Class Of Complexes Research Articles

(NHC)Pd(OAc)2]: Highly Active Carboxylate Pd(II)-NHC (NHC = N-Heterocyclic Carbene) Precatalysts for Suzuki-Miyaura and Buchwald-Hartwig Cross-Coupling of Amides by N-C(O) Activation.

In the past eight years, the selective cross-coupling of amides by N-C(O) bond activation has emerged as a highly attractive manifold for the manipulation of traditionally unreactive amide bonds. In this Special Issue on Next-Generation Cross-Coupling Chemistry, we report the Suzuki-Miyaura and Buchwald-Hartwig cross-coupling of amides by selective N-C(O) cleavage catalyzed by bench-stable, well-defined carboxylate Pd(II)-NHC (NHC = N-heterocyclic carbene) catalysts {[(NHC)Pd(O2CR)2]}. This class of Pd(II)-NHCs promotes cross-coupling under exceedingly mild room-temperature conditions owing to the facile dissociation of the carboxylate ligands to form the active complex. These readily accessible Pd(II)-NHC precatalysts show excellent functional group tolerance and are compatible with a broad range of amide activating groups. Considering the mild conditions for the cross-coupling and the facile access to carboxylate Pd(II)-NHC complexes, we anticipate that this class of bench-stable complexes will find wide application in the activation of amide N-C(O) and related acyl X-C(O) bonds.

Ruthenium(II) complexes of curcumin and β-diketone derivatives: effect of structural modifications on their cytotoxicity.

Ruthenium(II) complexes (Ru1-Ru3) with the general formula [Ru(O-O)(PPh3)2(bipy)]PF6, bearing two triphenylphosphine (PPh3), bipyridine (bipy) and a series of natural and synthetic β-diketones (O,O) ligands were synthesized and characterized using various analytical techniques. The interaction between the complexes and calf thymus DNA (CT-DNA) was investigated and demonstrated a weak interaction. The cytotoxicity of the complexes was investigated against breast cancer cells (MDA-MB-231 and MCF-7), lung cancer cells (A549), cisplatin-resistant ovarian cancer cells (A2780cis), as well as non-tumour lung (MRC-5) and non-tumour breast (MCF-10A) cell lines. All complexes exhibited cytotoxic activity against all the cell lines studied, with half maximal inhibitory concentration (IC50) values ranging from 0.39 to 13 µM. Notably, the three complexes demonstrated selectivity against the A2780cis cell line, with IC50 ranging from 0.39 to 0.82 µM. Among them, Ru2 exhibited the highest cytotoxicity, with an IC50 value of 0.39 µM. Consequently, this new class of complexes shows good selectivity towards cisplatin-resistant ovarian cancer cells and it is promising for further investigation as anti-cancer agents.

Three-Charge (0, -1, -2) Ligand-Based Binuclear and Mononuclear Deep-Red Phosphorescent Iridium Complexes Bearing Benzo[d]oxazole-2-Thiol Ligand.

A new class of three-charge (0, -1, -2) ligand-based binuclear and mononuclear iridium complexes bearing benzo[d]oxazole-2-thiol ligand have been synthesized. Notably, the binuclear complexes (IrIr1 and IrIr2) can be generated at low temperatures by reacting the iridium complex precursors (2a and 2b) with equal amounts of the benzo[d]oxazole-2-thiol ligands, while the corresponding mononuclear complexes (Ir1 and Ir2) are formed at high temperatures. X-ray diffraction analysis shows that the benzo[d]oxazole-2-thiol ligand plays an unusual and interesting bridging role in binuclear complexes and induces rich intermolecular and intramolecular interactions, while in mononuclear complexes, it forms an interesting four-membered ring coordination. More importantly, all complexes experienced efficient deep-red emission in the 628-674 nm range, and the mononuclear complexes have higher luminescent efficiency and longer excited state lifetime than the binuclear complexes. As a result, organic light-emitting diode devices incorporating two mononuclear complexes (Ir1 and Ir2) as guest material of the light-emitting layer can obtain good maximum external quantum efficiency (3.5% and 5.5%) in the deep-red region (629 and 632 nm) with CIE coordinates (0.61, 0.33) and (0.62, 0.34), along with a low turn-on voltage (2.8 V).

