Dearomative Alkylation-Based Two-Step cis-Diastereoselective Synthesis of Indoline-2,3-Fused Chromans and Tetrahydropyrans.

Herein, we describe a two-step, cis-diastereoselective synthesis of indoline-2,3-fused chromans from 3-substituted indoles. The method proceeds without intermediacy of ortho-quinone methides and leverages the dual function of TBS-protected 2-hydroxybenzyl iodides both as highly reactive alkylating agents in a t-BuONa/Et3B-promoted dearomative alkylation step and as a source of masked phenoxide nucleophiles in a subsequent TBAF-induced one-pot deprotection-cyclization step of the resulting indolenines. Importantly, this two-step protocol can also be extended to access indoline-2,3-fused tetrahydropyrans. These syntheses of indoline-2,3-fused chromans and tetrahydropyrans proceed with operational convenience, use easily accessible substrates and reagents, and feature broad substrate scope, high yields and complete diastereoselectivity. Furthermore, the synthesized products have the potential to undergo late-stage functionalization.

Constructing spirooxindoles from non-oxindole precursors: a one-pot nitro-reduction/double lactamization approach to spiro[indoline-3,3'-quinoline]-2,2'-diones.

2-(2-Nitrobenzyl)-2-(2-nitrophenyl)malonates, readily prepared by SNAr-arylation of diethyl malonate with o-fluoronitrobenzenes, followed by SN2-alkylatioin of the resulting products with o-nitrobenzyl bromides, undergo a tandem Fe/AcOH-promoted nitro-reduction and double lactamization sequence to afford spiro[indoline-3,3'-quinoline]-2,2'-diones in high overall yields. The method is operationally simple, economical, and has a broad substrate scope. The synthetic practicality of this methodology was illustrated by performing the reaction on a gram scale with the same efficiency.

Copper(II)-catalyzed, site-selective C(sp)2-H amination using 8-aminoimidazo[1,2-a]pyridine (8-AIP) as a directing group.

An efficient copper(II)-catalyzed regioselective ortho C(sp2)-H amination of arenes/heteroarenes has been developed with the assistance of 8-AIP (8-aminoimidazo[1,2-a]pyridine) as an efficacious 6,5-fused bicyclic removable chelating auxiliary. This operationally simple approach is scalable, has a broad substrate scope, and is highly compatible with functional groups. Furthermore, post-diversification of the synthesized derivatives demonstrates the methodology's synthetic adaptability.

Palladium-Catalyzed, Site-Selective C(sp2)8-H Halogenation and Nitration of 4-Quinolone Derivatives.

Selective installation of halo and nitro groups in heterocyclic backbone through a transition-metal-catalyzed C-H bond activation strategy is immensely alluring to access high-value scaffolds. Here in, we disclosed N-pyrimidyl-directed assisted palladium(II)-catalyzed C(sp2)8-H halogenation and nitration of substituted 4-quinolone derivatives in the presence of N-halosuccinimide and tert-butyl nitrite, respectively, offering structurally diversified 8-halo/nitro-embedded 4-quinolone frameworks in high yields. Mechanistic studies indicated that the reaction follows an organometallic pathway with a reversible C-H metalation step. This operationally simple protocol is scalable with a broad substrate scope and excellent functional group compatibility. Moreover, the postdiversifications of the synthesized derivatives are also showcased to ensure the synthetic versatility of the methodology.

Federated Graph Anomaly Detection via Contrastive Self-Supervised Learning.

Attribute graph anomaly detection aims to identify nodes that significantly deviate from the majority of normal nodes, and has received increasing attention due to the ubiquity and complexity of graph-structured data in various real-world scenarios. However, current mainstream anomaly detection methods are primarily designed for centralized settings, which may pose privacy leakage risks in certain sensitive situations. Although federated graph learning offers a promising solution by enabling collaborative model training in distributed systems while preserving data privacy, a practical challenge arises as each client typically possesses a limited amount of graph data. Consequently, naively applying federated graph learning directly to anomaly detection tasks in distributed environments may lead to suboptimal performance results. We propose a federated graph anomaly detection framework via contrastive self-supervised learning (CSSL) federated CSSL anomaly detection framework (FedCAD) to address these challenges. FedCAD updates anomaly node information between clients via federated learning (FL) interactions. First, FedCAD uses pseudo-label discovery to determine the anomaly node of the client preliminarily. Second, FedCAD employs a local anomaly neighbor embedding aggregation strategy. This strategy enables the current client to aggregate the neighbor embeddings of anomaly nodes from other clients, thereby amplifying the distinction between anomaly nodes and their neighbor nodes. Doing so effectively sharpens the contrast between positive and negative instance pairs within contrastive learning, thus enhancing the efficacy and precision of anomaly detection through such a learning paradigm. Finally, the efficiency of FedCAD is demonstrated by experimental results on four real graph datasets.

