High-quality nanocavities through multimodal confinement of hyperbolic polaritons in hexagonal boron nitride.

Compressing light into nanocavities substantially enhances light-matter interactions, which has been a major driver for nanostructured materials research. However, extreme confinement generally comes at the cost of absorption and low resonator quality factors. Here we suggest an alternative optical multimodal confinement mechanism, unlocking the potential of hyperbolic phonon polaritons in isotopically pure hexagonal boron nitride. We produce deep-subwavelength cavities and demonstrate several orders of magnitude improvement in confinement, with estimated Purcell factors exceeding 108 and quality factors in the 50-480 range, values approaching the intrinsic quality factor of hexagonal boron nitride polaritons. Intriguingly, the quality factors we obtain exceed the maximum predicted by impedance-mismatch considerations, indicating that confinement is boosted by higher-order modes. We expect that our multimodal approach to nanoscale polariton manipulation will have far-reaching implications for ultrastrong light-matter interactions, mid-infrared nonlinear optics and nanoscale sensors.

Full adoption of the most effective strategies to mitigate methane emissions by ruminants can help meet the 1.5 °C target by 2030 but not 2050.

To meet the 1.5 °C target, methane (CH4) from ruminants must be reduced by 11 to 30% by 2030 and 24 to 47% by 2050 compared to 2010 levels. A meta-analysis identified strategies to decrease product-based (PB; CH4 per unit meat or milk) and absolute (ABS) enteric CH4 emissions while maintaining or increasing animal productivity (AP; weight gain or milk yield). Next, the potential of different adoption rates of one PB or one ABS strategy to contribute to the 1.5 °C target was estimated. The database included findings from 430 peer-reviewed studies, which reported 98 mitigation strategies that can be classified into three categories: animal and feed management, diet formulation, and rumen manipulation. A random-effects meta-analysis weighted by inverse variance was carried out. Three PB strategies­namely, increasing feeding level, decreasing grass maturity, and decreasing dietary forage-to-concentrate ratio­decreased CH4 per unit meat or milk by on average 12% and increased AP by a median of 17%. Five ABS strategies­namely CH4 inhibitors, tanniferous forages, electron sinks, oils and fats, and oilseeds­decreased daily methane by on average 21%. Globally, only 100% adoption of the most effective PB and ABS strategies can meet the 1.5 °C target by 2030 but not 2050, because mitigation effects are offset by projected increases in CH4 due to increasing milk and meat demand. Notably, by 2030 and 2050, low- and middle-income countries may not meet their contribution to the 1.5 °C target for this same reason, whereas high-income countries could meet their contributions due to only a minor projected increase in enteric CH4 emissions.

Diverging cell wall strategies for drought adaptation in two maize inbreds with contrasting lodging resistance.

The plant cell wall is a plastic structure of variable composition that constitutes the first line of defence against environmental challenges. Lodging and drought are two stressful conditions that severely impact maize yield. In a previous work, we characterised the cell walls of two maize inbreds, EA2024 (susceptible) and B73 (resistant) to stalk lodging. Here, we show that drought induces distinct phenotypical, physiological, cell wall, and transcriptional changes in the two inbreds, with B73 exhibiting lower tolerance to this stress than EA2024. In control conditions, EA2024 stalks had higher levels of cellulose, uronic acids and p-coumarate than B73. However, upon drought EA2024 displayed increased levels of arabinose-enriched polymers, such as pectin-arabinans and arabinogalactan proteins, and a decreased lignin content. By contrast, B73 displayed a deeper rearrangement of cell walls upon drought, including modifications in lignin composition (increased S subunits and S/G ratio; decreased H subunits) and an increase of uronic acids. Drought induced more substantial changes in gene expression in B73 compared to EA2024, particularly in cell wall-related genes, that were modulated in an inbred-specific manner. Transcription factor enrichment assays unveiled inbred-specific regulatory networks coordinating cell wall genes expression. Altogether, these findings reveal that B73 and EA2024 inbreds, with opposite stalk-lodging phenotypes, undertake different cell wall modification strategies in response to drought. We propose that the specific cell wall composition conferring lodging resistance to B73, compromises its cell wall plasticity, and renders this inbred more susceptible to drought.