Embedding calculus and grope cobordism of knots

We show that embedding calculus invariants evn are surjective for long knots in an arbitrary 3-manifold. This solves some remaining open cases of Goodwillie–Klein–Weiss connectivity estimates, and at the same time confirms one half of the conjecture that for classical knots evn are universal additive Vassiliev invariants over the integers. In addition, we give a sufficient condition for this conjecture to hold over a coefficient group, which is by recent results of Boavida de Brito and Horel fulfilled for the rationals and for the p-adic integers in a range. Therefore, embedding calculus invariants are strictly more powerful than the Kontsevich integral.Furthermore, our work shows they are more computable as well. Namely, the main theorem computes the first possibly non-vanishing invariantevnof a knot which is grope cobordant to the unknot to be precisely equal to the equivalence class of the underlying decorated tree of the grope in the associated graph complex. Actually, our techniques apply beyond dimension 3, offering a description of the layers in embedding calculus for long knots in a manifold of any dimension, and suggesting that certain generalised gropes realise the corresponding graph complex classes.

Influence of expression and purification protocols on Gα biochemical activity: kinetics of plant and mammalian G protein cycles.

Heterotrimeric G proteins are a class of signal transduction complexes with broad roles in human health and agriculturally important plant traits. In the classic paradigm, guanine nucleotide binding to the Gα subunit regulates the activation status of the complex. Using the Arabidopsis thaliana Gα subunit, GPA1, we developed a rapid StrepII-tag mediated purification method that facilitates isolation of protein with increased enzymatic activities as compared to conventional methods, and is demonstrably also applicable to mammalian Gα subunits. We subsequently utilized domain swaps of GPA1 and human GNAO1 to demonstrate the instability of recombinant GPA1 is a function of the interaction between the Ras and helical domains, and can be partially uncoupled from the rapid nucleotide binding kinetics displayed by GPA1.

The expanding scope of ship design practice

As the former International Chair of IMDC, the initiator of the continuing series of IMDC State of Art (SoA) Reports and the lead author of most IMDC SoA Reports on design methodology from 1997 to 2018, the author has both pioneered and observed an increasingly broader scope in the practice of the design of particularly complex vessels. The paper commences with reviewing some key publications, not just to recent IMDCs, that have tracked the manner in which “ship design” (in the broadest sense) has become more sophisticated – especially in the crucial early stages of design. The diversity of ship design practice, not just due to computer-based methods, is readily observable. Moreover, the impact of computer aided design in ship design has not just been to better analyse ship performance (e. g. in hydrodynamics, strength and ship infrastructure systems behaviour) but also in the increasing use of graphical tools and design methods to enable “better ship design”. In a growing number of, mainly, academic centres, but also in some government agencies and design consultancies, there is a clear desire to better understand how to design “ships” and to manage the ship design process, especially for the most complex and novel classes of vessels. In particular, the objectives being sought when conceptualising and synthesising a range of ship options (as part of the requirement elucidation approach) in an ever-increasing scoping of the relevant issues, amounts to developing a more holistic approach. This is not just due to an increasingly complex ship acquisition and ownership environment, but also due to environmental and socio-economic (especially system safety) concerns. Overlaying all this are the opportunities or the spectre of Artificial Intelligence (or perhaps more immediately those of Machine Learning) and its likely impact on engineering practice as well as those other professions in the “marine design enterprise”. The paper concludes by emphasising that while ship design has distinct differences, when compared with most other large scale engineering design practice, the lead ship design profession of the naval architect has somehow to deal with this expanding scope in the practice of “ship design”. This means the education and on the job development thrust must broaden if the ship design profession is not to be side-lined into acting as mere hull engineers. It is argued, such a specific role will be more vulnerable in an increasingly Machine Learning dominated future, than the holistic ship creating and systems architectural alternative. Finally an ambitious vision for future ship designers is given alongside a summary of the specific main contributions by the author to ship design methodology.

Smart bistable coordination complexes

AbstractSmart molecules have attracted increasing attention due to their transformative role in creating the next generation of smart structures and devices. Smart bistable coordination complexes are a class of functional complexes which have two stable states that can be reversibly switched in response to external stimuli. Such bistable molecules play a vital role in various applications, such as sensors, data storage, spintronics, smart windows, optical switches, information encryption and decryption, displays, actuators, etc. Herein, the recent research studies into the development of these smart bistable metal coordination complexes are reviewed. According to the different external stimuli, these smart bistable coordination systems have been classified and summarized, including light‐responsive systems, thermally‐responsive systems, electrically‐responsive systems, mechanically‐responsive systems, and some other cases. These systems are further subdivided according to the changes in signals (e.g., color, fluorescence, spin state, crystalline phase) under external stimuli. The design principles of each type of smart bistable metal complexes as well as their broad and innovative applications are comprehensively described. Finally, the challenges and opportunities in this field are briefly analyzed and discussed.

