bluuebunny/crossref_metadata_2025_split huggingface dataset:
Halogen Bond Assisted Light Responsiveness of Para‐Quinone Methides for 1,6‐Conjugate Addition Reactions
Authors: Kumar Sunil , Justin Thomas K. R. 
Published: August 2024

AbstractThe ability to change the essential characteristics of the molecular systems using light is highly promising and finds use in photocatalysis and materials chemistry. A critical requirement for such systems is that molecules should directly absorb light in the visible region. Though small molecule activation by visible light is challenging, they on complexation with certain species respond to visible light favourably. Herein, we disclose the catalytic application of CBr4 as a halogen bond donor catalyst to activate para‐quinone methides towards visible light photo‐catalysed reactions. This protocol facilitates 1,6‐conjugate addition reactions with various nucleophiles, forming C−C and C−O bonds in para‐quinone methides, yielding the desired products in good to excellent yields. Mechanistic investigations reveal that para‐quinone methide responds to visible light only when complexed with CBr4. The synthetic utility of this protocol is demonstrated through the one‐pot synthesis of spiro‐cyclohexadienone compounds from 2‐naphthol and para‐quinone methide.
A Two‐Step Intermolecular Interaction Of Molecular Macroions With Multivalent Counterions
Authors: Xiao Kexing , Zhou Yifan , Xu Xiaohan , Szymanowski Jennifer E. S. , Yang Yuqing , Afsari Bahareh , Burns Peter C. , Liu Tianbo 
Published: August 2024

AbstractMacroion‐counterion interaction is essential for regulating the solution behaviors of hydrophilic macroions, as simple models for polyelectrolytes. Here, we explore the interaction between uranyl peroxide molecular cluster Li68K12(OH)20[UO2(O2)OH]60 (U60) and multivalent counterions. Different from interaction with monovalent counterions that shows a simple one‐step process, isothermal titration calorimetry, combined with light/X‐ray scattering measurements and electron microscopy, confirm a two‐step process for their interaction with multivalent counterions: an ion‐pairing between U60 and the counterion with partial breakage of hydration shells followed by strong U60‐U60 attraction, leading to the formation of large nanosheets with severe breakage and reconstruction of hydration shells. The detailed studies on macroion‐counterion interaction can be nicely correlated to the microscopic (self‐assembly) and macroscopic (gelation or phase separation) phase transitions in the dilute U60 aqueous solutions induced by multivalent counterions.
Selective and Scalable Deuteration of Heteroarenes Using Nickel‐Based Nanoparticles†
Authors: Qiu Feiyu , Yang Lingyun , Gao Yuan , Yang Jiapei , Lei Aiwen , Li Wu 
Published: August 2024

Comprehensive SummaryDeuterium labelling possesses wide applications in pharmaceuticals, chemical science and materials science. Development of efficient methodologies for the synthesis of deuterium labelled compounds, especially hydrogen isotope exchange (HIE), continued to receive an impressive attention over the years. Herein, we developed a nitrogen doped nano‐scale nickel catalyst for deuterium incorporation of a variety of nitrogen heterocycles using D2O as the isotope source. The usefulness of this approach has been demonstrated by 10 g‐scale for complex pharmaceuticals. This methodology represents a practical and scalable deuteration and the air‐ and water‐stable nanocatalyst enables efficient labelling in a straightforward manner.
Palladium‐Catalyzed Construction of Phthalides Bearing Two Adjacent Stereocenters through Retro‐oxa‐Michael Addition
Authors: Liu Li‐Xia , Niu Tong , Bai Yu‐Qing , Zhou Yong‐Gui 
Published: August 2024

Comprehensive SummaryOptically active phthalides are prevalent in many natural and bioactive products. Herein, a novel dynamic kinetic resolution of isobenzofuranone derivatives through palladium‐catalyzed asymmetric allylic alkylation has been developed to synthesize phthalide derivatives bearing vicinal quaternary and tertiary stereocenters with high yields, showing excellent chemo‐, enantio‐ and diastereoselectivity. Furthermore, gram‐scale experiment underwent smoothly and the transformation of product could build a bridged bicyclic skeleton.
Enhanced One/Two‐Photon Initiating Performance of Nitro‐Carbazole‐Styrene Based Oxime/Ketoxime Esters
Authors: Xie Jie , Wang Yonghui , Wang Xiaobin , Fang Xuefeng , Zhu Qinyan , Cao Chun , Jin Ming 
Published: August 2024