Hospital Volume of Elective Abdominal Aortic Aneurysm Repair as a Predictor of Mortality After Ruptured Abdominal Aortic Aneurysm Repair.

OBJECTIVE: Registry data suggest that centralising abdominal aortic aneurysm (AAA) surgery decreases the mortality rate after AAA repair. However, the impact of higher elective volumes on ruptured AAA (rAAA) repair associated mortality rates remains uncertain. This study aimed to examine associations between intact AAA (iAAA) repair volume and post-operative rAAA death. METHODS: Using data from official national registries between 2015 - 2019, all iAAA and rAAA repairs were separately analysed across 10 public hospitals. The following were assessed: 30 day and 12 month mortality rate following open surgical repair (OSR) and endovascular aneurysm repair (EVAR). Associations between the 5 year hospital iAAA repair volumes (organised into tertiles) and rAAA associated mortality rate were analysed, regardless of treatment modality. Receiver operating characteristic (ROC) curves were generated to identify iAAA volume thresholds for decreasing the rAAA mortality rate. Subanalysis by treatment type was conducted. Threshold analysis was repeated with the Markov chain Monte Carlo (MCMC) procedure to confirm the findings. RESULTS: A total of 1 599 iAAAs (80.2% EVAR, 19.8% OSR) and 196 rAAAs (66.3% EVAR, 33.7% OSR) repairs were analysed. The median and interquartile range of the volume/hospital/year for all iAAA repairs were 39.2 (31.2, 47.4). The top volume iAAA tertile exhibited lower rAAA associated 30 day (odds ratio [OR] 0.374; p = .007) and 12 month (OR 0.264; p < .001) mortality rates. The ROC analysis revealed a threshold of 40 iAAA repairs/hospital/year (EVAR + OSR) for a reduced rAAA mortality rate. Middle volume hospitals for open iAAA repair had reduced 30 day (OR 0.267; p = .033) and 12 month (OR 0.223; p = .020) mortality rates, with a threshold of five OSR procedures/year. The MCMC procedure found similar thresholds. No significant association was found between elective EVAR volumes and ruptured EVAR mortality. CONCLUSION: Higher iAAA repair volumes correlated with a lower rAAA mortality rate, particularly for OSR. The recommended iAAA repair threshold is 40 procedures/year and five procedures/year for OSR. These findings support high elective volumes for improving the rAAA mortality rate, especially for OSR.

Effect of a blend of cinnamaldehyde, eugenol, and Capsicum oleoresin on methane emission and lactation performance of Holstein-Friesian dairy cows.

This study aimed to investigate the effect of administering a standardized blend of cinnamaldehyde, eugenol, and Capsicum oleoresin (CEC) to lactating dairy cattle for 84 d (i.e., 12 wk) on enteric CH4 emission, feed intake, milk yield and composition, and body weight. The experiment involved 56 Holstein-Friesian dairy cows (145 ± 31.1 d in milk at the start of the trial; mean ± standard deviation) in a randomized complete block design. Cows were blocked in pairs according to parity, lactation stage, and current milk yield, and randomly allocated to 1 of the 2 dietary treatments: a diet including 54.5 mg of CEC/kg of DM or a control diet without CEC. Diets were provided as partial mixed rations in feed bins, which automatically recorded individual feed intake. Additional concentrate was fed in the GreenFeed system that was used to measure emissions of CO2, CH4, and H2. Feeding CEC decreased CH4 yield (g/kg DMI) by on average 3.4% over the complete 12-wk period and by on average 3.9% from 6 wk after the start of supplementation onward. Feeding CEC simultaneously increased feed intake and body weight, and tended to increase milk protein content, whereas no negative responses were observed. These results must be further investigated and confirmed in longer-term in vivo experiments.

Aromatic 1,4,2,3-Diazadiborole Featuring an Unsymmetrical B=B Entity: A Versatile Synthon for Unusual Boron Heterocycles.