Tuning Excited State Character in Iridium(III) Photosensitizers and Its Influence on TTA-UC.

A series of mixed ligand, photoluminescent organometallic Ir(III) complexes have been synthesized to incorporate substituted 2-phenyl-1H-naphtho[2,3-d]imidazole cyclometalating ligands. The structures of three example complexes were categorically confirmed using X-ray crystallography each sharing very similar structural traits including evidence of interligand hydrogen bond contacts that account for the shielding effects observed in the 1H NMR spectra. The structural iterations of the cyclometalated ligand provide tuning of the principal electronic transitions that determine the visible absorption and emission properties of the complexes: emission can be tuned in the visible region between 550 and 610 nm and with triplet lifetimes up to 10 μs. The nature of the emitting state varies across the series of complexes, with different admixtures of ligand-centered and metal-to-ligand charge transfer triplet levels evident. Finally, the use of the complexes as photosensitizers in triplet-triplet annihilation energy upconversion (TTA-UC) was investigated in the solution state. The study showed that the complexes possessing the longest triplet lifetimes showed good viability as photosensitizers in TTA-UC. Therefore, the use of an electron-withdrawing group on the 2-phenyl-1H-naphtho[2,3-d]imidazole ligand framework can be used to rationally promote TTA-UC using this class of complex.

Coconut-sourced MCT oil: its potential health benefits beyond traditional coconut oil

AbstractPlant dietary lipids remain one of the most intriguing and complex classes of biological molecules. Among them, medium-chain triglycerides (MCTs) have garnered recognition for their unique physico-chemical properties and potential health benefits. Despite their classification as saturated fats, they stand apart from other saturated fatty acids due to their distinctive characteristics, positioning them as a valuable component in nutrition. While traditional dietary fats primarily contain long-chain triglycerides (LCTs), MCTs consist of medium-chain fatty acids (MCFAs), naturally found in coconut and palm oils. The structural dissimilarity grants MCTs advantageous attributes, encompassing rapid digestion and absorption, providing a swift source of energy. Importantly, MCT oil derived from coconuts surpasses traditional coconut oil in efficiency and speed of energy conversion due to its higher concentration of readily metabolizable MCTs, making it a superior choice in human nutrition. This comprehensive study delves deeply into the potential of coconut-derived MCT oil, illuminating its chemical constituents, production from coconut oil, distinctive physical and chemical properties, and metabolic characteristics. Additionally, it highlights a range of potential biological activities of the oil, including its efficacy in managing gastrointestinal disorders and promising roles in anticancer, neuroprotective, and antimicrobial effects. The report also discusses the extensive applications of MCT oil across diverse industrial and technological sectors, as well as its utilization in structured lipids, oleogels, and as a carrier for capsaicin. Addressing safety concerns and providing dosage guidelines, this paper emphasizes MCT oil as an alternative to coconut oil in various applications, offering a holistic perspective on its benefits.

Stealth transgenes enable CAR-T cells to evade host immune responses

BackgroundAdoptive cell therapy, such as chimeric antigen receptor (CAR)-T cell therapy, has improved patient outcomes for hematological malignancies. Currently, four of the six FDA-approved CAR-T cell products use the FMC63-based...

Concurrent Learning Robust Adaptive Fault Tolerant Boundary Regulation of Hyperbolic Distributed Parameter Systems.

This article develops a robust adaptive boundary output regulation approach for a class of complex anticollocated hyperbolic partial differential equations subjected to multiplicative unknown faults in both the boundary sensor and actuator. The regulator design is based on the internal model principle, which amounts to stabilize a coupled cascade system, which consists of a finite-dimensional internal model driven by a hyperbolic distributed parameter system (DPS). To this end, a systematic sliding mode equipped with a backstepping approach is developed such that the robust state feedback control can be realized. Moreover, since the available information is a faulty boundary measurement at the right side point, state estimation is required. However, due to the presence of boundary unknown faults, we need to solve an issue of joint fault-state estimation. Restrictive persistent excitation conditions are usually required to guarantee the exact estimation of faults but are unrealistic in practice. To this end, a novel concurrent learning (CL) adaptive observer is proposed so that exponential convergence is obtained. It is the first time that the spirit of CL is introduced to the field of DPSs. Consequently, the observer-based adaptive boundary fault tolerant control scheme is developed, and rigorous theoretical analysis is given such that the exponential output regulation can be achieved. Finally, the effectiveness of the proposed methodology is demonstrated via comparative simulations.