Towards net zero: A technological review on the potential of space-based solar power and wireless power transmission.

The global need for energy is increasing at a high rate and is expected to double or increase by 50%, according to some studies, in 30 years. As a result, it is essential to look into alternative methods of producing power. Solar photovoltaic (PV) power plants utilize the sun's clean energy, but they're not always dependable since they depend on weather patterns and requires vast amount of land. Space-based solar power (SBSP) has emerged as the potential solution to this issue. SBSP can provide 24/7 baseload carbon-free electricity with power density over 10 times greater than terrestrial alternatives while requiring far less land. Solar power is collected and converted in space to be sent back to Earth via Microwave or laser wirelessly and used as electricity. However, harnessing its full potential necessitates tackling substantial technological obstacles in wireless power transmission across extensive distances in order to efficiently send power to receivers on the ground. When it comes to achieving a net-zero goal, the SBSP is becoming more viable option. This paper presents a review of wireless power transmission systems and an overview of SBSP as a comprehensive system. To introduce the state-of-the-art information, the properties of the system and modern SBSP models along with application and spillover effects with regard to different sectors was examined. The challenges and risks are discussed to address the key barriers for successful project implementation. The technological obstacles stem from the fact that although most of the technology is already available none are actually efficient enough for deployment so with, private enterprises entering space race and more efficient system, the cost of the entire system that prevented this notion from happening is also decreasing. With incremental advances in key areas and sustained investment, SBSP integrated with other renewable could contribute significantly to cross-sector decarbonization.

Personalized Federated Graph Learning on Non-IID Electronic Health Records.

Understanding the latent disease patterns embedded in electronic health records (EHRs) is crucial for making precise and proactive healthcare decisions. Federated graph learning-based methods are commonly employed to extract complex disease patterns from the distributed EHRs without sharing the client-side raw data. However, the intrinsic characteristics of the distributed EHRs are typically non-independent and identically distributed (Non-IID), significantly bringing challenges related to data imbalance and leading to a notable decrease in the effectiveness of making healthcare decisions derived from the global model. To address these challenges, we introduce a novel personalized federated learning framework named PEARL, which is designed for disease prediction on Non-IID EHRs. Specifically, PEARL incorporates disease diagnostic code attention and admission record attention to extract patient embeddings from all EHRs. Then, PEARL integrates self-supervised learning into a federated learning framework to train a global model for hierarchical disease prediction. To improve the performance of the client model, we further introduce a fine-tuning scheme to personalize the global model using local EHRs. During the global model updating process, a differential privacy (DP) scheme is implemented, providing a high-level privacy guarantee. Extensive experiments conducted on the real-world MIMIC-III dataset validate the effectiveness of PEARL, demonstrating competitive results when compared with baselines.

Digital twin: Data exploration, architecture, implementation and future.

A Digital Twin (DT) is a digital copy or virtual representation of an object, process, service, or system in the real world. It was first introduced to the world by the National Aeronautics and Space Administration (NASA) through its Apollo Mission in the '60s. It can successfully design a virtual object from its physical counterpart. However, the main function of a digital twin system is to provide a bidirectional data flow between the physical and the virtual entity so that it can continuously upgrade the physical counterpart. It is a state-of-the-art iterative method for creating an autonomous system. Data is the brain or building block of any digital twin system. The articles that are found online cover an individual field or two at a time regarding data analysis technology. There are no overall studies found regarding this manner online. The purpose of this study is to provide an overview of the data level in the digital twin system, and it involves the data at various phases. This paper will provide a comparative study among all the fields in which digital twins have been applied in recent years. Digital twin works with a vast amount of data, which needs to be organized, stored, linked, and put together, which is also a motive of our study. Data is essential for building virtual models, making cyber-physical connections, and running intelligent operations. The current development status and the challenges present in the different phases of digital twin data analysis have been discussed. This paper also outlines how DT is used in different fields, like manufacturing, urban planning, agriculture, medicine, robotics, and the military/aviation industry, and shows a data structure based on every sector using recent review papers. Finally, we attempted to give a horizontal comparison based on the features of the data across various fields, to extract the commonalities and uniqueness of the data in different sectors, and to shed light on the challenges at the current level as well as the limitations and future of DT from a data standpoint.