The replacement of a CC unit with an isoelectronic BN unit in aromatic systems can give rise to molecules and materials with fascinating properties. We report here the synthesis, characterization, and reactivity of a 1,4,2,3-diazadiborole species, 2, featuring an unprecedented 6π-aromatic BN-heterocyclic moiety that is isoelectronic to cyclopentadienide (Cp-). Bearing an unsymmetrical B=B entity, 2 exhibits reactivity toward oxidants, protic reagents, electrophiles, and unsaturated substrates. This reactivity facilitates the synthesis of a variety of novel mono- and bicyclic organoboron derivatives through mechanisms including ring retention, cleavage/recombination, annulation, and expansion. These findings reveal innovative synthetic routes to BN-embedded aromatic compounds via desymmetrization, affording unique building blocks for synthetic chemistry.

The puzzle of plant hybridisation: a high propensity to hybridise but few hybrid zones reported.

An interesting conundrum was recently revealed by R. Abbott when he found that the number of hybrid zones reported in the literature for plants is very low, given the propensity of plants to hybridise. In another literature survey on hybrid zones performed over the period 1970-2022, we found that the number of hybrid zones reported for vertebrates was 2.3 times greater than that reported for vascular plants, even though there are about six times more vascular plant species than vertebrates. Looking at the number of papers reporting hybrid zones, there are 4.9 times more on vertebrates than on vascular plants. These figures support the relevance of this conundrum. In this paper we aim to shed light on this question by providing a structured discussion of the causes that may underlie this conundrum. We propose six non-mutually exclusive factors, namely lack or deficit of spatial structure, lack or deficit of genetic structure, effects of hybridisation between non-closely related species, lability of plant hybrid zones over time, botanists' perception of hybridisation, and deficit of population genetic data. There does not appear to be a single factor that explains our puzzle, which applies to all cases of plants where hybridisation is detected but no hybrid zone is reported. It is argued that some plant features suggest that the puzzle is not, at least entirely, due to insufficient knowledge of the specific cases, a hypothesis that should be addressed with a wider range of empirical data across different taxonomic groups.

Plasma and milk metabolomics in lactating sheep divergent for feed efficiency.

Enhancing the ability of animals to convert feed into meat or milk by optimizing feed efficiency (FE) has become a priority in livestock research. Although untargeted metabolomics is increasingly used in this field and may improve our understanding of FE, no information in this regard is available in dairy ewes. This study was conducted to (1) discriminate sheep divergent for FE and (2) provide insights into the physiological mechanisms contributing to FE through high-throughput metabolomics. The ultra-high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-Q/TOF-MS) technique was applied to easily accessible animal fluids (plasma and milk) to assess whether their metabolome differs between high- and low-feed efficient lactating ewes (H-FE and L-FE groups, respectively; 8 animals/group). Blood and milk samples were collected on the last day of the 3-wk period used for FE estimation. A total of 793 features were detected in plasma and 334 in milk, with 100 and 38 of them, respectively, showing differences between H-FE and L-FE. The partial least-squares discriminant analysis separated both groups of animals regardless of the type of sample. Plasma allowed the detection of a greater number of differential features; however, results also supported the usefulness of milk, more easily accessible, to discriminate dairy sheep divergent for FE. Regarding pathway analysis, nitrogen metabolism (either anabolism or catabolism) seemed to play a central role in FE, with plasma and milk consistently indicating a great impact of AA metabolism. A potential influence of pathways related to energy/lipid metabolism on FE was also observed. The variable importance in the projection plot revealed 15 differential features in each matrix that contributed the most for the separation in H-FE and L-FE, such as l-proline and phosphatidylcholine 20:4e in plasma or l-pipecolic acid and phosphatidylethanolamine (18:2) in milk. Overall, untargeted metabolomics provided valuable information into metabolic pathways that may underlie FE in dairy ewes, with a special relevance of AA metabolism in determining this complex phenotype in the ovine. Further research is warranted to validate these findings.

Early life supplementation with a natural blend containing turmeric, thymol, and yeast cell wall components to optimize rumen anatomical and microbiological development and productivity in dairy goats.