In defense of platinum: Amino acidic polydentate ligands as a shield against sulphur-donor nucleophilic attacks

The interactions of sulfur-containing peptides and proteins with platinum-based anticancer agents are of significant interest in the field of bioinorganic chemistry. We previously modified the lead compound potassium {trichlorido[η2-(but-3-en-1-yl)-2-acetoxybenzoate]platinate(II)} (Pt-butene-ASA) by exchanging two chlorido ligands for an amino acid chelating ligand to improve its stability in aqueous solutions. In the current study, we demonstrate how this amino acid ligand strengthens the inertness of this class of complexes against sulfur-containing compounds. We incubated four complexes, each bearing an amino acid chelating ligand, with various sulfur-containing compounds of biological interest, such as DMSO, methionine, glutathione, and substance P. The reactions were monitored using NMR spectroscopy and mass spectrometry, allowing the identification by combination with IR ion spectroscopy of exotic pentacoordinate platinum(II) complexes as reaction intermediates. The results indicated that the reactivity of complexes 1–4 ((ethene,N-trans)(l-alaninato-N,O)chlorido(η2-ethene)platinate(II), (ethene,O-trans)(β-alaninato-N,O)chlorido(η2-ethene)platinate(II), (l-histidinato-N,N)chlorido(η2-ethene)platinate(II), and (olefin,N-trans)(l-alaninato-N,O)chlorido(η2-(but-3-en-1-yl)-2-acetoxy benzoate)platinate(II), respectively) is determined by the inner coordination sphere, and the addition of an amino acid ligand significantly reduces the rate of nucleophilic substitutions by sulfur-containing nucleophiles. In particular, the N,ethylene-trans isomers reacted only to a low extent with the free thiol in glutathione, while the O,ethylene-trans isomer was completely consumed within 2 h. Complex 4, the new lead compound, showed low reactivity towards S-nucleophiles in general, which confirms the concept of using amino acids as biocompatible bidentate ligands to adjust the reactivity and stability of this kind of metallodrugs.

Observer‐based event‐triggered consensus control of nonlinear cyber‐physical systems under backlash‐like hysteresis and denial‐of‐service attacks

AbstractIn this article, we investigate the problem of event‐triggered distributed consensus control for a class of complex cyber‐physical systems (CPSs), where unknown backlash‐like hysteresis inputs and denial‐of‐service (DoS) attacks are considered in actuators and communication channels, respectively. In the first place, when communication networks are subjected to malicious DoS attacks, the connection weights of network communication topologies experience disruptions. To solve this issue, this work proposes a solution by constructing topological models for communication networks employing switching topologies and utilizing observers to estimate the combined measurement errors during the time interval of DoS attacks. Secondly, to address the repercussions of DoS attacks on control units and to optimize the utilization of communication resources, a distributed control protocol based on an event‐triggered scheme and employing locally deployed estimators is designed to significantly decrease the update frequency of control signals. Meanwhile, utilizing Lyapunov stability theory, the boundedness of all signals in the closed‐loop system is validated, thereby accomplishing the goal of consensus control. At last, the efficacy of the proposed control scheme is demonstrated through two simulation examples.

Abstract 3931: Breast cancer genomic architecture contributes to immune escape across metastasis