Comprehensive SummaryPhotoinitiators of the oxime ester (OXE) or ketoxime ester (OXE‐CO) type can rapidly undergo N—O bond cleavage and generate free radicals to initiate photopolymerization under LED excitation, occupying an important position in the field of photocuring. However, the commercial OXEs, e.g., OXE 01 and 02 with λmax's at 326 and 344 nm, respectively, still do not well match the emission spectra of LEDs. Developing novel OXEs/OXE‐COs with high photosensitivity for long‐wavelength LEDs has great significance. Here, four new OXEs/OXE‐COs with nitro‐carbazole‐styrene conjugated chromophore were designed, synthesized, and used as photoinitiators. Results demonstrated that all photoinitiators had strong absorption within the UV–vis range (λmax: 381—392 nm, εmax: 8200—11500 M−1·cm−1). Molecular design of the oxime ester cleavage to produce a small volume methyl group and a methacryl group with an unsaturated double bond brings high activity and low migration, respectively, in one‐photon polymerization under 365—450 nm LEDs excitation. Moreover, OXEs/OXE‐COs with PETA exhibited a wide processing window, high resolution (line accuracy~100 nm) and good nano‐patterning capability under 780 nm femtosecond laser irradiation in two‐photon polymerization, indicating their great potential in 2D/3D microfabrication technologies.
C, N, and P contributions to sediments of two Venezuelan coastal lagoons and their relationships with the adsorption of P
Authors: López‐Hernández Danilo , Morales Leidy , Umbría‐Salinas Karelys , Valero Astolfo , Melendez Williams , López‐Contreras Ana 
Published: August 2024

AbstractIn Unare and Píritu Coastal Lagoons, a study was carried out to assess the effect of C, N, and P load contributions on the capability of the sediments to immobilize phosphates. To achieve the later, the geochemical data of the sediments were coupled to the P‐sorption index of Bache and Williams (IBW). In both lagoons, the sediments showed a pH > 7 because of calcareous sedimentation. The inorganic carbon values in the lagoons displayed a spatial distribution with higher concentrations toward the shores, that is defined by the carbonate lithology. On the contrary, the inner part of the lagoons was characterized by the presence of organic materials associated to the clay. The phosphorus content in the Unare Lagoon ranged from 290 to 625 mg kg−1, whereas in the Píritu Lagoon the values fluctuated between 213 and 1013 mg kg−1. The highest concentrations of phosphorus in both lagoons could be linked to sewage and runoff input from agricultural and livestock activities around the lagoon systems. The IBW displayed adsorption average values of 21.97 and 27.42 for Unare and Píritu Lagoon, respectively, corresponding to a rather low P sorption. In Unare Lagoon, the IBW showed positive correlations with C, N and Felabile but negative with P. However, in the Píritu Lagoon, despite the analogous lithology of the lagoons, a slightly positive non‐significative correlation between IBW and IC was only found. Although the sediments adsorb P with a rather low capacity, they can mitigate the eutrophication process in the studied lagoons.
Building an intrusion detection system on UNSW‐NB15: Reducing the margin of error to deal with data overlap and imbalance
Authors: Zoghi Zeinab , Serpen Gursel 
Published: August 2024

SummaryThis study addresses the challenge of data imbalance and class overlap in machine learning for intrusion detection, proposing that targeted algorithmic adjustments can significantly enhance model performance. Our hypothesis contends that an ensemble framework, adeptly integrating novel threshold‐adjustment algorithms, can improve classification sensitivity and specificity. To test this, we developed an ensemble model comprising Balanced Bagging (BB), eXtreme Gradient Boosting (XGBoost), and Random Forest (RF), fine‐tuned using grid search for BB and XGBoost, and augmented with the Hellinger metric for RF to tackle data imbalance. The innovation lies in our algorithms, which adeptly adjust the discrimination threshold to rectify the class overlap problem, enhancing the model's ability to discern between negative and positive classes. Utilizing the UNSW‐NB15 dataset, we conducted a comparative analysis for binary and multi‐category classification. Our ensemble model achieved a binary classification accuracy of 97.80%, with a sensitivity rate of 98.26% for detecting attacks, and a multi‐category classification accuracy and sensitivity that reached up to 99.73% and 97.24% for certain attack types. These results substantially surpass those of existing models on the same dataset, affirming our model's superiority in dealing with complex data distributions prevalent in network security domains.
Dual‐task enhanced global–local temporal–spatial network for depression recognition from facial videos
Authors: Shen Jinjie , Wu Jing , Xing Yan , Hu Min , Wang Xiaohua , Li Daolun , Zha Wenshu 
Published: August 2024