Ruminants are born with an anatomically, microbiologically, and metabolically immature rumen. Optimizing the rearing of young ruminants represent an important challenge in intensive dairy farms. Therefore, the objective of this study was to evaluate the effects of dietary supplementation of young ruminants with a plant extract blend containing turmeric, thymol, and yeast cell wall components such as mannan oligosaccharides and ß-glucans. One hundred newborn female goat kids were randomly allocated to 2 experimental treatments, which were unsupplemented (CTL) or supplemented with the blend containing plant extracts and yeast cell wall components (PEY). All animas were fed with milk replacer, concentrate feed, and oat hay, and were weaned at 8 wk of age. Dietary treatments lasted from wk 1 to 22 and 10 animals from each treatment were randomly selected to monitor feed intake, digestibility, and health-related indicators. These latter animals were euthanized at wk 22 of age to study the rumen anatomical, papillary, and microbiological development, whereas the remaining animals were monitored for reproductive performance and milk yield during the first lactation. Results indicated that PEY supplementation did not lead to feed intake or health issues because PEY animals tended to have a higher concentrate intake and lower diarrheal incidence than CTL animals. No differences between treatments were noted in terms of feed digestibility, rumen microbial protein synthesis, health-related metabolites, or blood cell counts. Supplementation with PEY promoted a higher rumen empty weight, and rumen relative proportion to the total digestive tract weight, than CTL animals. This was accompanied with a higher rumen papillary development in terms of papillae length and surface area in the cranial ventral and caudal ventral sacs, respectively. The PEY animals also had higher expression of the MCT1 gene, which is related to volatile fatty acid absorption by the rumen epithelium, than CTL animals. The antimicrobial effects of the turmeric and thymol could explain the decreased the rumen absolute abundance of protozoa and anaerobic fungi. This antimicrobial modulation led to a change in the bacterial community structure, a decrease in the bacteria richness, and to the disappearance (i.e., Prevotellaceae_UCG-004, Bacteroidetes_BD2-2, Papillibacter, Schwartzia, and Absconditabacteriales_SR1) or decline of certain bacterial taxa (i.e., Prevotellaceae_NK3B31_group, and Clostridia_UCG-014). Supplementation with PEY also decreased the relative abundance of fibrolytic (i.e., Fibrobacter succinogenes and Eubacterium ruminantium) and increased amylolytic bacteria (Selenomonas ruminantium). Although these microbial changes were not accompanied with significant differences in the rumen fermentation, this supplementation led to increased body weight gain during the preweaning period, higher body weight during the postweaning period, and higher fertility rate during the first gestation. On the contrary, no residual effects of this nutritional intervention were noted on the milk yield and milk components during the first lactation. In conclusion, supplementation with this blend of plant extracts and yeast cell wall component in early life could be considered as a sustainable nutritional strategy to increase body weight gain and optimize the rumen anatomical and microbiological development in young ruminants, despite having minor productive implications later in life.

Stable Ketenyl Anions via Ligand Exchange at an Anionic Carbon as Powerful Synthons.

Under an atmosphere of carbon monoxide (CO), a (phosphino)diazomethyl anion salt [[P]-CN2 ][K(18-C-6)(THF)] (1) ([P]=[(CH2 )(NDipp)]2 P; 18-C-6=18-crown-6; Dipp=2,6-diisopropylphenyl) undergoes a facile N2 /CO exchange reaction giving the (phosphino)ketenyl anion salt [[P]-CCO][K(18-C-6)] (2). Oxidation of 2 with elemental Se affords the (selenophosphoryl)ketenyl anion salt [P](Se)-CCO][K(18-C-6)] (3). These ketenyl anions feature a strongly bent geometry at the P-bound carbon and this carbon atom is highly nucleophilic. The electronic structure of the ketenyl anion [[P]-CCO]- of 2 is examined by theoretical studies. Reactivity investigations demonstrate 2 as a versatile synthon for derivatives of ketene, enolate, acrylate and acrylimidate moieties.

Geometrically Constrained Organoboron Species as Lewis Superacids and Organic Superbases.

This report unveils an advancement in the formation of a Lewis superacid (LSA) and an organic superbase by the geometrical deformation of an organoboron species towards a T-shaped geometry. The boron dication [2]2+ supported by an amido diphosphine pincer ligand features both a large fluoride ion affinity (FIA>SbF5 ) and hydride ion affinity (HIA>B(C6 F5 )3 ), which qualifies it as both a hard and soft LSA. The unusual Lewis acidic properties of [2]2+ are further showcased by its ability to abstract hydride and fluoride from Et3 SiH and AgSbF6 respectively, and effectively catalyze the hydrodefluorination, defluorination/arylation, as well as reduction of carbonyl compounds. One and two-electron reduction of [2]2+ affords stable boron radical cation [2]⋅+ and borylene 2, respectively. The former species has an extremely high spin density of 0.798e at the boron atom, whereas the latter compound has been demonstrated to be a strong organic base (calcd. pKBH + (MeCN)=47.4) by both theoretical and experimental assessment. Overall, these results demonstrate the strong ability of geometric constraining to empower the central boron atom.

