to 2.4 km3 represent rock types related to physical segregation processes, indicating limited melt extraction. Such crystal–melt segregation processes in tonalitic to granodioritic plutons are observed worldwide and facilitate the extraction of granitic liquids. This mechanism as observed in the Western Adamello tonalite potentially contributes to the accumulation of crystal-poor rhyolites and the segregation of metal-rich brines.

Unveiling the topographic cue rendered by micropatterns for steering cell differentiation by using extrinsic photobiomodulation

It is known that cell culture micropatterns have the ability to facilitate stem cell differentiation induced by specialized chemical factors and different differentiation directions have different optimal micropattern shapes. In this study, by utilizing extrinsic photobiomodulation (EPM) with verteporfin as photosensitizer and light irradiation of 690 nm wavelength as a universal, unbiased, and synchronizing way of inducing differentiation of human umbilical cord Wharton's Jelly mesenchymal stem cells (WJ-MSCs), the topographic cue for cell type specification conveyed in microislands is investigated. It is found that the topographic cues are encoded in the symmetry and aspect ratio of microislands and conformation of cells to microislands is necessary for acquiring the cue. F-actin vertical columns form and cell thickness increases for cells on microislands, and the two effects are enhanced by EPM and correlate with cell differentiation. EPM treatment poises cells in a stationary state to initiate differentiation and the process of making commitment takes two days. Our findings reveal the way to fully exploit topographic cues for promoting and controlling cell differentiation.

Partial melt composition of enstatite chondritic mantle around the rheological transition at 23 GPa: Implications for the chemical differentiation of the Earth's mantle

Terrestrial planets are thought to be made of chondritic materials. However, previous studies have suggested that the Earth's upper mantle is depleted in some incompatible refractory lithophile elements (RLEs), such as U and Th in comparison with chondritic values. To explain the compositional contradiction between the upper mantle and chondrites, a hidden reservoir for incompatible RLEs in the lower mantle has been proposed. These studies have invoked a possible formation of hidden reservoir for incompatible RLEs during magma ocean solidification and by subsequent mantle overturn due to the gravitational instability of Fe-rich dense cumulates. However, the density of partial melt and its fate in a crystallizing deep magma ocean is still debated. Here we report partial melt compositions of enstatite chondritic mantle at 23 GPa as a function of the extent of melting. The results show that bridgmanite crystallized in a chondritic magma ocean becomes enriched in Fe and Ca with decreasing extent of melting and prevents the crystallization of ferropericlase and CaSiO3 perovskite (Davemaoite). At the rheological transition (the extent of melting of 40% based on mass balance calculation), where the solid-liquid separation efficiently occurs even in the case of equilibrium crystallization, the solid part is mostly composed of bridgmanite with a trace amount of majorite, and the melt becomes enriched in FeO and CaO compared to the initial chondritic composition. The calculated density of the melt at the rheological transition is lighter than bridgmanite, but denser than majorite, suggesting that the melt may have ponded at the bottom of the mantle transition zone. The melt ponded around 660 km depth may have been enriched in incompatible RLEs and formed the hidden reservoir for missing RLEs if this melt-bearing region is stable against subsequent mantle convection.

Screening Earth Analog Exoplanets on the Basis of a Predicted Nitrogen over Phosphorus Ratio

Since the first discovery in 1995, data for over 5300 exoplanets have been documented in the NASA archive, revealing a vast diversity. Identifying life-enabling analogs of the Earth among this rapidly expanding catalog is of major interest. The stability of liquid water at the planetary surface defining the concept of the habitable zone (HZ) around the host star, may be necessary for the emergence of life as we know it but not sufficient. The practically constant atomic ratio nitrogen:phosphorous = 16:1 in oceanic surface layers of our planet Earth was discovered by Redfield in 1934. It corresponds to phytoplanktonic biomass in suspension and appears optimal to fertilize phytoplankton development and therefore the food pyramid of marine life. Loladze and Elser have shown that it corresponds to a homeostatic protein:RNA ratio and is therefore “rooted in the stoichiometry of the foundational structures of life.” I show that according to the recent theory of the chemical differentiation of planets, this optimal ratio is also an intrinsic chemical property of our planet Earth uniquely determined in the solar system by its average orbital radius. On that basis, I propose a criterion of fertility within the HZ of a stellar system, which when applied to screen the public database allows us to sort out an extended list of up to 74 Earth analogs. The latter and its future extensions could provide priority targets for focused detection techniques.