Abstract Clinically, breast tumors are stratified based on the expression of three receptors - estrogen receptor (ER), progesterone receptor (PR) and human epidermal growth factor receptor-2 (HER2). Breast cancer is a highly heterogeneous disease, and a more detailed understanding of its genomic drivers, mechanisms of immune evasion, and evolution may inform more effective and personalized treatment. Previously, we established a genome-driven breast cancer classification scheme that defines 11 integrative subgroups (ICs) of disease with distinct copy number aberrations (CNAs), transcriptional profiles, and clinical outcomes. Specifically, we identify four subgroups of ER+ disease (IC1, IC2, IC6, IC9) with a persistent risk of lethal distant relapse up to two decades after diagnosis, each with focal copy number drivers and two distinct subgroups of triple-negative disease (Curtis et al. Nature 2012; Rueda et al. Nature 2019). These findings nominate new therapeutic strategies, however, it is not known how mutational processes and genomic architecture differ across the ICs to sculpt the development and evolution of disease, nor how their microenvironments differ. To interrogate the genomic and immune landscape of breast cancer throughout the disease continuum, we established a meta-cohort of 2,873 breast tumors spanning pre-invasive (ductal carcinoma in situ), primary invasive, and metastatic breast cancer, including 1,865 with whole-genome sequencing, 1,738 with whole-transcriptome sequencing, and 730 with both modalities. We developed a fully containerized bioinformatic workflow to interrogate copy number alterations, complex classes of structural variation, and neoantigens. Analysis of this large clinically curated compendium identifies highly concordant mutational signatures and higher order genomic features in high-risk ER+ (IC1,2,6,9) and HER2+ (IC5) tumors, including distinct patterns of structural variation. In contrast, triple-negative tumors (predominantly IC10) were characterized by global genomic instability and tandem duplications, whilst a third group is largely genomically stable. These distinct genomic architectures were associated with specific tumor microenvironments. As expected, triple-negative tumors were immune-enriched. In contrast high-risk ER+ and HER2+ tumors demonstrated immune-depleted profiles, as compared to typical risk ER+ tumors. These microenvironment classifications were maintained from primary tumors to metastatic lesions, except triple-negative tumors that exhibited increased immune depletion during metastasis. Taken together, our data demonstrate that complex structural alterations established early in breast cancer contribute to immune evasion, and persist throughout the life history of the tumor through metastasis. Citation Format: Lise Mangiante, Kathleen Houlahan, Cristina Sotomayor Vivas, Alvina Adimoelja, Seongyeol Park, Aziz Khan, Sophie Pribus, Zhicheng Ma, Jennifer Caswell-Jin, Christina Curtis. Breast cancer genomic architecture contributes to immune escape across metastasis [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2024; Part 1 (Regular Abstracts); 2024 Apr 5-10; San Diego, CA. Philadelphia (PA): AACR; Cancer Res 2024;84(6_Suppl):Abstract nr 3931.

Nickel-Catalyzed Ethylene Copolymerization with Vinylalkoxysilanes: A Computational Study.

Since the discovery of α-diimine catalysts in 1995, an extensive series of Brookhart-type complexes have shown their excellence in catalyzing ethylene polymerizations with remarkable activity and a high molecular weight. However, although this class of palladium complexes has proven proficiency in catalyzing ethylene copolymerization with various polar monomers, the α-diimine nickel catalysts have generally exhibited a much worse performance in these copolymerizations compared to their palladium counterparts. Recently, Brookhart et al. reported a notable exception, demonstrating that α-diimine nickel catalysts could catalyze the ethylene copolymerization with some vinylalkoxysilanes effectively, producing functionalized polyethylene incorporating trialkoxysilane (-Si(OR)3) groups. This breakthrough is significant since Pd-catalyzed copolymerizations are commercially less usable due to the high cost of palladium. Thus, the utilization of Ni, given its abundance in raw materials and cost-effectiveness, is a landmark in ethylene/polar vinyl monomer copolymerization. Inspired by these findings, we used density functional theory (DFT) calculations to investigate the mechanistic study of ethylene copolymerization with vinyltrimethoxysilane (VTMoS) catalyzed by Brookhart-type nickel catalysts, aiming to elucidate the molecular-level understanding of this unique reaction. Initially, the nickel complexes and cationic active species were optimized through DFT calculations. Subsequently, we explored the mechanisms including the chain initiation, chain propagation, and chain termination of ethylene homopolymerization and copolymerization catalyzed by Brookhart-type complexes. Finally, we conducted an energetic analysis of both the in-chain and chain-end of silane enchainment. It was found that chain initiation is the dominant step in the ethylene homopolymerization catalyzed by the α-diimine Ni complex. The 1,2- and 2,1-insertion of vinylalkoxysilane exhibit similar barriers, explaining the fact that both five-membered and four-membered chelates were identified experimentally. After the VTMoS insertion, the barriers of ethylene reinsertion become higher, indicating that this step is the rate-determining step, which could be attributed to the steric hindrance between the incoming ethylene and the bulky silane substrate. We have also reported the energetic analysis of the distribution of polar substrates. The dominant pathway of chain-end -Si(OR)3 incorporation is suggested as chain-walking → ring-opening → ethylene insertion, and the preference of chain-end -Si(OR)3 incorporation is primarily attributed to the steric repulsion between the pre-inserted silane group and the incoming ethylene molecule, reducing the likelihood of in-chain incorporation.