Optimization of the Polarization Profile of Conical-Shaped Shells Piezoelectric Sensors.

Conical shell structures are frequently submitted to severe static and dynamic mechanical loads that can result in situations that affect the service of the systems that are part of, or even cause catastrophic failures. For this reason, a common solution is to design an active deformation control system, usually using piezoelectric patches strategically distributed along the surface of the shell structure. Moreover, these elements may be part of an energy recovery system. This paper details the methodology to topologically optimize the placement of piezoelectric elements through a characteristic function, analysing static and free vibration loading cases by means of the finite element method. Then, the optimal arrangement of the electrode with different polarization profiles is distributed throughout the entire structure. The nature of the loading cases studied corresponds to a general situation where static loads and dynamics vibration are considered. The objective function of the problem only depends linearly on the displacement fields, and therefore, the optimal electrode profile can be obtained for any combination of loads. As a consequence, this technique allows for maximising the electric charge obtained, which results in a greater capacity for monitoring, actuation and/or energy harvesting.

Whole Transcriptome Analyses of Apricots and Japanese Plum Fruits after 1-MCP (Ethylene-Inhibitor) and Ethrel (Ethylene-Precursor) Treatments Reveal New Insights into the Physiology of the Ripening Process.

The physiology of Prunus fruit ripening is a complex and not completely understood process. To improve this knowledge, postharvest behavior during the shelf-life period at the transcriptomic level has been studied using high-throughput sequencing analysis (RNA-Seq). Monitoring of fruits has been analyzed after different ethylene regulator treatments, including 1-MCP (ethylene-inhibitor) and Ethrel (ethylene-precursor) in two contrasting selected apricot (Prunus armeniaca L.) and Japanese plum (P. salicina L.) cultivars, 'Goldrich' and 'Santa Rosa'. KEEG and protein-protein interaction network analysis unveiled that the most significant metabolic pathways involved in the ripening process were photosynthesis and plant hormone signal transduction. In addition, previously discovered genes linked to fruit ripening, such as pectinesterase or auxin-responsive protein, have been confirmed as the main genes involved in this process. Genes encoding pectinesterase in the pentose and glucuronate interconversions pathway were the most overexpressed in both species, being upregulated by Ethrel. On the other hand, auxin-responsive protein IAA and aquaporin PIP were both upregulated by 1-MCP in 'Goldrich' and 'Santa Rosa', respectively. Results also showed the upregulation of chitinase and glutaredoxin 3 after Ethrel treatment in 'Goldrich' and 'Santa Rosa', respectively, while photosystem I subunit V psaG (photosynthesis) was upregulated after 1-MCP in both species. Furthermore, the overexpression of genes encoding GDP-L-galactose and ferredoxin in the ascorbate and aldarate metabolism and photosynthesis pathways caused by 1-MCP favored antioxidant activity and therefore slowed down the fruit senescence process.

Monitoring Apricot (Prunus armeniaca L.) Ripening Progression through Candidate Gene Expression Analysis.

This study aimed at the monitoring of the apricot (Prunus armeniaca L.) ripening progression through the expression analysis of 25 genes related to fruit quality traits in nine cultivars with great differences in fruit color and ripening date. The level of pigment compounds, such as anthocyanins and carotenoids, is a key factor in food taste, and is responsible for the reddish blush color or orange skin and flesh color in apricot fruit, which are desirable quality traits in apricot breeding programs. The construction of multiple linear regression models to predict anthocyanins and carotenoids content from gene expression allows us to evaluate which genes have the strongest influence over fruit color, as these candidate genes are key during biosynthetic pathways or gene expression regulation, and are responsible for the final fruit phenotype. We propose the gene CHS as the main predictor for anthocyanins content, CCD4 and ZDS for carotenoids content, and LOX2 and MADS-box for the beginning and end of the ripening process in apricot fruit. All these genes could be applied as RNA markers to monitoring the ripening stage and estimate the anthocyanins and carotenoids content in apricot fruit during the ripening process.