SummaryIn previous studies on facial video depression recognition, although convolutional neural network (CNN) has become a mainstream method, its performance still has room for improvement due to the insufficient extraction of global and local information and the neglect of the correlation of temporal and spatial information. This paper proposes a novel dual‐task enhanced global–local temporal–spatial network (DTE‐GLTS) to enhance the extraction capability of global and local features and deepen the analysis of temporal–spatial information correlation. We design a dual‐task learning mode that utilizes the data‐efficient image transformer (Deit) as the main body to learn the global features of video sequences and guides Deit to learn local features with the pre‐trained temporal–spatial fusion network (TSF). In addition, we propose the TSF mechanism to more effectively fuse temporal–spatial information in video sequences, strengthen the correlation between frames and pixels, and embed it in Resnet to form the TSF network. To the best of our knowledge, this is the first application of Deit and dual‐task learning mode in the field of facial video depression recognition. The experimental results on AVEC 2013 and AVEC 2014 show that our method achieves competitive performance, with mean absolute error/root mean square error (MAE/RMSE) scores of 6.06/7.73 and 5.91/7.68, respectively, while significantly reducing the number of parameters.
Recommending cloud services based on social trust: An overview
Authors: Lebib Fatma Zohra , Kichou Saida 
Published: August 2024

AbstractThe continued expansion and development of the business requires great computing power and massive data storage systems. Cloud services deliver these resources in a simple, flexible and secure way. There is now a wide range of similar cloud services with different capabilities, which requires a recommendation system. Recommendation based on Quality of Service (QoS) is the first generation of service recommendation systems that only takes into account the rating information of all users without distinction. However, these systems suffer from many shortcomings, such as cold start and data sparsity issues, as well as poor accuracy and reliability of recommendation results. To address these issues and improve the quality of recommendations, a new generation of recommender systems has emerged, such as context‐aware, domain‐specific, and trust‐aware recommender systems. These systems now focus more on how to leverage social data generated from user interactions with each other in social networks to recommend more suitable and reliable services in response to user needs. Due to the importance of considering trust in cloud environments, this study aims to provide an overview of the research on trust‐based cloud service recommendation approaches proposed so far and highlights the current trend towards use new technologies such as deep learning to deal with certain challenges.
Enhanced multi‐key privacy‐preserving distributed deep learning protocol with application to diabetic retinopathy diagnosis
Authors: Antwi‐Boasiako Emmanuel , Zhou Shijie , Liao Yongjian , Obiri Isaac Amankona , Kuada Eric , Danso Ebenezer Kwaku , Acheampong Edward Mensah 
Published: August 2024

SummaryIn this work, privacy‐preserving distributed deep learning (PPDDL) is re‐visited with a specific application to diagnosing long‐term illness like diabetic retinopathy. In order to protect the privacy of participants datasets, a multi‐key PPDDL solution is proposed which is robust against collusion attacks and is also post‐quantum robust. Additionally, the PPDDL solution provides robust network security in terms of integrity of transmitted ciphertexts and keys, forward secrecy, and prevention of man‐in‐the‐middle attacks and is extensively verified using Verifpal. Proposed solution is evaluated on retina image datasets to detect diabetic retinopathy, with deep learning accuracy results of 96.30%, 96.21% and 96.20% for DDL, DDL + SINGLE and DDL + MULTI scenarios respectively. Results from our simulation indicate that accuracy of the PPDDL is maintained while protecting the privacy of the datasets of participants. Our proposed solution is also efficient in terms of the communication and run‐time costs.
Research on insulator image segmentation and defect recognition technology based on U‐Net and YOLOv7
Authors: Chen Jiawen , Cai Chao , Yan Fangbin , Zhou Bowen 
Published: August 2024

