Despite the widespread and increasing usage of Pd-catalyzed C-N cross couplings, finding good conditions for these reactions can be challenging. Practitioners mostly rely on few methodology studies ...or anecdotal experience. This is surprising, since the advent of data-driven experimentation and the large amount of knowledge in databases allow for data-driven insight. In this work, we address this by analyzing more than 62 000 Buchwald-Hartwig couplings gathered from CAS, Reaxys and the USPTO. Our meta-analysis of the reaction performance generates data-driven cheatsheets for reaction condition recommendation. It also provides an interactive tool to find rarer ligands with optimal performance regarding user-selected substrate properties. With this we give practitioners promising starting points. Furthermore, we study bias and diversity in the literature and summarize the current state of the reaction data, including its pitfalls. Hence, this work will also be useful for future data-driven developments such as the optimization of reaction conditions
via
machine learning.
An analysis of the entire literature on Pd-catalyzed C-N couplings enables data-driven insight and provides recommendations for reaction conditions.
The control of quantum dot (QD) photoluminescence (PL) is a challenge for many applications. It is well known that plasmonic resonances can enhance this PL. In this work, we couple QDs with silver ...nanoparticles and immerse the system in a photochromic organic material. As these molecules are optical switches going from a transparent to a colored isomer by absorbing UV light, we observe on one hand a Förster Resonant Energy Transfer (FRET) between the QD emission and the absorbing isomer and on the other hand a plasmonic PL enhancement. The photochromic transition leads to the optical control of the FRET, allowing us to control the QD de-excitation preferences (radiative or non-radiative) and so the emitted light.
Connecting literary discourse analysis, rhetoric, and argumentation theory, this study focuses on a “childhood memory” of Albert Cohen that reappears in four autobiographical texts and three ...interviews. The different occurrences of this episode of the insults uttered on his tenth birthday by an anti-Semitic street vendor are interesting for what is repeated from one occurrence to another, but above all for what varies. Extending the study by Claire Stolz of the story published in La France libre, in 1945, I insist here on the epideictic rhetoric that runs through its resumption in the review Esprit, in September 1945, and on the judicial and deliberative dimension of Ô vous, frères humains (1972), and Carnets 1978. The analysis of racist insults highlights the way in which epideictic blame crosses the perverted use of speech that characterizes the eloquence of the street vendor.
La linguistique du texte a pour tâche la théorisation et la description des opérations de segmentation qui délimitent des unités de rang et de longueur différentes, et la théorisation et la ...description des différents effets de continuité créés par les opérations de liage de ces unités. À la structuration phrastique-périodique par la morpho-syntaxe et la prosodie à l’oral, la ponctuation à l’écrit, le palier micro-textuel ajoute six facteurs de texture transphrastique : les liages référentiels et isotopiques, les liages du signifiant, l’ensemble des phénomènes de connexion, les relations d’implicitation, la cohésion énonciative et la cohésion illocutoire. À partir de trois textes (publicitaire, littéraire et discours politique oral), cet article illustre systématiquement et détaille ces six formes de liage transphrastique des unités textuelles de base.
Decagram quantities of enantiopure (+)‐mefloquine have been produced via kinetic resolution of racemic mefloquine using a ROMP‐gel supported chiral acyl hydroxamic acid resolving agent. The requisite ...monomer was prepared in a few synthetic steps without chromatography and polymerization was safely performed on a >30 gram scale under ambient conditions. The reagent was readily regenerated and reused multiple times for the resolution of 150 grams of (±)‐mefloquine and other chiral N‐heterocylces.
Pearl Jam: A novel ROMP‐gel supported reagent allows the preparation of enantiopure (+)‐erythro‐mefloquine on a decagram scale from its racemate. The monomer synthesis does not require chromatographic purification, and polymerization can be carried out safely on a >30 gram scale. PEARL is readily recovered after each cycle and has been applied for resolution of a broad range of N‐heterocycles.