Development of (NO)Fe(N2S2) as a Metallodithiolate Spin Probe Ligand: A Case Study Approach.

ConspectusThe ubiquity of sulfur-metal connections in nature inspires the design of bi- and multimetallic systems in synthetic inorganic chemistry. Common motifs for biocatalysts developed in evolutionary biology include the placement of metals in close proximity with flexible sulfur bridges as well as the presence of π-acidic/delocalizing ligands. This Account will delve into the development of a (NO)Fe(N2S2) metallodithiolate ligand that harnesses these principles. The Fe(NO) unit is the centroid of a N2S2 donor field, which as a whole is capable of serving as a redox-active, bidentate S-donor ligand. Its paramagnetism as well as the ν(NO) vibrational monitor can be exploited in the development of new classes of heterobimetallic complexes. We offer four examples in which the unpaired electron on the {Fe(NO)}7 unit is spin-paired with adjacent paramagnets in proximal and distal positions.First, the exceptional stability of the (NO)Fe(N2S2)-Fe(NO)2 platform, which permits its isolation and structural characterization at three distinct redox levels, is linked to the charge delocalization occurring on both the Fe(NO) and the Fe(NO)2 supports. This accommodates the formation of a rare nonheme {Fe(NO)}8 triplet state, with a linear configuration. A subsequent FeNi complex, featuring redox-active ligands on both metals (NO on iron and dithiolene on nickel), displayed unexpected physical properties. Our research showed good reversibility in two redox processes, allowing isolation in reduced and oxidized forms. Various spectroscopic and crystallographic analyses confirmed these states, and Mössbauer data supported the redox change at the iron site upon reduction. Oxidation of the complex produced a dimeric dication, revealing an intriguing magnetic behavior. The monomer appears as a spin-coupled diradical between {Fe(NO)}7 and the nickel dithiolene monoradical, while dimerization couples the latter radical units via a Ni2S2 rhomb. Magnetic data (SQUID) on the dimer dication found a singlet ground state with a thermally accessible triplet state that is responsible for magnetism. A theoretical model built on an H4 chain explains this unexpected ferromagnetic low-energy triplet state arising from the antiferromagnetic coupling of a four-radical molecular conglomerate. For comparison, two (NO)Fe(N2S2) were connected through diamagnetic group 10 cations producing diradical trimetallic complexes. Antiferromagnetic coupling is observed between {Fe(NO)}7 units, with exchange coupling constants (J) of -3, -23, and -124 cm-1 for NiII, PdII, and PtII, respectively. This trend is explained by the enhanced covalency and polarizability of sulfur-dense metallodithiolate ligands. A central paramagnetic trans-Cr(NO)(MeCN) receiver unit core results in a cissoid structural topology, influenced by the stereoactivity of the lone pair(s) on the sulfur donors. This {Cr(NO)}5 radical bridge, unlike all previous cases, finds the coupling between the distal Fe(NO) radicals to be ferromagnetic (J = 24 cm-1).The stability and predictability of this S = 1/2 moiety and the steric/electronic properties of the bridging thiolate sulfurs suggest it to be a likely candidate for the development of novel molecular (magnetic) compounds and possibly materials. The role of synthetic inorganic chemistry in designing synthons that permit connections of the (NO)Fe(N2S2) metalloligand is highlighted as well as the properties of the heterobi- and polymetallic complexes derived therefrom.