AbstractThis study focuses on aerial images in power line inspection, using a small sample size and concentrating on accurately segmenting insulators in images and identifying potential “self‐explode” defects through deep learning methods. The research process consists of four key steps: image segmentation of insulators, identification of small connected regions, data augmentation of original samples, and detection of insulator defects using the YOLO v7 model. In this paper, due to the small sample size, sample expansion is considered first. A sliding window approach is adopted to crop images, increasing the number of training samples. Subsequently, the U‐Net neural network model for semantic segmentation is used to train insulator images, thereby generating preliminary mask images of insulators. Then, through connected region area filtering techniques, smaller connected regions are removed to eliminate small speckles in the predicted mask images, obtaining more accurate insulator mask images. The evaluation metric for image recognition, the dice coefficient, is 93.67%. To target the identification of insulator defects, 35 images with insulator defects from the original samples are augmented. These images are input into the YOLO v7 network for further training, ultimately achieving effective detection of insulator “self‐explode” defects.
Generation of Murine Chimeric Antigen Receptor‐Modified T Cells for In Vivo Studies in Syngeneic Tumor Models
Authors: Hosseini Mina , Akbari Behnia , Shahverdi Ahmad Reza , Hadjati Jamshid , Faramarzi Mohammad Ali , Mirzaei Hamid Reza , Yazdi Mohammad Hossein 
Published: August 2024

AbstractCAR‐T cell therapy has emerged as a potent and effective tool in the immunotherapy of refractory cancers. However, challenges exist in their clinical application, necessitating extensive preclinical research to optimize their function. Various preclinical in vitro and in vivo models have been proposed for such purpose; among which immunocompetent mouse models serve as an invaluable tool in studying host immune interactions within a more realistic simulation of the tumor milieu. We hereby describe a standardized protocol for the generation of high‐titer γ‐retroviral vectors through transfection of the HEK293T packaging cell line. The virus‐containing supernatant is further concentrated using an inhouse concentrator solution, titrated, and applied to mouse T cells purified via a convenient and rapid method by nylon‐wool columns. Using the method presented here, we were able to achieve high titer γ‐retrovirus and highly pure mouse T cells with desirable CAR transduction efficiency. The mouse CAR T cells produced through this protocol demonstrate favorable CAR expression and viability, thus making them suitable for further in vitro/in vivo assays. © 2024 Wiley Periodicals LLC.Basic Protocol 1: Production of γ‐retroviral vectors from retrovirus‐backbone plasmidsBasic Protocol 2: Concentration of γ‐retrovirus‐containing supernatantsBasic Protocol 3: Titration of concentrated γ‐retrovirusBasic Protocol 4: Isolation and activation of mouse T cellsBasic Protocol 5: Transduction of activated mouse T cells, assessment of CAR expression, and expansion of CAR T cells for further in vitro/in vivo studiesSupport Protocol: Surface staining of cells for flow cytometric assessment of CAR expression
Promoting radical empathy: Changes in empathy and perspective taking at a youth summer camp that centers restorative practices
Authors: Merrilees Christine E. , Taber‐Thomas Bradley C. , Klotz Madeline 
Published: August 2024

AbstractEmpathy is crucial to promoting positive intergroup relations; research suggests engaging in restorative practices, autonomy granting, and creativity support empathy development. The current study uses a daily diary to evaluate changes in empathy, creativity, feeling in control/empowered in a small sample (N = 41) of adolescents during a two‐week session of summer camp that centers restorative practices. The results suggest participants increase significantly in emotional empathy, perspective taking, and creativity during their time at camp. The results also suggest that on days participants feel more in control and have expressed more creativity, they report more empathy and perspective taking. These findings provide important evidence using intensive longitudinal data that youth programming that centers restorative practices, autonomy support, and creativity may support empathy development.
Diaminopropane‐Functionalized Metal‐Organic Frameworks with Controllable Diamine Loss and One‐Channel Flipped CO2 Adsorption Mode
Authors: Kang Minjung , Youn Jeongwon , Choe Jong Hyeak , Lee Jung‐Hoon , Hong Chang Seop 
Published: August 2024