Intracranial Virotherapy for a Canine Hemangioma.

Intracranial hemangiomas are rare neoplastic lesions in dogs that usually appear with life-threatening symptoms. The treatment of choice is tumor resection; however, complete resection is rarely achieved. The patient's prognosis therefore usually worsens due to tumor progression, and adjuvant treatments are required to control the disease. Oncolytic viruses are an innovative approach that lyses the tumor cells and induces immune responses. Here, we report the intratumoral inoculation of ICOCAV15 (an oncolytic adenovirus) in a canine intracranial hemangioma, as adjuvant treatment for incomplete tumor resection. The canine patient showed no side effects, and the tumor volume decreased over the 12 months after the treatment, as measured by magnetic resonance imaging using volumetric criteria. When progressive disease was detected at month 18, a new dose of ICOCAV15 was administered. The patient died 31.9 months after the first inoculation of the oncolytic adenovirus. Furthermore, tumor-infiltrated immune cells increased in number after the viral administrations, suggesting tumor microenvironment activation. The increased number of infiltrated immune cells, the long survival time and the absence of side effects suggest that ICOCAV15 could be a safe and effective treatment and should be further explored as a novel therapy for canine hemangiomas.

Fascial Innervation: A Systematic Review of the Literature.

Currently, myofascial pain has become one of the main problems in healthcare systems. Research into its causes and the structures related to it may help to improve its management. Until some years ago, all the studies were focused on muscle alterations, as trigger points, but recently, fasciae are starting to be considered a new, possible source of pain. This systematic review has been conducted for the purpose of analyze the current evidence of the muscular/deep fasciae innervation from a histological and/or immunohistochemical point of view. A literature search published between 2000 and 2021 was made in PubMed and Google Scholar. Search terms included a combination of fascia, innervation, immunohistochemical, and different immunohistochemical markers. Of the 23 total studies included in the review, five studies were performed in rats, four in mice, two in horses, ten in humans, and two in both humans and rats. There were a great variety of immunohistochemical markers used to detect the innervation of the fasciae; the most used were Protein Gene Marker 9.5 (used in twelve studies), Calcitonin Gene-Related Peptide (ten studies), S100 (ten studies), substance P (seven studies), and tyrosine hydroxylase (six studies). Various areas have been studied, with the thoracolumbar fascia being the most observed. Besides, the papers highlighted diversity in the density and type of innervation in the various fasciae, going from free nerve endings to Pacini and Ruffini corpuscles. Finally, it has been observed that the innervation is increased in the pathological fasciae. From this review, it is evident that fasciae are well innerved, their innervation have a particular distribution and precise localization and is composed especially by proprioceptors and nociceptors, the latter being more numerous in pathological situations. This could contribute to a better comprehension and management of pain.

Effect of Myofascial Induction Therapy in Pterygoid Muscles of Woodwinds and String Musicians on Muscular Stiffness of the Upper Trapezius.

PURPOSE: Considering the fascial continuity and its biomechanical characteristics, the purpose of this study was to assess the change in muscular stiffness (Dm) of the upper trapezius muscles after the application of myofascial induction therapy (MIT) to the masticatory muscles of musicians. METHODS: This was a pre-posttest design involving one treatment. SUBJECTS: The total sample was 33 subjects (n = 33). The experimental group comprised 18 violin, viola, and woodwind players, and the control group was comprised of 15 non-musicians. The outcome measures included pre-posttest measurements with tensiomyography of the upper trapezius (muscle stiffness, Dm), and baseline neck disability (Neck Disability Index), and pain (SF-36 questionnaire). The experimental group received MIT for 5 minutes on each side of the lateral pterygoid muscle. The control group assumed a supine position for 10 minutes. RESULTS: After the intervention, there was a significant difference in Time per Group (F = 2.896, p = 0.034, ƞ2p = 0.367, and w = 0.755). There were statistically significant differences in pre-post and side-by-side analyses for the Dm of the upper trapezius in the experimental group as well as between the two groups. CONCLUSION: MIT of the lateral pterygoids is effective in decreasing upper trapezius stiffness as measured by an increase in the Dm measured by tensiomyography. The greatest change occurred in musicians with a lower percentage of Neck Disability Index at baseline.