C(sp2)-H selenylation of substituted benzo[4,5]imidazo[2,1-b]thiazoles using phenyliodine(iii)bis(trifluoroacetate) as a mediator.

Herein, an expeditious metal-free regioselective C-H selenylation of substituted benzo[4,5]imidazo[2,1-b]thiazole derivatives was devised to synthesize structurally orchestrated selenoethers with good to excellent yields. This PIFA [bis(trifluoroacetoxy)iodobenzene]-mediated protocol operates under mild conditions and offers broad functional group tolerance. In-depth mechanistic investigation supports the involvement of radical pathways. Furthermore, the synthetic utility of this methodology is portrayed through gram-scale synthesis.

Diastereocontrolled Construction of Spiroindolenines via Hexafluoroisopropanol-Promoted Dearomative Epoxide-Indole Cyclization.

Herein, we report the discovery of the ipso-selective, dearomatizing spirocyclization of indole-tethered epoxides as a fundamentally new approach for constructing spiroindolenines equipped with three contiguous stereogenic centers under complete diastereocontrol (dr >99:1) and in high yields. Promoted by hexafluoroisopropanol, the protocol features a broad substrate scope, easy scale-up, and versatile transformations of the synthesized spiroindolenines.

Cyber-agricultural systems for crop breeding and sustainable production.

The cyber-agricultural system (CAS) represents an overarching framework of agriculture that leverages recent advances in ubiquitous sensing, artificial intelligence, smart actuators, and scalable cyberinfrastructure (CI) in both breeding and production agriculture. We discuss the recent progress and perspective of the three fundamental components of CAS - sensing, modeling, and actuation - and the emerging concept of agricultural digital twins (DTs). We also discuss how scalable CI is becoming a key enabler of smart agriculture. In this review we shed light on the significance of CAS in revolutionizing crop breeding and production by enhancing efficiency, productivity, sustainability, and resilience to changing climate. Finally, we identify underexplored and promising future directions for CAS research and development.

Synthesis of benzimidazole-fused 1,4-benzoxazepines and benzosultams spiro-connected to a 2-oxindole core via a tandem epoxide-opening/SNAr approach.

While hundreds of literature reports describe the preparation of spirooxindole-based five- and six-membered heterocycles, the construction of seven-membered heterocyclic rings spiro-connected to a 2-oxindole core has so far been less developed. Herein, we disclose a base-mediated (4 + 3) annulation of spiro-epoxyoxindoles and 2-(2-fluoroaryl)-1H-benzoimidazoles or 2-fluoro-N-arylbenzenesulfonamides toward the synthesis of two new classes of spirooxindole-based polycyclic systems. Mechanistically, this conceptually simple and high atom-economical reaction proceeds via an SN2-like intermolecular epoxide ring-opening, accompanied by a concomitant intramolecular SNAr reaction. From a synthetic aspect, the notable features of the process are its full regioselectivity, operational simplicity using readily available substrates under transition-metal-free conditions, high yields, and broad substrate scope.

Copper(II)-Mediated, Site-Selective C(sp2)-H Sulfonamidation of 1-Naphthylamines.

An operationally simple and efficient protocol for copper(II)-mediated, picolinamido-directed C8-H sulfonamidation of 1-naphthylamine derivatives with various sulfonamides has been developed. Remarkably, this cross-dehydrogenative C-H/H-N coupling reaction exhibits a broad substrate scope with excellent functional group tolerance, is scalable, and enables an expeditious route to a library of unsymmetrical N-arylated sulfonamides in good to excellent yields with exclusive site selectivity.