Local, colocal, and antilocal properties of modules and complexes over commutative rings

This paper is a commutative algebra introduction to the homological theory of quasi-coherent sheaves and contraherent cosheaves over quasi-compact semi-separated schemes. Antilocality is an alternative way in which global properties are locally controlled in a finite affine open covering. For example, injectivity of modules over non-Noetherian commutative rings is not preserved by localizations, while homotopy injectivity of complexes of modules is not preserved by localizations even for Noetherian rings. The latter also applies to the contraadjustedness and cotorsion properties. All the mentioned properties of modules or complexes over commutative rings are actually antilocal. They are also colocal, if one presumes contraadjustedness. Generally, if the left class in a (hereditary complete) cotorsion theory for modules or complexes of modules over commutative rings is local and preserved by direct images with respect to affine open immersions, then the right class is antilocal. If the right class in a cotorsion theory for contraadjusted modules or complexes of contraadjusted modules is colocal and preserved by such direct images, then the left class is antilocal. As further examples, the class of flat contraadjusted modules is antilocal, and so are the classes of acyclic, Becker-coacyclic, or Becker-contraacyclic complexes of contraadjusted modules. The same applies to the classes of homotopy flat complexes of flat contraadjusted modules and acyclic complexes of flat contraadjusted modules with flat modules of cocycles.

Pride and Probability

Abstract Bayesian agents, argues Belot (2013), are orgulous: they believe in inductive success even when guaranteed to fail on a topologically typical collection of data streams. Here we shed light on how pervasive this phenomenon is. We identify several classes of inductive problems for which Bayesian convergence to the truth is topologically typical. However, we also show that, for all sufficiently complex classes, there are inductive problems for which convergence is topologically atypical. Lastly, we identify specific topologically typical collections of data streams, observing which guarantees convergence to the truth across all problems from certain natural classes of effective inductive problems.

Pharmacological Improvement of Cystic Fibrosis Transmembrane Conductance Regulator Function Rescues Airway Epithelial Homeostasis and Host Defense in Children with Cystic Fibrosis.

Rationale: Pharmacological improvement of cystic fibrosis transmembrane conductance regulator (CFTR) function with elexacaftor/tezacaftor/ivacaftor (ETI) provides unprecedented improvements in lung function and other clinical outcomes in patients with cystic fibrosis (CF). However, ETI effects on impaired mucosal homeostasis and host defense at the molecular and cellular levels in the airways of patients with CF remain unknown. Objectives: To investigate effects of ETI on the transcriptome of nasal epithelial and immune cells from children with CF at the single-cell level. Methods: Nasal swabs from 13 children with CF and at least one F508del allele aged 6 to 11 years were collected at baseline and 3 months after initiation of ETI, subjected to single-cell RNA sequencing, and compared with swabs from 12 age-matched healthy children. Measurements and Main Results: Proportions of CFTR-positive cells were decreased in epithelial basal, club, and goblet cells, but not in ionocytes, from children with CF at baseline and were restored by ETI therapy to nearly healthy levels. Single-cell transcriptomics revealed an impaired IFN signaling and reduced expression of major histocompatibility complex classes I and II encoding genes in epithelial cells of children with CF at baseline, which was partially restored by ETI. In addition, ETI therapy markedly reduced the inflammatory phenotype of immune cells, particularly of neutrophils and macrophages. Conclusions: Pharmacological improvement of CFTR function improves innate mucosal immunity and reduces immune cell inflammatory responses in the upper airways of children with CF at the single-cell level, highlighting the potential to restore epithelial homeostasis and host defense in CF airways by early initiation of ETI therapy.

Density Functional Calculation and Evaluation of the Spectroscopic Properties and Luminescent Material Application Potential of the N-Heterocyclic Platinum(II) Tetracarbene Complexes.

A series of reported Pt(II) carbene complexes possibly have the ability to serve as the new generation of blue emitters in luminescent devices because of their narrow emission spectra, high photoluminescence quantum yields (PLQYs), and rigid molecular skeleton. However, the combination of all carbene ligands with different multidentate structures will affect the overall planarity and horizontal dipole ratio to varying degrees, but the specific extent of this effect has not previously been analyzed in detail. In this work, density functional computation is used to study a class of platinum tetracarbene bidentate complexes with similar absorption and emission band characteristics, which is the main reason for the remarkable difference in quantum efficiency due to subtle differences in electronic states caused by different ligands. From the calculation results, the major reason, which results in significantly decrease in quantum efficiency for [Pt(cyim)2]2+, is that [Pt(cyim)2]2+ can reach the non-radiative deactivation metal-centered d-d excited state through an easier pathway compared with [Pt(meim)2]2+. The result, based on changes in the dihedral angle between ligands, can achieve the goal of improving and designing materials by adjusting the degree of the dihedral angle. (meim: bis(1,1'-dimethyl-3,3'-methylene-diimidazoline-2,2'-diylidene); cyim: bis(1,1'-dicyclohexyl-3,3'-methylene-diimidazoline-2,2'-diylidene).