Crystalline Neutral Diboron Analogues of Cyclopropanes.

Although Schleyer's computations in 1979 predicted that the ground state of the parent diborirane features a planar-tetracoordinate carbon atom (anti van't Hoff-Le Bel geometry), this work demonstrates that substitution of C coupled with N-heterocyclic carbene (NHC) coordination provides access to isolable diborirane derivatives 3 and 4 with van't Hoff-Le Bel geometry. Species 3 and 4 are isoelectronic with cyclopropane and the highly strained B2 C rings feature 2c-2e bent σ bonds. Consequently, the B-B and B-C bonds in 3 are cleaved in the presence of hydride, proton, and chalcogens. The former two reactions gave NHC-coordinated fluorenyldihydridoborane 5 and dichlorofluorenylborane 6, respectively, whereas the latter transformations afforded novel thiaborirane 8 and selenaborirane 9. In addition, transfer hydrogenation of 3 with ammonia borane (H3 N⋅BH3 ) led to the formation of (µ-hydrido)diborane 7 via selective cleavage of the B-B bond. These reactivities show potential for their future application in organic synthesis.

Unveiling Hetero-Enyne Reactivity of Aryliminoboranes: Dearomative Hetero-Diels-Alder-Like Reactions.

Being isoelectronic with alkynes, iminoboranes with a polar B≡N triple bond have been exclusively investigated as a potent 1,2-dipole in synthetic chemistry. Herein, we disclose the unprecedented reactivity of aryliminoboranes via the BNCC π conjugation, namely hetero-enyne behavior. This allows for facile dearomative Diels-Alder-like reactions of aryliminoboranes with aldehydes. This cycloaddition features mild conditions, is catalyst-free, and has a broad substrate scope and good functional group tolerance. Kinetic and computational studies reveal its second-order reaction and concerted cyclization mechanism. This report unveils new synthetic application of iminoboranes beyond their classical reaction patterns.

Hybridization and cryptic speciation in the Iberian endemic plant genus Phalacrocarpum (Asteraceae-Anthemideae).

Understanding the role and impact of reticulation in phylogenetic inquiry has improved with extended use of high throughput sequencing data. Yet, due to the dynamism of genomes over evolutionary time, disentangling old hybridization events remains a serious challenge. Phalacrocarpum (DC.) Willk. is one of the 27 Iberian endemic plant genera, currently considered monotypic but including three subspecies. Its uncertain phylogenetic relationships within tribe Anthemideae (Asteraceae) point to an Early Miocene divergence from its sister group, and its persistent taxonomic instability has been proposed to be due to hybridization. We aim at understanding the evolutionary history of this genus using SNPs called from a genotyping-by-sequencing (GBS) analysis, Sanger sequences-from three plastid DNA regions (psbJ-petA, petB-petD, trnH-psbA) and the nuclear ribosomal ITS regions (cloned)-as well as leaf morphometric multivariate analysis. SNP data and Sanger sequences strongly support the unforeseen existence of a cryptic species in the eastern populations of P. oppositifolium subsp. anomalum. Broad molecular and morphometric patterns of variation found in conflictive populations from the Sanabria Valley region convincingly identify a recent previously undocumented hybrid zone. By contrast, evidence is less conclusive on relationships between subspecies hoffmannseggii, oppositifolium and a second conflictive group distributed along the Galician-Portuguese border (Orense massifs). Although genetic clustering analysis of SNP data suggests that the former subspecies was the maternal progenitor in hybridization events that gave rise to the other two groups, we found considerable uniqueness of ITS ribotypes and plastid haplotypes in them. This result, in the context of Pleistocene climatically-driven range shifts in NW Iberian Peninsula, can be due to periods of isolation, genetic bottlenecks and drift superimposed on old hybridization events. Our study confirms the idea that unravelling old hybridization events may be compromised by the suite of evolutionary processes accumulated subsequently, particularly in areas with a history of climatic instability.