Radiocarbon (14C) accelerator mass spectrometry as a convenient tool for differentiation of flavor chemicals of synthetic origin from biobased sources and their in-vivo toxicity assessment

Plants are known to be the natural factory for the production of flavor chemicals. Essential oils comprised of aldehyde as a functional group are potent in deciphering flavor effects in beverages and fresh and prepared food products. In the majority, these are manufactured through synthetic routes, resulting in high product carbon footprints or CO2 equivalents in total greenhouse gas emission. FDA has banned some of the synthetic flavor chemicals due to the health hazards associated with them. However, consumer's preference for natural is at stake due to the absence of quantitative traceability tools. The accelerator mass spectrometer (AMS) analysis revealed a distinction between natural and fossil-derived citral and its blends in Cymbopogon essential oils. The plant-derived citral contained a percent modern carbon (pMC) value in the range of 99–100 %. In contrast, the fossil fuel-derived citral showed zero pMC. Similarly, blends of Cymbopogon oils with 30–50 % (w/w) of fossil origin citral contained pMC equivalent to the proportions of modern carbon. These results showed the usefulness of AMS in quantifying the amount of 14C associated with flavor ingredients. Besides, acute oral toxicity data revealed Cymbopogon oils as the safe flavoring substance at the highest 2000 mg/kg body weight dose in Swiss albino mice.

Comparation of the Aqueous Extraction Methods of the Tarenaya Aculeata Leaves in Relation to the Chemical Composition and Photoprotector, Antibacterial and Antioxidant Potentials

Medicines and cosmetics based on natural products have been in demand since ancient times. This study aimed to compare extracts and fractions of T. aculeata, obtained by different extraction methods, in addition to evaluating the antioxidant, antibacterial and photoprotective capacity of the samples. The chemical differentiation of the content different extracts and fractions were evaluated using statistical programs and the levels of phenolic compounds and tannins were evaluated using spectroscopic methods. The results of the statistical analysis showed greater similarity in the extracts obtained by the infusion and decoction methods. The toxicity assay by Artemia Salina showed that the aqueous extracts obtained by all methodologies are non-toxic, promising for its use as a cosmetic, and antioxidant activity was more evident for the fractions. Broad-spectrum antibacterial activity was attributed to both extracts and fractions. In order to obtain a sustainable photoprotective product, the aqueous extracts were selected and incorporated into a commercial cream in order to obtain a multifunctional product, the aqueous extract obtained by the infusion method being the one that presented the best sun protection factor results (17.27), with good results of stability.

Chemical profiles, differentiation, and quality evaluation of Radix et Rhizoma Thalictri Foliolosi based on LC-MS

Radix et Rhizoma Thalictri Foliolosi (RRTF) belongs to one of the alkaloid-rich traditional Chinese medicines in Ranunculaceae, which possesses anti-inflammatory, anti-tumor, and several other pharmacological activities. However, due to lack of research on chemical composition, serious confusion in the origin, and ambiguity in pharmacological mechanisms, it is quite urgent to establish quality control standards based on modern research and to increase the widespread usage. Aiming to clarify the differential compounds among three species of RRTF (TFD, TFB, and TCW), targeted and untargeted acquisition strategies based on high resolution mass spectrometry were established. Plant metabolomics analysis and multivariate statistical analysis were accomplished to screen out differential markers which were answerable for categorizing different species of RRTF. A network pharmacology analysis was further performed to predict the bioactive constituents and pharmacological mechanisms. Moreover, multi-components quantitative analysis under multiple reaction monitoring mode and multiple logistic regression analysis were conducted to estimate the rationality of the quality markers (Q-markers). Ultimately, the targeted alkaloid detection list was built as premise relying on alkaloid cleavage pathway, and a total 87 compounds were identified. The 25 representative differential metabolites were screened out successfully and divided into three categories to differentiate TFD, TFB, and TCW. 14 active components and 25 presumptive targets of RRTF were found to play a central role according to network pharmacology analysis. The abundance of screened 12 Q-marker showed significant differences in the three varieties. In conclusion, the study systematically investigated the material basis of RRTF, distinguished and evaluated the quality of RRTF effectively, and predicted its pharmacodynamic material basis.

