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.

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.

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.

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.

Regioselectivity of the SEAr-based cyclizations and SEAr-terminated annulations of 3,5-unsubstituted, 4-substituted indoles.

Indole-3,4- and 4,5-fused carbo- and heterocycles are ubiquitous in bioactive natural products and pharmaceuticals, and hence, a variety of synthetic approaches toward such compounds have been developed. Among these, cyclization and annulation of 3,5-unsubstituted, 4-substituted indoles involving an electrophilic aromatic substitution (SEAr) as the ring closure are particularly attractive, because they avoid the use of 3,4- or 4,5-difunctionalized indoles as starting materials. However, since 3,5-unsubstituted, 4-substituted indoles have two potential ring-closure sites (indole C3 and C5 positions), such reactions in principle can furnish either or both of the indole 3,4- and 4,5-fused ring systems. This Commentary will briefly highlight the issue by summarizing recent relevant literature reports.

One-Pot Double Intramolecular Cyclization Approach to Tetralin-Based Cis-Fused Tetracyclic Compounds.

Presented herein is a BF3·OEt2-mediated, diastereoselective one-pot double cyclization of 4-aryl-2-[(arylthio)methyl]butanals leading to the formation of cis-tetrahydro-6H-naphtho[2,1-c]thiochromenes for the first time. Mechanistically, the formation of the title products involves the one-pot intramolecular Friedel-Crafts hydroxyalkylation/intramolecular Friedel-Crafts alkylation cascade. This synthetic methodology is featured by its high atom economy, broad substrate scope, mild transition-metal-free reaction conditions, capability to assemble two new rings in one pot, and moderate to high yields (up to 94% yield). It was then applied in the synthesis of a thia analogue of brazilane and a chromeno[3,4-c]chromene derivative. Moreover, the methodology was successfully extended to the synthesis of cis-hexahydrobenzo[c]phenanthrenes. Specifically, 1,5-diarylpentan-3-ones were first subjected to the Corey-Chaykovsky reaction, and the resulting epoxides, without being chromatographically isolated, were treated with BF3·OEt2 to afford the cyclized products in high yields (up to 84% yield over two steps).

Organocatalytic synthesis of (Het)biaryl scaffolds via photoinduced intra/intermolecular C(sp2)-H arylation by 2-pyridone derivatives.

A unique N,O-bidentate ligand 6-oxo-1,6-dihydro-pyridone-2-carboxylic acid dimethylamide (L1) catalyzed direct C(sp2)-H (intra/intermolecular) arylation of unactivated arenes has been developed to expedite access to (Het)biaryl scaffolds under UV-irradiation at room temperature. The protocol tolerated diverse functional groups and substitution patterns, affording the target products in moderate to excellent yields. Mechanistic investigations were also carried out to better understand the reaction pathway. Furthermore, the synthetic applicability of this unified approach has been showcased via the construction of biologically relevant 4-quinolone, tricyclic lactam and sultam derivatives.

The C-H functionalization of N-alkoxycarbamoyl indoles by transition metal catalysis.

Indole and its congeners are ubiquitous nitrogen-containing organic scaffolds present in a plethora of natural products, marketed drugs, and other organic functional molecules. Recent years have witnessed tremendous advances in the diversification of this motif and its biological applications via transition-metal-catalyzed auxiliary assisted site-selective inert C-H functionalization. In this burgeoning field, N-methoxy/ethoxy/pivaloxy amide functionality has emerged as a most potent auxiliary/DG (directing group) for a wide range of C-C and C-heteroatom bond formations, providing a new advance for forging structurally fabricated polycyclic indole frameworks. This review aims to highlight evolved transformations, like arylation, alkylation, alkenylation, allylation, amidation, difluorovinylation, deuteration, hydroarylation, etc., and the applications of N-alkoxycarbamoyl indole derivatives made within the period of 2014-August 2021. Additionally, explicit mechanistic underpinnings have also been provided in the appropriate places.