Simian T-lymphotropic virus 1 (STLV-1) enters human populations through contact with nonhuman primate (NHP) bushmeat. We tested whether differences in the extent of contact with STLV-1-infected NHP ...bushmeat foster regional differences in prevalence of human T-lymphotropic virus 1 (HTLV-1). Using serological and PCR assays, we screened humans and NHPs at two Sub-Saharan African sites where subsistence hunting was expected to be less (Taï region, Côte d'Ivoire CIV) or more (Bandundu region, Democratic Republic of the Congo DRC) developed. Only 0.7% of human participants were infected with HTLV-1 in CIV (
= 574), and 1.3% of humans were infected in DRC (
= 302). Two of the Ivorian human virus sequences were closely related to simian counterparts, indicating ongoing zoonotic transmission. Multivariate analysis of human demographic parameters and behavior confirmed that participants from CIV were less often exposed to NHPs than participants from DRC through direct contact, e.g., butchering. At the same time, numbers of STLV-1-infected NHPs were higher in CIV (39%;
= 111) than in DRC (23%;
= 39). We conclude that similar ultimate risks of zoonotic STLV-1 transmission-defined as the product of prevalence in local NHP and human rates of contact to fresh NHP carcasses-contribute to the observed comparable rates of HTLV-1 infection in humans in CIV and DRC. We found that young adult men and mature women are most likely exposed to NHPs at both sites. In view of the continued difficulties in controlling zoonotic disease outbreaks, the identification of such groups at high risk of NHP exposure may guide future prevention efforts.
Multiple studies report a high risk for zoonotic transmission of blood-borne pathogens like retroviruses through contact with NHPs, and this risk seems to be particularly high in tropical Africa. Here, we reveal high levels of exposure to NHP bushmeat in two regions of Western and Central tropical Africa. We provide evidence for continued zoonotic origin of HTLV-1 in humans at CIV, and we found that young men and mature women represent risk groups for zoonotic transmission of pathogens from NHPs. Identifying such risk groups can contribute to mitigation of not only zoonotic STLV-1 transmission but also transmission of any blood-borne pathogen onto humans in Sub-Saharan Africa.
The cannabinoid receptor 2 (CB2) system is described to modulate various pathological conditions, including inflammation and fibrosis. A series of new heterocyclic small‐molecule CB2 receptor ...agonists were identified from a high‐throughput screen. Lead optimization gave access to novel, highly potent, and selective (over CB1) triazolopyrimidine derivatives. A preliminary structure–activity relationship was established, and physicochemical properties in this compound class were significantly improved toward better solubility, lipophilicity, and microsomal stability. An optimized triazolopyrimidine derivative, (3S)‐1‐5‐tert‐butyl‐3‐(1‐cyclopropyltetrazol‐5‐yl)methyltriazolo4,5‐dpyrimidin‐7‐ylpyrrolidin‐3‐ol (39), was tested in a kidney ischemia–reperfusion model, in which it showed efficacy at a dose of 10 mg kg−1 (p.o.). A significant depletion of the three measured kidney markers indicated a protective role of CB2 receptor activation toward inflammatory kidney damage. Compound 39 was also protective in a model of renal fibrosis. Oral treatment with 39 at 3 mg kg−1 per day significantly decreased the amount of fibrosis by ∼40 % which was induced by unilateral ureter obstruction.
Kidney protection: A series of small‐molecule CB2 receptor agonists was identified in a high‐throughput screen. Lead optimization work gave access to novel triazolopyrimidine derivatives, highly potent on CB2 and selective over CB1. Optimized compound 39 was efficacious in an in vivo model for kidney ischemia–reperfusion and in an in vivo model of renal fibrosis (unilateral ureter obstruction) upon p.o. administration.
Active plasmonics is a key focus for the development of advanced plasmonic applications. By selectively exciting the localized surface plasmon resonance sustained by the short or the long axis of ...silver nanorods, we demonstrate a polarization-dependent strong coupling between the plasmonic resonance and the excited state of photochromic molecules. By varying the width and the length of the nanorods independently, a clear Rabi splitting appears in the dispersion curves of both resonators.
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