The GUAPOS project

Context. The G31.41+0.31 Unbiased ALMA sPectral Observational Survey (GUAPOS) project targets the hot molecular core (HMC) G31.41+0.31 (G31) to reveal the complex chemistry of one of the most chemically rich high-mass star-forming regions outside the Galactic center (GC). Aims. In the third paper of the project we present a study of nine O-bearing (CH3OH, 13CH3OH, CH318OH , CH3CHO, CH3OCH3, CH3COCH3, C2H5OH, aGg′-(CH2OH)2, and gGg′-(CH2OH)2) and six N-bearing (CH3CN,13CH3CN, CH313CN, C2H3CN, C2H5CN, and C2H513CN) complex organic molecules toward G31. The aim of this work is to characterize the abundances in G31 and to compare them with the values estimated in other sources. Moreover, we searched for a possible chemical segregation between O-bearing and N-bearing species in G31, which hosts four compact sources as seen with higher angular resolution data. In the discussion we also include the three isomers of C2H4O2 and the O- and N-bearing molecular species NH2CHO, CH3NCO, CH3C(O)CH2, and CH3NHCHO, which were analyzed in previous GUAPOS papers. Methods. Observations were carried out with the interferometer ALMA and cover the entire Band 3 from 84 to 116 GHz (~32 GHz bandwidth) with an angular resolution of 1.2″ × 1.2″ (~4400 au × 4400 au) and a spectral resolution of ~0.488 MHz (~1.3–1.7 km s−1). The transitions of the 14 molecular species were analyzed with the tool SLIM of MADCUBA to determine the physical parameters of the emitting gas. Moreover, we analyzed the morphology of the emission of the molecular species. Results. The values of abundances with respect to H2 in G31 range from 10−6 to 10−10 for the different species. We compared the abundances with respect to methanol of O-bearing, N-bearing, and O- and N-bearing COMs in G31 with 27 other sources, including other hot molecular cores inside and outside the GC, hot corinos, shocked regions, envelopes around young stellar objects, and quiescent molecular clouds, and with chemical models. Conclusions. From the comparison with other sources there is not a unique template for the abundances in hot molecular cores, pointing toward the importance of the thermal history for the chemistry of the various sources. The abundances derived from the chemical models are in good agreement, within a factor of 10, with those of G31. From the analysis of the maps we derived the peak positions of all the molecular species toward G31. Different species peak at slightly different positions, and this, together with the different central velocities of the lines obtained from the spectral fitting, point to chemical differentiation of selected O-bearing species.

Untargeted cannabinomics reveals the chemical differentiation of industrial hemp based on the cultivar and the geographical field location

Cannabis sativa has long been harvested for industrial applications related to its fibers. Industrial hemp cultivars, a botanical class of Cannabis sativa with a low expression of intoxicating Δ9-tetrahydrocannabinol (Δ9-THC) have been selected for these purposes and scarcely investigated in terms of their content in bioactive compounds. Following the global relaxation in the market of industrial hemp-derived products, research in industrial hemp for pharmaceutical and nutraceutical purposes has surged. In this context, metabolomics-based approaches have proven to fulfill the aim of obtaining comprehensive information on the phytocompound profile of cannabis samples, going beyond the targeted evaluation of the major phytocannabinoids. In the present paper, an HRMS-based metabolomics study was addressed to seven distinct industrial hemp cultivars grown in four experimental fields in Northern, Southern, and Insular Italy. Since the role of minor phytocannabinoids as well as other phytocompounds was found to be critical in discriminating cannabis chemovars and in determining its biological activities, a comprehensive characterization of phytocannabinoids, flavonoids, and phenolic acids was carried out by LC-HRMS and a dedicated data processing workflow following the guidelines of the metabolomics Quality Assurance and Quality Control Consortium. A total of 54 phytocannabinoids, 134 flavonoids, and 77 phenolic acids were annotated, and their role in distinguishing hemp samples based on the geographical field location and cultivar was evaluated by ANOVA-simultaneous component analysis. Finally, a low-level fused model demonstrated the key role of untargeted cannabinomics extended to lesser-studied phytocompound classes for the discrimination of hemp samples.

Sedimentary Genesis and Model Analysis of Shale Lithofacies in Jiyang Depression

Based on core observation, rock thin sections, logging data, and testing data, taking the shale of the upper submember of the 4th Member to the lower submember of the 3rd Member of Paleogene Shahejie Formation in Jiyang Depression of Bohai Bay Basin as an example, we determine the lithofacies division scheme, divide the main lithofacies types, analyze the sedimentary origin and development location of different shale lithofacies, establish the continental lake basin sedimentary model, determine the types and enrichment areas of favorable lithofacies, and provide guidance for the exploration and development of Shale oil. The results show that: (1) According to the mineral composition, sedimentary structure, and organic matter abundance, the division scheme of shale lithofacies in the study area is proposed, and the shale lithofacies of the study area was mainly divided into 17 types. (2) Based on the lithologic changes, the lacustrine sedimentary shale area was divided into muddy water area, transition area, and clear water area. (3) Under the background of locally uplifted slope paleogeomorphology, considering the combined effects of climate, topography, hydrodynamic, mechanical, and chemical differentiation of sediments and biological habits, the sedimentary model of shale was established. (4) Organic-rich shale was mainly deposited between the clear water area and the end of the muddy water area, with the characteristics of water, brackish water, strong reduction, and water stratification, and was mainly enriched in the low-lying parts of paleotopography.