A review on self-healing featured soft robotics.

Soft robots are becoming more popular because they can solve issues stiff robots cannot. Soft component and system design have seen several innovations recently. Next-generation robot-human interactions will depend on soft robotics. Soft material technologies integrate safety at the material level, speeding its integration with biological systems. Soft robotic systems must be as resilient as biological systems in unexpected, uncontrolled situations. Self-healing materials, especially polymeric and elastomeric ones, are widely studied. Since most currently under-development soft robotic systems are composed of polymeric or elastomeric materials, this finding may provide immediate assistance to the community developing soft robots. Self-healing and damage-resilient systems are making their way into actuators, structures, and sensors, even if soft robotics remains in its infancy. In the future, self-repairing soft robotic systems composed of polymers might save both money and the environment. Over the last decade, academics and businesses have grown interested in soft robotics. Despite several literature evaluations of the soft robotics subject, there seems to be a lack of systematic research on its intellectual structure and development despite the rising number of articles. This article gives an in-depth overview of the existing knowledge base on damage resistance and self-healing materials' fundamental structure and classifications. Current uses, problems with future implementation, and solutions to those problems are all included in this overview. Also discussed are potential applications and future directions for self-repairing soft robots.

Base-Mediated, Chemo- and Regioselective (4+2) Annulation of Indole-2-carboxamides with 2,3-Epoxy Tosylates toward 1,2-Fused Indoles.

Base-mediated [4+2] annulation of indole-2-carboxamides with 2,3-epoxy tosylates has been explored. The protocol delivers 3-substituted pyrazino[1,2-a]indol-1-ones in high yields in diastereoselective fashion, and neither 4-substituted pyrazino[1,2-a]indol-1-ones nor tetrahydro-1H-[1,4]diazepino[1,2-a]indol-1-ones are generated, irrespective of whether the distal epoxide C3 substituent is alkyl or aryl, or the epoxide is cis- or trans-configured. This reaction proceeds in one pot via N-alkylation of the indole scaffold with 2,3-epoxy tosylates, concomitantly followed by 6-exo-selective epoxide-opening cyclization. Notably, the process is chemo- and regioselective with respect to both the starting materials. To our knowledge, the process represents the first successful example of one-pot annulation of indole-based diheteronucleophiles with epoxide-based dielectrophiles.

An epoxide-opening cyclization/double Smiles rearrangement cascade approach to N-aryl-1,4-benzoxazines and N-arylindolines.

Reported herein is a transition-metal-free protocol for a regio- and diastereoselective synthesis of hydroxyalkyl group-embedded N-arylbenzo[b][1,4]oxazines and N-arylindolines based on an epoxide-opening cyclization/double Smiles rearrangement cascade of p-nosylamide-tethered epoxides. To the best of our knowledge, this is the first report of the integration of epoxide-opening cyclization with Smiles rearrangement in a cascade fashion, enabling simultaneous construction and N-arylation of N-heterocycles. The reaction employs substrates derived from commercially available 2-nitrophenols and easily accessible allylic halides/alcohols, and exhibits a broad substrate scope and delivers the products in high yields.

Non-Invasive Portable Technologies for Monitoring Breast Cancer Related Lymphedema to Facilitate Telehealth: A Scoping Review.

Breast cancer related lymphedema (BCRL) is a common, debilitating condition that can affect up to one in five breast cancer surviving patients (BCSP). BCRL can significantly reduce the quality of life (QOL) of patients and poses a significant challenge to healthcare providers. Early detection and continuous monitoring of lymphedema is crucial for the development of client-centered treatment plans for post-cancer surgery patients. Therefore, this comprehensive scoping review aimed to investigate the current technology methods used for the remote monitoring of BCRL and their potential to facilitate telehealth in the treatment of lymphedema. Initially, five electronic databases were systematically searched and analyzed following the PRISMA flow diagram. Studies were included, specifically if they provided data on the effectiveness of the intervention and were designed for the remote monitoring of BCRL. A total of 25 included studies reported 18 technological solutions to remotely monitor BCRL with significant methodological variation. Additionally, the technologies were categorized by method of detection and wearability. The findings of this comprehensive scoping review indicate that state-of-the-art commercial technologies were found to be more appropriate for clinical use than home monitoring, with portable 3D imaging tools being popular (SD 53.40) and accurate (correlation 0.9, p 0.05) for evaluating lymphedema in both clinic and home settings with expert practitioners and therapists. However, wearable technologies showed the most future potential for accessible and clinical long-term lymphedema management with positive telehealth outcomes. In conclusion, the absence of a viable telehealth device highlights the need for urgent research to develop a wearable device that can effectively track BCRL and facilitate remote monitoring, ultimately improving the quality of life for patients following post-cancer treatment.