AbstractDiamine‐functionalized metal–organic frameworks (MOFs) based on Mg2(dobpdc) (dobpdc4−=4,4’‐dioxidobihyenyl‐3,3’‐dicarboxylate) are considered promising CO2 adsorbents owing to their characteristic stepwise adsorption behavior. However, the high temperatures required for CO2 desorption from diamine‐Mg2(dobpdc)‐based adsorbents induce gradual diamine loss. Additionally, the existence of an exotic CO2 adsorption mode remains experimentally unanswered. Herein, we present CO2 adsorbents obtained by functionalizing Mn2(dobpdc) with a series of diaminopropane derivatives. The low regeneration energies of these adsorbents allow for CO2 desorption at temperatures lower than those reported for Mg‐based analogs. Our first‐principles density functional theory calculations indicated that the bond strength between the diamine and Mn ions in Mn2(dobpdc) is greater than that between the diamine and Mg ions in Mg2(dobpdc). This stronger bonding prevents diamine loss even at high temperatures and enables efficient regeneration. Additionally, the computational and experimental results showed that MOFs functionalized with primary–tertiary diamine exhibit unique one‐channel flipped adsorption structures that have not been previously observed. Our findings provide valuable insights into the role of metal ions in diamine loss for the future development of efficient amine‐based CO2 adsorbents.
Copper‐Catalyzed Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Diformylfuran Assisted by TEMPOL in Liquid Sunlight Methanol
Authors: Li Xing‐Long , Qing Shao‐Jun , Sun Xun , Yu Zhen , Xu Hua‐Jian , Fu Yao 
Published: August 2024

Abstract2,5‐diformylfuran (DFF) is a significant biomass‐derived compound with diverse applications in novel furan‐based materials, fragrances, fuel additives, and drug synthesis. A pivotal challenge in DFF synthesis was developing a method to produce DFF under mild conditions using sustainable feedstocks. In this study, an affordable 4‐hydroxy‐2,2,6,6‐tetramethylpiperidine (TEMPOL)‐ assisted Cu(OAc)2 catalytic system for aerobic oxidation reaction of HMF to DFF in liquid sunlight methanol solvent was developed. The effects of parameters such as metal species, catalyst amount, solvent species, base structure, and reaction temperature were systematically investigated. The evolution of product distribution in the reaction solution at various times was monitored and analyzed using 1H‐NMR spectroscopy. FT‐IR and ESI‐MS characterizations were employed to integrate experimental findings and elucidate the reaction mechanism. The highest DFF yield of 96 % and complete conversion of HMF were obtained. Furthermore, a total DFF yield of 68.6 % was achieved from fructose using a two‐steps method, demonstrating the potential for scalable production. The establishment of this catalytic system presents a novel approach for the selective preparation of DFF from sustainable feedstock.
Intense Pulsed Light Hair Removal
Authors: Leal‐Silva Hector , Leal‐Delgado Sebastián 
Published: August 2024

AbstractBackgroundThe use of intense pulsed light (IPL) for hair removal has proven to be quite effective for conditions such as hypertrichosis and hirsutism, as well as other skin conditions related to the pilosebaceous unit. IPL was developed in the 1990s and uses a broad spectrum of light to penetrate the skin and reach the hair follicle, enabling treatment for various skin types and hair colors. This review covers the history, mechanism of action, effectiveness, patient selection, and clinical applications of IPL hair removal.MethodsTo conduct this review, a comprehensive literature search was conducted to identify relevant peer‐reviewed articles in English discussing the clinical use or application‐based outcomes of this technology specifically for hair removal. The search covered the period from January 1990 to May 2024.ResultsThe review of 33 peer‐reviewed articles shows that IPL has significantly advanced hair removal treatment since its inception. A popular choice in clinical practice due to its efficacy, safety, and versatility, IPL hair removal has been successfully used in patients with skin conditions like acne, folliculitis, rosacea, and hyperpigmentation, offering additional benefits compared to laser hair removal.ConclusionIPL hair removal is a safe and effective option for reducing unwanted hair and improving skin appearance. It can also treat multiple skin conditions simultaneously with a low risk of side effects. Additionally, it's less painful than laser hair removal, making it an attractive option for long‐lasting hair removal, especially for patients with co‐existing dermatological conditions.