Subtle Introgression Footprints at the End of the Speciation Continuum in a Clade of Heliconius Butterflies.

Quantifying gene flow between lineages at different stages of the speciation continuum is central to understanding speciation. Heliconius butterflies have undergone an adaptive radiation in wing color patterns driven partly by natural selection for local mimicry. Color patterns are also known to be used as assortative mating cues. Therefore, wing pattern divergence is considered to play a role in speciation. A corollary is that mimicry between closely related species may be associated with hybridization and interfere with reproductive isolation. Here, we take a multifaceted approach to explore speciation history, species boundaries, and traits involved in species differentiation between the two closely related species, Heliconius hecale and Heliconius ismenius. We focus on geographic regions where the two species mimic each other and contrast this with geographic regions where they do not mimic each other. To examine population history and patterns of gene flow, we tested and compared a four-population model accounting for linked selection. This model suggests that the two species have remained isolated for a large part of their history, yet with a small amount of gene exchange. Accordingly, signatures of genomic introgression were small except at a major wing pattern allele and chemosensing genes and stronger in the mimetic populations compared with nonmimetic populations. Behavioral assays confirm that visual confusion exists but that short-range cues determine strong sexual isolation. Tests for chemical differentiation between species identified major differences in putative pheromones which likely mediate mate choice and the maintenance of species differences.

3D physico-chemical model of a pre-stellar core

Context. Pre-stellar cores represent the earliest stage of the formation process of stars and planets. By characterizing the physical and chemical structure of these cores, we can establish the initial conditions for star and planet formation and determine to what degree the chemical composition of pre-stellar cores is inherited by the later stages. Aims. We aim to determine the underlying causes of spatial chemical segregation observed in pre-stellar cores and study the effects of the core structure and external environment on the chemical structure of pre-stellar cores. Methods. A three-dimensional (3D) magnetohydrodynamic model of a pre-stellar core embedded in a dynamic star-forming cloud was post-processed with a sequentially continuum radiative transfer, a gas-grain chemical model, and a line-radiative transfer model. The results were analyzed and compared to observations of CH3OH and c-C3H2 in L1544. We compared nine different chemical models to the observations to determine which initial conditions are compatible with the observed chemical segregation in the prototypical pre-stellar core L1544. Results. The model is able to reproduce several aspects of the observed chemical differentiation in L1544. Extended methanol emission is shifted towards colder and more shielded regions of the core envelope, while c-C3H2 emission overlaps with the dust continuum, which is consistent with the observed chemical structure. Furthermore, these results are consistent across a broad spectrum of chemical models. Increasing the strength of the interstellar radiation field or the cosmic-ray ionization rate with respect to the typical values assumed in nearby star-forming regions leads to synthetic maps that are inconsistent with the observed chemical structure. Conclusions. Our model shows that the observed chemical dichotomy in L1544 can arise as a result of uneven illumination due to the asymmetrical structure of the 3D core and the environment within which the core has formed. This highlights the importance of the 3D structure at the core-cloud transition on the chemistry of pre-stellar cores. The reported effect is likely to affect later stages of the formation process of stars and planets through chemical inheritance.

Chemical Differentiation around Five Massive Protostars Revealed by ALMA: Carbon-chain Species and Oxygen/Nitrogen-bearing Complex Organic Molecules

We present Atacama Large Millimeter/submillimeter Array Band 3 data toward five massive young stellar objects (MYSOs), and investigate relationships between unsaturated carbon-chain species and saturated complex organic molecules (COMs). An HC5N (J = 35–34) line has been detected from three MYSOs, where nitrogen (N)-bearing COMs (CH2CHCN and CH3CH2CN) have been detected. The HC5N spatial distributions show compact features and match with a methanol (CH3OH) line with an upper-state energy around 300 K, which should trace hot cores. The hot regions are more extended around the MYSOs where N-bearing COMs and HC5N have been detected compared to two MYSOs without these molecular lines, while there are no clear differences in the bolometric luminosity and temperature. We run chemical simulations of hot-core models with a warm-up stage, and compare with the observational results. The observed abundances of HC5N and COMs show good agreements with the model at the hot-core stage with temperatures above 160 K. These results indicate that carbon-chain chemistry around the MYSOs cannot be reproduced by warm carbon-chain chemistry, and a new type of carbon-chain chemistry occurs in hot regions around MYSOs.