A small molecule potent IRAK4 inhibitor abrogates lipopolysaccharide-induced macrophage inflammation in-vitro and in-vivo.

Increasing evidence supports vanillin and its analogs as potent toll-like receptor signaling inhibitors that strongly attenuate inflammation, though, the underlying molecular mechanism remains elusive. Here, we report that vanillin inhibits lipopolysaccharide (LPS)-induced toll-like receptor 4 activation in macrophages by targeting the myeloid differentiation primary-response gene 88 (MyD88)-dependent pathway through direct interaction and suppression of interleukin-1 receptor-associated kinase 4 (IRAK4) activity. Moreover, incubation of vanillin in cells expressing constitutively active forms of different toll-like receptor 4 signaling molecules revealed that vanillin could only able to block the ligand-independent constitutively activated IRAK4/1 or its upstream molecules-associated NF-κB activation and NF-κB transactivation along with the expression of various proinflammatory cytokines. A significant inhibition of LPS-induced IRAK4/MyD88, IRAK4/IRAK1, and IRAK1/TRAF6 association was evinced in response to vanillin treatment. Furthermore, mutations at Tyr262 and Asp329 residues in IRAK4 or modifications of 3-OMe and 4-OH side groups in vanillin, significantly reduced IRAK4 activity and vanillin function, respectively. Mice pretreated with vanillin followed by LPS challenge markedly impaired LPS-induced IRAK4 activation and inflammation in peritoneal macrophages. Thus, the present study posits vanillin as a novel and potent IRAK4 inhibitor and thus providing an opportunity for its therapeutic application in managing various inflammatory diseases.

ICl-Mediated Functional Group Interconversion from Methyl Homopropargyl Ether to α-Iodo-γ-chloroketone.

An ICl-mediated highly chemo- and regioselective functional group interconversion from methyl homopropargyl ether to α-iodo-γ-chloro-ketone is reported. Density functional theory (DFT)-calculated reaction coordinate and potential energy surface support the high chemo-selectivity observed for the formation of α-iodo-γ-chloroketone over furan. The five-membered oxonium ring formation-ring opening mechanism is a potential template for the preparation of polyfunctionalized carbonyl compounds.

Diastereoselective Synthesis of Indoline- and Pyrrole-Embedded Tetracycles via an Unprecedented Dearomative Indole-C3-Alkylation/Aza-Friedel-Crafts Cascade Reaction.

Dearomative indole C3-alkylation─intramolecular iminium trapping cascade reaction of indole-C3-tethered nucleophiles is a well-known blueprint for accessing 2,3-fused indolines. In exploring this strategy, synthetic chemists have utilized diverse classes of electrophilic reagents. However, the tethered nucleophiles have mainly been limited to heteronucleophiles and enolates; exploitation of tethered arenes/heteroarenes remains unknown. We herein describe the first examples of pyrrole-intercepted dearomative indole C3-allylation and benzylation of indole-tethered pyrroles toward the synthesis of 2,3-cis-fused tetracyclic indolines featuring a C3 all-carbon quaternary stereocentre. Our methodology capitalizes on the capability of NaOtBu/Et3B combination to direct the intermolecular alkylation to take place regioselectively at the indole C3 position over the other reactive sites (indole N and C2 and pyrrole C2 positions) and leverages the high nucleophilicity of the pyrrole template for the concomitant aza-Friedel-Crafts ring closure that traditionally would require an additional acid-catalyzed synthetic step. This cascade reaction is accomplished with broad substrate scope and excellent yields and chemo-, regio-, and diastereoselectivities.